JP7192369B2 - Packaging material manufacturing method, package body, lid material, label - Google Patents

Description

The present invention provides a method for producing a packaging material having a barrier function, an easy-to-open function, or an easy-to-dismantle function in order to form a package for storing foods, medicines, toiletries, etc., and a package using the same, It relates to lid materials and labels.

Conventional easy-to-open packaging has a means of providing orientation to the plastic material itself, or adding a cyclic polyolefin or an inorganic substance to provide an easy-to-break portion in the resin structure. As a physical means, a means is used in which a hole is formed in the plastic base material or a scratching process is used to create an easy-to-cut trigger in the plastic base material.

However, in the case of such a physical easy-opening means, there is a problem that microscopic through-holes are generated in the plastic base material due to lack of processing accuracy.

In addition, as one of means for imparting a gas barrier function to the package, a method of providing an inorganic compound deposition film has recently been widely used.

On the other hand, if an attempt is made to impart easy-opening properties to a barrier packaging material provided with an inorganic compound vapor deposition film by physical means, the inorganic compound vapor deposition film is likely to crack due to external pressure. There was a problem that the vapor-deposited film was damaged by pressing pressure, and the barrier function was impaired.

On the other hand, as in Patent Document 1 and Patent Document 2, for example, a method of achieving both easy-openability and barrier properties by providing a barrier inorganic compound deposited film on a base material provided with non-penetrating minute recesses. There is
However, even with this method, since hard fine particles are pushed in to form minute recesses in the manufacturing process, the deposited film may be cracked even if it is not penetrated, and the barrier property may be impaired.

Japanese Patent No. 3568557 Japanese Patent No. 6159494

Accordingly, an object of the present invention is to provide a method for manufacturing an easy-open packaging material, a package body, a lid material, and a label, which can achieve both easy-openability and gas barrier properties.

The present invention is intended to solve the above problems,
The invention according to claim 1 is a step of forming a plurality of semi-through holes by pressing a roll embedded with high hardness fine particles against one surface of a base material made of a plastic film;
forming a barrier coating layer containing an organic polymer on the other surface of the substrate;
a step of attaching a sealant layer to the surface on which the barrier coating layer is formed;
and the barrier coating layer comprises at least
(i) general formula Si(OR ¹ ) ₄ ... at least one of the silicon compound represented by formula (1) and a hydrolyzate thereof;
(ii) general formula (R ² Si(OR ³ ) ₃ )n...at least one of a silicon compound represented by formula (2) and a hydrolyzate thereof;
(iii) a water-soluble polymer having a hydroxyl group;
A method for producing a packaging material, characterized in that it is a film obtained by applying, heating, and drying a coating liquid containing
(where R ¹ and R ³ above are one of CH ₃ , C ₂ H ₅ or C ₂ H ₄ OCH ₃ and R ² is an organic functional group)

In addition, the invention according to claim 2 is characterized in that the depth of the semi-through hole is 30 to 70% of the thickness of the base material. Manufacturing the packaging material according to claim 1 The method.

The invention according to claim 3 is a step of providing a plurality of semi-through holes on one surface of the base material;
Further, a step of forming a vapor deposition layer made of an inorganic compound on the other surface of the base material;
forming a barrier coating layer containing an organic polymer on the other surface of the vapor deposition layer;
A method for manufacturing a packaging material according to claim 1 or 2, characterized by comprising:

According to the manufacturing method of the packaging material of the present invention, a large number of semi-penetrating minute recesses are formed in a simple process to impart easy-opening properties, and furthermore, by using a barrier coating layer, the semi-penetrating process can be performed. It is possible to provide a packaging material in which the barrier film is not cracked and the barrier properties are not impaired even if the packaging material is subjected to a heat treatment.
Moreover, according to the packaging body using the packaging material obtained by this manufacturing method, it is possible to provide a packaging body that is compatible with easy-openability and barrier properties, and can also be applied to lid materials, labels, and the like.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows one Example of the packaging material which concerns on this invention. 1 is a schematic cross-sectional view showing a conventional packaging material; FIG. 1 is a schematic plan view showing an example of a bag-like package according to the present invention; FIG. FIG. 4 is a schematic plan view showing another embodiment of the bag-shaped package according to the present invention; FIG. 4 is a schematic plan view showing another embodiment of the bag-shaped package according to the present invention; BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic plan view which shows one Example of the cup-shaped packaging container which concerns on this invention. FIG. 10 is a schematic plan view showing a conventional bag-shaped package;

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

First, FIG. 2 is a schematic cross-sectional view showing a layer structure of a conventional packaging material. . Such a structure can provide gas barrier properties as a packaging material. 22 may crack or the like, and the packaging material 8 itself may be damaged.

On the other hand, FIG. 1 is a schematic cross-sectional view showing the layer structure of an example of the packaging material of the present invention. The depth is such that it does not penetrate the substrate 1, and is formed as a semi-through hole 5 as shown in the figure. Details of the minute recesses will be described later.
On the other side of the plastic base material 1, a vapor deposition layer 2 made of an inorganic compound, a barrier coating layer 3 containing an organic polymer, and a sealant layer 4 are sequentially laminated to form a packaging material 7. there is

According to such a structure, the plastic substrate 1 has a thin portion due to the semi-through hole 5 , so that the strength of the portion is reduced and easy opening property is imparted. Since the presence of the barrier coating layer 3 containing molecules increases the strength, there is an effect that the packaging material 7 is less likely to be damaged even when subjected to pressure from the outside.

The embodiment shown in FIG. 1 is an example, and the present invention is not limited to this. For example, in addition to the layers shown in FIG. 1, other functional films such as an overcoat layer, an undercoat layer, a pattern layer, and a protective layer may be added.

Next, a bag-like package using the packaging material of the present invention will be described in comparison with a conventional bag-like package with reference to the drawings.

First, FIG. 7 shows a conventional general bag-like package (pouch).
A conventional bag-like package 50 shown in FIG. 7 is produced by using the packaging material 8 described above, by bonding two packaging materials 8 together or by folding one packaging material 8, and has a content storage portion. A seal portion 11 is formed by bonding the periphery of 12 together.

On the other hand, FIG. 3 is a plan view showing an embodiment of the package of the present invention.
The packaging body 10 shown in FIG. 3 is produced using the packaging material 7, and the whole area of the packaging body 10 including the content storage portion 12 and the sealing portion 11 therearound is half-penetrated above the base material 1. A hole is provided and is referred to as a full-surface semi-through hole portion 3 .
Here, as shown in FIG. 1, the full-surface semi-through holes 3 are composed of a plurality of minute recesses, that is, semi-through holes 5, and the depth of the semi-through holes is such that they do not penetrate the substrate 1. formed. A method for forming such minute recesses will be described later.
Since the package 10 according to the present invention is provided with semi-through holes on the entire surface, the package 10 can be easily opened regardless of the location of the package.

FIG. 4 is a plan view showing another embodiment of the package of the present invention.
The packaging body 20 in FIG. 4 does not have a semi-through hole in the region of the content storage portion 12, and has a semi-through hole (micro recess) on the base material 1 in the region of the surrounding seal portion 11. This is referred to as a seal portion semi-through hole portion 14 . Also in this semi-through hole portion 14 of the seal portion, the depth of the semi-through hole is formed to a depth that does not penetrate the base material 1 . Since the package 20 is provided with a semi-through hole only in the region of the seal portion 2, it can be easily opened from any position of the seal portion 2, and the content storage portion 1 does not have a semi-through hole. It is hard to tear, and trouble such as leakage of the contents does not occur easily.

FIG. 5 is also a plan view showing another embodiment of the package of the present invention.
The packaging body 30 of FIG. 5 is provided with a semi-through hole (micro recess) in a linear region having a constant width on the base material 1 so as to traverse part of the content storage part 12 and the sealing part 11. This is referred to as an unsealing wire semi-penetrating portion 15 . Also in this opening line semi-penetration part 15 , the depth of the semi-penetration hole is formed to a depth that does not penetrate the base material 1 . The package 30 has an opening line semi-penetrating portion 15
It can be easily unsealed along the unsealing line.

FIG. 6 is also a plan view showing another embodiment of the package of the present invention.
The package shown in FIG. 6 shows a PTP (Press Through Pack) package 40, which includes a storage portion 17 for storing contents such as tablets, and a lid member 16 for covering and sealing the entire opening of the storage portion 17. A part of the lid member 16 is formed with an unsealing line semi-through hole portion 18 in which a large number of semi-through holes (micro recesses) are provided in a region having a constant width. This PTP package 40 can be easily broken along the semi-penetration hole 18 by pressing the molded part of the storage part 17 with a finger to apply pressure, and the contents can be taken out.

In addition, although not shown, the present invention can also be applied to a label used, for example, for packaging that covers a container. That is, it is possible to form a band-shaped semi-through-hole portion provided with a large number of semi-through holes similar to the cover member 16 in a portion of the label. With such a label, when disposing of the container, the semi-through hole can be used as a dismantling line to easily dismantle the label for separate disposal.

(Manufacturing method of minute recesses)
Next, a method for forming minute concave portions as semi-through holes in the substrate will be described.
As a method, in order to efficiently form a large number of minute depressions in a certain area on the plastic base material of the packaging material, minute projections are formed on a printing plate roll, and this is applied to the base material. A method can be employed in which the shape is transferred to the substrate surface as minute recesses by pressing.
In this method, high-hardness fine particles may be used as the material for the microprojections, and for example, a roll embedded with diamond powder or emery sand is used. By sandwiching the packaging material film between such rolls with fine protrusions and flat rolls and pressing against the film, a packaging material having a large number of semi-penetrating fine recesses formed on one side, as shown in FIG. 1, is obtained. can be manufactured.

When preparing the above roll with microprotrusions, the grain size of the diamond powder or diamond powder may be appropriately selected according to the material and thickness of the plastic substrate to be transferred and the depth of semi-penetration. The height of the protruding particles is preferably lower than the thickness of the plastic substrate film.

According to findings based on the inventor's studies, it is preferable that the depth of the minute recesses is 30% to 70% of the thickness of the substrate. If the depth of the minute recesses is less than 30% of the thickness of the base material, the effect of easy opening is low. sexuality may be impaired.
Moreover, the size of the pores of the minute recesses is preferably 0.5 to 100 μm in diameter.
If the size of the microrecesses is less than 0.5 μm, it is difficult to form them with the required depth. be.

Further, the density of semi-penetrating minute recesses is preferably 10,000 to 20,000,000/m ² . If the density is less than 10,000/m ² , the easy-to-open effect is low. On the other hand, it is difficult to increase the density of minute recesses to more than 20,000,000,000/m ² due to processing restrictions.

The formation of a large number of semi-penetrating fine recesses may be provided on a base material provided with a barrier coat layer, an inorganic compound deposition layer, or an anchor coat layer, which will be described later. Alternatively, it may be performed after the sealant layer is provided. In order to avoid physical damage to the barrier coat layer, inorganic compound deposition layer, or anchor coat layer, a large number of semi-penetrating fine recesses should be formed in advance in the base film before laminating these layers. is preferred.

The barrier coating layer having gas barrier properties may be appropriately selected depending on the desired function. However, as mentioned above, the vapor deposition film of inorganic compounds alone may cause cracks in the film due to pressure from the substrate side, etc., and may impair the barrier properties. problems can be eliminated. The barrier coat layer will be further described later.

Based on the above knowledge, the method for manufacturing the packaging material of the present invention includes the following steps.
(A) A step of pressing a roll embedded with high-hardness fine particles against one surface of a plastic substrate to form semi-through holes composed of a plurality of minute recesses;
(B) forming a barrier coating layer containing an organic polymer on the other surface of the plastic substrate;
(C) A step of bonding a sealant layer to the surface on which the barrier coating layer is formed.
By manufacturing the packaging material by such a process, the package using this packaging material can have easy opening properties in the part provided with the semi-through hole, and the barrier coating containing the organic polymer can be obtained. The layer has the effect of preventing damage to the barrier film.

The barrier coating layer will be described in detail below. As the barrier coat layer containing an organic polymer, for example, materials such as the following barrier coat films (1) to (3) can be used.

<Barrier coating layer (1)>
The barrier coating layer (1) is an aqueous solution containing at least one of a water-soluble polymer and (a) one or more alkoxides of one or more metals and/or hydrolysates thereof, or (b) tin chloride. Alternatively, it consists of a coating agent containing a water/alcohol mixed solution as a main component. A solution in which a water-soluble polymer and tin chloride are dissolved in an aqueous solvent (water or water/alcohol mixture), or a solution in which an alkoxide such as a metal is directly added to the solution, or a solution mixed with a solution that has undergone a treatment such as hydrolysis in advance is used. It is formed by coating on a base material and drying by heating. Each component contained in the coating agent is described in detail below.

Water-soluble polymers used in coating agents include polyvinyl alcohol, polyvinylpyrrolidone, starch, methylcellulose, carboxymethylcellulose, sodium alginate and the like. In particular, polyvinyl alcohol (hereinafter referred to as PVA) is most excellent in gas barrier properties. The PVA referred to here is generally obtained by saponifying polyvinyl acetate, and ranges from so-called partially saponified PVA in which several tens of percent of acetic acid groups remain to fully saponified PVA in which only a few percent of acetic acid groups remain. Including but not limited to.

Also, tin chloride may be stannous chloride (SnCl ₂ ), stannic chloride (SnCl ₄ ), or a mixture thereof, and both anhydrides and hydrates can be used.

Further, the alkoxide is an _alkoxide of a metal _, etc. _, represented by the general _{formula M (} OR )n (M: metals such as Si, Ti, Al and Zr, etc., R: alkyl groups such as CH ₃ and C ₂ H ₅ ). Among them, tetraethoxysilane and triisopropoxyaluminum are preferable because they are relatively stable in an aqueous solvent after hydrolysis.

Each of the components described above can be added to the coating agent either singly or in combination, and within the range that does not impair the barrier properties of the coating agent, an isocyanate compound, a silane coupling agent, a dispersant, a stabilizer, or a viscosity adjuster. Known additives such as agents and coloring agents can be added.

For example, the isocyanate compound added to the coating agent has two or more isocyanate groups (NCO groups) in its molecule. TTI), tetramethylxylene diisocyanate (hereinafter referred to as TMXDI) and other monomers, and polymers and derivatives thereof.

For example, the silane coupling agent added to the coating agent contains an isocyanate-based silane coupling agent, an epoxy-based silane coupling agent, or an amino-based silane coupling agent, so that the adhesion to the substrate becomes stronger. preferable. More preferred are epoxy-based silane coupling agents, such as 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -glycidoxypropylmethyldiethoxysilane, or 3-glycidoxypropyltriethoxysilane. Among them, 3-glycidoxypropylmethyldimethoxysilane or 3-glycidoxypropyltrimethoxysilane is preferable for enhancing adhesion.
The content of the silane coupling agent in the barrier coating layer of the present invention is particularly preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the barrier coating layer after drying.

<Barrier coat layer (2)>
The barrier coating layer (2) is
(i) general formula Si(OR ¹ ) ₄ ... at least one of the silicon compound represented by formula (1) and a hydrolyzate thereof;
(ii) general formula (R ² Si(OR ³ ) ₃ )n...at least one of a silicon compound represented by formula (2) and a hydrolyzate thereof;
(iii) a water-soluble polymer having a hydroxyl group;
obtained by applying, heating, and drying a coating liquid containing
(where R ¹ and R ³ above are one of CH ₃ , C ₂ H ₅ or C ₂ H ₄ OCH ₃ and R ² is an organic functional group)

The barrier coating layer (2) is sufficiently insolubilized by containing these three components. By hydrolysis, R ² Si(OR ³ ) ₃ of general formula (2) forms a hydrogen bond with Si(OR ¹ ) ₄ of general formula (1) and water-soluble polymer, so it is difficult to become pores in the barrier. On the other hand, the organic functional groups form a network to prevent the water-soluble polymer from swelling due to the addition of water to its hydrogen bonds, thereby significantly improving water resistance.

The pores of the barrier refer to portions that facilitate gas permeation without forming a dense network in the membrane.

In general formula (1), R ¹ can be any of those represented by CH ₃ , C ₂ H ₅ , C ₂ H ₄ OCH ₃ and the like. Among them, tetraethoxysilane is preferable because it is relatively stable in an aqueous solvent after hydrolysis.

This swelling can be prevented by adding the compound of general formula (2).

In general formula (2), the organic functional group (R ² ) is preferably a non-aqueous functional group such as vinyl, epoxy, methacryloxy, ureido and isocyanate. Since the non-aqueous functional group is hydrophobic, the water resistance is further improved.

When the compound represented by general formula (2) is a polymer, it is preferably a trimer, more preferably a general formula (NCO--R ⁴ Si(OR ³ ) ₃ ) ₃ (wherein R ⁴ is (CH ₂ )n, where n is 1 or more). This is a condensate of 3-isocyanatoalkylalkoxysilane.

A 3-glycidoxypropyl group or a 2-(3,4 epoxycyclohexyl) group can be preferably used as the organic functional group R ² of the general formula (2). These organic functional groups form hydrogen bonds with Si(OR ¹ ) ₄ of the general formula (1) and the water-soluble polymer by hydrolysis, so that they hardly become pores in the barrier and do not impair gas barrier properties. Water resistance can be improved.

<Barrier coating layer (3)>
The barrier coat layer (3) includes a layer (A) described below and a layer (B) containing a polyvalent metal compound.

The layer (A) comprises a polycarboxylic acid-based polymer (A1) (hereinafter "(A1) component"), a silane coupling agent represented by the following general formula (3), a hydrolyzate thereof and a condensate thereof. At least one silicon-containing compound (A2) selected from the group consisting of The mass of the component (A2) is the mass in terms of the silane coupling agent).
R ⁵ Si(OR ⁶ ) ₃ Formula (3)
[In formula (1), R ⁵ is an organic group containing a glycidyloxy group or an amino group, R ⁶ is an alkyl group, and the three R ^6s may be the same or different. ]

By having the layer (B) containing the polyvalent metal compound together with the layer (A), the gas barrier precursor laminate is subjected to at least one treatment selected from the group consisting of retort treatment, boiling treatment and humidity conditioning treatment. When applied, the component (A1) contained in the layer (A) reacts with the polyvalent metal compound contained in the layer (B), and the carboxy group of the component (A1) undergoes ionic cross-linking with the polyvalent metal ion. It is possible to form a gas barrier laminate having excellent gas barrier properties.

As the component (A1), from the viewpoint of the gas barrier properties of the resulting gas barrier laminate, at least one polymerizable monomer selected from the group consisting of acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid and crotonic acid. A polymer containing a structural unit derived from a polymer is preferred, and a polymer containing a structural unit derived from at least one polymerizable monomer selected from the group consisting of acrylic acid, maleic acid, methacrylic acid and itaconic acid. Coalescing is particularly preferred.
In the polymer, the proportion of structural units derived from at least one polymerizable monomer selected from the group consisting of acrylic acid, maleic acid, methacrylic acid and itaconic acid is preferably 80 mol% or more. , more preferably 90 mol % or more (provided that the total of all structural units constituting the polymer is 100 mol %).
The polymer may be a homopolymer or a copolymer. When the polymer is a copolymer containing structural units other than the above structural units, the other structural units include, for example, ethylenically unsaturated monomers copolymerizable with the aforementioned ethylenically unsaturated carboxylic acids. Structural units derived from mers and the like are included.

(A2) component is a group consisting of a silane coupling agent represented by the general formula (3) (hereinafter sometimes referred to as "silane coupling agent (1)"), hydrolysates thereof and condensates thereof at least one silicon-containing compound selected from
In addition, the component (A2), even in a small amount, improves the adhesiveness to each layer (A) of the base material, vapor deposition layer, and anchor coat layer, and improves heat resistance, water resistance, and the like.

Examples of the organic group for R ⁵ in the general formula (3) include a glycidyloxyalkyl group and an aminoalkyl group. As the alkyl group for R ⁶ , an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group or an ethyl group is particularly preferable.
Specific examples of the silane coupling agent (1) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like. mentioned. Among these, γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltrimethoxysilane are preferred.

Layer (A) contains component (A1) and component (A2) in a weight ratio of 99.5:0.5 to 80.0:20.0. However, the mass of the component (A2) is the mass in terms of the silane coupling agent (1). That is, as described above, the component (A2) is usually mixed with the silane coupling agent (1), its hydrolyzate, and the condensate thereof, but the mass of the component (A2) is the silane coupling agent ( 1), that is, the charged amount of the silane coupling agent (1).
Within the above range, a gas barrier precursor laminate having excellent abuse resistance can be obtained. In addition, the gas barrier laminate obtained from the gas barrier precursor laminate has excellent gas barrier properties. In addition, it has excellent adhesion to each of the base material, the anchor coat, and the deposition layer, and delamination hardly occurs when the gas barrier laminate is obtained from the gas barrier precursor laminate.

From the viewpoint of gas barrier properties, the thickness of layer (A) is preferably in the range of 0.01 to 5 μm, more preferably in the range of 0.02 to 3 μm, still more preferably in the range of 0.04 to 1.2 μm. is in the range.

Layer (B) contains a polyvalent metal compound.
A polyvalent metal compound is a compound of a polyvalent metal whose metal ion has a valence of 2 or more.
Examples of polyvalent metals include alkaline earth metals such as beryllium, magnesium and calcium; transition metals such as titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper and zinc; aluminum and silicon. Calcium or zinc is particularly preferable as the polyvalent metal from the viewpoint of heat resistance, water resistance and transparency. That is, the polyvalent metal compound is preferably a calcium compound or a zinc compound.

Examples of polyvalent metal compounds include simple substances, oxides, hydroxides, carbonates, organic acid salts (such as acetates) or inorganic acid salts of polyvalent metals, ammonium complexes of polyvalent metal oxides, or 2 to 4 class amine complexes, or their carbonates or organic acid salts.
Among these polyvalent metal compounds, alkaline earth metals, cobalt, nickel, copper, zinc, aluminum or silicon oxides, hydroxides, Chlorides, carbonates or acetates, ammonium complexes of copper or zinc or their carbonates are preferably used.
Among these, from the viewpoint of industrial productivity, zinc oxide, aluminum oxide, calcium hydroxide, calcium carbonate, zinc acetate, and calcium acetate are preferred, and zinc oxide or calcium carbonate is particularly preferred.

When the layer (B) is formed by drying a coating film made of the coating liquid (b) containing the polyvalent metal compound, the form of the polyvalent metal compound may be particulate or non-particulate. It may be present or dissolved, but from the viewpoint of dispersibility, gas barrier properties, and productivity, it is preferably in the form of particles.
The average particle size of such particles is not particularly limited, but from the viewpoint of gas barrier properties and coatability, the average particle size is preferably 5 μm or less, more preferably 1 μm or less, and 0.1 μm or less. is particularly preferred.

Layer (B) may contain various additives in addition to the polyvalent metal compound, if necessary, within a range that does not impair the effects of the present invention. As the additive, for example, when the layer (B) is formed by drying a coating film made of a coating liquid (b) containing a polyvalent metal compound, Alternatively, it may contain a dispersible resin, a dispersant soluble or dispersible in the solvent, a surfactant, a softening agent, a stabilizer, a film-forming agent, a thickener, and the like.
Among the above, it is preferable to contain a resin that is soluble or dispersible in the solvent used for the coating liquid (b). Thereby, the coatability and film formability of the coating liquid (b) are improved. Examples of such resins include alkyd resins, melamine resins, acrylic resins, urethane resins, polyester resins, phenol resins, amino resins, fluorine resins, epoxy resins, and isocyanate resins.

Moreover, it is preferable to contain a dispersant that is soluble or dispersible in the solvent used for the coating liquid (b). This improves the dispersibility of the polyvalent metal compound. As the dispersant, an anionic surfactant or a nonionic surfactant can be used. The surfactants include (poly)carboxylates, alkyl sulfates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfosuccinates, alkyldiphenyletherdisulfonates, alkylphosphates, aromatic Phosphate ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, alkylallyl sulfate, polyoxyethylene alkyl phosphate, sorbitan alkyl ester, glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid various surfactants such as esters, polyethylene glycol fatty acid esters, polyoxyethylene sorbitan alkyl esters, polyoxyethylene alkyl allyl ethers, polyoxyethylene derivatives, polyoxyethylene sorbitol fatty acid esters, polyoxy fatty acid esters, polyoxyethylene alkylamines, etc. be done. These surfactants may be used alone or in combination of two or more.

When the layer (B) contains an additive, the mass ratio of the polyvalent metal compound to the additive (polyvalent metal compound: additive) is in the range of 30:70 to 99:1. preferably in the range of 50:50 to 98:2.

The thickness of layer (B) is preferably in the range of 0.01 to 5 μm, more preferably in the range of 0.03 to 3 μm, still more preferably in the range of 0.1 to 1.2 μm, from the viewpoint of gas barrier properties. is in the range.

The method of applying the coating agent is not particularly limited, and conventionally known means such as casting, dipping, roll coating, screen printing, gravure coating, spraying, and reverse coating can be used.

<Plastic substrate>
The substrate used in the present invention is made of a resin material and is preferably transparent. Examples of such resin materials include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene and polypropylene, polystyrene films, polyamide films such as 66-nylon, polycarbonate films, and polyacrylonitrile films. and engineering plastic films such as polyimide films. This resin material may be either stretched or unstretched, and preferably has mechanical strength and dimensional stability. This resin material is processed into a film and used as a base material. In particular, among these, films arbitrarily stretched in biaxial directions are preferably used.
Furthermore, when used as a packaging material, polyamide films and polyester films are preferred in consideration of cost, moisture resistance, filling suitability, texture, and disposability, with polyester films being more preferred.

<Surface treatment>
In order to strengthen the adhesion between the plastic substrate and the barrier coating layer or the deposited layer of inorganic compound, the surface of the substrate is preferably subjected to corona treatment, plasma treatment, or ozone treatment.
More preferably, pretreatment by reactive ion etching (RIE) using plasma is effective. By performing this RIE treatment, the generated radicals and ions are used to create chemical effects such as giving functional groups to the surface of the plastic base material, and the surface is ion-etched to remove impurities and smooth it out. Both physical effects can be obtained at the same time. By performing such a surface treatment, adhesion can be strengthened, and gas barrier properties can be improved.

Processing conditions such as processing speed and energy level should be appropriately set according to the type of substrate, application, characteristics of the electric discharge device, and the like. However, the plasma self-bias value is 200 V or more and 2000 V or less, and the Ed value defined by Ed = (plasma density) × (processing time) is 100 W·m ⁻² sec or more and 10000 W·m ⁻² sec or less. is preferred. Even if the value is slightly lower than the above value, the adhesiveness is exhibited to some extent, but the superiority is low compared to the untreated product. On the other hand, when the value is higher than the above value, the substrate surface is deteriorated due to excessively strong treatment, which causes deterioration of adhesion. Regarding the plasma gas and its mixture ratio, the flow rate differs between the introduced amount and the effective amount depending on the pump performance and installation position, so it should be set appropriately according to the application, base material, and device characteristics.

The thickness of the substrate is not subject to any particular limitation, but is practically preferably 3 to 200 μm, more preferably 6 to 30 μm, in consideration of suitability as a packaging material and workability.

Various well-known additives and stabilizers such as antistatic agents, plasticizers, lubricants, and antioxidants can also be applied to the surface of this substrate, if desired.

<Anchor coat layer>
The anchor coat layer includes, for example, polyols selected from acrylic polyols, polyvinyl acetals, poly-still polyols, polyurethane polyols, etc., and an organic polymer obtained by a two-liquid reaction with an isocyanate compound, or a polyisocyanate compound and water. organic compounds having urea bonds by reaction with polyethylenimine or derivatives thereof, polyolefin emulsions, polyimides, melamine, phenol, inorganic silica such as organically modified colloidal silica, silane coupling agents and hydrolysates thereof. Examples include those containing an organic silane compound as a main ingredient.
A combination of an acrylic polyol, an isocyanate compound, and a silane coupling agent is particularly preferred. By using a primer layer composed of this combination, stable and higher adhesion can be obtained between the substrate and the barrier coating layer or between the substrate and the deposited layer.

The combination of an acrylic polyol, an isocyanate compound, and a silane coupling agent is selected from the group consisting of trifunctional organosilanes represented by the following general formula (p1), metal alkoxides represented by the following general formula (p2), and hydrolysates thereof. It consists of a composite of at least one selected metal compound (P), a polyol compound (Q) and an isocyanate compound (R).
R ⁷ Si(OR ⁸ ) ₃ (p1)
M(OR ⁹ )n (p2)
[ ^In formula (p1), R ⁷ is an organic group containing an amino group, an isocyanate group, a sulfoxide group, an alkyl group, a vinyl group, or an epoxy group; R ⁸ is an alkyl group; They may be the same or different. In formula (p2), M is a metal element, n is the oxidation number of the metal element M, R ⁹ is an alkyl group, and when n is 3 or more, (n−1) R ⁹ They may be the same or different. ]

The metal compound (P) consists of a trifunctional organosilane and a hydrolyzate thereof, wherein R ⁷ in the general formula (p1) is an organic group containing an amino group, an isocyanate group or a sulfoxide group.

The thickness of the anchor coat layer after drying is generally desirably in the range of 0.005 to 5 μm, more preferably 0.01 to 1 μm. If the thickness is less than 0.01 μm, it is difficult to obtain a uniform coating film from the viewpoint of coating technology.

<Vapor Deposition Layer Made of Inorganic Compound>
Examples of inorganic compounds used in the deposited layer include oxides of silicon, aluminum, titanium, zirconium, tin, and magnesium; compounds of compounds.

This vapor deposition layer is formed by vacuum vapor deposition, sputtering, plasma vapor deposition, reactive vapor deposition, reactive sputtering, reactive ion It can be formed by a vacuum process such as plating. In particular, aluminum oxide and silicon oxide can be preferably used because they are colorless and transparent, have excellent water resistance in boil/retort sterilization, and can be used in a wide range of applications.

In aluminum oxide, the abundance ratio of aluminum (Al) and oxygen (O) is preferably Al:O=1:1.5 to 1:2.0. In silicon oxide, the abundance ratio of silicon (Si) and oxygen (O) is preferably Si:O=1:1.0 to 1:2.0.

The film thickness of the deposited layer varies somewhat depending on the application and the film thickness of the gas barrier coating layer, but is preferably in the range of several nm to 500 nm. However, if the thickness is less than 5 nm, there is a problem with the continuity of the thin film, and if the thickness exceeds 300 nm, cracks are likely to occur and the flexibility decreases.

<Sealant layer>
A sealant layer is formed as an adhesion part when forming a bag-like package or the like.
The sealant layer includes, for example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer. Resins such as coalesced resins and metal crosslinked products thereof are used, and the resin may be appropriately selected from among these resins.
Although the thickness is determined depending on the purpose, it is generally in the range of 15 to 200 μm. Depending on the shape of the package, the sealant layer may be provided on the base material side or may be provided on both sides.

As a method for forming the sealant layer, a dry lamination method in which a film made of the above resin is laminated with a one-component or two-component curing urethane adhesive, or a non-solvent method in which a non-solvent adhesive is used. A dry lamination method, an extrusion lamination method in which the above-described resin is heated and melted, extruded in a curtain shape, and laminated together can all be used for formation by a known lamination method.

Since the package of the present invention has the above structure, even if a sealing member made of a plastic film is used, by pressing the molded portion of the container with a finger, it can be opened in the same manner as a conventional PTP package using aluminum foil. The sealing member can be broken, and the tablet or the like can be easily taken out.
In addition, since the sealing member uses a barrier film in which a vapor deposition layer of inorganic oxide, an overcoat layer, and a vapor deposition layer of a metal compound are provided in this order, it has moisture resistance and oxygen barrier properties for protecting tablets and the like. It has sufficient protection function. In addition, since no aluminum foil is used for the sealing member, there is no problem when incinerating after use, and it can be easily disposed of.

1 ... Plastic base material (base material)
2 Vapor deposition layer 3 Barrier coating layer 4 Sealant layer 5 Semi-through holes 7, 8 Packaging material 10, 20, 30, 50 Bag-like package 40 ...PTP package 11...sealing part 12...contents accommodating part 13...full surface semi-through hole part 14...sealing part semi-through hole part 15...opening line semi-through hole part 16 ... Lid material 17 ... Storage part 18 ... Opening line semi-through hole part 22 ... Barrier inorganic vapor deposition layer

Claims (3)

A step of forming a plurality of semi-through holes by pressing a roll embedded with high-hardness fine particles against one surface of a base material made of a plastic film;
forming a barrier coating layer containing an organic polymer on the other surface of the substrate;
a step of attaching a sealant layer to the surface on which the barrier coating layer is formed;
and the barrier coating layer comprises at least
(i) general formula Si(OR ¹ ) ₄ ... at least one of the silicon compound represented by formula (1) and a hydrolyzate thereof;
(ii) general formula (R ² Si(OR ³ ) ₃ )n...at least one of a silicon compound represented by formula (2) and a hydrolyzate thereof;
(iii) a water-soluble polymer having a hydroxyl group;
A method for producing a packaging material, which is a film obtained by applying, heating, and drying a coating liquid containing
(where R ¹ and R ³ above are one of CH ₃ , C ₂ H ₅ or C ₂ H ₄ OCH ₃ and R ² is an organic functional group) 2. The method of manufacturing a packaging material according to claim 1, wherein the depth of the semi-through hole is 30 to 70% of the thickness of the base material. providing a plurality of semi-through holes in one surface of the base material;
Further, a step of forming a vapor deposition layer made of an inorganic compound on the other surface of the base material;
The method of manufacturing a packaging material according to claim 1 or 2, further comprising the step of forming a barrier coating layer containing an organic polymer on the other surface of the vapor deposition layer .

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