JP2023148009A - Laminate for blister pack and blister pack - Google Patents

Abstract

To provide a laminate for a blister pack which has excellent laminate strength and moldability, and has excellent moist heat resistance and external stress durability after molding, and to provide a blister pack which has excellent moist heat durability and external stress durability.SOLUTION: A laminate for a blister pack includes a constitution in which at least an outer layer side resin film layer (1), an outer layer side adhesive agent layer (2), a metal foil layer (3), an inner layer side adhesive agent layer (4) and an inner layer side resin film layer (5) are laminated in this order. The outer layer side adhesive agent layer (2) is formed by a polyurethane adhesive containing a main agent (A) containing polyurethane resin (a) having a hydroxy group and a hardening agent containing a polyisocyanate component (B). The polyurethane resin (a) having a hydroxy group is a reaction product of polyester polyol and polyisocyanate, and ester bond concentration is 9.20-10.50 mmol/g.SELECTED DRAWING: Figure 1

Description

The present invention relates to a blister pack laminate that is molded and used for packaging medicines, etc., and a blister pack that includes a lid material on the blister pack laminate, which has a good appearance and is excellent in appearance. The present invention relates to a laminate for a blister pack and a blister pack having adhesive strength, moldability, and external stress resistance.

As a container for packaging granular pharmaceutical tablets, sweets, etc., the outer resin film layer (1), the outer adhesive layer (2), the metal foil layer (3), the inner adhesive layer (4), and the heat seal layer are used. A blister pack is known in which a laminate for a blister pack having a structure in which (5) is laminated from the outside in this order is molded using vacuum foam or the like. In addition to functions to protect the contents, such as airtightness and moisture resistance, blister packs are required to have excellent moldability in order to package larger contents.

Patent Document 1 discloses a packaging material for molding that includes an adhesive layer between a heat-resistant resin layer and a thin metal layer using a two-component curing polyester urethane adhesive containing a specific polyester polyol and a polyfunctional isocyanate. It is disclosed that it can be used as a packaging material for pharmaceutical products.
Patent Document 2 discloses a laminate for a blister pack that includes an adhesive layer containing a main agent containing a polyester polyol and an epoxy compound, and a curing agent containing an isocyanate compound in a predetermined ratio.
Patent Document 3 discloses a packaging material comprising a laminate adhesive layer containing a polyisocyanate component, a polyester polyurethane polyol component having a specific weight average molecular weight, and an epoxy component having a specific epoxy equivalent, and is used as a packaging material for pharmaceuticals. It is stated that it can be used.

Japanese Patent Application Publication No. 2015-024862 International Publication No. 2018/047672 JP2019-156925A

In recent years, in order to package larger and more diverse contents, there has been an increasing demand for taller or more complex molding, and even better moldability is required. Furthermore, from the viewpoint of protecting the contents, it is required that the adhesive strength between each layer be maintained at a high level when stored for a long period of time in a high temperature and high humidity environment. Furthermore, from the viewpoint of protecting the contents, it is required that the metal foil in the laminate does not break when the molded part is deformed by external force.

However, the packaging materials described in Patent Documents 1 and 2 use non-urethanized polyester resin as the main ingredient and have a low molecular weight, so the lamination strength is not sufficient and they cannot be stored for long periods in high temperature and high humidity environments. However, there is a problem in that the adhesive layer deteriorates and adhesive strength cannot be maintained. Another problem is that the metal foil in the laminate tends to break when external stress is applied to the molded part.
The packaging material described in Patent Document 3 does not have sufficient laminate strength because the ester bond concentration of the polyurethane polyol is low, and the metal foil in the laminate is likely to break when external stress is applied to the molded part. There are challenges.
Therefore, an object of the present invention is to provide a laminate for a blister pack that has excellent lamination strength and moldability, and also has excellent moist heat resistance and external stress resistance after molding. Another object of the present invention is to provide a blister pack that has excellent heat and humidity resistance and external stress resistance.

As a result of intensive studies to solve the above problems, it was discovered that the above problems could be solved by the embodiments shown below, and the present invention was completed.

The laminate for a blister pack according to one aspect of the present invention includes at least an outer resin film layer (1), an outer adhesive layer (2), a metal foil layer (3), an inner adhesive layer (4), and A laminate for a blister pack having a structure in which the inner resin film layer (5) is laminated in this order, and the outer adhesive layer (2) contains a polyurethane resin (a) having a hydroxyl group. It is formed from a polyurethane adhesive containing a main ingredient (A) and a curing agent containing a polyisocyanate component (B), and the polyurethane resin (a) having a hydroxyl group is a combination of a polyester polyol and a polyisocyanate. It is a reaction product and is characterized by an ester bond concentration of 9.20 to 10.50 mmol/g.

A laminate for a blister pack according to one aspect of the present invention is characterized in that the polyurethane resin (a) having hydroxyl groups has a urethane bond concentration of 0.10 to 0.90 mmol/g.

The laminate for a blister pack according to one aspect of the present invention is characterized in that the hydroxyl group-containing polyurethane resin (a) has a hydroxyl value of 0.5 to 20 mgKOH/g.

The laminate for a blister pack according to one aspect of the present invention is a reaction product of a polyester polyol having a weight average molecular weight of 5,000 to 30,000 as the polyurethane resin (a) having hydroxyl groups and a polyisocyanate. It is characterized by

The laminate for a blister pack according to one aspect of the present invention is characterized in that the polyurethane resin (a) having hydroxyl groups has a weight average molecular weight of 50,000 to 100,000.

A laminate for a blister pack according to one aspect of the present invention is characterized in that the outer resin film layer (1) is made of polyamide.

A laminate for a blister pack according to one aspect of the present invention is characterized in that the inner resin film layer (5) is made of polyvinyl chloride.

A blister pack according to one aspect of the present invention is characterized in that the blister pack laminate includes a lid material.

A blister pack according to one aspect of the present invention is characterized in that the lid material includes a metal layer.

ADVANTAGE OF THE INVENTION According to the present invention, it is possible to provide a laminate for a blister pack that has excellent lamination strength and moldability, and is also excellent in heat-and-moisture resistance and external stress resistance after molding. Further, according to the present invention, it is possible to provide a blister pack that has excellent heat and humidity resistance and external stress resistance.

FIG. 1 is a schematic cross-sectional view of a blister pack laminate of the present invention. FIG. 1 is a schematic cross-sectional view of a blister pack of the present invention.

<Laminated body for blister pack>
The laminate for blister packs of the present invention comprises at least an outer resin film layer (1), an outer adhesive layer (2), a metal foil layer (3), an inner adhesive layer (4), and an inner resin film. The layers (5) are laminated in this order from the outside, and the outer adhesive layer (2) contains a base material (A) containing a polyurethane resin (a) having a hydroxyl group, and a polyisocyanate component ( The polyurethane resin (a) having a hydroxyl group is a reaction product of a polyester polyol and a polyisocyanate, and has an ester bond concentration of 9. It is a blister pack film with a concentration of .20 to 10.50 mmol/g.
Hereinafter, the present invention will be described in detail by citing preferred embodiments as examples.

<Outer adhesive layer (2)>
The outer adhesive layer (2) in the present invention is formed from a polyurethane adhesive containing a main resin (A) containing a polyurethane resin (a) having a hydroxyl group, and a curing agent containing a polyisocyanate component (B). .
First, the main ingredient will be explained. The main ingredient and the curing agent may contain known additives to the extent that the effects of the present invention are not impaired.

[Polyurethane resin (a) having hydroxyl group]
The polyurethane resin (a) having hydroxyl groups is a reaction product of polyester polyol and polyisocyanate, and is characterized by having an ester bond concentration of 9.20 to 10.50 mmol/g. The polyurethane resin (a) having a hydroxyl group can be obtained by subjecting a hydroxyl group in a polyol, including a polyester polyol described below, and an isocyanate group in a polyisocyanate to a urethanization reaction under conditions where the hydroxyl groups are in excess.

(Polyester polyol)
Examples of polyester polyols include, but are not limited to, polyester polyols obtained by reacting a carboxylic acid component and a hydroxyl group component.
Examples of the carboxylic acid component include dibasic acids having an aromatic ring such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and phthalic anhydride; adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, and tetrahydrophthalic anhydride. acid, aliphatic dibasic acids such as hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride; or dialkyl esters thereof, or mixtures thereof.
Examples of the hydroxyl group component include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, butylene glycol, neopentyl glycol, dineopentyl glycol, trimethylolpropane, glycerin, 1,6-hexanediol, 1 , 4-butanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, 1,9-nonanediol, polyoxyethylene glycol, polyoxypropylene glycol , polytetramethylene ether glycol, polyether polyol, polycarbonate polyol, polyolefin polyol, acrylic polyol, polyurethane polyol; or mixtures thereof.
The above carboxylic acid component and hydroxyl group component may each be used singly, but it is preferable to use two or more types in combination.

The carboxylic acid component preferably contains 5 to 55 mol% of an aliphatic dibasic acid based on the total carboxylic acid component. When the blending amount of the aliphatic dibasic acid is 5 mol % or more, the solvent solubility increases and the resulting polyester polyol solution has a low viscosity. This improves the coating properties of the polyurethane adhesive and provides a packaging material with better appearance. When the content is 55 mol% or less, the glass transition temperature of the polyester polyol can be easily adjusted, and the adhesive strength is further improved. From the same viewpoint, the amount of the aliphatic dibasic acid to be blended is more preferably 25 to 50 mol % based on the total carboxylic acid components.

The ester bond concentration of the polyester polyol is preferably 9.40 mmol/g to 10.80 mmol/g, more preferably 9.40 to 10.30 mmol/g, even more preferably 9.40 to 9.80 mmol/g.
It is preferable that the ester bond concentration of the polyester polyol is 9.40 mmol/g or more, since it has excellent solubility in ester solvents such as ethyl acetate, and the amount of isocyanate used for urethanization is not limited, so good adhesiveness can be exhibited. . A content of 10.80 mmol/g or less is preferable because it suppresses increase in viscosity and decrease in solvent solubility due to intermolecular interactions caused by ester bonds.

The ester bond concentration of polyester polyol can be calculated using the following formula.
Formula: Polyester bond concentration (mmol/g) = molar amount of carboxylic acid component charged x total number of carboxylic acid functional groups / (total charged amount x solid yield) x 1000
Taking the polyester of Synthesis Example 1 as an example,
Isophthalic acid (number of functional groups: 2): 148 g = 0.892 mol,
Terephthalic acid (number of functional groups: 2): 296 g = 1.783 mol,
Adipic acid (number of functional groups: 2): 260 g = 1.780 mol,
Total amount charged 1000.05g, yield 83.9%
Therefore, the ester bond concentration of polyester 1 is
(0.892×2+1.783×2+1.780×2)/(1000.5×0.839)×1000=10.63
It can be calculated as follows.

The weight average molecular weight of the polyester polyol is preferably 5,000 to 30,000, more preferably 15,000 to 25,000. When the weight average molecular weight is 5,000 or more, the adhesiveness to the base material is further improved and the processability is excellent. When the weight average molecular weight is 30,000 or less, the concentration of hydroxyl groups at the terminals of the polyester polyol can be easily prevented from becoming excessively low, and the polyurethane resin (a) having hydroxyl groups can be obtained by reacting with the polyisocyanate described below. In this case, prolongation of the reaction time can be easily prevented.

As the polyol constituting the polyurethane resin (a) having a hydroxyl group, conventionally known polyols can be used in combination with the above-mentioned polyester polyol. Examples of polyols that can be used in combination include the hydroxyl group components that can be used in the polyester polyol synthesis described above, and neobentyl glycol and 1,4-butanediol can be suitably used.

(Polyisocyanate)
Examples of the polyisocyanate constituting the polyurethane resin (a) having a hydroxyl group include aliphatic diisocyanates, cycloaliphatic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, trifunctional or higher functional polyisocyanate monomers, and monomers from the above diisocyanates. Various derivatives can be mentioned.

Examples of aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2 , 4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl caproate.

Examples of the alicyclic diisocyanate include 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and methyl -2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,4-bis(isocyanatemethyl)cyclohexane, and 1,3-bis(isocyanatemethyl)cyclohexane.

Examples of the aromatic diisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6- Examples thereof include tolylene diisocyanate or a mixture thereof, 4,4'-toluidine diisocyanate, dianisidine diisocyanate, and 4,4'-diphenyl ether diisocyanate.

Examples of the araliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis(1 -isocyanate-1-methylethyl)benzene or a mixture thereof.

Examples of trifunctional or higher-functional polyisocyanate monomers include triphenylmethane-4,4',4''-triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatetoluene, etc. Triisocyanate: Examples include tetraisocyanates such as 4,4'-diphenyldimethylmethane-2,2'-5,5'-tetraisocyanate.

Various derivatives derived from the diisocyanate include the diisocyanate, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, Addition with low molecular weight polyols with a molecular weight of less than 200 such as 3,3'-dimethylolpropane, cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, or castor oil, etc. body (adduct body); trimer (also referred to as trimer or nurate body) of the diisocyanate; biuret body; allophanate body; as well as 2,4,6-oxadiazinetrione ring obtained from carbon dioxide gas and the diisocyanate. A polyisocyanate having the following can be used.

The polyisocyanate constituting the polyurethane resin (a) having a hydroxyl group is preferably an aromatic isocyanate or an alicyclic diisocyanate, and more preferably tolylene diisocyanate from the viewpoint of moldability and adhesiveness after a high temperature and high humidity test. , 4,4'-diphenyl diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate.

The reaction temperature of the polyol and polyisocyanate when obtaining the polyurethane resin (a) having hydroxyl groups is preferably in the range of 50°C to 200°C, more preferably 80 to 150°C. In the urethanization reaction, the molar ratio of the isocyanate groups of the polyisocyanate to the hydroxyl groups in the polyol (number of moles of isocyanate groups/number of moles of hydroxyl groups) is preferably 0.1 to 0.9, more preferably 0. It is 3 to 0.8.

In the present invention, it is important that the ester bond concentration of the polyurethane resin (a) having hydroxyl groups constituting the outer adhesive layer is in the range of 9.20 mmol/g to 10.50 mmol/g. By controlling the adhesive within a predetermined range, the stability of the adhesive solution and the affinity for the base material due to ester bonds can be controlled, and excellent coating properties can be achieved. As a result, the resulting laminate does not have a decrease in adhesive strength between the layers even after a high temperature, high humidity, long-term durability test, has excellent moldability, and does not suffer from appearance defects such as floating between layers. Furthermore, the laminate does not break when the molded part is deformed by an external force.
When the ester bond concentration is less than 9.20 mmol/g, the solubility in ester solvents such as ethyl acetate decreases, and coatability decreases. Alternatively, the affinity for the base material due to ester bonds decreases, resulting in a decrease in adhesive strength. If it exceeds 10.50 mmol/g, intermolecular interactions due to ester bonds will increase, viscosity will increase, solvent solubility will decrease, and the appearance after aging will deteriorate due to coating defects.
The ester bond concentration of the polyurethane resin (a) having hydroxyl groups is preferably 9.20 to 10.10 mmol/g, more preferably 9.20 to 9.60 mmol/g.

The ester bond concentration of the polyurethane resin (a) having hydroxyl groups can be calculated using the following formula.
Calculation formula: Ester bond concentration (mmol/g) = ester bond concentration of polyester polyol x ratio of polyester polyol to the total mass of polyol and polyisocyanate constituting the urethane resin (mass%)
For example, the ester bond concentration of the polyurethane resin (a) having hydroxyl groups shown in Synthesis Example (a)-1 is:
Ester bond concentration = 10.63 x (100/102) = 10.42 mmol/g
becomes.

The urethane bond concentration of the polyurethane resin (a) having hydroxyl groups is preferably in the range of 0.10 to 0.90 mmol/g, more preferably 0.15 to 0.60 mmol/g, even more preferably 0.20 mmol/g. ~0.40 mmol/g. If it is 0.10 mmol/g or more, an excellent compatibility improvement effect can be obtained and the appearance and adhesiveness will be improved, so it is preferable. If it is 0.90 mmol/g or less, the urethane bond concentration will not be too high and the viscosity will be appropriate, resulting in excellent coatability and appearance, which is preferable.
By controlling the urethane bond concentration of the polyurethane resin (a) having hydroxyl groups, it is possible to improve the compatibility with the polyisocyanate component (B) as a curing agent, resulting in a high crosslinking density and improved durability and appearance. An excellent adhesive layer can be formed.

The urethane bond concentration can be calculated using Formula 1 below.
Formula 1:
Urethane bond concentration (mmol/g) = [(NCO content of polyisocyanate (mass%) ÷ 100) Blending ratio) ÷ 42 x 1000] + [(Number of urethane bonds inside polyisocyanate ÷ Polyisocyanate molecular weight) x (Blending ratio of polyisocyanate (mass %) relative to the total (mass %) of polyol and polyisocyanate constituting the urethane resin ratio) x 1000]

For example, the urethane bond concentration of the polyurethane resin (a) having hydroxyl groups shown in Synthesis Example (a)-1 is such that the NCO content of tolylene diisocyanate is 48.2% by mass, and the amount of polyisocyanate added to the polyol is 2% by mass. %, since the number of internal urethane bonds is zero,
Urethane bond concentration = 0.482×(2/102)/42×1000
=0.23 mmol/g.

The weight average molecular weight of the polyurethane resin (a) having hydroxyl groups is preferably 50,000 to 100,000, more preferably 50,000 to 80,000.
When the weight average molecular weight is 50,000 or more, the extensibility of the resin is further increased and the processability is further improved. When the weight average molecular weight is 100,000 or less, the viscosity of the adhesive solution can be easily prevented from becoming excessively high, and appearance defects are less likely to occur. Further, by controlling the weight average molecular weight to 50,000 to 80,000, it becomes easier to achieve both the extensibility of the resin and the viscosity of the adhesive solution, and it can be used more suitably.

The hydroxyl value of the polyurethane resin (a) having hydroxyl groups is preferably 0.5 to 20 mgKOH/g, more preferably 3 to 10 mgKOH/g. The hydroxyl group is used in a crosslinking reaction with the polyisocyanate component (B) described below, and as the crosslinking reaction progresses, the adhesive has a high molecular weight, and the heat resistance of the laminate can be improved. The above hydroxyl value can be determined, for example, by a method based on JIS K 1557-1.

The main component (A) of the polyurethane adhesive only needs to contain the above-mentioned polyurethane resin (a) having a hydroxyl group, and may further contain the following components as other components. Other components may be blended with either the base ingredient (A) or the curing agent containing the polyisocyanate component (B), or when blending the base ingredient (A) with the curing agent containing the polyisocyanate (B). Although it may be added, it is more preferable to blend it into the main ingredient (A).

(solvent)
The polyurethane adhesive may contain a solvent within a range that does not affect the base material during the drying process in order to adjust the coating liquid to an appropriate viscosity when the polyurethane adhesive is applied to the base material. Examples of solvents include ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and methoxyethyl acetate, and ether compounds such as diethyl ether and ethylene glycol dimethyl ether. Examples include aromatic compounds such as toluene and xylene, aliphatic compounds such as pentane and hexane, halogenated hydrocarbon compounds such as methylene chloride, chlorobenzene and chloroform, alcohols such as ethanol, isopropyl alcohol and n-butanol, and water. It will be done. These solvents may be used alone or in combination of two or more. Among these, ethyl acetate is preferably used.

(reaction accelerator)
The polyurethane adhesive can further contain a reaction accelerator to promote the urethanization reaction. As a reaction accelerator, metal catalysts such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dimalate; 1,8-diaza-bicyclo(5,4,0)undecene-7,1,5-diazabicyclo Tertiary amines such as (4,3,0) nonene-5,6-dibutylamino-1,8-diazabicyclo(5,4,0) undecene-7; reactive tertiary amines such as triethanolamine, etc. One or more reaction accelerators selected from these groups can be used.

(Silane coupling agent)
The polyurethane adhesive can further contain a silane coupling agent in order to improve adhesive strength to metal materials such as metal foil. Examples of the silane coupling agent include trialkoxysilane having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-aminopropyltriethoxysilane, and N-(2-aminoethyl)3-aminopropyltrimethoxysilane. trialkoxysilane having an amino group such as, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane having a glycidyl group. Examples include trialkoxysilane.

The content of the silane coupling agent is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the solid content of the polyurethane resin (a) having hydroxyl groups. By adding a silane coupling agent within the above range, the adhesive strength to metal foil can be further improved.

(Epoxy resin)
Epoxy resin can be added to the polyurethane adhesive in order to improve adhesive strength to metal materials such as metal foil. In particular, when an epoxy resin is added to the polyurethane resin (a) containing a polyester skeleton, the heat-and-moisture resistance can be further improved by reacting with the acid generated by hydrolysis during heat-and-moisture resistance.

Epoxy resins include, but are not limited to, bisphenol A epoxy resins, bisphenol F epoxy resins, phenol novolac epoxy resins, cresol novolak epoxy resins, polyglycerol polyglycidyl ether, 1,6 -Hexanediol diglycidyl ether, bisphenol A diglycidyl ether, propylene oxide modified bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Ether is an example.
These epoxy resins may be used alone or in combination of two or more.

Among these, epoxy resins having a weight average molecular weight of 400 to 10,000 are preferred from the viewpoint of adhesive strength and moist heat resistance. The amount of epoxy resin blended is preferably 5 to 50 parts by mass, more preferably 20 to 40 parts by mass, based on 100 parts by mass of the polyurethane resin (a) having hydroxyl groups, from the viewpoint of adhesive strength and heat and humidity resistance. It is. When the amount is 5 parts by mass or more, the heat and humidity resistance can be improved more effectively, and when the amount is 50 parts by mass or less, the hardness of the adhesive layer can be appropriately softened and sufficient adhesiveness can be easily developed.
The epoxy equivalent of the epoxy resin is preferably 200 to 5,000 g/eq, more preferably 200 to 1,000. By using an epoxy resin with an epoxy equivalent of 200 to 5,000 g/eq, both adhesive strength and laminate appearance can be achieved.

(phosphoric acid or its derivative)
The polyurethane adhesive can contain phosphoric acid or a phosphoric acid derivative in order to improve adhesive strength to metal-based materials such as metal foil. Any phosphoric acid may be used as long as it has at least one free oxygen acid, such as phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, and hypophosphoric acid, metaphosphoric acid, and pyrophosphoric acid. , condensed phosphoric acids such as tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid. Examples of phosphoric acid derivatives include those obtained by partially esterifying the above-mentioned phosphoric acid with an alcohol while leaving at least one free oxygen acid. Examples of these alcohols include aliphatic alcohols such as methanol, ethanol, ethylene glycol, and glycerin, and aromatic alcohols such as phenol, xylenol, hydroquinone, catechol, and phloroglycinol. Phosphoric acid or its derivatives may be used alone or in combination of two or more. The amount of phosphoric acid or its derivative added is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0. It is .05 to 1 part by mass.

The polyurethane adhesive may further contain leveling agents or antifoaming agents to improve the laminate appearance of the laminate. Leveling agents include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl-containing polydimethylsiloxane, polyetherester-modified hydroxyl-containing polydimethylsiloxane, acrylic copolymers, and methacryl. Examples thereof include polyether-modified polymethylalkylsiloxane, acrylic acid alkyl ester copolymer, methacrylic acid alkyl ester copolymer, and lecithin.

Examples of antifoaming agents include known ones such as silicone resins, silicone solutions, and copolymers of alkyl vinyl ethers, acrylic acid alkyl esters, and methacrylic acid alkyl esters.

The polyurethane adhesive may contain additives other than those mentioned above, as long as the effects of the present invention are not impaired. Examples of additives include inorganic fillers such as silica, alumina, mica, talc, aluminum flakes, and glass flakes, layered inorganic compounds, and stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, hydrolysis inhibitors, etc.) ), rust preventives, thickeners, plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, fillers, crystal nucleating agents, catalysts for adjusting curing reactions, and the like.

The base ingredient (A) is required to have storage stability that does not cause turbidity or viscosity change in appearance even at low or high temperatures in a solution obtained by blending the above-mentioned additives with the polyurethane resin (a) having a hydroxyl group. Incompatible areas that appear cloudy may become starting points for cracks during molding. Further, when the viscosity changes, it may become difficult to adjust the coating process.

<Polyisocyanate component (B)>
The polyisocyanate component (B) performs a crosslinking reaction with the hydroxyl groups in the polyurethane resin (A) having hydroxyl groups, increases the molecular weight of the adhesive layer, and plays a role in improving the internal cohesive force that exhibits energy elasticity. Furthermore, since isocyanate groups can react with water to form urea bonds with high cohesive force, the cohesive force of the adhesive layer can be increased by causing a self-crosslinking reaction during curing.
Normally, urethane bonds and urea bonds generated by crosslinking reactions have hydrogen bonds and are highly polar, so they have poor compatibility with resins and may cause poor appearance or defects during molding. By using a polyurethane resin (a) having a specific hydroxyl group in combination with a polyisocyanate component (B), it is possible to form an adhesive layer with excellent compatibility, good appearance, and toughness, and is suitable for blister packs. Good physical properties can be obtained as a laminate.

In addition, the polyisocyanate component (B) has the function of improving the interaction with the surface of the base material, which will be described later. If the polyisocyanate component (B) has a reactive functional group and a hydroxyl group on the surface of the base material, a chemical reaction may occur between the outer adhesive layer and the base material, resulting in a strong interaction between the outer adhesive layer and the base material. I can do it.
In this way, by using the polyisocyanate component (B), it is possible to form a strong outer adhesive layer, and the adhesive layer suppresses the expansion and contraction movement of the base material due to sudden environmental changes, thereby improving the adhesiveness. It becomes possible to maintain strength at a high level.

As the polyisocyanate compound (B), those listed in the section of (polyisocyanate) constituting the above-mentioned polyurethane resin (a) having a hydroxyl group can be used, and one type may be used alone, or two types may be used. The above may be used in combination.

Among them, preferred as the polyisocyanate compound (B) are a diisocyanate nurate, an adduct obtained by adding trimethylolpropane to a diisocyanate, a biuret type, a prepolymer having an isocyanate residue (a low polymer obtained from a diisocyanate and a polyol), It is a uretdione compound having an isocyanate residue, an allophanate compound, or a complex thereof.
In blister pack applications, aromatic isocyanates or derivatives thereof are preferred from the viewpoint of achieving both excellent heat resistance, high cohesive force, and processability.

Further, it is preferable that the polyisocyanate constituting the polyurethane resin (a) having a hydroxyl group and the polyisocyanate component (B) are the same because compatibility is further enhanced. That is, the polyisocyanate component (B) more preferably contains tolylene diisocyanate or an adduct obtained by adding trimethylolpropane to tolylene diisocyanate.

The content of the polyisocyanate component (B) is preferably 10 to 40% by mass, more preferably 20 to 30% by mass, based on the solid mass of the polyurethane resin (a) having hydroxyl groups. When the polyisocyanate component (B) is 10% by mass or more, the molecular weight of the adhesive layer can be efficiently increased. This improves the internal cohesive force and easily provides high adhesive strength. When the content is 40% by mass or less, the amount of highly polar urethane bonds and urea bonds generated by the crosslinking reaction can be appropriately controlled, and it is possible to easily suppress appearance deterioration and generation of defects during deformation due to processing.

<Manufacture of laminate for blister pack>
The method for manufacturing the laminate of the present invention is not particularly limited, and the laminate can be manufactured by any known method.
For example, the outer resin film layer (1) and the metal foil layer (3) are laminated using the polyurethane adhesive that forms the outer adhesive layer (2), and )/outer layer side adhesive layer (2)/metal foil layer (3) After obtaining the intermediate laminate having the structure, the inner layer side is attached to the metal foil layer (3) side of the intermediate laminate using an inner layer side adhesive. It can be manufactured by laminating resin film layers (5) (hereinafter referred to as manufacturing method 1).
Alternatively, the metal foil layer (3) and the inner resin film layer (5) are laminated using the inner layer adhesive, so that the metal foil layer (3)/inner adhesive layer (4)/inner resin film is laminated. After obtaining the intermediate laminate having the structure of layer (5), the metal foil layer (3) of the intermediate laminate and the outer resin film layer (1) are laminated using the above-mentioned polyurethane adhesive. (hereinafter referred to as manufacturing method 2).

In the case of manufacturing method 1, the above-mentioned polyurethane adhesive is applied to one side of the base material of either the outer resin film layer (1) or the metal foil layer (3), the solvent is evaporated, and then the uncured adhesive is applied. It is preferable to overlay the other base material on the outer adhesive layer under heat and pressure, and then age the outer adhesive layer at room temperature (for example, 25° C.) to less than 100° C. to cure the outer adhesive layer. When the aging temperature is less than 100°C, thermal contraction of the outer resin film layer (1) does not occur, resulting in a decrease in elongation at break and stress at break, which affect molding, and a decrease in molding productivity due to film curl. can be easily prevented.
The coating amount of the outer layer adhesive after drying is preferably about 1 to 15 g/m ² .

Similarly, in the case of manufacturing method 2, the above-mentioned polyurethane adhesive may be applied to either the outer resin film layer (1) or the metal foil layer (3) surface of the intermediate laminate.

As a method for forming the outer adhesive layer, a comma coater, dry laminator, roll knife coater, die coater, roll coater, bar coater, gravure roll coater, reverse roll coater, blade coater, gravure coater, microgravure coater, etc. are used. There are several methods.

<Outer layer side resin film layer (1)>
Although the outer resin film layer (1) is not particularly limited, it is preferable to use a stretched film made of polyamide or polyester, and polyamide is more preferable. Further, it may be colored with a pigment such as carbon black or titanium oxide. Further, the non-laminated surface of the outer resin film layer (1) may be coated with a coating agent or a slip agent for the purpose of preventing scratches and electrolyte resistance, and may be coated with printing ink for the purpose of design. It's okay. Further, the outer resin film layer (1) may be formed by laminating two or more layers of films in advance. The thickness of the outer resin film layer (1) is not particularly limited, but is preferably 12 to 100 μm.

<Metal foil layer (3)>
The metal foil layer (3) is not particularly limited, but is preferably an aluminum foil layer. The thickness of the metal foil layer (3) is not particularly limited, but is preferably 20 to 80 μm. In addition, the surface of the metal foil layer (3) is treated with chromate phosphate, chromate chromate, trivalent chromium, zinc phosphate, zirconium phosphate, zirconium oxide, titanium phosphate, hydrofluoric acid, and cerium phosphate. A known preservative treatment such as hydrotalcite treatment or the like may be applied.

<Inner adhesive layer (4)>
The adhesive forming the inner adhesive layer (4) is not particularly limited as long as it satisfies the performance required for the laminate for blister packs. For example, AD-502/CAT-10L, AD-585/CAT -10L (manufactured by Toyo Morton Co., Ltd.).
In addition, the inner adhesive layer (4), like the outer adhesive layer (2), is a reaction product of polyester polyol and polyisocyanate, and has an ester bond concentration of 9.20 to 10.50 mmol/ The layer may be formed from a polyurethane adhesive containing a main agent containing a polyurethane resin having a hydroxyl group, and a curing agent containing a polyisocyanate component.
The inner adhesive layer (4) is made by applying the inner adhesive to the metal foil layer (3) using a gravure coater or the like, drying the solvent, and applying the inner resin film layer (5) to the adhesive layer. It can be formed by superimposing them under heat and pressure, and then aging them at room temperature or under heating. Alternatively, the inner layer adhesive is melt-extruded onto the metal foil layer (3) using a T-die extruder to form an adhesive layer, the inner resin film layer (5) is overlaid on the adhesive layer, and the metal foil The inner adhesive layer (4) can be formed by bonding the layer (3) and the inner resin film layer (5).
When both the outer adhesive layer (2) and the inner adhesive layer (4) require aging, the outer resin film layer (1), the uncured outer adhesive layer, and the metal foil layer (3) After obtaining a laminate having a structure in which the uncured inner adhesive layer (4) and the inner resin film layer (5) are laminated in this order from the outside, aging is performed all at once. You can.

<Inner layer side resin film layer (5)>
The inner resin film layer (5) is not particularly limited, but preferably contains at least one type of thermoplastic selected from the group consisting of polyvinyl chloride, polyethylene, polypropylene, olefin copolymers, acid-modified products thereof, and ionomers. It is an unstretched film made of a plastic resin, and polyvinyl chloride is particularly preferably used. The thickness of the heat seal layer is not particularly limited, but is preferably 20 to 150 μm.

<Blister pack>
By providing the above-mentioned blister pack laminate with a lid material, the blister pack of the present invention can be obtained. Specifically, the blister pack is formed by molding a laminate to form a pocket portion in which the outer resin film layer (1) has a convex surface and the inner resin film layer (5) has a concave surface. The inner resin film layer (5) and the lid material are at least partially adhered to each other. The contents can be stored in the pocket between the laminate and the lid.
The lid material preferably includes a metal layer such as aluminum foil from the viewpoint of protecting the contents.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. "Parts" and "%" in Examples and Comparative Examples mean "parts by mass" and "% by mass" unless otherwise specified.

<Measurement of acid value (AV)>
Approximately 1 g of a sample (polyester polyol solution) was accurately weighed into a stoppered Erlenmeyer flask, and 100 ml of a toluene/ethanol (volume ratio: toluene/ethanol = 2/1) mixed solution was added to dissolve it. To this, a phenolphthalein test solution was added as an indicator and held for 30 seconds. Thereafter, the solution was titrated with a 0.1N alcoholic potassium hydroxide solution until it turned pale pink, and the acid value (mgKOH/g) was determined using the following formula.
Acid value (mgKOH/g) = (5.611 x a x F)/S
However, S: Sample amount (g)
a: Consumption amount (ml) of 0.1N alcoholic potassium hydroxide solution
F: Titer of 0.1N alcoholic potassium hydroxide solution

<Measurement of hydroxyl value (OHV)>
Precisely weigh approximately 1 g of a sample (polyester polyol, hydroxyl group-containing urethane resin (a), etc.) into a stoppered Erlenmeyer flask, and dissolve by adding 100 ml of toluene/ethanol (volume ratio: toluene/ethanol = 2/1) mixed solution. did. Furthermore, exactly 5 ml of an acetylating agent (a solution of 25 g of acetic anhydride dissolved in pyridine to a volume of 100 ml) was added, and the mixture was stirred for about 1 hour. To this, phenolphthalein test solution was added as an indicator and the test was continued for 30 seconds. Thereafter, the solution was titrated with a 0.5N alcoholic potassium hydroxide solution until it turned pale pink, and the hydroxyl value (mgKOH/g) was determined using the following formula.
Hydroxyl value (mgKOH/g) = [{(ba) x F x 28.05}/S] + D
However, S: Amount of sample collected (g)
a: Consumption amount (ml) of 0.5N alcoholic potassium hydroxide solution
b: Consumption amount (ml) of 0.5N alcoholic potassium hydroxide solution in blank experiment
F: Titer of 0.5N alcoholic potassium hydroxide solution
D: Acid value (mgKOH/g)

<Measurement of number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn)>
The average molecular weight and molecular weight distribution were determined using Showdex (registered trademark) (manufactured by Showa Denko K.K.), columns: KF-805L, KF-803L, and KF-802 (all trade names, manufactured by Showa Denko K.K.). A standard polystyrene equivalent value was used, which was measured with a column temperature of 40° C., THF as an eluent, a flow rate of 0.2 ml/min, detection by RI, and a sample concentration of 0.02% by mass.

<Synthesis of polyester polyol>
(Polyester 1)
148 parts of isophthalic acid, 296 parts of terephthalic acid, 260 parts of adipic acid, 250 parts of ethylene glycol, and 46 parts of neopentyl glycol were charged, and an esterification reaction was carried out at 170 to 230°C for 10 hours. After distilling off a predetermined amount of water, 0.05 part of tetraisobutyl titanate was added, the pressure was gradually reduced, and transesterification was carried out at 1.3 to 2.6 hPa and 230 to 250°C for 3 hours to obtain a number average molecular weight (Mn ) 9,200, weight average molecular weight (Mw) 19,000, molecular weight distribution (Mw/Mn) 2.07, hydroxyl value 14.0 mgKOH/g, acid value 0.2 mgKOH/g Polyester 1, which is a polyester polyol, Obtained with a yield of 83.9%. The ester bond concentration of Polyester 1 was 10.63 mmol/g.
Assuming that the excess hydroxyl component is distilled off almost evenly and the total of the carboxylic acid component and hydroxyl component is 200 mol%, the composition of the obtained polyester 1 is: isophthalic acid: terephthalic acid: adipic acid: ethylene Glycol:neopentyl glycol=20:40:40:90:10 (mol%).

(Polyester 2-12)
In the resulting polyester polyol, the carboxylic acid component and the hydroxyl group component were reacted in the same manner as in Polyester 1 so that the amount of the carboxylic acid component and the hydroxyl group component was as shown in Table 1. I got it.

The abbreviations in Table 1 are as follows.
PA: Orthophthalic acid IPA: Isophthalic acid TPA: Terephthalic acid SeA: Sebacic acid AdA: Adipic acid EG: Ethylene glycol NPG: Neopentyl glycol 1,6-HD: 1,6-hexanediol MPO: 2-methyl-1,3 -Propanediol DEG: diethylene glycol

<Synthesis of hydroxyl group-containing polyurethane resin (a)>
(Urethane (a)-1)
100 parts of the obtained polyester 1 and 40 parts of ethyl acetate were charged into a 1 liter 4-necked flask, heated to 80°C, and stirred until the solution became uniform. To this were added 2.0 parts of tolylene diisocyanate and 0.15 parts of dibutyltin dilaurate, and the mixture was reacted for 4 hours. After the reaction, 113 parts of ethyl acetate was added, ester bond concentration 10.42 mmol/g, urethane bond concentration 0.23 mmol/g, Mn 23,500, Mw 56,100, Tg 4°C, hydroxyl value 7.9 mgKOH/g, nonvolatile. A solution of urethane (a)-1, which is a polyurethane resin having 40% hydroxyl groups, was obtained.

(Urethane (a)-2 to (a)-15, comparison (a)-1)
Polyol and polyisocyanate were reacted in the same manner as urethane (a)-1 except that the blending amount was changed to the amount shown in Table 2, and urethane (a)-2 to ( a)-15 and comparison (a)-1 were obtained.

The abbreviations in Table 2 are as follows.
NPG: Neopentyl glycol TDI: Tolylene diisocyanate (Coronate T-80 (product name), manufactured by Tosoh Corporation, NCO content 48.2%)
MDI: 4,4'-diphenylmethane diisocyanate (Millionate MT (trade name), manufactured by Tosoh Corporation, NCO content 33.5%)
HDI: Hexamethylene diisocyanate (Desmodur (registered trademark) H (trade name), manufactured by Covestro, NCO content 49.9%)
IPDI: Isophorone diisocyanate (Desmodur I (trade name), manufactured by Covestro, NCO content 37.7%)

<Manufacture of laminate for blister pack>
[Example 1]
250 parts of urethane (a)-1 solution (100 parts on solid basis) and 1.0 part of glycidopropyltrimethoxysilane as an additive were added, stirred for 30 minutes, and then diluted with ethyl acetate to give a solid content concentration of 40. % of the main ingredient (A) was obtained. There, 20 parts (15 parts in terms of solids) of Coronate L (trade name, manufactured by Tosoh Corporation, solid content concentration 75%, NCO content 13.2%) were added, diluted with ethyl acetate, and the solid content concentration A 30% adhesive solution was prepared.
Using a dry laminator, apply the above adhesive solution for the outer adhesive layer (2) to one side of a stretched polyamide (nylon) film with a thickness of 25 μm, and after volatilizing the solvent, apply the adhesive solution to one side of a stretched polyamide (nylon) film with a thickness of 45 μm. The foils were laminated to obtain an intermediate laminate. The amount of adhesive applied after drying was 4 g/m ² .
Next, using a dry laminator, the above adhesive solution was applied to the other side of the aluminum foil of the obtained intermediate laminate, and after volatilizing the solvent, an unstretched polyvinyl chloride film with a thickness of 60 μm was laminated. A laminate was obtained. The amount of adhesive applied after drying was 4 g/m ² .
Next, aging was performed for 7 days at 60° C. and 30% RH (relative humidity) to cure the outer and inner adhesive layers to form the outer resin film layer (1)/outer adhesive layer. A laminate for a blister pack was obtained having the following structure: (2)/metal foil layer (3)/inner adhesive layer (4)/inner resin film layer (5).

[Examples 2 to 15, Comparative Examples 1 to 2]
A laminate for a blister pack was obtained by performing the same operations as in Example 1 except for changing the blending amount (parts) shown in Table 3.

<Evaluation of laminate for blister pack>
The obtained laminate was evaluated as follows. The results are shown in Table 3.

[Appearance evaluation of laminate]
The appearance of each of the obtained laminates was visually observed and evaluated based on the following criteria.
A: No whitening or foaming (good)
B: There is some whitening, but no foaming is seen (usable)
C: Whitening or foaming is observed (unusable)

[Lamination strength (before moist heat test)]
The obtained laminates were each cut into a size of 200 mm x 15 mm, and a T-peel test was performed using a tensile tester to determine the peel strength (N/15 mm width) between the stretched polyamide film and the aluminum foil. It was measured. The measurement was performed at a loading rate of 300 mm/min in an environment of 20° C. and 65% RH, and was evaluated based on the average value of 5 test pieces based on the following criteria.
A: Average value of peel strength is 7N or more (good)
B: Average value of peel strength is 4N or more and less than 7N (usable)
C: Average value of peel strength is less than 4N (unusable)

[Laminate strength (after wet heat test)]
The obtained laminate was placed in a constant temperature and humidity chamber at 85° C. and 85% RH and allowed to stand for 168 hours, then taken out from the constant temperature and humidity chamber and left to stand in an environment of 20° C. and 65% RH for 2 hours. The same actions as before the moist heat test were performed, and the average value of the peel strength (N/15 mm width) of the five test pieces was determined. The rate of change from before the moist heat test was calculated and evaluated based on the following criteria.
A: Peel strength change rate less than 10% (good)
B: Rate of change in peel strength is 10% or more and less than 20% (usable)
C: Peel strength change rate is 20% or more (unusable)

[Moldability evaluation]
The obtained laminate was cut into a size of 80×80 mm to obtain a blank. With the stretched polyamide film on the outside, one-step overhang molding is performed on the blank using a straight mold with free molding height to achieve the maximum molding height without breaking the aluminum foil or lifting between the layers. The moldability was evaluated based on the following criteria.
The punch shape of the mold used was a square with a side of 30 mm, the corner R was 2 mm, and the punch shoulder R was 1 mm. The hole shoulder R is 1 mm, the clearance between the punch and the die hole is 2 mm on one side, and the clearance causes an inclination depending on the molding height.
A: Maximum molding height is 6mm or more (good)
B: Maximum molding height is 4 mm or more and less than 6 mm (usable)
C: Maximum molding height is less than 4mm (unusable)

[Moisture and heat resistance of molded product]
The obtained laminate was cut into a size of 80×80 mm to obtain a blank. The blank was subjected to one-step overhang molding at a molding height of 3 mm using a straight mold with free molding height, with the stretched polyamide film facing outside, to obtain a molded product.
Next, the molded product was placed in a constant temperature and humidity chamber at 85°C and 85% RH and allowed to stand for 168 hours, and then taken out from the constant temperature and humidity chamber and visually checked to see if any floating occurred. evaluated.
The punch shape of the mold used was a square with a side of 30 mm, the corner R was 2 mm, and the punch shoulder R was 1 mm. The hole shoulder R is 1 mm.
A: No floating (good)
B: Lifting occurs on one of the four sides (usable)
C: Lifting occurs on two or more of the four sides (unusable)

[Resistance of molded product to external forces (external stress resistance)]
The obtained laminate was cut into a size of 80×80 mm to obtain a blank. The blank was subjected to one-step overhang molding at a molding height of 3 mm using a straight mold with free molding height, with the stretched polyamide film facing outside, to obtain a molded product. For the 10 molded products, the molded parts (corner parts) were pressed with fingers to deform them, and then it was confirmed whether or not the metal foil had broken, and evaluated according to the following criteria.
A: 1 or less metal foil breaks out of 10 (good)
B: 2 or 3 metal foil breaks out of 10 (usable)
C: 4 or more broken metal foils out of 10 (unusable)

The abbreviations in Table 3 are as follows.
SC-1: glycidopropyltrimethoxysilane EP-1: bisphenol A type epoxy resin (product name: JER834, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 245 g/eq, molecular weight: approximately 470)
EP-2: Bisphenol A type epoxy resin (product name: JER1001, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 470 g/eq, molecular weight: approximately 900)
NCO-1: trimethylolpropane adduct of tolylene diisocyanate (product name: Coronate L, manufactured by Tosoh Corporation, nonvolatile content 75%, NCO content 13.2%)

From the results in Table 3, the laminate of the present invention using the hydroxyl group-containing polyurethane resin (a) having a predetermined ester bond concentration as the main ingredient for forming the outer adhesive layer has excellent appearance, lamination strength, and moldability. was. Furthermore, the laminate strength was maintained after the heat and humidity test, and the molded product had excellent resistance to heat and humidity. Furthermore, the molded product had excellent resistance to external stress in the molded part, and breakage of the aluminum foil in the laminate was suppressed.
In particular, in Example 10, the ester bond concentration, urethane bond concentration, and weight average molecular weight of the polyurethane resin (a) having hydroxyl groups were within appropriate ranges, and therefore excellent results were obtained in all evaluations.
On the other hand, Comparative Example 1 corresponds to the example of JP 2019-156925A (Patent Document 3), but the ester bond concentration of the polyurethane polyol was low and the laminate strength was reduced. Furthermore, the molded product had poor moist heat resistance and external stress resistance.
Comparative Example 2 corresponds to the example of JP-A-2015-024862 (Patent Document 1), but the laminate strength was reduced because it did not have a urethane bond. Furthermore, the moldability was insufficient, and the molded product had poor resistance to heat and humidity and resistance to external stress.

(1): Outer resin film layer (2): Outer adhesive layer (3): Metal foil layer (4): Inner adhesive layer (5): Inner resin film layer (6): Contents ( 7): Lid material

Claims (9)

At least, the outer resin film layer (1), the outer adhesive layer (2), the metal foil layer (3), the inner adhesive layer (4), and the inner resin film layer (5) are laminated in this order. A laminate for a blister pack, comprising:
The outer adhesive layer (2) is formed from a polyurethane adhesive containing a main ingredient (A) containing a polyurethane resin (a) having a hydroxyl group, and a curing agent containing a polyisocyanate component (B). can be,
The hydroxyl group-containing polyurethane resin (a) is a reaction product of polyester polyol and polyisocyanate, and has an ester bond concentration of 9.20 to 10.50 mmol/g. . The laminate for a blister pack according to claim 1, wherein the polyurethane resin (a) having hydroxyl groups has a urethane bond concentration of 0.10 to 0.90 mmol/g. The laminate for a blister pack according to claim 1 or 2, wherein the polyurethane resin (a) having hydroxyl groups has a hydroxyl value of 0.5 to 20 mgKOH/g. The blister according to any one of claims 1 to 3, wherein the polyurethane resin (a) having a hydroxyl group is a reaction product of a polyester polyol having a weight average molecular weight of 5,000 to 30,000 and a polyisocyanate. Laminate for packs. The laminate for a blister pack according to any one of claims 1 to 4, wherein the polyurethane resin (a) having a hydroxyl group has a weight average molecular weight of 50,000 to 100,000. The laminate for a blister pack according to any one of claims 1 to 5, wherein the outer resin film layer (1) is made of polyamide. The laminate for a blister pack according to any one of claims 1 to 6, wherein the inner resin film layer (5) is made of polyvinyl chloride. A blister pack comprising the blister pack laminate according to any one of claims 1 to 7, and a lid material. 9. A blister pack according to claim 8, wherein the lidding material includes a metal layer.