HK1164225B

HK1164225B - Multilayer body and container

Info

Publication number: HK1164225B
Application number: HK12104878.5A
Authority: HK
Inventors: 关口朋伸; 山本政史; 山田和范; 菅野周平
Original assignee: 东洋铝株式会社
Priority date: 2009-02-13
Filing date: 2010-02-12
Publication date: 2014-08-01

Abstract

Disclosed are a multilayer body, a packaging material and a container, each of which can maintain excellent water repellent properties and non-adhesive properties. Specifically disclosed is a non-adhesive multilayer body wherein hydrophobic oxide fine particles having an average primary particle diameter of 3-100 nm adhere to at least a part of the outermost layer.

Description

Laminate and container

Technical area

The present invention relates to a laminate and a container. In particular, the present invention relates to the following techniques.

The present invention relates to a laminate and a packaging material. In particular, the present invention relates to a laminate used for tablecloths, napkins, aprons, table covers, floor mats, wall cloths, wall papers, labels (tapes), release papers, hang tags (tags), chair covers, waterproof sheets, umbrellas, ski materials, building materials, bed covers, shoe covers, boot covers, waterproof clothing, hydrophobic films, hydrophobic sheets, and the like, and a packaging material for packaging foods, beverages, pharmaceuticals, cosmetics, chemicals, and the like.

Further, the present invention relates to a non-adhesive container and a method for manufacturing the same. In particular, the present invention relates to a container having excellent non-adhesion of contents and a method for manufacturing the same. More particularly, the present invention relates to a non-adhesive container for storing foods, beverages, pharmaceuticals, cosmetics, chemicals, and the like, and a method for manufacturing the same.

In addition, the present invention relates to a packaging material and a method for manufacturing the same. More specifically, the present invention relates to a packaging material for packaging foods, beverages, pharmaceuticals, cosmetics, chemicals, and the like, and a method for producing the same. In particular, it relates to a packaging material having excellent non-adhesion of contents.

Furthermore, the invention relates to a packaging material. More specifically, the present invention relates to a packaging material for packaging foods, beverages, pharmaceuticals, cosmetics, chemicals, and the like. In particular, it relates to a packaging material having excellent non-adhesiveness and oxygen-absorbing properties for contents.

Background

Various packaging materials and containers have been known, and the contents thereof are also diversified. Among them, there are foods, beverages, pharmaceuticals, cosmetics, chemicals, etc., and examples thereof include jelly-like snacks, puddings, yogurts, liquid lotions, toothpastes, curries, syrups, vaselins, facial cleansers, facial mousses, etc. In addition, the properties of the contents are also various, and examples thereof include solid, semisolid, liquid, viscous substance, and gel-like substance.

The packaging material for packaging these contents is required to have not only sealing properties but also hot tack, light-shielding properties, heat resistance, durability, and the like according to the contents, packaging form, use, and the like. However, even a packaging material satisfying these characteristics still has the following problems. Namely, the content adheres to the packaging material. If the contents adhere to the packaging material, it is difficult to completely use the contents, and the unused portion is wasted. In addition, in order to completely use up the contents, it is necessary to separately collect the contents adhered to the packaging material, which takes time and labor. Therefore, the packaging material must have a property (non-adhesive property) that the contents are difficult to adhere to the packaging material, in addition to the above-described sealability and the like.

In contrast, there has been proposed a cover member for preventing the adhesion of a filler, in which: in a lid member having a base layer and a heat seal layer integrated with each other with an adhesive layer interposed therebetween, the heat seal layer is composed of a polyolefin having an adhesion preventing effect, the polyolefin including a glycerate, a polyglycerin fatty acid ester, a pentaerythritol fatty acid ester, a polyoxypropylene-polyoxyethylene block polymer, a sorbitan fatty acid ester, a polyoxyethylene alkyl ether, a fatty acid amide, and the like; the lid member has a thickness of more than 10 μm, and an intermediate layer made of polyolefin is provided between the adhesive layer and the heat seal layer (patent document 1).

Further, there has been disclosed an apparatus provided with an easily-cleaned surface coating film having heat resistance of at least 300 ℃, remarkable adhesion resistance and a thickness of 1 to 1000nm, wherein the surface coating film contains a metal oxide network and a hydrophobic substance, the hydrophobic substance is uniformly distributed with respect to the thickness of the surface coating film, and the surface coating film has hydrophobicity having a contact angle of more than 90 ° with respect to water (patent document 2).

Documents of the prior art

Patent document

[ patent document 1 ] Japanese unexamined patent publication No. 2002-37310

[ patent document 2 ] Japanese unexamined patent publication No. 2004-

However, the materials of patent documents 1 and 2, etc. have not been said to have a sufficient adhesion preventing effect. In this regard, further improvement is still required for further practical use.

Disclosure of Invention

Accordingly, a primary object of the present invention is to provide a laminate, a packaging material and a container which can continuously exhibit superior non-adhesion properties as compared with the prior art.

The present inventors have made extensive studies in view of the above-mentioned problems of the prior art, and as a result, have found that the above-mentioned object can be achieved by using a laminate having a specific structure, and even a packaging material, and finally have completed the present invention.

That is, the present invention relates to the following laminate, packaging material and container.

1. A non-adhesive laminate having hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm attached to at least a part of the outermost surface.

2. A laminate comprising a thermoplastic resin-containing layer and, adhered to at least a part of the surface thereof, hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100 nm.

3. The laminate according to claim 2, which contains filler particles in the layer containing the thermoplastic resin, wherein the filler particles contain at least 1 component selected from an organic component and an inorganic component.

4. The laminate according to claim 2, wherein the hydrophobic oxide fine particles are attached in an amount of 0.01 to 10g/m²。

5. The laminate according to item 2, wherein the hydrophobic oxide fine particles form a porous layer composed of a three-dimensional network structure.

6. The laminate according to claim 2, wherein the hydrophobic oxide fine particles have a specific surface area of 50 to 300m by the BET method²/g。

7. The laminate according to claim 2, wherein the hydrophobic oxide fine particles are hydrophobic silica.

8. The laminate of item 7, wherein the hydrophobic silica has trimethylsilyl groups on its surface.

9. The laminate according to claim 3, wherein the filler particles have an average particle diameter of 0.5 to 100 μm.

10. A packaging material comprising the laminate according to any one of claims 1 to 9.

11. A non-adhesive container for containing contents, wherein hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm are attached to at least a part of or the entire surface of the container in contact with the contents.

12. The non-adherent container according to claim 11, wherein the amount of the hydrophobic oxide fine particles adhered is 0.01 to 10g/m²。

13. The non-adherent container according to item 11, wherein the hydrophobic oxide fine particles form a porous layer composed of a three-dimensional network structure.

14. The non-adherent container according to claim 11, wherein the hydrophobic oxide fine particles have a specific surface area of 50 to 300m by the BET method²/g。

15. The non-adherent container according to item 11, wherein the hydrophobic oxide microparticles are hydrophobic silica.

16. The non-adherent container of claim 15, wherein the hydrophobic silica has trimethylsilyl groups on a surface thereof.

17. A product obtained by filling the non-adhesive container according to claim 11 with a content and sealing the content with a lid member.

18. A method for manufacturing a container for storing contents, the method comprising: and a step of adhering hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm to at least a part of or the entire surface of the container which is in contact with the content.

19. A method for manufacturing a container for storing contents, comprising the steps of: and a step of adhering hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm to at least a part of or the entire surface of the container in contact with the content and performing a heat treatment.

20. A packaging material comprising a laminate having at least a base material layer and a thermal adhesive layer, wherein the thermal adhesive layer is laminated as the outermost layer on one surface of the packaging material, and hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm are adhered to the outermost surface of the thermal adhesive layer not adjacent to other layers.

21. The packaging material according to claim 20, wherein the hydrophobic oxide fine particles are attached in an amount of 0.01 to 10g/m²。

22. The packaging material according to item 20, wherein the hydrophobic oxide fine particles form a porous layer composed of a three-dimensional network structure.

23. The packaging material according to item 20, wherein the hydrophobic oxide fine particles have a specific surface area of 50 to 300m by BET method²/g。

24. The packaging material of claim 20, wherein the hydrophobic oxide microparticles are hydrophobic silica.

25. The packaging material of item 24, wherein the hydrophobic silica has trimethylsilyl groups on its surface.

26. The packaging material of item 20, for use in: in the article in which the contents are packaged by the packaging material in a state where the contents can be in contact with the outermost surface on the side of the thermal adhesive layer.

27. A method for producing a packaging material comprising a laminate having at least a base material layer and a thermal adhesive layer, comprising a step of attaching hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm to the surface of the thermal adhesive layer.

28. The production method according to claim 27, further comprising a step of heating the laminate during and/or after the step of adhering the hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm to the surface of the thermal adhesive layer.

29. A lid member comprising a packaging material comprising a laminate comprising at least a base material layer and a thermal adhesive layer, wherein the thermal adhesive layer is laminated as the outermost layer on one surface of the packaging material, and hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm are adhered to the outermost surface of the thermal adhesive layer not adjacent to other layers, and the hydrophobic oxide fine particles form a porous layer having a three-dimensional network structure.

30. A packaging material which is used as a bag-shaped body, a molded container, a sheet-shaped package, or a tubular package and comprises a laminate comprising at least a base material layer and a thermal adhesive layer, wherein the thermal adhesive layer is laminated as an outermost layer on one surface of the packaging material, and hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm are adhered to an outermost surface of the thermal adhesive layer which is not adjacent to other layers, and the hydrophobic oxide fine particles form a porous layer having a three-dimensional network structure.

31. A packaging material comprising a laminate having at least a base material layer and a thermal adhesive layer, wherein the thermal adhesive layer is laminated as the outermost layer on one surface of the packaging material, at least one of the base material layer and the thermal adhesive layer contains an oxygen absorber, and hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm are adhered to the outermost surface of the thermal adhesive layer which is not adjacent to the other layer.

32. The packaging material according to item 31, wherein the attached amount of the hydrophobic oxide fine particles is 0.01 to 10g/m²。

33. The packaging material according to item 31, wherein the hydrophobic oxide fine particles form a porous layer composed of a three-dimensional network structure.

34. The packaging material according to item 31, wherein the hydrophobic oxide fine particles have a specific surface area of 50 to 300m by BET method²/g。

35. The packaging material of item 31, wherein the hydrophobic oxide microparticles are hydrophobic silica.

36. The packaging material of item 35, wherein the hydrophobic silica has trimethylsilyl groups on its surface.

37. The packaging material according to item 31, wherein the oxygen absorber contains metal particles, and at least 1 component of a resin component and an inorganic oxide is coated on at least a part of particle surfaces of the metal particles.

38. The packaging material according to item 31, which is used in an article in which a content is packaged by the packaging material in a state in which the content can be in contact with an outermost surface on the thermal adhesive layer side.

ADVANTAGEOUS EFFECTS OF INVENTION

< effects of the invention 1 >

The laminate and the packaging material according to claim 1 exhibit excellent hydrophobicity and non-adhesive property (or stain-proofing property). In particular, when filler particles containing at least 1 component of the organic component and the inorganic component are contained in the layer containing a thermoplastic resin (hereinafter also referred to as "thermoplastic resin layer"), the falling off of the hydrophobic oxide fine particles can be effectively suppressed or even prevented, and as a result, good hydrophobicity and non-adhesion can be more effectively and continuously exhibited.

In addition, in the laminate or the packaging material according to claim 1, when the thermoplastic resin layer is used as a thermal adhesive layer, excellent non-adhesion property can be continuously exhibited while maintaining good thermal adhesive property. That is, high non-adhesiveness can be obtained without being restricted by the kind, thickness, and the like of the heat adhesive layer and without impairing heat adhesiveness in practical use. More specifically, when thermal bonding is performed, the fine hydrophobic oxide particles present in the region to be thermally bonded are embedded in the thermal adhesive layer, and therefore thermal bonding is not inhibited, while the fine hydrophobic oxide particles present outside the region to be thermally bonded are retained on the thermal adhesive layer as they are, and therefore, high non-adhesiveness is exhibited.

For example, these laminates can be suitably used for tablecloths, napkins, aprons, table covers, floor mats, wall cloths, wallpaper, labels, release paper, hang tags, chair covers, waterproof sheets, umbrellas, skiing equipment, building materials, bed covers, shoe upper materials, boot covers, waterproof clothing, hydrophobic films, hydrophobic sheets, and the like. Such a laminate can also be used as a packaging material for packaging foods, beverages, pharmaceuticals, cosmetics, chemicals, and the like, either directly or by processing.

< effects of the invention 2 >

The non-adhesive container of claim 2 does not contain a controversial substance such as fluorine, and therefore exhibits excellent non-adhesion. Thus, the contents can be substantially completely taken out of the container, and thus, the loss due to the adhesion to the inner wall portion of the container can be suppressed or even prevented.

Further, according to the production method of the invention 2, the hydrophobic oxide fine particles are only required to be applied to at least a part of the surface of the container which is in contact with the content, and a complicated process is not required, which is advantageous in terms of production efficiency, cost, and the like. The material of the container is not limited, and for example, the container can be applied to any material container such as a glass container, a pottery, a paper container, a plastic container, a metal container, and a wooden container. Further, the non-adhesion property may be imparted to the container after the end of the process. Further, the non-adhesive property can be further maintained by applying the hydrophobic oxide fine particles and then performing heat treatment.

< effects of the invention 3 >

The packaging material of claim 3 can exhibit excellent non-adhesiveness while maintaining good hot-melt adhesiveness. That is, a high degree of non-adhesiveness can be obtained without being limited by the kind, thickness, etc. of the heat-sensitive adhesive layer and without impairing the heat-sensitive adhesive property in practical use. More specifically, when thermal bonding is performed, the fine hydrophobic oxide particles present in the region to be thermally bonded are embedded in the thermal adhesive layer, and therefore thermal bonding is not inhibited, while the fine hydrophobic oxide particles present outside the region to be thermally bonded are retained on the thermal adhesive layer as they are, and therefore, high non-adhesiveness is exhibited.

Further, according to the production method of the invention 3, since it is only necessary to provide the hydrophobic oxide fine particles to the thermal adhesive layer, it is not necessary to control the blending ratio of the additives in the raw materials constituting the thermal adhesive layer, and therefore, it is not necessary to control the blending ratio, and therefore, the production method is advantageous in terms of production efficiency, cost, and the like. In addition, as described above, it is also advantageous in that the thermal adhesion can be performed by attaching the hydrophobic oxide fine particles to the entire surface without considering the adhesion region of the thermal adhesive layer.

Such a packaging material can be effectively used for various applications such as a bag-shaped body such as a pillow bag (pillow pouch), a sleeve bag (cuff), a self-standing bag (Doypack), a three-side seal bag, and a four-side seal bag, a molded container, a sheet-shaped packaging material, and a tube-shaped packaging material, in addition to the use as a cover member.

< effects of the invention 4 >

The packaging material of the invention 4 can exhibit excellent non-adhesiveness and oxygen-absorbing property while maintaining good hot tack. That is, a high degree of non-adhesiveness can be obtained without being limited by the kind, thickness, etc. of the heat-sensitive adhesive layer and without impairing the heat-sensitive adhesive property in practical use. More specifically, when thermal bonding is performed, the fine hydrophobic oxide particles present in the region to be thermally bonded are embedded in the thermal adhesive layer, and therefore thermal bonding is not inhibited, while the fine hydrophobic oxide particles present outside the region to be thermally bonded are retained on the thermal adhesive layer as they are, and therefore, high non-adhesiveness is exhibited.

In addition, since at least one of the base material layer and the thermal adhesive layer contains an oxygen absorbent, the particles of the oxygen absorbent can exhibit a desired oxygen absorption performance while avoiding falling off due to contact with contents or the like. In particular, when the layer containing the hydrophobic oxide fine particles formed on the thermal adhesive layer is porous (that is, when the porous layer is formed), high non-adhesion property and higher oxygen absorption performance can be exhibited. In this case, oxygen remaining in the package or oxygen generated from the content can penetrate through the porous layer and more reliably reach the oxygen absorber contained in the heat-sensitive adhesive layer or the like. As a result, in addition to more efficient absorption/removal of oxygen by the oxygen absorber, a higher degree of non-adhesion can be exerted by forming the porous layer.

Such a packaging material can be effectively used in various applications such as a bag-shaped body such as a pillow bag, a sleeve bag, a self-supporting bag, a three-side seal bag, and a four-side seal bag, a molded container, a sheet-shaped packaging material, and a tubular packaging material, in addition to the use as a lid member.

Drawings

Fig. 1 is a schematic cross-sectional structure of an example of the laminate of the invention 1.

Fig. 2 is a schematic cross-sectional structure of a package produced by using the laminate of the invention 1 as a lid member of a container.

FIG. 3 is a photograph showing a partial cross-sectional view of the packaging materials of examples 1 to 4. In fig. 3, "Lotus leaf (Lotus) surface" indicates "porous layer surface composed of three-dimensional network structure of hydrophobic oxide fine particles".

FIG. 4 is a schematic view showing a cross-sectional structure of the non-adherent container according to claim 2.

FIG. 5 is a schematic sectional view showing a structure of the non-adhesive container according to claim 2 in which the contents are put therein and the lid member is thermally bonded,

fig. 6 is a schematic cross-sectional configuration of the packaging material of the invention 3.

Fig. 7 is a schematic cross-sectional structure of a package produced by using the packaging material of the invention 3 as a container lid member.

FIG. 8 is a graph showing the results of observing the cross-sectional structure of the packaging material obtained in the example by FE (field emission) -SEM.

Fig. 9 is a schematic view showing a cross-sectional configuration of a packaging material according to an embodiment of the invention 4.

Fig. 10 is a schematic view showing a cross-sectional structure of a package produced by using the packaging material of the invention 4 as a container lid member.

Detailed Description

The invention of claims 1 to 4 is an invention having, as a basic structure, a non-adhesive laminate in which hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm are adhered to at least a part of the outermost surface. It is characterized by a porous layer comprising hydrophobic oxide fine particles forming a three-dimensional network structure. This makes it possible to more effectively exhibit hydrophobicity or non-adhesiveness. The following describes the 1 st to 4 th inventions, respectively.

< invention 1 >

1. Laminate and packaging material

The laminate of the invention 1 is characterized in that: hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm are adhered to at least a part of the surface of a layer containing a thermoplastic resin (hereinafter also referred to as "thermoplastic resin layer").

Fig. 1 is a schematic cross-sectional structure of an example of the laminate of the invention 1. In the laminate of fig. 1, hydrophobic oxide microparticles 3 having a primary average particle diameter of 3 to 100nm are adhered to the surface of a thermoplastic resin layer 2 containing filler particles 6 laminated on a base material layer 1. The thermoplastic resin layer 2 is laminated as the outermost layer on the packaging material (laminate) side. In the outermost thermoplastic resin layer 2, hydrophobic oxide fine particles 3 having a primary average particle diameter of 3 to 100nm are adhered to the surface (outermost surface) on the side not adjacent to another layer (substrate layer in fig. 1). The hydrophobic oxide fine particles 3 are attached to and fixed to the thermoplastic resin layer 2. That is, the hydrophobic oxide fine particles are attached so as not to fall off even when the hydrophobic oxide fine particles are in contact with the content. In fig. 1, the hydrophobic oxide fine particles 3 may contain primary particles, but agglomerates (secondary particles) containing a large number of primary particles are preferable. In particular, the hydrophobic oxide fine particles are preferably formed into a porous layer having a three-dimensional network structure. That is, it is preferable that a porous layer having a three-dimensional network structure formed of hydrophobic oxide fine particles is laminated on the thermoplastic resin layer 2.

In the invention 1, when filler particles are contained in the thermoplastic resin layer, the cross section of the surface of the thermoplastic resin layer (the surface to which the hydrophobic oxide fine particles are attached) becomes uneven, and the hydrophobic oxide fine particles enter the recessed portions in an aggregated state, whereby the non-adhesion property can be maintained for a long period of time. That is, even if the hydrophobic oxide fine particles enter the concave portion and are fixed in the concave portion, the hydrophobic oxide fine particles enter the concave portion and are kept in contact with the content and the equipment or device in the process, and thus the falling off of the hydrophobic oxide fine particles can be effectively suppressed or prevented, and as a result, the excellent non-adhesion property can be continuously exhibited. In other words, good non-adhesion property can be exhibited for a long period of time.

Fig. 2 is a schematic cross-sectional structural view of a package produced using the laminate of the invention 1 as a container lid member. In fig. 2, the hydrophobic oxide fine particles 3 and the filler particles 6 are not marked. The container 4 is filled with the content 5 and sealed in a state where the opening thereof is in contact with the thermoplastic resin layer 2 of the laminate. That is, the laminate (packaging material) of the present invention is used in a state where the hydrophobic oxide fine particles adhering to the thermoplastic resin layer 2 can come into contact with the content 5. Even in such a case, since the thermoplastic resin layer 2 is protected by the fine hydrophobic oxide particles and thus has excellent non-adhesion properties, even if the content is in contact with (or close to) the vicinity of the thermoplastic resin layer 2, the content adheres to the thermoplastic resin layer and is blocked by the fine hydrophobic oxide particles (or the porous layer composed of the fine hydrophobic oxide particles) and bounces off. Therefore, the content is not attached to the thermoplastic resin layer, and the content is repelled by the hydrophobic oxide fine particles (or the porous layer made of the hydrophobic oxide fine particles) and returns to the container. The material of the container 4 may be suitably selected from metals, synthetic resins, glass, paper, and composite materials thereof, and the kind, composition, and the like of the thermoplastic resin layer may be suitably adjusted depending on the material.

Thermoplastic resin (layer)

As the thermoplastic resin, known thermoplastic resins can be used. For example, in addition to acrylic resins, polystyrene, ABS resins, vinyl chloride resins, polyethylene resins, polypropylene resins, polyamide resins, polycarbonate resins, polyacetal resins, fluorine resins, silicone resins, polyester resins, and the like, mixed resins thereof, copolymers containing combinations of monomers constituting these (resins), modified resins, and the like can be used.

The thickness of the thermoplastic resin layer is not particularly limited, but is preferably about 0.01 μm to 5mm, more preferably about 0.01 μm to 2mm, from the viewpoint of productivity, cost, and the like. When the thermoplastic resin layer is to function as a thermal adhesive layer, the thickness is preferably 1 to 150 μm in consideration of the thermal adhesive property. In particular, in the case of the packaging material of the present invention, when thermal bonding is performed, the hydrophobic oxide fine particles present in the thermal bonding region are embedded in the thermoplastic resin layer, and the thermoplastic resin layer becomes the outermost surface, so that thermal bonding can be performed. Therefore, in the above thickness range, it is preferable to set the thickness so that the hydrophobic oxide fine particles can be embedded in the thermoplastic resin layer in as large an amount as possible.

The content of the thermoplastic resin in the thermoplastic resin layer varies depending on the kind of the thermoplastic resin, the presence or absence of the filler particles and other additives, but is usually 20 to 100% by weight, preferably 30 to 99% by weight, and more preferably 50 to 99% by weight.

In the present invention, another layer (referred to as a base layer) may be laminated on the thermoplastic resin (layer) for the purpose of reinforcing the thermoplastic resin (layer) or imparting other properties (moisture penetration resistance, oxygen penetration resistance, light-shielding property, heat resistance, impact resistance, and the like) as required. In this case, generally, as shown in fig. 1, the substrate layer, the thermoplastic resin layer, and the hydrophobic oxide fine particles are sequentially stacked to form a 3-layer structure.

When the substrate layer is used, a known material can be used for the substrate layer. For example, it may be suitable to use: paper, synthetic paper, resin film with vapor deposited layer, synthetic resin sheet, aluminum foil, other metal foil, metal sheet, woven fabric, nonwoven fabric, leather, synthetic leather, wood, glass plate, etc., or a composite/laminate thereof.

On the base material layer, each layer used for known packaging materials, building materials, clothing materials, daily necessities, and the like may be laminated at an arbitrary position. Examples thereof include: a printing layer, a printing protective layer (so-called OP layer), a coloring layer, an adhesive layer, an adhesion reinforcing layer, a primer coating layer, a fixing coating layer, an anti-slip agent layer, a slip agent layer, an anti-fogging agent layer, and the like.

The method of laminating the base material layer and the thermoplastic resin layer are not limited, and for example, known methods such as a dry lamination method, an extrusion lamination method, a wet lamination method, and a heat lamination method can be used.

When the thermoplastic resin layer is to function as a thermal adhesive layer, a known thermal adhesive material can be used. For example, a layer formed of an adhesive such as a lacquer-type adhesive, an easy-peeling (easy-peeling) adhesive, or a hot-melt adhesive may be used in addition to the known sealing film. That is, in the present specification, the thermoplastic resin also includes a known thermal adhesive containing a resin component. In the invention 1, a paint-type adhesive or a hot-melt adhesive is particularly preferable, and a hot-melt adhesive layer formed by a paint-type adhesive is particularly preferable. In the case of forming the hot-melt layer, the hydrophobic oxide fine particles can be directly attached to the hot-melt layer by applying the hot-melt adhesive in a molten state and then applying the hydrophobic oxide fine particles before cooling and solidifying, and therefore, the laminate (or packaging material) of the invention 1 can be easily produced continuously.

Filled particles

In the invention 1, the thermoplastic resin layer may contain filler particles as needed. By dispersing the filler particles in the thermoplastic resin layer, more excellent abrasion resistance and the like can be imparted to the thermoplastic resin layer.

The filler particles may contain at least 1 component selected from organic components and inorganic components.

As the inorganic component, for example, 1) metals such as aluminum, copper, iron, titanium, silver, and calcium, or alloys or intermetallic compounds (intermetallic compounds) containing these metals, 2) oxides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, and iron oxide, 3) inorganic acid salts or organic acid salts such as calcium phosphate and calcium stearate, 4) glass, 5) ceramics such as aluminum nitride, boron nitride, silicon carbide, and silicon nitride, and the like can be suitably used.

Examples of the organic component include organic polymer components (or resin components) such as acrylic resins, polyurethane resins, melamine resins, amino resins, epoxy resins, polyethylene resins, polystyrene resins, polypropylene resins, polyester resins, cellulose resins, vinyl chloride resins, polyvinyl alcohol, ethylene-ethyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-ethyl acrylate copolymers, polyacrylonitrile, and polyamides.

The filler particles of claim 1 may contain both inorganic and organic components in addition to the particles composed of the inorganic component or the particles composed of the organic component. Among them, it is particularly preferable to use at least 1 type of particles among acrylic resin particles, hydrophilic silica particles, calcium phosphate particles, carbon powder, calcined calcium particles, unfired calcium particles, calcium stearate particles, and the like.

The average particle diameter (in terms of laser diffraction particle size distribution) of the filler particles is preferably about 0.5 to 100 μm, more preferably 1 to 50 μm, most preferably 5 to 30 μm. If the thickness is less than 0.5 μm, it is not suitable from the viewpoints of handling property, the above-mentioned formation of irregularities, and the like. On the other hand, if it exceeds 100 μm, it is not suitable from the viewpoint of falling-off of filler particles, dispersibility, and the like.

The shape of the filler particles is not limited, and may be any of spherical, spheroid, irregular, teardrop, flat, hollow, porous, and the like.

The content of the filler particles in the thermoplastic resin layer may be suitably changed depending on the kind of the thermoplastic resin or the filler particles, desired physical properties, and the like, but is preferably 1 to 80% by weight, more preferably 3 to 50% by weight, based on the weight of the solid content in general.

The method of containing the filler particles is not particularly limited, but generally, a method of adding the filler particles to a raw material (thermoplastic resin-containing composition) for forming the thermoplastic resin layer, and the like can be mentioned. The mixing method may be either dry mixing or wet mixing. In general, the main component of the thermoplastic resin layer is composed of 1) a thermoplastic resin or a monomer or oligomer constituting the thermoplastic resin, 2) a solvent, and 3) a crosslinking agent and the like as required, and therefore, it is only necessary to add filler particles to a mixture of these components and mix them.

Hydrophobic oxide fine particles

The hydrophobic oxide fine particles adhering to the thermoplastic resin layer have a primary average particle diameter of usually 3 to 100nm, preferably 5 to 50nm, more preferably 5 to 20 nm. When the primary average particle diameter is in the above range, the hydrophobic oxide fine particles are appropriately aggregated, and a gas such as air can be held in the voids in the aggregate, and as a result, excellent non-adhesion can be obtained. That is, the aggregated state can be maintained even after adhering to the thermoplastic resin layer, and therefore, excellent non-adhesion can be exhibited. In the present invention, the hydrophobic oxide fine particles may be attached to one side or both sides of the thermoplastic resin (layer).

In the invention 1, the primary average particle size can be measured by a scanning electron microscope (FE-SEM), and when the analysis ability of the scanning electron microscope is low, the measurement can be performed by another electron microscope such as a transmission electron microscope. Specifically, the average of the longest diameter and the shortest diameter of the particles in the case of a spherical shape and the average of the longest diameter and the shortest diameter in the case of a non-spherical shape are regarded as the diameters, and the average of the diameters of 20 particles arbitrarily selected is regarded as the primary average particle diameter by observation with a scanning electron microscope or the like.

The specific surface area (BET method) of the hydrophobic oxide fine particles is not particularly limited, but is usually 50 to 300m²A specific preferred range is 100 to 300m²/g。

The hydrophobic oxide fine particles are not particularly limited as long as they have hydrophobicity, and may be hydrophobized by surface treatment. For example, fine particles obtained by surface-treating hydrophilic oxide fine particles or the like with a silane coupling agent to make the surface hydrophobic may be used. The kind of the oxide is not limited as long as it has hydrophobicity. For example, at least 1 kind of silica (silica), alumina, titanium oxide, and the like can be used. These may be known products or commercially available products. Examples of the silica include: the product names "AEROSIL R972", "AEROSIL R972V", "AEROSIL R972 CF", "AEROSIL R974", "AEROSIL RX 200", and "AEROSIL RY 200" (referred to above as Nippon AEROSIL Co., Ltd.), "AEROSILR 202", "AEROSILR 805", and "AERO RY 805)"SIL R812 "," AEROSIL R812S ", and the like (manufactured by Evonik Degussa GmbH). Titanium oxide can be exemplified by the product name "Aeroxidetio₂T805 "(manufactured by Evonik Degussa GmbH), and the like. Examples of alumina are: fine particles having a hydrophobic surface, which are obtained by treating a product name "AEROXIDE Alu C" (manufactured by Evonik Degussa GmbH) or the like with a silane coupling agent.

Among these, hydrophobic silica fine particles are preferably used. In particular, from the viewpoint of obtaining more excellent non-adhesive properties, hydrophobic silica fine particles having a trimethylsilyl group on the surface are preferable. Examples of commercially available products corresponding to these compounds include "AEROSILR 812" and "AEROSILR 812S" (all manufactured by Evonik Degussa GmbH).

The amount of the hydrophobic oxide fine particles to be adhered to the thermoplastic resin layer (weight after drying) is not particularly limited, but is usually preferably 0.01 to 10g/m²And more preferably 0.2 to 1.5g/m²At a rate of 0.2 to 1g/m²Most preferred. By setting the range, not only more excellent non-adhesion property can be obtained over a long period of time, but also it is more advantageous in terms of suppressing the falling-off of the hydrophobic oxide fine particles, cost, and the like. The hydrophobic oxide fine particles adhering to the thermoplastic resin layer preferably form a porous layer having a three-dimensional network structure, and the thickness thereof is preferably about 0.1 to 5 μm, more preferably about 0.2 to 2.5. mu.m. By adhering in such a porous layer state, the layer can contain more air, and more excellent non-adhesion can be exhibited.

The hydrophobic oxide fine particles may be attached to the entire surface of the thermoplastic resin layer (the entire surface of the surface on the opposite side to the substrate layer side), or may be attached to a region other than the thermal bonding region (so-called adhesive region) in the thermoplastic resin layer. In the present invention, even if the hydrophobic oxide fine particles adhere to the entire surface of the thermoplastic resin layer, most or all of the hydrophobic oxide fine particles existing in the thermal bonding region are buried in the thermoplastic resin layer, and thermal bonding is not hindered, and therefore, it is preferable that the hydrophobic oxide fine particles adhere to the entire surface of the thermoplastic resin layer even in industrial production.

Packaging material and other uses

The laminate of the invention 1 can be used as it is or after processing in various other applications such as packaging materials. Other applications are not limited as long as they are in the fields where non-adhesion, stain resistance, hydrophobicity, and the like are required, and examples thereof include tablecloths, napkins, aprons, table covers, floor mats, wallcoverings, wallpaper, labels, release paper, hang tags, chair covers, waterproof sheets, umbrellas, ski tools, building materials, bed covers, shoe covers, boots, waterproof clothing, hydrophobic films, and hydrophobic sheets.

2. Laminate and method for producing packaging material

For example, the laminate (packaging material) of the invention 1 can be obtained by a method of producing a laminate or a packaging material having at least a thermoplastic resin layer, the method comprising: and a step (hereinafter, also referred to as "adhesion step") of adhering hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm to the surface of the thermoplastic resin layer.

The thermoplastic resin layer may be used as it is, as long as it is in the form of a film or a sheet. A known base material layer may be laminated by a known method as needed. For example, a thermoplastic resin layer may be formed by the method described in the above paragraph 1 on a single-layer substrate or a laminate material produced by a dry lamination method, an extrusion lamination method, a wet lamination method, a heat lamination method, or the like. When the filler particles are used, as described above, the filler particles may be contained in advance in the raw material for forming the thermoplastic resin layer.

The method for carrying out the step of attaching the hydrophobic oxide fine particles is not particularly limited. For example, known methods such as a roll coating method, a gravure coating method, a bar coating method, a doctor blade film forming method, a brush coating method, and a powder electrostatic coating method can be used. In the roll coating method or the like, the adhesion step can be performed by a method of forming a coating film on the thermoplastic resin layer using a dispersion obtained by dispersing the hydrophobic oxide fine particles in a solvent and then drying the coating film. The solvent in this case is not limited, and other than water, organic solvents such as alcohols (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butyl diglycol, 1, 5-pentanediol, n-pentane, n-hexane, and hexanol can be appropriately selected. In this case, a small amount of a dispersant, a colorant, a precipitation inhibitor, a viscosity modifier, or the like may be used in combination. The amount of the hydrophobic oxide fine particles dispersed in the solvent may be about 10 to 100 g/L. In the drying, either natural drying or forced drying (heat drying) may be used, but forced drying is industrially preferable. The drying temperature is not limited as long as it does not affect the thermoplastic resin layer, but is usually preferably 150 ℃ or lower, and more preferably 80 to 120 ℃.

In the production method of claim 1, the laminate may be heated during and/or after the adhesion step. The adhesion (fixing force) of the hydrophobic oxide fine particles to the thermoplastic resin layer can be further improved by heating the laminate. In this case, the heating temperature T may be appropriately set depending on the type of the thermoplastic resin layer, and is usually preferably within a range of Tm-50. ltoreq. T.ltoreq.Tm +50 with respect to the melting point Tm (melting start temperature). degree.C. of the thermoplastic resin layer used.

The laminate thus obtained can be used as packaging material either directly or after processing. The processing method can be the same as that of the known packaging material. For example, embossing, half-cutting, notching, and the like are not performed.

< invention 2 >

1. Non-adhesive container

The non-adhesive container according to claim 2 is a container for containing contents, wherein: hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm are attached to at least a part or the entire surface of the container in contact with the content.

First, the container body of the invention 2 only needs to be capable of storing contents, and existing products or commercially available products can be used. The material is not limited, and for example, a glass container, a ceramic container, a paper container, a plastic container, a metal container, a wood container, a container made of 2 or more kinds of these composite materials, or the like may be used. The container body may have a known form such as a dish, a tray, a bag, a cup, a bottle, a pot, a box, a barrel, a nearly cylindrical form, or a packing sheet (leaf for packing). The container body is preferably a container made of a molded body. For example, a container made of a molded body of paper, plastic, or metal can be mentioned. The container body may be exemplified by: a container is composed of a laminate material including a layer composed of a rigid material. In the non-adhesive container according to claim 2, it is preferable to exclude "a packaging material comprising a laminate comprising at least a base material layer and a thermal adhesive layer, wherein the thermal adhesive layer is laminated as an outermost layer on one surface of the packaging material, and hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm are adhered to an outermost surface of the thermal adhesive layer which is not adjacent to other layers. "except for.

The non-adherent container of claim 2 is characterized in that: hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm are attached to at least a part of or the entire surface of the container which is in contact with the content. In this case, the hydrophobic oxide fine particles may be adhered to the surface of the container body not in contact with the content, and the adhesion of the hydrophobic oxide fine particles to the entire surface (that is, the entire surface including the surface not in contact with the content) is not hindered. The adhesive agent may be attached to a part of a surface in contact with the content or may be attached to the entire surface (entire surface) of the surface.

The hydrophobic oxide fine particles adhered to the non-adhesive container of the invention 2 are hardly recognizable with the naked eye and are transparent or translucent. Therefore, when a transparent glass container or a nearly transparent plastic container is used as the container body, the transparency can be maintained even after the hydrophobic oxide fine particles are attached. In addition, when the inner surface of the container has a pattern or design, the pattern or design can be recognized by the hydrophobic oxide fine particles (or other layer).

In the invention 2, the laminate comprising the thermoplastic resin layer containing filler particles according to the invention 1 can also be used. That is, the following inventions are also included:

a container comprising a laminate of thermoplastic resin layers containing filler particles, wherein the hydrophobic oxide fine particles are adhered to at least a part of or the entire surface of the container which is in contact with the contents.

For example, such a container can be formed by forming a thermoplastic resin layer by a method such as in-mold (in-mold) molding, coating, melt-injecting, spraying, transferring, embedding, and bonding, using a thermoplastic resin in which filler particles are included in advance in a portion to which the hydrophobic oxide fine particles are to be attached, and attaching the hydrophobic oxide fine particles to the formed portion, whereby good hydrophobicity and non-adhesiveness can be maintained more effectively in the same manner as in the invention 1. The thermoplastic resin and the filler particles may have the same configurations as those described in the description of the invention 1. That is, the thermoplastic resin (layer) and the filler particles described in claim 1 can be used in the same configuration, and the configuration in the preferable range described in claim 1 is preferably used.

Further, the region where the thermoplastic resin layer containing filler particles is formed is not particularly limited. For example, the coating layer may be formed on any of 1) a region to which only the hydrophobic oxide fine particles are attached, 2) a region including a portion to which the hydrophobic oxide fine particles are not attached, and 3) the entire surface (the entire inner surface).

FIG. 4 is a schematic sectional view of the non-adherent container according to claim 2. In the non-adherent container of FIG. 4, hydrophobic oxide fine particles 3 having a primary average particle diameter of 3 to 100nm are adhered to the surfaces (bottom surface and partial side surfaces) of the container main body 4 on the side of the content contained therein. The hydrophobic oxide fine particles 3 are attached to and fixed to the container main body 4. That is, the hydrophobic oxide fine particles are attached to such an extent that the hydrophobic oxide fine particles do not fall off even when they come into contact with the content. In fig. 4, the hydrophobic oxide fine particles 3 may contain primary particles, but preferably contain a large amount of aggregates (secondary particles) of the primary particles. In particular, the hydrophobic oxide fine particles are preferably formed into a porous layer having a three-dimensional network structure. That is, it is preferable that at least a part of the surface of the container body 4 is laminated with: a porous layer having a three-dimensional network structure formed of hydrophobic oxide fine particles.

Fig. 5 is a schematic cross-sectional view showing a structure in which the contents are sealed by filling the contents in the non-adhesive container of the invention 2 and thermally bonding the lid member. In fig. 5, the hydrophobic oxide fine particles 3 are not shown. The container 4 is filled with the content 5, and is sealed in a state where the opening thereof is in contact with the thermal adhesive layer 2 of the lid. In this case, even when the hydrophobic oxide fine particles are adhered to the surface of the opening of the container, the hydrophobic oxide fine particles existing in the thermally adhered region are embedded in the thermal adhesive layer at the time of thermal adhesion, and the thermal adhesive layer and the container body 4 are brought into direct contact with each other, thereby enabling thermal adhesion. When the material of the container body 4 is thermoplastic plastic, it can be melted with a cap made of the same plastic, for example.

The material of the lid member is not particularly limited, and a known material or a laminated material may be used, and it is only necessary to appropriately select the material or the required properties of the container body 4. For example, a single body such as paper, synthetic paper, resin film with a vapor deposited layer, aluminum foil, or a composite material or a laminated material of these materials can be used.

Of these materials, the layers used in the known lid member may be laminated at arbitrary positions. Examples thereof include a printing layer, a printing protective layer (so-called OP layer), a coloring layer, a thermal adhesive layer, an adhesion reinforcing layer, a primer coating layer, a fixing coating layer, an anti-slip agent layer, a slip agent layer, and an anti-fogging agent layer.

Further, although a hot-glue lid member is used in fig. 5, it is not limited thereto, and other known types may be used. For example, a snap lid, a screw lid, a cover film (wrap film), a heat shrinkable film, an anvil lid, a cap (cap), and the like can be used. Of course, the hydrophobic oxide fine particles may be attached to the inner surface and/or the outer surface of the lid member.

The hydrophobic oxide fine particles adhering to the container main body 4 have a primary average particle diameter of usually 3 to 100nm, preferably 5 to 50nm, more preferably 5 to 20 nm. When the primary average particle diameter is within the above range, the hydrophobic oxide fine particles are appropriately aggregated, and a gas such as air can be held in the voids in the aggregate, and as a result, excellent non-adhesion can be obtained. That is, the aggregated state can be maintained even after adhering to the container body, and therefore, excellent non-adhesion can be exhibited.

In the invention 2, the primary average particle size can be measured by a scanning electron microscope (FE-SEM), and when the analysis ability of the scanning electron microscope is low, the measurement can be carried out by another electron microscope such as a transmission electron microscope. Specifically, the average of the longest diameter and the shortest diameter of the particles in the case of a spherical shape and the average of the longest diameter and the shortest diameter in the case of a non-spherical shape are regarded as the diameters, and the average of the diameters of 20 particles arbitrarily selected is regarded as the primary average particle diameter by observation with a scanning electron microscope or the like.

The hydrophobic oxide fine particles are not particularly limited as long as they have hydrophobicity, and may be hydrophobized by surface treatment. For example, fine particles obtained by surface-treating hydrophilic oxide fine particles or the like with a silane coupling agent to make the surface hydrophobic may be used. The kind of the oxide is not limited as long as it has hydrophobicity. For example, at least 1 kind of silica (silica), alumina, titanium oxide, and the like can be used. These may be available as existing products or commercially available products. Examples of the silica include: the product names "AEROSIL R972", "AEROSIL R972V", "AEROSIL R972 CF", "AEROSIL R974", "AEROSIL RX 200", "AEROSIL RY 200" (the above are Nippon AEROSIL Co., Ltd.), "AEROSIL R202", "AEROSIL 805", "AER RYOSIL R812 "," AEROSIL R812S ", and the like (manufactured by Evonik Degussa GmbH). Titanium oxide can be exemplified by the product name "AEROXIDE TiO₂T805 "(manufactured by Evonik Degussa GmbH), and the like. Examples of alumina are: fine particles having a hydrophobic surface obtained by treating the particles with a silane coupling agent under the product name "AEROXIDEALU C" (manufactured by Evonik Degussa GmbH).

Among these, hydrophobic silica fine particles are preferable. In particular, from the viewpoint of obtaining more excellent non-adhesive properties, hydrophobic silica fine particles having a trimethylsilyl group on the surface are preferable. Examples of commercially available products corresponding to these compounds include "AEROSILR 812" and "AEROSILR 812S" (all manufactured by Evonik Degussa GmbH).

The amount of the hydrophobic oxide fine particles to be adhered to the container main body (weight after drying) is not particularly limited, but is usually preferably 0.01 to 10g/m²And more preferably 0.2 to 1.5g/m²At a rate of 0.3 to 1g/m²Most preferred. By setting the range, not only more excellent non-adhesion property can be obtained over a long period of time, but also it is more advantageous in terms of suppressing the falling-off of the hydrophobic oxide fine particles, cost, and the like. The hydrophobic oxide fine particles adhering to the container main body 4 are preferably formed into a porous layer having a three-dimensional network structure, and the thickness thereof is preferably about 0.1 to 5 μm, more preferably about 0.2 to 2.5. mu.m. By adhering in such a porous layer state, the layer can contain more air, and more excellent non-adhesion can be exhibited.

2. Method for manufacturing non-adhesive container

The non-adherent container according to claim 2 can be produced by a method comprising the steps of:

hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100nm are attached to at least a part of the surface of the container body which is in contact with the content or the entire surface of the container body.

The container body may be a known container as described above. The method of carrying out the attachment process is not particularly limited. For example, known methods such as dipping, brush coating, roll coating, and electrostatic powder coating can be used. In the case of dipping, brush coating, or roll coating, the deposition step can be carried out by using a dispersion in which hydrophobic oxide fine particles are dispersed in a solvent, forming a coating film on the container body, and then drying the coating film. The solvent in this case is not limited, and other than water, organic solvents such as alcohols (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butyl diglycol, 1, 5-pentanediol, n-pentane, n-hexane, and hexylene alcohol can be appropriately selected. In this case, a small amount of a dispersant, a colorant, a precipitation inhibitor, a viscosity modifier, or the like may be used in combination. The amount of the hydrophobic oxide fine particles dispersed in the solvent may be about 10 to 100 g/L. In the drying, either natural drying or forced drying (heat drying) may be used, but forced drying is industrially preferable. The drying temperature is also dependent on the material of the container, but is not particularly limited, but from the viewpoint of maintaining the non-adhesion, it is usually preferably 250 ℃ or lower, and more preferably 120 to 200 ℃.

In the manufacturing method of claim 2, the body may be heated during and/or after the adhesion step. The adhesion (fixing force) of the hydrophobic oxide fine particles can be further improved by heating the container main body. In this case, the heating temperature is not particularly limited, and is usually about 120 to 200 ℃.

The production method of claim 2 may further comprise a step of forming a thermoplastic resin layer containing filler particles before the step of adhering the hydrophobic oxide fine particles. For example, the method may further include: the thermoplastic resin layer is formed in advance by in-mold (in-mold) molding, coating, melt-injecting, spraying, transferring, embedding, bonding, or the like, using a thermoplastic resin composition containing filler particles, on a portion to which the hydrophobic oxide fine particles are to be adhered in the non-adhesive container. The hydrophobic oxide fine particles can be attached to the formed portion by the above-described attaching step. Thus, a non-adhesive container which can maintain good hydrophobicity and non-adhesion more effectively can be provided. The thermoplastic resin and the filler particles may have the same configurations as those described in the description of the invention 1. In other words, the thermoplastic resin and the filler particles described in claim 1 can be used in the same composition, and the composition described in claim 1 is preferably used in the preferred range.

Further, the region where the thermoplastic resin layer containing filler particles is formed is not particularly limited. For example, the fine hydrophobic oxide particles may be attached only to the surface, may be not attached to the surface, or may be entirely attached to the surface.

< invention 3 >

1. Packaging material

The packaging material of claim 3 is a packaging material comprising a laminate having at least a base material layer and a thermal adhesive layer, wherein: the thermal adhesive layer is laminated as an outermost layer on one surface of the packaging material, and hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm are attached to an outermost surface of the thermal adhesive layer which is not adjacent to other layers.

Fig. 6 is a schematic cross-sectional configuration of the packaging material of the invention 3. The packaging material of fig. 6 is composed of a laminate in which a thermal adhesive layer 2 is laminated on a base material layer 1. The thermal adhesive layer 2 is laminated on the outermost layer of one side of the packaging material (laminated body). In the outermost thermal adhesive layer 2, hydrophobic oxide fine particles 3 having a primary average particle diameter of 3 to 100nm are adhered to the surface (outermost surface) on the side not adjacent to the other layer (base material layer in fig. 6). The hydrophobic oxide fine particles 3 are attached to and fixed to the thermoplastic resin layer 2. That is, the hydrophobic oxide fine particles are attached to such an extent that the hydrophobic oxide fine particles do not fall off even when they come into contact with the content. In fig. 6, the hydrophobic oxide fine particles 3 may contain primary particles, but preferably contain aggregates (secondary particles) of a large amount of primary particles. In particular, the hydrophobic oxide fine particles are preferably formed into a porous layer having a three-dimensional network structure. That is, a porous layer having a three-dimensional network structure formed of hydrophobic oxide fine particles is preferably laminated on the thermoplastic resin layer 2.

Fig. 7 is a schematic cross-sectional structure view of a package produced by using the packaging material of the invention 3 as a container lid member. In fig. 7, the hydrophobic oxide fine particles 3 are not marked. The container 4 is sealed in a state filled with the content 5 and the opening thereof is in contact with the thermal adhesive layer 2 of the packaging material. That is, the packaging material of the invention 3 can be used in a state where the hydrophobic oxide fine particles adhered to the thermal adhesive layer 2 can be in contact with the content 5. Even in such a case, the thermal adhesive layer 2 is protected by the hydrophobic oxide fine particles and has excellent non-adhesion property, and even if the content is in contact with (or close to) the vicinity of the thermal adhesive layer 2, the content is blocked by the hydrophobic oxide fine particles (or the porous layer composed of the hydrophobic oxide fine particles) and bounces off when the content adheres to the thermoplastic resin layer. Therefore, the content is not adhered to the thermal adhesive layer, and the content is repelled by the hydrophobic oxide fine particles (or the porous layer made of the hydrophobic oxide fine particles) and returned into the container. The material of the container 4 may be suitably selected from metals, synthetic resins, glass, paper, and composite materials thereof, and the kind, composition, and the like of the thermal adhesive layer may be suitably adjusted depending on the material. Thus, the packaging material of the invention 3 can be suitably used for the following articles: the product is obtained by packaging the contents with a packaging material in a state where the contents can be in contact with the outermost surface on the thermal adhesive layer side (particularly, the hydrophobic oxide fine particles (or the porous layer composed of the hydrophobic oxide fine particles)).

The substrate layer may be made of a known material or a laminate material. For example, it may be suitable to use: paper, synthetic paper, resin film with vapor deposited layer, aluminum foil, or a composite/laminate thereof.

Of these materials, the layers used in known packaging materials may be laminated at arbitrary positions. Examples thereof include: a printing layer, a printing protective layer (so-called OP layer), a coloring layer, an adhesive layer, an adhesion reinforcing layer, a primer coating layer, a fixing coating layer, an anti-slip agent layer, a slip agent layer, an anti-fogging agent layer, and the like.

The lamination method when using the base material layer is not limited, and for example, a known method such as a dry lamination method, an extrusion lamination method, a wet lamination method, or a heat lamination method can be used.

The thickness of the base material layer is not limited, and generally, it is only necessary to be appropriately set within a range of 15 to 500 μm from the viewpoint of strength, flexibility, cost, and the like of the packaging material.

The thermal adhesive layer can be made of known materials. For example, a layer formed of an adhesive such as a lacquer-type adhesive, an easy-peeling (easy-peeling) adhesive, or a hot-melt adhesive may be used in addition to the known sealing film. In the present invention, a paint type adhesive or a hot melt adhesive is particularly preferable, and in particular, a hot adhesive layer (hot melt layer) formed by a paint type adhesive can be preferably used. In the case of forming the hot-melt layer, the hydrophobic oxide fine particles can be directly attached to the hot-melt layer by applying the hot-melt adhesive in a molten state and then applying the hydrophobic oxide fine particles before cooling and solidifying, and therefore, the packaging material of the invention 3 can be easily produced continuously.

The thickness of the thermal adhesive layer is not particularly limited, but is preferably about 2 to 150 μm in view of sealing property, productivity, cost, and the like. In particular, in the case of the packaging material of the present invention, when heat bonding is performed, the hydrophobic oxide fine particles present in the heat-bonding region are embedded in the heat-bonding layer, and the heat-bonding layer becomes the outermost surface, and heat bonding can be performed. Therefore, in the above thickness range, it is preferable to set the thickness so that the hydrophobic oxide fine particles can be embedded in the thermal adhesive layer in as large an amount as possible.

The hydrophobic oxide fine particles adhering to the thermal adhesive layer generally have a primary average particle diameter of 3 to 100nm, preferably 5 to 50nm, and more preferably 5 to 20 nm. When the primary average particle diameter is in the above range, the hydrophobic oxide fine particles are appropriately aggregated, and a gas such as air can be held in the voids in the aggregate, and as a result, excellent non-adhesion can be obtained. That is, the aggregated state can be maintained even after the adhesive is attached to the thermal adhesive layer, and thus excellent non-adhesive properties can be exhibited.

In the invention 3, the primary average particle size can be measured by a scanning electron microscope (FE-SEM), and when the analysis ability of the scanning electron microscope is low, the measurement can be performed by another electron microscope such as a transmission electron microscope. Specifically, the average of the longest diameter and the shortest diameter of the particles in the case of a spherical shape and the average of the longest diameter and the shortest diameter in the case of a non-spherical shape are regarded as the diameters, and the average of the diameters of 20 particles arbitrarily selected is regarded as the primary average particle diameter by observation with a scanning electron microscope or the like.

The hydrophobic oxide fine particles are not particularly limited as long as they have hydrophobicity, and may be hydrophobized by surface treatment. For example, fine particles obtained by surface-treating hydrophilic oxide fine particles or the like with a silane coupling agent to make the surface hydrophobic may be used. The kind of the oxide is not limited as long as it has hydrophobicity. For example, at least 1 kind of silica (silica), alumina, titanium oxide, and the like can be used. These may be known or commercially available products. Examples of the silica include: the product names "AEROSIL R972", "AEROSIL R972V", "AEROSIL R972 CF", "AEROSIL R974", "AEROSIL RX 200", "AEROSIL RY 200" (manufactured by Nippon AEROSIL Co., Ltd., "AEROSIL R202", "AEROSIL 805", "AEROSIL R812" 812S ", and" Evonik Degussa GmbH "(manufactured by Evonik Degussa GmbH, etc.). Titanium oxide can be exemplified by the product name "AEROXIDE TiO₂T805 "(manufactured by Evonik Degussa GmbH), and the like. Examples of alumina are: fine particles having a hydrophobic surface, which are obtained by treating a product name "AEROXIDE Alu C" (manufactured by Evonik Degussa GmbH) or the like with a silane coupling agent.

Among these, hydrophobic silica fine particles are particularly preferably used. In particular, hydrophobic silica fine particles having a trimethylsilyl group on the surface are preferable from the viewpoint of obtaining more excellent non-adhesive properties. Examples of commercially available products corresponding to the compounds include "AEROSIL R812" and "AEROSIL R812S" (all manufactured by Evonik Degussa GmbH).

The amount of the hydrophobic oxide fine particles to be adhered to the thermal adhesive layer (weight after drying) is not particularly limited, but is usually preferably 0.01 to 10g/m²And more preferably 0.2 to 1.5g/m²At a rate of 0.3 to 1g/m²Most preferred. By setting the range, not only more excellent non-adhesion property can be obtained over a long period of time, but also it is more advantageous in terms of suppressing the falling-off of the hydrophobic oxide fine particles, cost, and the like. The hydrophobic oxide fine particles adhering to the thermal adhesive layer preferably form a porous layer having a three-dimensional network structure, and the thickness thereof is preferably about 0.1 to 5 μm, more preferably about 0.2 to 2.5. mu.m. By adhering in such a porous layer state, the layer can contain more air, and more excellent non-adhesion can be exhibited.

The hydrophobic oxide fine particles may be attached to the entire surface of the thermal adhesive layer (the entire surface on the opposite side to the base layer side), or may be attached to a region other than the thermal adhesive region (so-called adhesive region) in the thermal adhesive layer. In the present invention, even if the hydrophobic oxide fine particles are adhered to the entire surface of the thermal adhesive layer, most or all of the hydrophobic oxide fine particles existing in the thermal adhesive region are buried in the thermal adhesive layer, and thermal adhesion is not hindered.

2. Method for producing packaging material

The packaging material according to claim 3 is preferably produced by a method for producing a packaging material comprising a laminate comprising at least a base material layer and a thermal adhesive layer, the method comprising a step of adhering hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm to the surface of the thermal adhesive layer (hereinafter also referred to as "adhering step").

The production of the laminate itself can be carried out by a known method. For example, the thermal adhesive layer may be formed by the method described in the above 1, for a single-layer substrate or a laminated material produced by a dry lamination method, an extrusion lamination method, a wet lamination method, a heat lamination method, or the like.

The method of carrying out the attachment process is not particularly limited. For example, known methods such as a roll coating method, a gravure coating method, a bar coating method, a doctor blade film forming method, a brush coating method, and a powder electrostatic coating method can be used. In the case of the roll coating method, the deposition step can be performed by using a dispersion in which hydrophobic oxide fine particles are dispersed in a solvent, forming a coating film on the container body, and then drying the coating film. In this case, the solvent is not limited, and organic solvents such as alcohols (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butyl diglycol, 1, 5-pentanediol, n-pentane, n-hexane, and hexylene alcohol may be appropriately selected in addition to water. In this case, a small amount of a dispersant, a colorant, a precipitation inhibitor, a viscosity modifier, or the like may be used in combination. The amount of the hydrophobic oxide fine particles dispersed in the solvent may be about 10 to 100 g/L. In the drying, either natural drying or forced drying (heat drying) can be used, but forced drying is industrially preferable. The drying temperature is not limited as long as it does not affect the thermal adhesive layer, but is preferably below 150 ℃, and more preferably 80-120 ℃.

In the production method of claim 3, the laminate may be heated during and/or after the adhesion step. The adhesion (fixing force) of the hydrophobic oxide fine particles can be further improved by heating the laminate. In this case, the heating temperature T may be appropriately set depending on the kind of the thermal adhesive layer, and is usually preferably within a range of Tm-50. ltoreq. T.ltoreq.Tm +50 with respect to the melting point Tm (melting start temperature). degree.C. of the thermal adhesive layer used. The packaging material of claim 3 can be subjected to embossing, half-cutting, notching, and the like as needed, as in the case of the known packaging material, and even this is not a hindrance.

< invention 4 >

1. Packaging material

The packaging material according to claim 4 is a packaging material comprising a laminate having at least a base material layer and a thermal adhesive layer, and is characterized in that: the thermal adhesive layer is laminated as the outermost layer of one surface of the packaging material, at least one of the base material layer and the thermal adhesive layer contains an oxygen absorber, and hydrophobic oxide particles having a primary average particle diameter of 3 to 100nm are attached to the outermost surface of the thermal adhesive layer which is not adjacent to the other layer.

Fig. 9 is a schematic cross-sectional structure of the packaging material according to the embodiment of the invention 4. The packaging material of fig. 9 is composed of a laminate in which a thermal adhesive layer 2 is laminated on a base material layer 1. The thermal adhesive layer 2 is laminated on the outermost layer of one side of the packaging material (laminated body). In the packaging material, the oxygen absorber 6 is contained in the thermal adhesive layer 2. Among them, some particles of the oxygen absorber 6 are also present between the base material layer 1 and the thermal adhesive layer 2. In the outermost thermal adhesive layer 2, hydrophobic oxide fine particles 3 having a primary average particle diameter of 3 to 100nm are adhered to the surface (outermost surface) on the side not adjacent to the other layer (base material layer in fig. 9). The hydrophobic oxide fine particles 3 are attached to and fixed to the thermoplastic resin layer 2. That is, the hydrophobic oxide fine particles are attached to such an extent that they do not fall off even when the hydrophobic oxide fine particles are in contact with the content. In fig. 9, the hydrophobic oxide fine particles 3 may contain primary particles, but agglomerates (secondary particles) containing a large amount of primary particles are preferable. In particular, the hydrophobic oxide fine particles preferably form a porous layer having a three-dimensional network structure. That is, a porous layer having a three-dimensional network structure formed of hydrophobic oxide fine particles is preferably laminated on the thermoplastic resin layer 2.

Fig. 10 is a schematic cross-sectional structure view of a package produced by using the packaging material of the invention 4 as a container lid member. In fig. 10, the hydrophobic oxide fine particles 3 and the oxygen absorber 6 are not marked. The container 4 is sealed with the content 5 filled therein and with the opening thereof in contact with the thermal adhesive layer 2 of the packaging material. That is, the packaging material according to claim 4 can be used in a state where the hydrophobic oxide fine particles adhered to the thermal adhesive layer 2 can be brought into contact with the content 5. Even in such a case, the thermal adhesive layer 2 is protected by the hydrophobic oxide fine particles and has excellent non-adhesion, and even when the content is in contact with (or close to) the vicinity of the thermal adhesive layer 2, the content is blocked by the hydrophobic oxide fine particles (or the porous layer composed of the hydrophobic oxide fine particles) and bounces off when the content adheres to the thermoplastic resin layer. Therefore, the content is not adhered to the thermal adhesive layer, and the content is repelled by the hydrophobic oxide fine particles (or the porous layer made of the hydrophobic oxide fine particles) and returned into the container. The material of the container 4 may be suitably selected from metals, synthetic resins, glass, paper, and composite materials thereof, and the kind, composition, and the like of the thermal adhesive layer may be suitably adjusted depending on the material.

The substrate layer may be made of a known material or a laminate material. For example, it is suitable to use: paper, synthetic paper, resin film with vapor deposited layer, aluminum foil, or a composite material/laminate material thereof.

Of these materials, the layers used in known packaging materials may be laminated at arbitrary positions. Examples thereof include: a printing layer, a printing protective layer (so-called OP layer), a coloring layer, an adhesive layer, an adhesion reinforcing layer, a primer coating layer, a fixing coating layer, an anti-slip agent layer, a slip agent layer, an anti-fogging agent layer, and the like. Further, a resin layer containing an oxygen absorbent described later may be laminated as necessary.

The lamination method when using the laminate material is not limited, and for example, a known method such as a dry lamination method, an extrusion lamination method, a wet lamination method, or a heat lamination method can be used.

The thermal adhesive layer can be made of known materials. For example, a layer formed of an adhesive such as a lacquer-type adhesive, an easy-peeling (easy-peeling) adhesive, or a hot-melt adhesive may be used in addition to the known sealing film. In the invention 4, a paint type adhesive or a hot melt adhesive is particularly preferable, and in particular, a hot adhesive layer (hot melt layer) formed by a paint type adhesive is preferably used. In the case of forming the hot-melt layer, the hydrophobic oxide fine particles can be directly attached to the hot-melt layer by applying the hot-melt adhesive in a molten state and then applying the hydrophobic oxide fine particles before cooling and solidifying, and therefore, the packaging material of claim 4 can be easily produced continuously.

The thickness of the thermal adhesive layer is not particularly limited, but is preferably about 2 to 150 μm in view of sealing property, productivity, cost, and the like. In particular, in the case of the packaging material of claim 4, when heat bonding is performed, the hydrophobic oxide fine particles present in the heat-bonded region are embedded in the heat-bonding layer, and the heat-bonding layer becomes the outermost surface, and heat bonding can be performed. Therefore, in the above thickness range, it is preferable to set the hydrophobic oxide fine particles to a thickness that allows the hydrophobic oxide fine particles to be embedded in the thermal adhesive layer in as large an amount as possible.

In the invention 4, the primary average particle size can be measured by a scanning electron microscope (FE-SEM), and when the analysis ability of the scanning electron microscope is low, the measurement can be performed by another electron microscope such as a transmission electron microscope. Specifically, the average of the longest diameter and the shortest diameter of the particles in the case of a spherical shape and the average of the longest diameter and the shortest diameter in the case of a non-spherical shape are regarded as the diameters, and the average of the diameters of 20 particles arbitrarily selected is regarded as the primary average particle diameter by observation with a scanning electron microscope or the like.

The hydrophobic oxide fine particles are not particularly limited as long as they have hydrophobicity, and may be hydrophobized by surface treatment. For example, fine particles obtained by surface-treating hydrophilic oxide fine particles or the like with a silane coupling agent to make the surface hydrophobic may be used. The kind of the oxide is not limited as long as it has hydrophobicity. For example, at least 1 kind of silica (silica), alumina, titanium oxide, and the like can be used. These may be known or commercially available products. Examples of the silica include: the product names "AEROSIL R972", "AEROSIL R972V", "AEROSIL R972 CF", "AEROSIL R974", "AEROSIL RX 200", "AEROSIL RY 200" (manufactured by Nippon AEROSIL Co., Ltd., "AEROSIL 202", "AEROSIL 805", "AEROSIL R812" 812S ", and" Evonik Degussa GmbH ", etc. Titanium oxide can be exemplified by the product name "Aeroxidetio₂T805 "(manufactured by Evonik Degussa GmbH), and the like. Examples of alumina are: fine particles having a hydrophobic surface obtained by treating the particles with a silane coupling agent under the product name "AEROXIDEALU C" (manufactured by Evonik Degussa GmbH).

Among these, hydrophobic silica fine particles are preferably used. In particular, hydrophobic silica fine particles having a trimethylsilyl group on the surface are preferable from the viewpoint of obtaining more excellent non-adhesive properties. Examples of commercially available products corresponding to these compounds include "AEROSILR 812" and "AEROSILR 812S" (all manufactured by Evonik Degussa GmbH).

The amount of the hydrophobic oxide fine particles to be adhered to the thermal adhesive layer (weight after drying) is not particularly limited, but is usually preferably 0.01 to 10g/m²And more preferably 0.2 to 1.5g/m²At a rate of 0.3 to 1g/m²Most preferred. By setting the range, not only more excellent non-adhesion property can be obtained over a long period of time, but also it is more advantageous in terms of suppressing the falling-off of the hydrophobic oxide fine particles, cost, and the like. The hydrophobic oxide fine particles attached to the thermal adhesive layer preferably form a porous layer having a three-dimensional network structure, and the thickness thereof is preferably about 0.1 to 5 μm, more preferablyPreferably about 0.2 to 2.5 μm. By adhering in such a porous layer state, the layer can contain more air, and more excellent non-adhesion can be exhibited.

The hydrophobic oxide fine particles may be attached to the entire surface of the thermal adhesive layer (the entire surface of the surface opposite to the base layer side), or may be attached to a region other than the thermal adhesive region (so-called adhesive region) in the thermal adhesive layer. In the invention 4, even if the hydrophobic oxide fine particles are adhered to the entire surface of the thermal adhesive layer, most or all of the hydrophobic oxide fine particles existing in the thermal adhesive region are buried in the thermal adhesive layer, and the thermal adhesive is not hindered, and therefore, the hydrophobic oxide fine particles are preferably adhered to the entire surface of the thermal adhesive layer even in industrial production.

In the packaging material according to claim 4, the oxygen absorber is contained in at least one of the base material layer and the thermal adhesive layer.

As the oxygen absorbent, a known or commercially available inorganic oxygen absorbent or organic oxygen absorbent can be used. More specifically, there may be mentioned: for example, an inorganic oxygen absorbent containing at least 1 kind of fine powder of iron, silicon, aluminum, etc. as a main component; and an organic oxygen absorbent containing at least 1 of ascorbic acid, unsaturated fatty acid, and the like as a main component. In particular, a main agent capable of irreversibly adsorbing oxygen is preferable. Further, as the main agent of the inorganic oxygen absorbent, a main agent in which a resin component or an oxide is coated on at least a part of the surface of the metal particles may be used. For example, when aluminum-based particles are used as the metal particles, the reaction rate of aluminum and oxygen is generally high, and the reaction rate can be controlled by coating part or all of the surfaces of the aluminum-based particles with a resin component. The aluminum-based particles coated with the resin component (resin-coated Al-based particles) can be prepared by a known method, in addition to commercially available products. For example, a known method can be used for coating with an oxide (inorganic oxide). More specifically, in addition to the so-called sol-gel method, a method described in japanese patent No. 3948934 (a method in which a dispersion solution containing aluminum particles, an organosilicon compound, and a hydrolysis catalyst is adjusted in pH to hydrolyze the organosilicon compound and deposit a silica film on the surfaces of the aluminum particles to obtain oxide-coated aluminum particles) or the like can be used.

The content of the oxygen absorbent can be suitably set in accordance with the required oxygen absorption performance, etc., but it is usually preferable that the content of the main agent in the base material layer or the hot adhesive layer is 0.3 to 30% by weight, and more preferably 1 to 20% by weight. By setting the above range, excellent oxygen absorption performance can be obtained while maintaining desired hot tack and the like.

The oxygen absorber only needs to be contained in at least one of the base material layer and the thermal adhesive layer, but is preferably contained in at least the thermal adhesive layer from the viewpoint that the oxygen absorbing performance can be obtained more effectively. The method of including the oxygen absorber in these layers is not limited as long as the oxygen absorber can be uniformly dispersed. Examples thereof include: a method of mixing an oxygen absorbent with a raw material for forming a base material layer or a thermal adhesive layer in advance. The mixing may be carried out by a known mixer, stirrer or the like. In this case, either dry mixing or wet mixing may be used.

Hereinafter, an inorganic oxygen absorbent using aluminum-based particles (or resin-coated Al-based particles) as a main agent and a preferred embodiment thereof will be described as a typical example of the oxygen absorbent.

The aluminum-based particles are not particularly limited as long as they exhibit a specific oxygen-absorbing property, and for example, various aluminum alloy particles and the like can be used in addition to pure aluminum particles.

The average particle diameter of the aluminum-based particles is preferably about 1 to 100 μm. When the average particle diameter is less than 1 μm, it is not preferable from the viewpoint of handling property and the like. On the other hand, when the average particle diameter exceeds 100. mu.m, the specific surface area is decreased, and it is preferable to avoid the decrease in oxygen absorption capacity. The shape of the aluminum-based particles is not limited, and may be, for example, any of a spherical shape, a spheroid shape, an irregular shape, a teardrop shape, a flat shape, and the like.

The resin component (polymer) coated on the surface of the aluminum-based particle is preferably an oligomer having at least 1 polymerizable double bond and a copolymer obtained by reacting at least 2 monomers. The ratio of the amount of each oligomer or monomer used can be arbitrarily set.

The oligomer or monomer constituting the polymer is not particularly limited as long as it has at least 1 polymerizable double bond.

Monomers having at least 1 polymerizable double bond are exemplified by: unsaturated carboxylic acids (such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, citric acid, maleic acid or maleic anhydride), nitriles thereof (such as acrylonitrile or methacrylonitrile) or esters thereof (such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, glycidyl acrylate, cyclohexyl acrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane triacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, itaconic anhydride, maleic anhydride, itaconic anhydride, maleic anhydride, and the like, N-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methoxyethyl methacrylate, butoxyethyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate or tetramethylolmethane trimethacrylate), and the like. Further, examples of the cyclic unsaturated compound (e.g., cyclohexene) and the acyclic unsaturated compound (e.g., styrene, α -methylstyrene, vinyltoluene, divinylbenzene, cyclohexene ethylene monooxide, divinylbenzene monooxide, vinyl acetate, vinyl propionate and diallylbenzene) can be given.

For example, when divinylbenzene, allylbenzene, diallylbenzene or a mixture thereof is used as the monomer having at least 2 polymerizable double bonds, the stability is further improved by the crosslinking action (more stable coating can be performed), and therefore, it is particularly preferable to use a monomer having at least 2 polymerizable double bonds.

Examples of the oligomer having at least 1 polymerizable double bond include epoxidized 1, 2-polybutadiene, acrylic-modified polyester, acrylic-modified polyether, acrylic-modified urethane, acrylic-modified epoxy resin, and acrylic-modified spiro hydrocarbon (each having a polymerization degree of about 2 to 20). Among them, at least 1 kind of epoxidized 1, 2-polybutadiene and acrylic modified polyester is preferable. The polymerization degree is preferably about 3 to 10. The use of an oligomer makes the polymerization reaction proceed slowly, so that the reaction efficiency becomes extremely high, and is more preferable than the use of a monomer alone.

The method of coating the aluminum-based particles is not particularly limited. Examples thereof include: 1) a method in which a resin component is dissolved or dispersed in a solvent, and aluminum-based particles are impregnated or immersed in the obtained solution or dispersion, and then dried to coat the surfaces of the particles with the resin component; and 2) a method of preparing a mixed solution containing aluminum particles and a solution or dispersion containing a monomer or oligomer capable of constituting a specific resin component, and then polymerizing the monomer or oligomer to coat the surface of the particles with the polymer (resin component).

In the invention 4, the method of 2) is particularly preferably employed. As such a method, for example, a dispersion liquid in which aluminum particles are dispersed in an organic solvent is prepared, at least 2 kinds of oligomers and monomers having at least 1 polymerizable double bond are dissolved in the dispersion liquid, and the mixture is heated in the presence of a polymerization initiator, whereby the copolymer can be coated on the particle surface.

The organic solvent may be exemplified by: aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and mineral spirits; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chlorobenzene, trichlorobenzene, perchloroethylene and trichlorobenzene; alcohols such as methanol, ethanol, n-propanol and n-butanol; ketones such as 2-propanone and 2-butanone; esters such as ethyl acetate and propyl acetate; tetrahydrofuran; diethyl ether and ethyl propyl ether.

Further, as the polymerization initiator, a publicly known high-temperature or medium-temperature polymerization initiator can be used, for example: organic peroxides such as di-t-butyl peroxide, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, anisyl hydroperoxide and t-butyl hydroperoxide; or an azo compound such as α, α' -azobisisobutyronitrile.

The polymerization temperature (heating temperature) is not limited, and may be appropriately set within a range of 60 to 200 ℃.

In the invention 4, the polymerization reaction may be carried out in an inert gas atmosphere such as nitrogen, helium, or argon, as required for the purpose of improving the polymerization efficiency.

The resin-coated Al-based particles produced as described above may be recovered by a known solid-liquid separation method, purification method, or the like, as necessary.

In the case of the invention 4, when aluminum-based particles are used as the main agent, aluminum compound particles are preferably used as the auxiliary agent. Examples of the aluminum compound include at least 1 kind of aluminum oxide (aluminum), aluminum hydroxide, aluminate, and aluminosilicate. Among them, alumina is particularly preferably used. By using alumina particles, more effective oxygen absorption performance can be exhibited by utilizing the catalytic action thereof.

The ratio of the aluminum-based particles to the auxiliary agent is not particularly limited, but is preferably 3: 7 to 7: 3 in terms of mass ratio.

Further, an electrolyte may be added to effectively promote the oxygen absorption of the aluminum-based particles as required. At least 1 of calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, sodium chloride, potassium chloride, calcium chloride, sodium carbonate, calcium carbonate, and the like can be added as an electrolyte in an appropriate amount as needed.

Further, when the aluminum-based particles absorb oxygen, hydrogen may be generated by a side reaction, and in this case, a hydrogen generation inhibitor such as silver oxide, titanium, zeolite, activated carbon, or sulfide may be added to the oxygen absorbent in an amount of 1ppm to 10% by mass, if necessary.

Further, in order to facilitate the oxygen absorption reaction of the aluminum-based particles, the oxygen absorbent may contain 5 to 85 mass% of water, if necessary.

2. Method for producing packaging material

For example, the packaging material according to claim 4 is preferably produced by a method for producing a packaging material comprising a laminate having at least a base layer and a thermal adhesive layer, the method comprising: and a step (hereinafter, also referred to as "adhesion step") of adhering hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm to the surface of the thermal adhesive layer.

Further, the oxygen absorber described in the above 1 can be used. As described above, these substances may be contained in the raw material for forming the base layer and/or the thermal adhesive layer in advance.

The method for carrying out the step of attaching the hydrophobic oxide fine particles is not particularly limited. For example, known methods such as a roll coating method, a gravure coating method, a bar coating method, a doctor blade film forming method, a brush coating method, and a powder electrostatic coating method can be used. In the case of the roll coating method, the deposition step can be performed by using a dispersion in which hydrophobic oxide fine particles are dispersed in a solvent, forming a coating film on the container body, and then drying the coating film. In this case, the solvent is not limited, and organic solvents such as alcohols (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butyl diglycol, 1, 5-pentanediol, n-pentane, n-hexane, and hexylene alcohol may be appropriately selected in addition to water. In this case, a small amount of a dispersant, a colorant, a precipitation inhibitor, a viscosity modifier, or the like may be used in combination. The amount of the hydrophobic oxide fine particles dispersed in the solvent may be about 10 to 100 g/L. In the drying, either natural drying or forced drying (heat drying) can be used, but forced drying is industrially preferable. The drying temperature is not limited as long as it does not affect the thermal adhesive layer, but is preferably below 150 ℃, and more preferably 80-120 ℃.

In the production method of claim 4, the laminate may be heated during and/or after the adhesion step. The adhesion (fixing force) of the hydrophobic oxide fine particles can be further improved by heating the laminate. In this case, the heating temperature T may be appropriately set depending on the kind of the thermal adhesive layer, and is usually preferably within a range of Tm-50. ltoreq. T.ltoreq.Tm +50 with respect to the melting point Tm (melting start temperature). degree.C. of the thermal adhesive layer used. The packaging material of the present invention can be subjected to embossing, half-cutting, notching, and the like as needed, as in the case of the known packaging material, and even this is not a hindrance.

Examples

Now, the characteristics of the invention 1 to the invention 4 will be described more specifically by referring to examples and comparative examples. The scope of the invention is not limited to the embodiments.

< example of the invention 1 >

Examples 1-1 to 1-9 and comparative example 1-1

Samples were prepared by adhering hydrophobic oxide microparticles to a laminate having a thermoplastic resin layer. Specifically, each sample was prepared as follows.

(1) Production of laminate

(example 1-1, comparative example 1-1)

For a basis weight of 55g/m²On one side of the paper (b) is applied a surface printing and OP coating (over pr)int coat) using a polyurethane-based dry lamination adhesive (weight after drying 3.5 g/m)²(ii) a Abbreviated as D), a deposition surface of a polyethylene terephthalate film (abbreviated as AL deposition PET) having a thickness of 16 μm on which aluminum has been deposited is bonded to the other surface. A heat-sealing varnish (comprising 160 parts by weight of a polyester resin, 10 parts by weight of an acrylic resin, and 40 parts by weight of a solvent (a mixed solvent of toluene and MEK), which will be referred to simply as "varnish") was applied as a thermoplastic resin layer on the polyethylene terephthalate film of the adhesive material, and the resultant coating was dried to give a weight of about 3g/m²(drying conditions were 150 ℃ C.. times.10 seconds). Thus, a laminate of "OP/print/paper/D/AL evaporated PET/lacquer" construction was obtained.

(examples 1-2 to 1-6)

1 to 20 parts by weight (shown in the table) of acrylic resin beads (average particle size: 30 μm, manufactured by dropletization chemical Co., Ltd.) were further added to the heat-sealing paint, and the mixture was coated so that the weight after drying was 3g/m²A laminate was produced in the same manner as in example 1-1 except that the drying conditions were changed to 150 ℃ C.. times.10 seconds.

(examples 1-7 to 1-8)

In example 1-1, 10 parts by weight of acrylic resin beads (average particle diameter: 15 μm, manufactured by waterlogging chemical Co., Ltd.) were further added to and mixed with the heat-seal paint, and the mixture was coated so as to have a dried weight of 3g/m²A laminate was produced in the same manner as in example 1-1 except that the drying conditions were changed to 150 ℃ C.. times.10 seconds.

(examples 1 to 9)

In example 1-1, 10 parts by weight of acrylic resin beads (average particle diameter: 8 μm, manufactured by waterlogging chemical Co., Ltd.) were further added to and mixed with the heat-sealing paint, and the mixture was coated so as to have a dried weight of 3g/m²A laminate was produced in the same manner as in example 1-1 except that the drying conditions were changed to 150 ℃ C.. times.10 seconds.

(2) Attachment of hydrophobic oxide microparticles

(examples 1-1 to 1-9)

Hydrophobic oxide fine particles (product name "AEROSIL R812S", manufactured by Evonik Degussa GmbH, BET specific surface area: 220 m)²(iv)/g, primary average particle diameter: 7nm) of the above-mentioned aqueous solution was dispersed in 100mL of ethanol to prepare a coating solution. Applying the coating liquid to the surface of the thermoplastic resin layer of the laminate produced in the step (1) by a bar coating method so that the weight of the coating liquid after drying is 0.11 to 0.4g/m²(shown in the table), the sample (packaging material) was obtained by drying the sample at 100 ℃ for about 10 seconds to evaporate ethanol.

Comparative example 1-1

The laminate of example 1-1, to which the hydrophobic oxide fine particles did not adhere, was used as a test sample.

(3) Observation of porous layer comprising hydrophobic oxide microparticles

The structure of the layer composed of the hydrophobic oxide fine particles in the packaging material of the example was observed by FE-SEM. As a result, a porous layer having a three-dimensional network structure formed by the hydrophobic oxide fine particles was observed in any of the packaging materials. FIG. 3 is a photograph showing a partial cross-sectional view of the packaging materials of examples 1 to 4 as an example thereof. Note that the same structure is observed in other embodiments.

Test examples 1-1 (unsealing Strength)

The opening strength was examined for the samples obtained in the examples and comparative examples.

The lid member was cut out from each packaging material in the shape of a lid member (a rectangle 62mm in length by 67mm in width with a tab), and a package was produced. Specifically, a container made of polystyrene and having a flange (flange) attached thereto (formed to have a flange width of 4mm, a flange outer diameter of 60mm × 65mm □, a height of about 48mm, and an inner volume of about 100 cm)³) The lid member is heat sealed to the flange of the container to form a package. The heat sealing conditions are as follows: at a temperature of 210 ℃ and a pressure2kg/cm²Next, a 2mm wide ring (concave) seal was applied for 1 second. The cap member tab on each package was pulled at a speed of 100 mm/min in the direction of an angle of elevation of 45 degrees from the opening start point, the maximum load at the time of opening was regarded as the opening strength (N), and N was measured for each package at 6 points to obtain the average value thereof. The results are shown in tables 1 and 2.

Test examples 1 to 2 (sealing Strength)

The sealing strength test was carried out using the package produced in test example 1-1 as a test sample, based on the sealing strength test method of { milk and milk product component specification and other provincial treaties (No. 17 of 4/16-day-old-Ministry of fat-and-live province in 1979 (Showa 54), etc. }. In this case, air was continuously introduced into the container, and the internal pressure (mmHg) at the time of air leakage was measured. The measurement was performed at n points 3 for each package, but all measurements reached a measurement upper limit of 300mmHg or more. The results are shown in tables 1 and 2.

Test examples 1 to 3 (initial yogurt non-adherent)

The thermoplastic resin layer side of each laminate was used as a test surface, the test surface was fixed to a horizontal platform with a clamp, commercially available yogurt (product name "Mei Li Hai" soft yogurt, 1 drop manufactured by Kogyo milk Co., Ltd.: about 0.4g) was dropped from a very close distance, the horizontal platform was inclined, the yogurt was qualified when the droplets were rolled, and the yogurt was not rolled even when the platform was inclined at 90 degrees but was not qualified when it was merely flowed downward. The results are shown in tables 1 and 2.

Test examples 1 to 4 (inverted test)

85g of commercially available yogurt (product name "Mei Li Hai" soft yogurt, manufactured by Kogyo Kaisha) was filled in each of the flanged polystyrene containers used in test example 1-1, and the lid member was heat-sealed in the same manner as in test example 1-1. After each package was turned upside down (with the opening facing downward) and maintained for 10 seconds, each package was returned to a normal state (i.e., a state in which the opening faces upward), and the cap member was opened with a finger to visually observe the state of the thermoplastic resin layer side surface of each cap member. The yogurt was not adhered, and the yogurt was not adhered. The results are shown in tables 1 and 2.

Test examples 1 to 5 (vibration test)

Each package was produced in the same manner as in test examples 1 to 4, and the package was vibrated at 30Hz (30 times of vertical reciprocating vibration within 1 minute) at an amplitude of 2.2mm (vertical direction) and an acceleration of about 1G for 20 minutes using a vibration tester (IDEX co., ltd., BF-30U), and then the lid member was opened with a finger, and the weight of yogurt attached to each lid member was measured. When the ratio is less than 0.5g/cup, the product is qualified, and when the ratio is more than 0.5g/cup, the product is unqualified. The results are shown in tables 1 and 2.

Test examples 1 to 6 (abrasion resistance test)

Using the surface of each laminate on the thermoplastic resin layer side as a test surface, the test was performed with a reciprocating frequency of 100 times, a load of 200g, a target material: the abrasion resistance test was carried out by a chemical vibration abrasion resistance tester (JIS K5701-1) under the condition of chromium plating. The yogurt non-adhesion test was performed in the same manner as in test example 3 after the abrasion resistance test, and the test was not satisfactory when the yogurt was dropped, but when the platform was tilted by 90 degrees, the yogurt was not dropped and only flowed downward. The results are shown in tables 1 and 2.

Test examples 1 to 7 (contact Angle)

The thermoplastic resin layer side of each laminate was used as a test surface, and the contact angle of pure water was measured using a contact angle measuring apparatus (solid-liquid interface analyzer "Drop Master 300", manufactured by interfacial science corporation). The results are shown in tables 1 and 2.

TABLE 1

TABLE 2

As is clear from the results in tables 1 and 2, the conventional product (comparative example) was completely unable to exhibit non-adhesiveness (yoghurt-phobic property) and the contact angle of pure water also reached 85 degrees, whereas the invention 1 (example) exhibited high non-adhesiveness. And also exhibits good performance in terms of opening strength, sealing property (sealing strength), and the like, without impairing the practical use. From the results of the contact angle, it was also found that the laminate and the packaging material of the invention 1 exhibited high hydrophobicity.

In particular, the laminate and the packaging material of claim 1 exhibit a pure water contact angle of 150 degrees or more on the outermost surface (surface to which the hydrophobic oxide fine particles are attached) on the thermoplastic resin layer side, and have excellent content non-adhesiveness not seen in conventional packaging materials. In addition, when the thermoplastic resin layer contains inorganic particles or organic particles as filler particles, the abrasion resistance is greatly improved, and the falling-off of the hydrophobic oxide fine particles can be effectively suppressed or even prevented, so that good non-adhesion can be continuously obtained.

< example of the invention 2 >

Example 2-1

Hydrophobic oxide fine particles (product name "AEROSIL R812S", manufactured by Evonik Degussa GmbH, BET specific surface area: 220 m)²(iv)/g, primary average particle diameter: 7nm)50g was dispersed in 1000ML ethanol to prepare a coating solution. A commercially available polypropylene container (having a flange width of about 3mm, a flange outer diameter of about 70mm, a height of about 110mm, and an internal volume of about 200cc) was immersed in the coating liquid. The amount of the coating liquid deposited was 0.5g/m in terms of the weight after drying (═ solid deposition amount)². After the dipping treatment, the ethanol was evaporated with warm air at 25 ℃ for 30 seconds (drying treatment) to obtain a sample(container).

Examples 2 to 2

Hydrophobic oxide fine particles (product name "AEROSIL R812S", manufactured by Evonik Degussa GmbH, BET specific surface area: 220 m)²(iv)/g, primary average particle diameter: 7nm)50g was dispersed in 1000ML ethanol to prepare a coating solution. A commercially available container made of paper/polyethylene with a flange (polyethylene 100 μm coated on a flange having a width of about 3mm, an outer diameter of about 70mm, a height of about 55mm, and an inner volume of about 130 cm)³A container made of a paper having a thickness of about 300 μm and formed by molding polyethylene inside the container) was immersed in the coating liquid. The amount of the coating liquid deposited was 0.5g/m in terms of the weight after drying (═ solid deposition amount)². After the dipping treatment, the ethanol was evaporated with warm air at 25 ℃ to obtain a sample (container).

Examples 2 to 3

Hydrophobic oxide fine particles (product name "AEROSIL R812S", manufactured by Evonik Degussa GmbH, BET specific surface area: 220 m)²(iv)/g, primary average particle diameter: 7nm) was dispersed in ethanol 1000M1 to prepare a coating solution. A commercially available flanged polystyrene container (flange width: about 3mm, flange outer diameter: about 88mm, height: about 63mm, internal volume: about 176cc) was immersed in the coating liquid. The amount of the coating liquid deposited was 0.5g/m in terms of the weight after drying (═ solid deposition amount)². After the dipping treatment, the ethanol was evaporated with warm air at 25 ℃ (drying treatment) to obtain a sample (container).

Comparative example 2-1

A commercially available polypropylene container used in example 2-1 was used as a specimen.

Comparative examples 2 to 2

The commercially available paper/polyethylene container used in example 2-2 was used as a specimen.

Comparative examples 2 to 3

The commercially available polystyrene containers used in examples 2 to 3 were used as samples.

Test example 2-1

< Observation of porous layer comprising hydrophobic oxide Fine particles >

The structures of the layers of the hydrophobic oxide fine particles were observed in the containers of examples 2-1 to 2-3 by FE-SEM. As a result, a porous layer having a three-dimensional network structure formed by the hydrophobic oxide fine particles was observed.

< contact Angle >

The contact angle of pure water was measured using a contact angle measuring apparatus (solid-liquid interface analyzer "Drop Master 300", manufactured by interfacial science corporation) using the inner surface of each container bottom of examples 2-1 to 2-3 as a test piece (test surface), and all of the results were 150 degrees or more.

< adhesion test >

The weight (a) of each container of examples 2-1 to 2-3 and comparative examples 2-1 to 2-3 was measured in advance, 100g of a commercially available yogurt (product name "soft yogurt in the lima sea," manufactured by guokai milk corporation) was filled in each container, the container was turned upside down (with the opening portion facing downward) for 10 seconds to discharge the contents, and the weight (B) of each container was measured while the container was returned to a normal state (with the opening portion facing upward). The amount of B-A deposited was determined as the amount of yogurt deposited. The results of the measurement with n being 10 are shown in table 3.

TABLE 3

As is clear from the results in table 3, the conventional product (comparative example) had a filling amount of about 6 to 16% adhering to the container and remained, whereas the example had a filling amount reduced to about 1% or less (almost no adhesion). The container of the invention 2 shows a pure water contact angle of 150 degrees or more and has excellent non-adhesion to the contents, which is not seen in the known containers.

Examples 2 to 4

A sample (container) was produced in the same manner as in example 2-1, except that the drying treatment after the dipping treatment was carried out with hot air at 140 ℃.

Examples 2 to 5

A sample (container) was produced in the same manner as in example 2-1, except that the drying treatment after the dipping treatment was carried out with hot air at 160 ℃.

Test examples 2 to 2

< persistence improvement test >

The weight (A) of each container of examples 2-1, 2-4 and 2-5 was measured in advance, 100g of commercially available yogurt (product name "Meiweihai" soft yogurt, manufactured by Kogyo Co., Ltd.) was filled in each container, and the coating solution used in example 1 was dried to give a weight of 0.5g/m²The lid member was applied onto a surface of a thermal adhesive layer of a laminated lid member composed of an aluminum foil having a thickness of 40 μm and a thermal adhesive layer, and was thermally bonded to an end face (flange or the like) of an opening portion of each of the containers to form a package. After the package was vibrated under conditions of 1 minute, 30Hz (30 times vertical reciprocating vibration in 1 minute), 2.2mm amplitude (vertical direction), and acceleration of about 40G using a vibration tester (BF-30U manufactured by ltd), the lid member was opened and removed (the lid member did not adhere yogurt), the container was inverted vertically (with the opening facing downward) for 10 seconds to discharge the contents, and the weight (B) of the container was measured while each container was returned to a normal vertical state (with the opening facing upward). The amount of B-A deposited as yogurt was determined. The results of the measurement with n being 10 are shown in table 4.

TABLE 4

As is clear from the results in table 4, the effect of maintaining the non-adhesion property (durability) can be further improved by performing the heat treatment after the hydrophobic oxide fine particles are adhered.

< example of the invention 3 >

Example 3-1 to example 3-9 and comparative example 3-1 to comparative example 3-3

Samples were prepared by attaching hydrophobic oxide microparticles to laminates having various types of thermal adhesive layers shown in table 5. Specifically, each sample was prepared as follows.

(1) Production of laminate

< Hot melt type >

A polyurethane dry lamination adhesive (weight after drying: 3.5 g/m) was applied to one side of an aluminum foil (1N30, flexible foil; abbreviated as AL) having a thickness of 15 μm²(ii) a Abbreviated as D) was laminated on the printed surface of a polyethylene terephthalate film (abbreviated as PET) having a thickness of 12 μm and subjected to back printing (abbreviated as printing) to prepare a base material layer. The aluminum surface of the base layer was subjected to a fixing coating (main component: polyester resin; abbreviated as AC) treatment, and then, the resultant was pressed and laminated to dry a low density polyethylene resin (abbreviated as LDPE) to a film thickness of 20 μm. Further, hot melt agents (35 parts by weight of wax, 35 parts by weight of rosin and 30 parts by weight of ethylene-vinyl acetate copolymer; abbreviated as HM) were gravure-hot-melt-coated on the low-density polyethylene so that the weight of the coating after drying was 20g/m². Thus, a laminate of "PET/print/D/AL/AC/LDPE/HM" construction was produced.

< dosage forms of sealing >

A polyurethane dry layer was applied to one side of an aluminum foil (1N30, soft foil; abbreviated as AL) having a thickness of 15 μmAdhesive pressing (weight after drying 3.5 g/m)²(ii) a Abbreviated as D) was laminated on the printed surface of a polyethylene terephthalate film (abbreviated as PET) having a thickness of 12 μm and subjected to back printing (abbreviated as printing) to prepare a base material layer. After the aluminum surface of the base layer was subjected to a fixing coating (main component: polyester resin; abbreviated as AC), a sealant film (main component: metallocene catalyst polyethylene; abbreviated as sealant) having a thickness of 30 μm was extruded and laminated using a low density polyethylene resin (film thickness 20 μm after drying; abbreviated as LDPE). Thus, a laminate of "PET/print/D/AL/AC/LDPE/sealant" construction was prepared.

< paint type >

A polyurethane dry lamination adhesive (weight after drying: 3.5 g/m) was applied to one side of an aluminum foil (1N30, flexible foil; abbreviated as AL) having a thickness of 15 μm²(ii) a Abbreviated as D) was laminated on the printed surface of a polyethylene terephthalate film (abbreviated as PET) having a thickness of 12 μm and subjected to back printing (abbreviated as printing) to prepare a base material layer. On the aluminum surface of the substrate layer, a polyurethane dry lamination adhesive (weight after drying 3.5 g/m)²(ii) a Abbreviated as D) was laminated on a separately prepared polyethylene terephthalate film (abbreviated as PET) having a thickness of 12 μm, and dried to have a weight of 5g/m²The heat-seal paint (main component: acrylic resin + polyester resin: paint for short) was applied in the manner of (1). Thus, a laminate of "PET/print/D/AL/D/PET/lacquer" construction was produced.

(2) Attachment of hydrophobic oxide microparticles

Hydrophobic oxide fine particles (product name "AEROSIL R812S", manufactured by Evonik Degussa GmbH, BET specific surface area: 220 m)²(g), average primary particle diameter: 7nm) was dispersed in 100ml of ethanol to prepare a coating solution. Applying the coating liquid to the surface of the thermal adhesive layer of the laminate produced in the step (1) by gravure coating or bar coating, wherein the weight (solid content deposition) after drying is 0.3 to 1.0g/m²Then, it took about 10 seconds to dry at 100 ℃ to evaporate the ethanol, and a sample (packaging material) was obtained.

(3) Observation of the porous layer comprising the hydrophobic oxide microparticles (confirmation)

In the packaging materials of the examples, the structure of the layer composed of the hydrophobic oxide fine particles was observed by FE-SEM. As a result, a porous layer having a three-dimensional network structure formed by the hydrophobic oxide fine particles was observed for all the packaging materials. The observation results of example 3-4(A) as an example thereof are shown in FIG. 8. As shown in fig. 8, a layer in which black and white are mixed is visible on the thermal adhesive layer (sealant). The white portion is a porous layer made of a hydrophobic oxide. As described above, it was found that a porous layer composed of hydrophobic oxide fine particles was formed by applying the coating liquid and drying it.

Test example 3-1 (unsealing Strength)

The samples obtained in the examples and comparative examples were examined for the opening strength. Packages were produced by using lid members obtained by cutting lid member shapes (circular shapes with a pull ring and a diameter of 75 mm) from the respective package materials in examples 3-1 to 3-6 and comparative examples 3-1 to 3-2. Specifically, the container was made of a flanged paper/polyethylene container (formed to have a flange width of 3mm, a flange outer diameter of 70mm, a height of about 55mm, and an inner volume of about 130 cm)³100 μm polyethylene was coated on a paper sheet having a thickness of about 300 μm and the polyethylene was positioned inside the container) and the lid member was heat sealed to produce a package. The heat sealing conditions are as follows: at a temperature of 160 ℃ and a pressure of 1kg/cm²The next run was carried out for 1 second. The tab of the lid member of each package was pulled at a speed of 100 mm/min in the direction of an angle of elevation of 45 degrees from the opening start point, the maximum load at the time of opening was regarded as the opening strength (N), and the average value was determined by measuring each package at 6 points where N is equal to. The results are shown in Table 5.

Examples 3-7 to 3-9 and comparative examples 3-3

A package was produced by using a lid member obtained by cutting out a lid member shape (a rectangle having a pull ring and a length of 62 mm. times.67 mm) from each package material. Specifically, a container made of polystyrene and having a flange (formed to have a flange width of 4mm, a flange outer diameter of 60 mm. times.65 mm □, a height of about 48mm, and an internal volume of about 100 cm)³) The lid member is heat sealed to the flange of the container to form a package. The heat sealing conditions are as follows: at a temperature of 210 ℃ and a pressure of 2kg/cm²Next, a 2mm wide ring (concave) seal was applied for 1 second. In order to pull the lid member tab of each package at a speed of 100 mm/min in the direction of an angle of elevation of 45 degrees from the opening start point, the maximum load at the time of opening was regarded as the opening strength (N), and N was measured for each package at 6 points to obtain the average value thereof. The results are shown in Table 5.

Test example 3-2 (sealing Strength)

The sealing strength test was carried out using the package produced in test example 3-1 as a test sample, based on the sealing strength test method of { milk and milk product component specification and other provincial treaties (No. 17 of 4/16-day-old-Ministry of fat-and-live province in 1979 (Showa 54), etc. }. In this, air was continuously flowed into the container, and the internal pressure (mmHg) at the time of air leakage was measured. Each package was measured at n-3 points, and the average value was calculated. The results are shown in Table 5.

Test examples 3 to 3 (contact Angle)

The contact angle of pure water was measured using a contact angle measuring apparatus (solid-liquid interface analyzer "Drop Master 300", manufactured by Kyowa interface science Co., Ltd.) with the hot adhesive layer side of each packaging material as a test surface. The results are shown in Table 5.

Test examples 3-4 (lower corner)

The hot-adhesive layer side of each packaging material was used as a test surface, the surface was fixed to a horizontal platform with a clamp, and commercially available milk fruits (product name "Mei Li Hai" soft yogurt, 1 drop manufactured by Gu Rui Dai Co., Ltd.: about 0.4g) were dropped from a very close distance, and the horizontal platform was inclined to determine the angle at which the yogurt liquid drops rolled. The results are shown in Table 5. In addition, comparative example 3-1 to comparative example 3-3 did not drip down even at 90 degrees, but flowed downward.

Test examples 3 to 5 (delivery test)

The package used in test example 3-1 was filled with 100g (flanged paper/polyethylene container) and 85g (flanged polystyrene container) of commercially available yogurt (product name "Meiweihai" soft yogurt, product of firm fruit milk Co., Ltd.) respectively, and the lid member was heat-sealed in the same manner as in test example 3-1. After the package filled with yogurt was transported by long-distance truck for a distance of 1500km, the lid material was opened with a finger, and the state of the surface of each lid member on the heat-adhesive layer side was visually observed. The results are shown in Table 5. Further, the evaluation was as follows: "good" when no yogurt was adhered, "good" when some of the peripheral portions were adhered in a ring shape (the adhering area ratio was 20% or less), and "fair" when the adhesion was more pronounced (the adhering area ratio was more than 20% and less than 90%), and "poor" when the adhesion was almost all visible (the adhering area ratio was 90% or more). At this time, ". circlei" and ". smallcircle" were both evaluated as good.

TABLE 5

Note: the coating weights are the dried weights

A: gravure coating method B: bar coating method

More than 150: over 150 DEG

As is clear from the results in table 5, the conventional product (comparative example) exhibited no non-adhesiveness at all, whereas the invention 3 (example) exhibited high non-adhesiveness. It was also found that the sealing film exhibited good performance without impairing the practical utility even in the viewpoint of the opening strength and the sealing property (sealing value). Further, from the results of the contact angle and the falling angle, it is also known that the packaging material of the present invention exhibits a high degree of non-adhesiveness. In particular, the outermost surface (surface to which the hydrophobic oxide fine particles are attached) on the heat-sealable layer side of the packaging material according to claim 3 shows a pure water contact angle of 150 degrees or more, and has excellent non-adhesiveness to contents, which is not seen in known packaging materials.

< example of the 4 th invention >

Examples 4-1 to 4-3 and comparative example 4-1

Samples were made and evaluated as follows.

(1) Preparing hot adhesive

(1-1) Hot Adhesives containing iron as oxygen absorber

As the iron as an oxygen absorbent, a commercially available product ("Ageless" manufactured by Mitsubishi gas chemical corporation) was used, and 10 wt% to 40 wt% of a heat seal varnish (main component: 160 parts by weight of a polyester resin + 10 parts by weight of an acrylic resin + 40 parts by weight of a solvent (a mixed solvent of toluene and MEK)) was added and mixed to prepare a heat adhesive of example 4-1.

(1-2) Hot Adhesives containing aluminum-based oxygen absorber

As a main component of the aluminum-based oxygen absorbent, pure aluminum powder (atomize powder manufactured by Toyo aluminum Co., Ltd., average particle diameter: 8 μm, BET specific surface area: 0.7 m) was used²And a resin-coated powdery aluminum having a surface of the powdery aluminum coated with a resin (resin coating amount: 3g/100g of aluminum)). The method for coating the resin on the surface of the aluminum powder comprises the following steps: a four-necked flask having a capacity of 3 liters was charged with 1.5g of epoxidized 1, 2-polybutadiene, 3.5g of trimethylolpropane triacrylate, 0.3g of acrylic acid, 1.4g of divinylbenzene, 1440g of mineral essence, and 200g of untreated aluminum powder, and the mixture was thoroughly stirred and mixed while introducing nitrogen gas. The temperature in the system was raised to 80 ℃ and 1.1g of α, α' -Azobisisobutyronitrile (AIBN) was added, and the mixture was reacted at 80 ℃ for 6 hours while continuing to stir. After the reaction, the mixed solution is filtered and dried at 140 ℃ to obtain the resin-coated aluminum powder.

Next, 1g of a main component of the aluminum-based oxygen absorbent and an α -alumina powder (TM-DAR, manufactured by Daming chemical Co., Ltd., average particle diameter: 0.1 μm, BET specific surface area: 14.5 m) were mixed and stirred²1g, 0.5g of calcium oxide (99.9% pure, made by Wako pure medicines) and 0.5g of zeolite A-4 (3.5 μm average particle size, made by Wako pure medicines), followed by addition of a binder (main component: 160 parts by weight of a polyester resin, 10 parts by weight of an acrylic resin, and 40 parts by weight of a solvent (a mixed solvent of toluene and MEK), 27g of the above components were mixed with stirring, and 1g of water was further added thereto to prepare hot adhesives of examples 4-2 and 4-3.

(2) Production of packaging Material

A polyurethane dry lamination adhesive (weight after drying: 3.5 g/m) was applied to one side of an aluminum foil (1N30, flexible foil; abbreviated as AL) having a thickness of 15 μm²(ii) a Abbreviated as D) was laminated on the printed surface of a polyethylene terephthalate film (abbreviated as PET) having a thickness of 12 μm and subjected to back printing (abbreviated as printing) to prepare a base layer. The aluminum surface of the substrate layer was coated with a polyurethane dry lamination adhesive (weight after drying: 3.5 g/m)²(ii) a Abbreviated as D), was bonded to a separately prepared polyethylene terephthalate film (abbreviated as PET) having a thickness of 12 μm, and each of the hot adhesives prepared in (1-1) and (1-2) was applied thereto so as to give a dried weight of 3g/m²。

In comparative example 4-1, a packaging material was produced in the same manner as described above, except that a hot adhesive containing no oxygen absorbent (main component: 160 parts by weight of polyester resin + 10 parts by weight of acrylic resin + 40 parts by weight of solvent (mixed solvent of toluene and MEK)) was used.

(3) Attachment of hydrophobic oxide microparticles

Hydrophobic oxide fine particles (product name "AEROSIL R812S", manufactured by Evonik Degussa GmbH, BET specific surface area: 220 m)²(g), average primary particle diameter: 7nm) of the above-mentioned aqueous solution was dispersed in 100mL of ethanol to prepare a coating solution. The coating liquid was applied to the surface of the hot-tack layer of the packaging material produced in (2) by bar coating, and the weight (solid content deposition) after drying was 0.5g/m²Then, it took about 10 seconds to dry at 100 ℃ to evaporate the ethanol, and a sample was obtained. In addition, the sample of comparative example 4-1 was not attachedHydrophobic oxide fine particles are attached.

(4) Observation of porous layer comprising hydrophobic oxide microparticles

In the packaging materials of the examples, the structure of the layer composed of the hydrophobic oxide fine particles was observed by FE-SEM. As a result, a porous layer having a three-dimensional network structure formed by the hydrophobic oxide fine particles was observed for all the packaging materials.

(5) Determination of residual oxygen in a vessel

A package was produced using a lid member obtained by cutting out the shape of the lid member (a rectangle with a tab, 62mm in length × 67mm in width) from each sample. Specifically, a container made of polystyrene and having a flange (formed to have a flange width of 4mm, a flange outer diameter of 60 mm. times.65 mm □, a height of about 48mm, and an internal volume of about 105 cm)³) 80g of water was filled in the container, and the lid member was heat-sealed to produce packages, respectively. The heat sealing conditions are as follows: at a temperature of 220 ℃ and a pressure of 3kgf/cm²Next, a ring (concave) seal having a width of about 2mm was performed for 1 second. After standing at room temperature for 72 hours, the residual oxygen concentration in the container was measured by an apparatus "OXYGENANNALYZER (LC-750, manufactured by TORAY)". The results are shown in Table 6.

(6) Amount of air (gas) remaining in the container

The package produced in the same manner as in (5) above was placed in a water tank, the lid of the specimen was opened, the air (gas) released from the container was collected by a measuring cylinder, and the amount of gas was measured in water. The results are shown in Table 6.

(7) Non-adhesive and spreadability of yogurt

A package was produced in the same manner as in (5) above except that the content was a commercially available yogurt (product name "soft yogurt in the seas," manufactured by firm fruit milk co., ltd.), and after standing in a refrigerator set at 5 ℃ for 72 hours, the container was poured upside down (with the lid side of the container facing downward), and then returned to the original state (with the lid side of the container facing upward), and the lid was opened after repeating 3 times. The evaluation of non-adhesion was carried out by visually observing the state of the lid, and the state of the lid with yogurt was "failed", and the state of the lid without yogurt was "passed". In the evaluation of the scattering property, the case where the yogurt droplets were scattered outside the container when the lid was opened was regarded as "failed", and the case where the yogurt droplets were not scattered was regarded as "passed". The results are shown in Table 6.

(8) Contact angle

The hot-adhesive layer side of each packaging material was used as a test surface, and the contact angle of pure water was measured using a contact angle measuring apparatus (solid-liquid interface analyzer "Drop Master 300", manufactured by Kyowa interface science Co., Ltd.). The results are shown in Table 6.

TABLE 6

As is clear from the results in table 6, the conventional product (comparative example) exhibited no non-adhesiveness at all, whereas the 4 th invention (example) exhibited high non-adhesiveness. Further, it can be seen from the results of the contact angle that the packaging material of the present invention exhibits high non-adhesiveness.

In particular, the outermost surface (surface to which the hydrophobic oxide fine particles are attached) on the heat-adhesive layer side of the packaging material of claim 4 shows a pure water contact angle of 150 degrees or more, and has excellent non-adhesion to contents, which has not been observed in conventional packaging materials. Further, since the lid member of the present invention contains an oxygen absorbent in at least one of the base layer and the thermal adhesive layer, it can be effectively stored for a long period of time by preventing putrefaction and deterioration, and it has an effect of preventing the contents from scattering and flying out by reducing the pressure in the package.

Claims

1. A packaging material comprising a laminate having at least a base material layer and a heat-seal adhesive layer, wherein,

the thermal adhesive layer is laminated as the outermost layer of one surface of the packaging material, and hydrophobic oxide fine particles having a primary average particle diameter of 3 to 100nm are adhered to the outermost surface of the thermal adhesive layer not adjacent to other layers, and the amount of the hydrophobic oxide fine particles adhered is 0.01 to 10g/m²，

The hydrophobic oxide fine particles form a porous layer composed of a three-dimensional network structure.

2. The packaging material of claim 1,

the hydrophobic oxide fine particles have a specific surface area of 50 to 300m by a BET method²/g。

3. The packaging material of claim 1,

the hydrophobic oxide fine particles are hydrophobic silica.

4. The packaging material of claim 3,

the hydrophobic silica has a trimethylsilyl group on its surface.

5. The packaging material of claim 1,

it is used for: in an article in which contents are packaged by a packaging material and a container in a state where the contents can be in contact with the outermost surface on the thermal adhesive layer side.

6. The packaging material of claim 1,

when thermal bonding is performed, the hydrophobic oxide fine particles present in the region to be thermally bonded are embedded in the thermal adhesive layer.

7. The packaging material of claim 1,

the container is filled with contents and sealed with its opening in contact with the thermal adhesive layer of the packaging material.

8. The packaging material of claim 1,

the thermal adhesive layer contains filler particles containing at least 1 component selected from an organic component and an inorganic component.

9. The packaging material of claim 8,

the filler particles have an average particle diameter of 0.5 to 100 μm.

10. The packaging material of claim 1,

at least one of the substrate layer and the thermal adhesive layer contains an oxygen absorber.

11. The packaging material of claim 1,

the porous layer is formed by a method of forming a coating film on the thermal adhesive layer using a dispersion obtained by dispersing hydrophobic oxide fine particles in a solvent, and then drying the coating film.

12. The packaging material of claim 1,

the packaging material serves as a lid member.

13. A method for producing a packaging material according to claim 1, wherein,

the method includes a deposition step performed by a method of forming a coating film on a thermal adhesive layer using a dispersion obtained by dispersing hydrophobic oxide fine particles in a solvent, and then drying the coating film.

14. The manufacturing method according to claim 13,

the adhesion step is performed by a roll coating method, a gravure coating method, a bar coating method, a doctor blade film forming method, or a brush coating method.