JP7160221B1 - Laminates for blister packs and blister packs - Google Patents

Abstract

[PROBLEMS] To provide a laminate for a blister pack which has excellent lamination strength and moldability, and which is excellent in moist heat resistance and external stress resistance after molding, and a blister pack which is excellent in moist heat resistance and external stress resistance. [Means for Solving the Problem] The above-mentioned problems are solved by at least an outer layer side resin film layer (1), an outer layer side adhesive layer (2), a metal foil layer (3), an inner layer side adhesive layer (4) and an inner layer side resin film layer ( 5) are laminated in this order, and the outer layer side adhesive layer (2) is a main agent (A) containing a polyurethane resin (a) having a hydroxyl group and a curing agent containing a polyisocyanate component (B). 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 9.20 to 10.50 mmol. /g of the blister pack laminate. [Selection drawing] Fig. 1

Description

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

As a container for packaging granular pharmaceutical tablets, confectionery, etc., an outer layer side resin film layer (1), an outer layer side adhesive layer (2), a metal foil layer (3), an inner layer side adhesive layer (4) and a heat seal layer (5) is known as a blister pack formed by forming a blister pack laminate in this order from the outside by vacuum forming or the like. Blister packs are required to have functions such as airtightness and moisture resistance to protect the contents, as well as excellent moldability in order to pack larger contents.

In Patent Document 1, a molding packaging material provided with an adhesive layer using a two-component curable polyester urethane adhesive containing a specific polyester polyol and a polyfunctional isocyanate between a heat-resistant resin layer and a thin metal layer is provided. It is disclosed and described that it can be used as a packaging material for pharmaceuticals.
Patent Document 2 discloses a blister pack laminate provided with 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 provided with a laminated 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. stated to be available.

JP 2015-024862 A WO2018/047672 JP 2019-156925 A

In recent years, in order to package a larger variety of contents, there is an increasing demand for taller and more complicated molding, and more excellent moldability is required. In addition, from the viewpoint of protecting the contents, it is required that the adhesive strength between each layer is maintained high even when stored for a long period of time in a high-temperature and high-humidity environment. Moreover, from the viewpoint of protecting the contents, it is required that the metal foil in the laminate does not break when the molded portion is deformed by an external force.

However, the packaging materials described in Patent Documents 1 and 2 use a polyester resin that is not urethaned as a main agent and have a low molecular weight, so the lamination strength is not sufficient, and long-term storage in a high-temperature and high-humidity environment is not possible. However, there is a problem that the adhesive layer deteriorates and the adhesive strength cannot be maintained. Moreover, there is a problem that the metal foil in the laminate is likely to break when an external stress is applied to the molded part.
In the packaging material described in Patent Document 3, since the polyurethane polyol has a low ester bond concentration, the lamination strength is not sufficient, and the metal foil in the laminate tends to break when external stress is applied to the molded part. I have a problem.
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a laminate for blister packs that has excellent lamination strength and moldability, as well as excellent moisture and heat resistance and external stress resistance after molding. Another object of the present invention is to provide a blister pack excellent in resistance to moist heat and resistance to external stress.

As a result of earnest studies to solve the above problems, the inventors have found that the above problems can be solved by the following embodiments, and have completed the present invention.

The blister pack laminate 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 configuration in which inner layer side resin film layers (5) are laminated in this order, wherein the outer layer side adhesive layer (2) contains a polyurethane resin (a) having a hydroxyl group. It is formed from a polyurethane adhesive containing a main agent (A) and a curing agent containing a polyisocyanate component (B), and the polyurethane resin (a) having a hydroxyl group is a mixture of a polyester polyol and a polyisocyanate. It is a reaction product and is characterized by having an ester bond concentration of 9.20 to 10.50 mmol/g.

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

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

The blister pack laminate 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, which is the polyurethane resin (a) having a hydroxyl group, and a polyisocyanate. characterized by

The blister pack laminate according to one aspect of the present invention is characterized in that the weight average molecular weight of the polyurethane resin (a) having a hydroxyl group is 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 layer-side resin film layer (1) is polyamide.

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

A blister pack according to an aspect of the present invention is characterized in that the blister pack laminate is provided with a lid member.

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

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a laminate for blister packs that has excellent lamination strength and moldability, as well as excellent moisture and heat resistance and external stress resistance after molding. Further, according to the present invention, a blister pack having excellent resistance to moist heat and resistance to external stress can be provided.

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

<Laminate for blister pack>
The blister pack laminate 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 layer (5) has a configuration in which it is laminated from the outside in this order, and the outer layer side adhesive layer (2) is composed of a main agent (A) containing a polyurethane resin (a) having a hydroxyl group and a polyisocyanate component ( B) and a curing agent, wherein 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. .20-10.50 mmol/g blister pack film.
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail by citing preferred embodiments as examples.

<Outer layer side adhesive layer (2)>
The outer layer side adhesive layer (2) in the present invention is formed from a polyurethane adhesive containing a main agent (A) containing a polyurethane resin (a) having a hydroxyl group and a curing agent containing a polyisocyanate component (B). .
First, the main agent will be explained. The main agent and curing agent may contain known additives as long as they do not impair the effects of the present invention.

[Polyurethane resin (a) having hydroxyl group]
The hydroxyl group-containing polyurethane resin (a) is a reaction product of a polyester polyol and a polyisocyanate, and is characterized by having an ester bond concentration of 9.20 to 10.50 mmol/g. Polyurethane resin (a) having hydroxyl groups can be obtained by subjecting hydroxyl groups in a polyol containing a polyester polyol to be described later and isocyanate groups in a polyisocyanate to a urethanization reaction under conditions in which 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, naphthalene dicarboxylic acid, and phthalic anhydride; adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, tetrahydrophthalic anhydride. acids, aliphatic dibasic acids such as hexahydrophthalic anhydride, maleic anhydride, and 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.
Each of the carboxylic acid component and the hydroxyl group component may be used alone, but it is preferable to use two or more of them 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 content of the aliphatic dibasic acid is 5 mol % or more, the solvent solubility is enhanced, and the obtained polyester polyol solution has a low viscosity. As a result, the coating properties of the polyurethane adhesive are improved, and a packaging material having a more excellent appearance can be obtained. When it 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 point of view, the content of the aliphatic dibasic acid is more preferably 25 to 50 mol % based on the total carboxylic acid component.

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, still more preferably 9.40 to 9.80 mmol/g.
When the ester bond concentration of the polyester polyol is 9.40 mmol/g or more, the solubility in an ester solvent such as ethyl acetate is excellent, and the amount of isocyanate used for urethanization is not limited, so good adhesiveness can be exhibited, which is preferable. . When it is 10.80 mmol/g or less, it is preferable because an increase in viscosity and a decrease in solvent solubility due to intermolecular interaction due to an ester bond are suppressed.

The ester bond concentration of polyester polyol can be calculated by the following formula.
Formula: Polyester bond concentration (mmol/g) = charged molar amount of carboxylic acid component × total number of carboxylic acid functional groups / (total charged amount × solid yield) × 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 (2 functional groups): 296 g = 1.783 mol,
Adipic acid (2 functional groups): 260 g = 1.780 mol,
Total charge 1000.05g, Yield 83.9%
and the ester bond concentration of polyester 1 is
(0.892×2+1.783×2+1.780×2)/(1000.5×0.839)×1000=10.63
can be calculated as

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 substrate is further improved and the workability is excellent. When the weight-average molecular weight is 30,000 or less, it is possible to easily prevent the concentration of hydroxyl groups at the ends of the polyester polyol from becoming excessively low, and a polyurethane resin (a) having hydroxyl groups is obtained by reacting with a polyisocyanate described later. In this case, the extension 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 polyester polyols described above. Polyols that can be used in combination include, for example, hydroxyl group components that can be used in the synthesis of polyester polyols described above, and neopentyl glycol and 1,4-butanediol can be preferably used.

(polyisocyanate)
Polyisocyanates constituting the polyurethane resin (a) having a hydroxyl group include, for example, aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, trifunctional or higher polyisocyanate monomers, and diisocyanates. Various derived derivatives are 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, 2,6-diisocyanatomethylcaproate.

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

Examples of aromatic diisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4- or 2,6- tolylene diisocyanate or mixtures thereof, 4,4'-toluidine diisocyanate, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate.

Examples of araliphatic diisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis(1 -isocyanato-1-methylethyl)benzene or mixtures thereof.

Tri- or more functional polyisocyanate monomers include, for example, triphenylmethane-4,4′,4″-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, and the like. triisocyanate; tetraisocyanate 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, 3,3′-Dimethylolpropane, cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, or other low-molecular-weight polyols having a molecular weight of less than 200, or addition with castor oil, etc. trimer (also referred to as trimer or nurate) of the diisocyanate; biuret; Polyisocyanate having a; and the like 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, and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate.

The reaction temperature between the polyol and the polyisocyanate in obtaining the polyurethane resin (a) having hydroxyl groups is preferably in the range of 50°C to 200°C, more preferably 80°C 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 0.9. 3 to 0.8.

In the present invention, it is important that the ester bond concentration of the hydroxyl-containing polyurethane resin (a) constituting the outer adhesive layer is in the range of 9.20 mmol/g to 10.50 mmol/g. is controlled within a predetermined range, the stability of the adhesive solution and the affinity to the substrate due to the ester bond are controlled, and excellent coatability is exhibited. As a result, the resulting laminate has excellent moldability without lowering the adhesive strength between layers even after the high-temperature, high-humidity, long-term durability test, and does not cause appearance defects such as separation 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 an ester solvent such as ethyl acetate is lowered, resulting in poor coatability. Alternatively, the affinity to the substrate due to the ester bond is lowered, and the adhesive strength is lowered. If it exceeds 10.50 mmol/g, the intermolecular interaction due to the ester bond increases, the viscosity increases, the solvent solubility decreases, and the appearance after aging deteriorates 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 by the following formula.
Formula: Ester bond concentration (mmol/g) = ester bond concentration of polyester polyol x ratio of polyester polyol to total mass of polyol and polyisocyanate constituting urethane resin (% by mass)
For example, the ester bond concentration of the hydroxyl group-containing polyurethane resin (a) 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 a hydroxyl group is preferably in the range of 0.10 to 0.90 mmol/g, more preferably 0.15 to 0.60 mmol/g, still more preferably 0.20. ~0.40 mmol/g. When it is 0.10 mmol/g or more, an excellent effect of improving compatibility can be obtained, and appearance and adhesiveness are improved, which is preferable. When it is 0.90 mmol/g or less, the urethane bond concentration is not excessive and the viscosity is appropriate, which is preferable because it is excellent in coatability and appearance.
By controlling the urethane bond concentration of the polyurethane resin (a) having a hydroxyl group, compatibility with the polyisocyanate component (B), which is a curing agent, can be improved, the crosslink density is high, and durability and appearance are improved. An excellent adhesive layer can be formed.

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

For example, the urethane bond concentration of the polyurethane resin (a) having a hydroxyl group shown in Synthesis Example (a)-1 is that the NCO content of tolylene diisocyanate is 48.2% by mass, and the amount of polyisocyanate added to the polyol is 2 mass. %, since the number of internal urethane bonds is zero,
Urethane bond concentration = 0.482 x (2/102)/42 x 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 enhanced and the workability is further improved. When the weight-average molecular weight is 100,000 or less, it is possible to easily prevent the viscosity of the adhesive solution from becoming excessively high, and the occurrence of poor appearance is even less likely. Further, by controlling the weight average molecular weight to 50,000 to 80,000, it becomes easier to achieve both the elongation of the resin and the viscosity of the adhesive solution, and it can be used more preferably.

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. A hydroxyl group is used for a cross-linking reaction with a polyisocyanate component (B), which will be described later. As the cross-linking reaction progresses, the adhesive increases in molecular weight and the heat resistance of the laminate can be improved. The hydroxyl value can be determined, for example, by a method conforming to JIS K 1557-1.

The main agent (A) of the polyurethane adhesive should just contain the polyurethane resin (a) having a hydroxyl group, and may contain the following components as other components. Other components may be blended with either the main component (A) or the curing agent containing the polyisocyanate component (B), and when blending the main component (A) and the curing agent containing the polyisocyanate (B) Although it may be added, it is more preferable to mix it with the main agent (A).

(solvent)
The polyurethane adhesive may contain a solvent within a range that does not affect the substrate during the drying process in order to adjust the viscosity of the coating liquid to an appropriate level when the polyurethane adhesive is applied to the substrate. 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. 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 normal butanol; 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 may further contain a reaction accelerator to accelerate the urethanization reaction. Reaction promoters include metallic catalysts such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dimaleate; 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; One or two or more reaction accelerators selected from these groups can be used.

(Silane coupling agent)
The polyurethane adhesive may further contain a silane coupling agent in order to improve the adhesive strength to metallic materials such as metal foil. Examples of the silane coupling agent include trialkoxysilanes 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, 3-glycidoxypropyltriethoxysilane having a glycidyl group trialkoxysilane and the like.

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

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

Examples of epoxy resins include, but are not limited to, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, 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 ethers.
One of these epoxy resins may be used alone, or two or more of them may be used in combination.

Among them, an epoxy resin having a weight average molecular weight of 400 to 10,000 is preferable from the viewpoint of adhesive strength and moist heat resistance. The amount of the epoxy resin to be 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 a hydroxyl group, from the viewpoint of adhesive strength and heat and humidity resistance. is. When the content is 5 parts by mass or more, moist heat resistance can be improved more effectively, and when the content is 50 parts by mass or less, the hardness of the adhesive layer is moderately softened, and sufficient adhesiveness can be easily exhibited.
The epoxy equivalent of the epoxy resin is preferably 200-5,000 g/eq, more preferably 200-1,000. By using an epoxy resin with an epoxy equivalent weight of 200 to 5,000 g/eq, both adhesion and laminate appearance can be achieved.

(Phosphorus acid or its derivative)
Polyurethane adhesives can contain phosphoric acid or phosphoric acid derivatives in order to improve adhesive strength to metallic materials such as metal foils. The phosphoric acid may have at least one free oxyacid, and examples thereof include hypophosphorous acid, phosphorous acid, orthophosphoric acid, phosphoric acids such as hypophosphoric acid, metaphosphoric acid, and pyrophosphoric acid. , tripolyphosphoric acid, polyphosphoric acid, ultraphosphoric acid, and other condensed phosphoric acids. Examples of phosphoric acid derivatives include those obtained by partially esterifying the above phosphoric acid with alcohols while leaving at least one free oxyacid. 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 derivative may be used individually by 1 type, and may be used in combination of 2 or more type. The amount of phosphoric acid or a derivative thereof added is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0 parts by mass with respect to 100 parts by mass of the polyurethane resin (a) having a hydroxyl group. 0.05 to 1 part by mass.

The polyurethane adhesive may further contain leveling agents or defoamers to improve the laminate appearance of the laminate. Examples of leveling agents include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, polyether ester-modified hydroxyl group-containing polydimethylsiloxane, acrylic copolymer, methacrylic system copolymers, polyether-modified polymethylalkylsiloxanes, acrylic acid alkyl ester copolymers, methacrylic acid alkyl ester copolymers, lecithin and the like.

Antifoaming agents include known ones such as silicone resins, silicone solutions, and copolymers of alkyl vinyl ethers, alkyl acrylates and alkyl methacrylates.

The polyurethane adhesive may contain additives other than those described 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, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, hydrolysis inhibitors, etc. ), rust inhibitors, thickeners, plasticizers, antistatic agents, lubricants, antiblocking agents, coloring agents, fillers, crystal nucleating agents, catalysts for adjusting the curing reaction, and the like.

The main component (A) is required to have storage stability that does not cause turbidity in appearance or change in viscosity 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. The cloudy incompatible part in appearance may become the starting point of cracks during molding. Moreover, when the viscosity changes, it may become difficult to adjust the coating process.

<Polyisocyanate component (B)>
The polyisocyanate component (B) performs a cross-linking reaction with the hydroxyl groups in the hydroxyl-containing polyurethane resin (A) to increase the molecular weight of the adhesive layer and improve the internal cohesive force that develops energy elasticity. In addition, since the isocyanate group can react with water to form a urea bond with high cohesive strength, self-crosslinking reaction during curing can increase the cohesive strength of the adhesive layer.
Normally, urethane bonds and urea bonds generated by a cross-linking reaction have hydrogen bonds and are highly polar, so they are inferior in compatibility with resins and may cause poor appearance or defects during molding. By using a combination of the polyurethane resin (a) having a predetermined hydroxyl group and the polyisocyanate component (B), it is possible to form a strong adhesive layer with excellent compatibility and a good appearance, which is used 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 substrate, which will be described later. In this case, the reactive functional groups in the polyisocyanate component (B) and the hydroxyl groups on the surface of the base material chemically react to develop a strong interaction between the outer layer side adhesive layer and the base material. can be done.
Thus, by using the polyisocyanate component (B), it is possible to form a strong outer layer side adhesive layer, and the adhesive layer suppresses the expansion and contraction movement of the base material due to sudden environmental changes, resulting in adhesion. It becomes possible to maintain strength at a high level.

As the polyisocyanate compound (B), those listed in the section of (polyisocyanate) constituting the polyurethane resin (a) having a hydroxyl group can be used. You may use the above together.

Among them, the polyisocyanate compound (B) is preferably 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), A uretdione derivative having an isocyanate residue, an allophanate derivative, 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 cohesion and workability.

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 the compatibility is further enhanced. More preferably, the polyisocyanate component (B) 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 content of the hydroxyl group-containing polyurethane resin (a). When the polyisocyanate component (B) is 10% by mass or more, the molecular weight of the adhesive layer can be efficiently increased. As a result, internal cohesive strength is improved, and high adhesive strength can be easily obtained. When it is 40% by mass or less, the amount of highly polar urethane bonds and urea bonds generated by the cross-linking reaction can be appropriately controlled, and appearance deterioration and defects during deformation due to processing can be easily suppressed.

<Production of laminate for blister pack>
The method for producing the laminate of the present invention is not particularly limited, and the laminate can be produced by a known method.
For example, the outer layer side resin film layer (1) and the metal foil layer (3) are laminated using the polyurethane adhesive that forms the outer layer side adhesive layer (2), and the outer layer side resin film layer (1) is laminated. )/outer layer side adhesive layer (2)/metal foil layer (3) is obtained. It can be produced by laminating the resin film layer (5) (hereinafter referred to as production method 1).
Alternatively, the metal foil layer (3) and the inner resin film layer (5) are laminated using an inner layer side adhesive to obtain a metal foil layer (3)/inner layer side adhesive layer (4)/inner layer side resin film. After obtaining the intermediate laminate having the structure of the layer (5), the metal foil layer (3) and the outer resin film layer (1) of the intermediate laminate are laminated using the polyurethane adhesive described above. (hereinafter referred to as manufacturing method 2).

In the case of production method 1, the polyurethane adhesive described above is applied to one side of the base material of either the outer layer side resin film layer (1) or the metal foil layer (3), and after the solvent is volatilized, the adhesive is uncured. It is preferable that the other base material is superimposed on the outer layer side adhesive layer of No. under heat and pressure, and then aged at room temperature (eg, 25° C.) to less than 100° C. to cure the outer layer side adhesive layer. When the aging temperature is less than 100°C, the outer resin film layer (1) does not undergo heat shrinkage, so that the breaking elongation and breaking stress that affect molding are reduced, and the molding productivity is reduced due to film curling. can be easily prevented.
The coating amount of the outer layer side adhesive after drying is preferably about 1 to 15 g/m ² .

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

As a method for forming the outer layer side 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, micro gravure coater, etc. are used. method.

<Outer layer side resin film layer (1)>
Although the outer layer side resin film layer (1) is not particularly limited, it is preferable to use a stretched film made of polyamide or polyester, more preferably polyamide. It may also be colored with a pigment such as carbon black or titanium oxide. In addition, 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 scratch prevention and electrolytic solution resistance, and may be coated with a printing ink for the purpose of design. may In addition, the outer layer side resin film layer (1) may be preliminarily laminated with two or more layers of films. Although the thickness of the outer layer-side resin film layer (1) is not particularly limited, it is preferably 12 to 100 μm.

<Metal foil layer (3)>
Although the metal foil layer (3) is not particularly limited, it is preferably an aluminum foil layer. Although the thickness of the metal foil layer (3) is not particularly limited, it is preferably 20 to 80 μm. 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. A known antiseptic treatment such as treatment, hydrotalcite treatment, etc. may be applied.

<Inner layer side adhesive layer (4)>
The adhesive that forms the inner layer side adhesive layer (4) is not particularly limited as long as it satisfies the performance required for the laminate for blister packs. -10L (manufactured by Toyo-Morton Co., Ltd.).
Further, the inner layer side adhesive layer (4) is a reaction product of polyester polyol and polyisocyanate similarly to the outer layer side adhesive layer (2), and has an ester bond concentration of 9.20 to 10.50 mmol/ It may be a layer formed from a polyurethane adhesive containing a base material containing a polyurethane resin having a hydroxyl group (g) and a curing agent containing a polyisocyanate component.
For the inner layer side adhesive layer (4), the inner layer side adhesive is applied to the metal foil layer (3) using a gravure coater or the like, the solvent is dried, and the inner layer side resin film layer (5) is applied to the adhesive layer. It can be formed by stacking under heat and pressure and then aging at room temperature or under heat. Alternatively, the inner layer side adhesive is melt extruded onto the metal foil layer (3) with a T-die extruder to form an adhesive layer, the inner layer side resin film layer (5) is superimposed on the adhesive layer, and the metal foil is By laminating the layer (3) and the inner layer side resin film layer (5), the inner layer side adhesive layer (4) can be formed.
When both the outer layer side adhesive layer (2) and the inner layer side adhesive layer (4) require aging, the outer layer side resin film layer (1), the uncured outer layer side adhesive layer, and the metal foil layer (3) After obtaining a laminate having a configuration in which the uncured inner layer side adhesive layer (4) and the inner layer side resin film layer (5) are laminated in this order from the outside, they are aged together. may

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

<blister pack>
The blister pack of the present invention can be obtained by providing the above-described blister pack laminate with a lid member. Specifically, in the blister pack, the laminate is molded 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 layer side resin film layer (5) and the lid member are at least partially adhered to each other. Contents can be stored in the pocket portion between the laminate and the lid member.
From the viewpoint of protecting the contents, the lid material preferably contains a metal layer such as aluminum foil.

EXAMPLES The present invention will now be described more specifically with reference to examples and comparative examples. "Parts" and "%" in Examples and Comparative Examples mean "mass parts" and "mass%" unless otherwise specified.

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

<Measurement of hydroxyl value (OHV)>
Accurately weigh about 1 g of a sample (polyester polyol, hydroxyl group-containing urethane resin (a), etc.) in a stoppered Erlenmeyer flask, add 100 ml of toluene/ethanol (volume ratio: toluene/ethanol = 2/1) mixture and dissolve. did. 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 further added and stirred for about 1 hour. To this, phenolphthalein test solution was added as an indicator and maintained 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 by the following formula.
Hydroxyl value (mgKOH/g) = [{(ba) x F x 28.05}/S] + D
However, S: sample collection amount (g)
a: consumption of 0.5N alcoholic potassium hydroxide solution (ml)
b: Consumption (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 measured using Shodex (registered trademark) (manufactured by Showa Denko KK), columns: KF-805L, KF-803L, and KF-802 (all trade names, manufactured by Showa Denko KK). A column temperature of 40° C., THF as an eluent, a flow rate of 0.2 ml/min, a detection of RI, and a sample concentration of 0.02% by mass were measured in terms of standard polystyrene.

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

(Polyester 2-12)
In the polyester polyol obtained, the carboxylic acid component and the hydroxyl group component are reacted in the same manner as in Polyester 1 so that the charged amounts of the carboxylic acid component and the hydroxyl group component have a compounding ratio as shown in Table 1, and polyesters 2 to 12 are prepared. got

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 placed in a 1-liter four-necked flask, heated to 80° C., and stirred until the solution became uniform. To this, 2.0 parts of tolylene diisocyanate and 0.15 parts of dibutyltin dilaurate were added and reacted for 4 hours. After completion of 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 urethane (a)-1 solution, which is a polyurethane resin having a hydroxyl group content of 40%, was obtained.

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

Abbreviations in Table 2 are as follows.
NPG: neopentyl glycol TDI: tolylene diisocyanate (Coronate T-80 (trade 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%)

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

[Examples 2 to 15, Comparative Examples 1 to 2]
A blister pack laminate was obtained in the same manner as in Example 1 except that the amount (parts) shown in Table 3 was changed.

<Evaluation of laminate for blister pack>
The obtained laminate was evaluated as follows. Table 3 shows the results.

[Appearance Evaluation of Laminate]
The appearance of each laminate obtained was visually observed and evaluated according to the following criteria.
A: No whitening or foaming (good)
B: Slight whitening, but no foaming (usable)
C: Whitening or foaming is observed (cannot be used)

[Laminate strength (before wet heat test)]
The resulting laminate was cut into pieces each having a size of 200 mm x 15 mm, and a T-type peel test was performed using a tensile tester to measure 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 load rate of 300 mm/min under an environment of 20° C. and 65% RH, and the average value of five test pieces was evaluated according to the following criteria.
A: The average value of peel strength is 7 N or more (good)
B: The average value of peel strength is 4N or more and less than 7N (usable)
C: The average value of peel strength is less than 4N (cannot be used)

[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 removed from the constant temperature and humidity chamber and allowed to stand at 20° C. and 65% RH for 2 hours. , the same behavior as before the wet heat test was performed, and the average value of the peel strength (N/15 mm width) of five test pieces was obtained. The rate of change from before the wet heat test was calculated and evaluated according to the following criteria.
A: Change rate of peel strength is less than 10% (good)
B: Change rate of peel strength is 10% or more and less than 20% (usable)
C: change rate of peel strength is 20% or more (cannot be used)

[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 of the blank, one-stage overhang molding is performed with a straight mold with no molding height, and the maximum molding height is achieved without breaking the aluminum foil or floating between layers. Based on the hardness, moldability was evaluated according to the following criteria.
The die used had a punch shape of 30 mm on each side, a corner R of 2 mm, and a punch shoulder R of 1 mm. The shoulder R of the hole is 1 mm, the clearance between the punch and the die hole is 2 mm on one side, and the clearance produces an inclination according to the molding height.
A: The maximum molding height is 6 mm or more (good)
B: The maximum molding height is 4 mm or more and less than 6 mm (usable)
C: The maximum molding height is less than 4 mm (cannot be used)

[Heat and humidity resistance of molding]
The obtained laminate was cut into a size of 80×80 mm to obtain a blank. With the stretched polyamide film facing outward, the blank was subjected to one-stage overhang molding at a molding height of 3 mm using a straight mold with a free molding height to obtain a molded product.
Next, the molded product was placed in a constant temperature and humidity chamber under an atmosphere of 85° C. and 85% RH and allowed to stand still for 168 hours. evaluated.
The die used had a punch shape of 30 mm on each side, a corner radius of 2 mm, and a punch shoulder radius of 1 mm. The hole shoulder R is 1 mm.
A: No floating (good)
B: Lifting occurs on one of the four sides (usable)
C: Floating occurs on two or more of the four sides (cannot be used)

[Resistance to force from the outside of the molding (external stress resistance)]
The obtained laminate was cut into a size of 80×80 mm to obtain a blank. With the stretched polyamide film facing outward, the blank was subjected to one-stage overhang molding at a molding height of 3 mm using a straight mold with a free molding height to obtain a molded product. For 10 moldings, the molded part (corner part) was deformed by pressing with a finger, and then it was checked whether the metal foil was broken and evaluated according to the following criteria.
A: Out of 10 pieces, 1 piece or less of metal foil was broken (good)
B: 2 or 3 broken metal foils out of 10 (usable)
C: 4 or more broken metal foils out of 10 (cannot be used)

Abbreviations in Table 3 are as follows.
SC-1: glycidopropyltrimethoxysilane EP-1: bisphenol A type epoxy resin (trade name: JER834, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 245 g/eq, molecular weight about 470)
EP-2: Bisphenol A type epoxy resin (trade name: JER1001, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 470 g/eq, molecular weight of about 900)
NCO-1: Trimethylolpropane adduct of tolylene diisocyanate (trade name: Coronate L, manufactured by Tosoh Corporation, non-volatile concentration 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 agent forming the outer layer side adhesive layer is excellent in appearance, laminate strength, and moldability. was In addition, the laminate strength after the wet heat test was maintained, and the molded product was excellent in wet heat resistance. Furthermore, the molded article was excellent in resistance to external stress in the molded part, and fracture 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 excellent results were obtained in all evaluations.
On the other hand, Comparative Example 1, which corresponds to the example of JP-A-2019-156925 (Patent Document 3), had a low ester bond concentration in the polyurethane polyol and a low laminate strength. In addition, the molded product was inferior in resistance to heat and humidity and resistance to external stress.
Comparative Example 2 corresponds to the example disclosed in Japanese Patent Application Laid-Open No. 2015-024862 (Patent Document 1). In addition, the moldability was insufficient, and the molded product was inferior in resistance to heat and humidity and resistance to external stress.

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

Claims (9)

At least, the outer layer side resin film layer (1), the outer layer side adhesive layer (2), the metal foil layer (3), the inner layer side adhesive layer (4) and the inner layer side resin film layer (5) are laminated in this order. A laminate for a blister pack, comprising:
The outer layer side adhesive layer (2) is formed from a polyurethane adhesive containing a main agent (A) containing a polyurethane resin (a) having a hydroxyl group and a curing agent containing a polyisocyanate component (B). can be,
The blister pack laminate, wherein 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 9.20 to 10.50 mmol/g. . 2. The blister pack laminate 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. 3. The blister pack laminate according to claim 1, wherein the hydroxyl group-containing polyurethane resin (a) 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. Pack laminate. The blister pack laminate 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 blister pack laminate according to any one of claims 1 to 5, wherein the outer layer side resin film layer (1) is polyamide. The laminate for a blister pack according to any one of claims 1 to 6, wherein the inner layer side resin film layer (5) is polyvinyl chloride. A blister pack comprising the blister pack laminate according to any one of claims 1 to 7 and a lid member. 9. The blister pack of Claim 8, wherein the lidding material comprises a metal layer.

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