JP5683827B2 - Non-adhesive container and manufacturing method thereof - Google Patents

Description

  The present invention relates to a non-adhesive container and a method for producing the same. In particular, the present invention relates to a container excellent in non-adhesiveness of contents and a manufacturing method thereof. More specifically, the present invention relates to a non-adhesive container for containing foods, beverages, pharmaceuticals, cosmetics, chemicals, and the like, and a method for manufacturing the same.

  A wide variety of containers are known in the past, but their contents are also diverse. For example, there are foods, beverages, pharmaceuticals, cosmetics, chemicals, and the like such as jelly confectionery, pudding, yogurt, liquid detergent, toothpaste, carrero, syrup, petrolatum, face wash cream, face wash mousse and the like. In addition, the contents have various properties such as solid, semi-solid, liquid, viscous material, and gel-like material.

  Containers for storing these contents are required to have preservability, as well as thermal adhesiveness, light shielding properties, heat resistance, durability, etc., depending on the contents, storage form, application, etc. . However, even a container satisfying these characteristics has the following problems. That is, there is a problem that the contents adhere to the container. If the contents adhere to the container, it becomes difficult to use up all of the contents, resulting in waste. In addition, in order to use up all the contents, the contents attached to the container must be collected separately, which is troublesome. For this reason, the container is required to have the property (non-adhesiveness) that the contents are difficult to adhere to the container, in addition to the storage stability as described above.

  On the other hand, Patent Document 1 states that “in an apparatus having a heat resistance of at least 300 ° C., a remarkable anti-adhesion property and an easily cleaned surface coating having a thickness of 1-1000 nm, Contains a metal oxide network and a hydrophobic material, the hydrophobic material being evenly distributed with respect to the thickness of the surface coating, the surface coating being hydrophobic and against water greater than 90 ° An apparatus with an easily cleaned surface coating characterized by having a contact angle is disclosed. (Patent Document 1).

JP 2004-130785 A

  However, the surface coating of the above device is formed by a sol-gel method, and the process is complicated. Moreover, since a fluorine-containing compound such as fluoroalkylsiloxane is used, the surface coating for the human body and the environment is used. There are concerns about the impact.

  The main object of the present invention is to provide a container that can be produced by a relatively simple process and that does not contain a concern substance such as fluorine and that can continuously exhibit excellent non-adhesiveness.

  As a result of intensive studies in view of the problems of the prior art, the present inventor has found that a container having a specific configuration can achieve the above object, and has completed the present invention.

That is, this invention relates to the following non-adhesive container and its manufacturing method.
1. A container for containing contents, and a coating made of a material for forming irregularities including filler particles and a resin component is applied to at least part or all of the surface of the container that comes into contact with the contents, Hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100 nm are attached on the surface, and the hydrophobic oxide fine particles form a porous layer having a three-dimensional network structure,
A non-adhesive container having a ten-point average roughness Rz of 7 to 500 μm and a cross-sectional curve maximum height Rmax of 12 to 1000 μm on the surface to which the hydrophobic oxide fine particles adhere .
2. Item ^2. The non-adhesive container according to Item 1, wherein the amount of hydrophobic oxide fine particles adhered is 0.01 to 10 g / m ² .
3. Item 3. The non-adhesive container according to Item 1 or 2, wherein the content of the filler particles in the unevenness forming material is 1 to 80% by weight based on the solid content weight.
4). Item 4. The non-adhesive container according to any one of Items 1 to 3, wherein the hydrophobic oxide fine particles have a specific surface area of 50 to 300 m ² / g by BET method.
5. Item 5. The non-adhesive container according to any one of Items 1 to 4 , wherein the surface to which the hydrophobic oxide fine particles adhere is in a micro uneven state, and the number of convex portions is 50 to 100,000 / cm ² .
6). Item 6. The non-adhesive container according to any one of Items 1 to 5 , wherein the hydrophobic oxide fine particles are hydrophobic silica.
7). Item 7. The non-adhesive container according to Item 6 , wherein the hydrophobic silica has a trimethylsilyl group on the surface thereof.
8). Item 8. The non-adhesive container according to any one of Items 1 to 7 , wherein the average particle size of the filled particles is 0.5 to 100 µm.
9. A product in which the non-adhesive container according to any one of Items 1 to 8 is filled with contents, and the contents are sealed with a lid.
10. A method for producing a container for containing contents, wherein 1) a liquid or semi-solid unevenness forming material or a starting material thereof is applied in a layered manner on a surface to which hydrophobic oxide fine particles are adhered. A step of forming a concavo-convex surface having a point average roughness Rz of 7 to 500 μm and a cross-sectional curve maximum height Rmax of 12 to 1000 μm; 2) an average primary particle diameter of 3 to 3 on the concavo-convex surface; A method for producing a non-adhesive container, comprising a step of adhering 100 nm hydrophobic oxide fine particles.

  The non-adhesive container of the present invention can exhibit excellent non-adhesiveness without containing a concern substance such as fluorine. Thereby, since almost all the contents can be taken out from the container, the loss of the amount adhering to the inner wall of the container can be suppressed or prevented.

  In addition, according to the production method of the present invention, it is only necessary to apply hydrophobic oxide fine particles to at least a part of the surface that comes into contact with the contents. Etc. are advantageous. Moreover, there is no restriction | limiting of the material of a container, For example, it can apply also to containers of any materials, such as a glass container, earthenware, a paper container, a plastic container, a metal container, and a wooden container. Moreover, non-adhesiveness can also be imparted to existing containers afterwards. Furthermore, non-adhesiveness can be further maintained by heat-treating after applying the hydrophobic oxide fine particles. Further, non-adhesiveness can be further maintained by keeping the surface of the portion to which the hydrophobic oxide fine particles are adhered in a minute uneven state.

It is a schematic diagram which shows the cut surface structure of the non-adhesive container of this invention. It is a schematic diagram of the cross-sectional structure which shows the state which put the contents in the non-adhesive container of this invention, and heat-bonded the cover material. It is a schematic diagram which shows the cut surface structure of the container which shows another embodiment of this invention.

DESCRIPTION OF SYMBOLS 1 Base material layer of lid 2 Thermal adhesive layer of lid 3 Hydrophobic oxide fine particle 4 Container body 5 Contents 6 Filling particle 7 Container body 8 Concavity and convexity forming material

1. Non-adhesive container The non-adhesive container of the present invention is a container for containing contents, and the hydrophobicity of the average primary particle diameter of 3 to 100 nm on at least part or all of the surface where the container contacts the contents It is characterized in that oxide fine particles are adhered.

  First, the container main body of this invention should just be what can accommodate the content, and can use a well-known thing or a commercial item. The material is not limited, and any material such as a glass container, ceramics, paper container, plastic container, metal container, wood container, or a container made of a composite material of two or more of these may be used. Moreover, the form of the container body is a known form such as a dish shape, tray shape, bag shape, cup shape, bottle shape, pan shape, box shape, barrel shape, substantially cylindrical shape, wrapping paper (packaging leaf), etc. There may be. Moreover, the container main body can use the container which consists of a molded object suitably. For example, the container which consists of a molded object of paper, a plastics, or a metal can be mentioned. Moreover, as a container main body, the container comprised from the laminated material containing the layer which consists of a rigid material can also be illustrated. In the present invention, the non-adhesive container is preferably a packaging material composed of a laminate having at least a base material layer and a thermal adhesive layer, wherein the thermal adhesive layer is an outermost layer on one surface of the packaging material. “Packaging material in which hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100 nm are adhered to the outermost surface, which is laminated and the thermal adhesive layer is not adjacent to other layers” is excluded.

  The non-adhesive container of the present invention is characterized in that hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100 nm are attached to at least a part or all of the surface in contact with the contents. In this case, the hydrophobic oxide fine particles may be attached to the surface of the container body that is not in contact with the contents, or may be attached to the entire surface of the container (including the entire surface that does not contact the contents). There is no problem. Moreover, you may adhere to a part of surface which contacts the contents, and you may adhere to all the said surfaces (entire surface).

  The hydrophobic oxide fine particles adhering to the non-adhesive container of the present invention can hardly be recognized with the naked eye, and thus are transparent or translucent. For this reason, when a transparent glass container or a nearly transparent plastic container is employed as the container body, the transparency can be maintained even after the hydrophobic oxide fine particles are adhered. In addition, when there is a pattern, a pattern, or the like on the inner surface of the container, the pattern, the pattern, or the like can be visually recognized through hydrophobic oxide fine particles (or a layer thereof).

  FIG. 1 shows a schematic diagram of a cut surface structure of a non-adhesive container of the present invention. In the non-adhesive container of FIG. 1, hydrophobic oxide fine particles 3 having an average primary particle diameter of 3 to 100 nm are attached to the surface (the bottom surface and a part of the side surface) on the container main body 4 side. The hydrophobic oxide fine particles 3 are adhered and fixed to the container body 4. That is, even if the hydrophobic oxide fine particles and the content come into contact with each other, the hydrophobic oxide fine particles are adhered to such an extent that they do not fall off. In FIG. 1, the hydrophobic oxide fine particles 3 may contain primary particles, but it is desirable that the hydrophobic oxide fine particles 3 contain many aggregates (secondary particles). In particular, it is more preferable that the hydrophobic oxide fine particles form 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 at least a part of the surface of the container body 4.

  FIG. 2 shows a schematic diagram of a cross-sectional structure of a product in which the non-adhesive container of the present invention is filled with the contents and the contents are sealed by thermally bonding the lid. In FIG. 2, the hydrophobic oxide fine particles 3 are shown in a omitted form. The container body 4 is filled with the contents 5 and sealed in such a state that the opening and the thermal adhesive layer 2 of the lid are in contact with each other. In this case, even when the hydrophobic oxide fine particles are attached to the surface of the opening of the container, the hydrophobic oxide fine particles present on the heat-bonded region are present in the heat-adhesive layer when thermally bonded. It is embedded, and the thermal bonding layer and the container body 4 are in direct contact, and thermal bonding can be performed. Further, when the material of the container body 4 is a thermoplastic plastic, it can be welded to a lid made of the same kind of plastic, for example.

  Note that the material of the lid member is not particularly limited, and a known material or a laminated material can be adopted, and may be appropriately selected according to the material and required characteristics of the container body 4. For example, a simple substance such as paper, synthetic paper, a resin film, a resin film with a vapor deposition layer, an aluminum foil, or a composite material / laminated material thereof can be suitably used.

  In these materials, each layer employed in a known lid material may be laminated at an arbitrary position. For example, printing layer, printing protective layer (so-called OP layer), colored layer, thermal adhesive layer, adhesive layer, adhesion reinforcing layer, primer coat layer, anchor coat layer, anti-slip agent layer, lubricant layer, anti-fogging agent layer, etc. Can be mentioned.

  In addition, in FIG. 2, although the heat-adhesive cover material is used, it is not limited to this, The thing of another well-known type can also be employ | adopted. For example, a fitting lid, a screw lid, a wrap film, a heat shrinkable film, a caulking lid, a cap, and the like can be appropriately selected. Of course, hydrophobic oxide fine particles can be attached to the inner surface and / or the outer surface of these lid members.

  The hydrophobic oxide fine particles adhering to the container body 4 have an average primary particle diameter of usually 3 to 100 nm, preferably 5 to 50 nm, more preferably 5 to 20 nm. By setting the average primary particle diameter in the above range, the hydrophobic oxide fine particles are in an appropriate aggregated state, and can hold a gas such as air in the voids in the aggregate, resulting in excellent non-adhesiveness. Can be obtained. That is, this agglomerated state is maintained even after adhering to the container body, so that excellent non-adhesiveness can be exhibited.

  In the present invention, the average primary particle diameter can be measured with a scanning electron microscope (FE-SEM). When the resolution of the scanning electron microscope is low, other electrons such as a transmission electron microscope are used. You may carry out together with a microscope. Specifically, when the particle shape is spherical, the diameter is considered as the diameter, and when the particle shape is non-spherical, the average value of the longest diameter and the shortest diameter is regarded as the diameter, and 20 arbitrarily selected by observation with a scanning electron microscope or the like. The average diameter of the particles is defined as the average primary particle diameter.

The specific surface area of the hydrophobic oxide fine particles (BET method) is not particularly limited, and usually 50 to 300 m ² / g, it is preferable that the particular 100 to 300 m ² / g.

The hydrophobic oxide fine particles are not particularly limited as long as they have hydrophobicity, and may be those hydrophobized by surface treatment. For example, fine particles in which hydrophilic oxide fine particles are subjected to a surface treatment with a silane coupling agent or the like to make the surface state hydrophobic can also be used. The type of oxide is not limited as long as it has hydrophobicity. For example, at least one of silica (silicon dioxide), alumina, titania and the like can be used. These may be known or commercially available. For example, as silica, product names “AEROSIL R972”, “AEROSIL R972V”, “AEROSIL R972CF”, “AEROSIL R974”, “AEROSIL RX200”, “AEROSIL RY200” (above, manufactured by Nippon Aerosil Co., Ltd.), “AEROSIL R202” "AEROSIL R805", "AEROSIL R812", "AEROSIL R812S" (above, manufactured by Evonik Degussa). Examples of titania include “AEROXIDE TiO ₂ T805” (manufactured by Evonik Degussa). Examples of alumina include fine particles in which the product name “AEROXIDE Alu C” (manufactured by Evonik Degussa) is treated with a silane coupling agent to make the particle surface hydrophobic.

  Among these, hydrophobic silica fine particles can be preferably used. In particular, hydrophobic silica fine particles having a trimethylsilyl group on the surface are preferable in that better non-adhesiveness can be obtained. Examples of commercially available products corresponding to this include “AEROSIL R812” and “AEROSIL R812S” (both manufactured by Evonik Degussa).

The amount (weight after drying) of the hydrophobic oxide fine particles to be adhered to the container body is not limited, but is usually preferably 0.01 to 10 g / m ^2, and preferably 0.2 to 1.5 g / m ^2. More preferably, it is most preferably 0.3-1 g / m ² . By setting within the above range, more excellent non-adhesiveness can be obtained over a long period of time, and it is further advantageous in terms of suppression of falling off of hydrophobic oxide fine particles and cost. The hydrophobic oxide fine particles adhering to the container body 4 preferably form a porous layer having a three-dimensional network structure, and the thickness is preferably about 0.1 to 5 μm, and 0.2 to 2.5 μm. The degree is further preferred. By adhering in such a porous layer state, the layer can contain a lot of air, and more excellent non-adhesiveness can be exhibited.

  Moreover, in this invention, non-adhesiveness can be further maintained effectively by making the surface of the part which adheres hydrophobic oxide microparticles | fine-particles into a micro uneven | corrugated state. That is, highly adhering non-adhesiveness can be obtained by adhering the hydrophobic oxide fine particles to the inner surface of the container having a fine uneven state formed on the surface in advance.

  The degree of the unevenness is not particularly limited, but the ten-point average roughness Rz of the surface to which the hydrophobic oxide fine particles adhere (hereinafter also referred to as “attachment surface”) is about 7 to 500 μm. In particular, 10 to 300 μm is more preferable, and 10 to 100 μm is most preferable. By setting within this range, non-adhesiveness can be more reliably and continuously exhibited. Ten-point average roughness Rz is defined by JIS B0601 (-1982). However, in the present invention, Rz in the arbitrary X-axis direction on the measurement surface and the Y-axis direction perpendicular to the X-axis is measured for each sample, and an arithmetic average value is adopted.

  In the non-adhesive container of the present invention, the maximum height Rmax of the cross-sectional curve of the adhering surface is preferably 12 to 1000 μm, more preferably 15 to 500 μm, and most preferably 15 to 200 μm. . By setting Rmax within the above range, non-adhesiveness can be more reliably and continuously exhibited. The section curve maximum height Rmax is defined by JIS B0601 (-1982). However, in the present invention, Rmax in the arbitrary X-axis direction on the measurement surface and the Y-axis direction perpendicular to the X-axis is measured for each sample, and an arithmetic average value is adopted.

In non-adherent container of the present invention, in the case of the attachment surface with fine irregularities, it is preferable to the number of protrusions and 50-100000 pieces / cm ^2, that the 70-80000 pieces / cm ² More preferably, it is most preferably 80 to 50000 pieces / cm ² . Within this range, the desired non-adhesiveness can be more reliably and continuously exhibited. The number of the convex portions / cm ² is a value calculated by the following equation.

Pc: Peak count (ASME B46.1: 1995)

  Pc can be measured using, for example, a contact-type surface roughness meter (product name “SURFCOM1400D-12”, manufactured by Tokyo Seimitsu Co., Ltd.), and any X-axis direction of the measurement surface per sample and perpendicular to the X-axis Each Pc in the Y-axis direction was measured, and an arithmetic average value was adopted.

  In the present invention, the means for making the adhesion surface uneven is not particularly limited. For example, in the case of a resin injection molded container, a resin container having minute irregularities can be molded by adjusting the surface roughness in the injection mold. Also, depending on the material of the container, fine unevenness can be mechanically imparted by a method such as sandblasting or polishing. For example, when it is difficult to mechanically give fine irregularities such as glass containers, the resin film with the surface shape formed into irregularities, the resin film with embossing, etc. laminated on the adhesion surface Can also be given. In addition, unevenness can be imparted by applying or laminating a film made of an unevenness forming material containing filler particles and a resin component. In the present invention, the method using the material for forming irregularities is preferable in that the surface roughness and the like can be precisely controlled. Hereinafter, a non-adhesive container according to this method will be described as a representative example with reference to FIG.

  FIG. 3 shows a schematic diagram of an example of the cross-sectional structure. In FIG. 3, hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100 nm on the surface of the irregularity forming material 8 including the filler particles 6 on the inner surface side of the main body 7 such as a glass container, a resin container, a metal container, and a paper container. 3 is attached. That is, the unevenness is imparted to a part or all of the adhesion surface, and the hydrophobic oxide fine particles 3 having an average primary particle diameter of 3 to 100 nm are adhered to the surface in such an irregularity state. When unevenness is imparted by the unevenness forming material, the surface of the unevenness forming material (surface to which the hydrophobic oxide fine particles adhere) becomes uneven, and the hydrophobic oxide fine particles enter the recessed portion in an aggregated state. It is considered that non-adhesion is enhanced. That is, in addition to the contents, even if contact with the device or apparatus in the process occurs, the hydrophobic oxide fine particles that have entered the concave portion enter the concave portion and are maintained in a fixed state, thereby maintaining hydrophobic oxidation. As a result of effectively suppressing or preventing the removal of the fine particles, excellent non-adhesiveness can be continuously exhibited. In other words, good wear resistance can be exhibited.

  As the resin component used in the material for forming irregularities, a known thermoplastic resin can be employed. For example, acrylic resin, polystyrene, ABS resin, vinyl chloride resin, polyethylene resin, polypropylene resin, polyamide resin, polycarbonate, polyacetal, fluorine resin, silicone resin, polyester resin, and blended resins of these Copolymers, modified resins and the like containing combinations of monomers to be used can be used. A thermosetting resin may be employed instead of the thermoplastic resin. For example, an epoxy resin, a melamine resin, a phenol resin, a silicone resin, an unsaturated polyester resin, or the like can be used.

  The thickness of the concavo-convex layer formed by the concavo-convex forming material in the case of providing concavo-convex on the inner surface of the container (here, the thickness refers to the thickness of the thickest part) is not particularly limited. From the viewpoint of cost and the like, the thickness is preferably about 0.1 μm to 5 mm, more preferably about 1 μm to 2 mm. Moreover, when making the uneven | corrugated layer formed with the uneven | corrugated material use as a thermal adhesive layer, it is preferable to set it as thickness of 5-150 micrometers in consideration of thermal adhesiveness. In this embodiment, when thermal bonding is performed, the hydrophobic oxide fine particles existing on the region to be thermally bonded are embedded in the unevenness forming material, and the unevenness forming material (thermal adhesive layer) becomes the outermost surface. Thermal bonding can be performed. For this reason, it is desirable to set the thickness within the above-mentioned thickness range so that the hydrophobic oxide fine particles can be embedded in the unevenness forming material as much as possible.

  The resin content (solid content) in the material for forming irregularities varies depending on the type of resin, the presence of filler particles and other additives, etc., but is usually 20 to 99% by weight, particularly 30 to 30%. It is preferable to set it as 98 weight%, More preferably, you may be 50-97 weight%.

  In the case where the adhesion between the unevenness forming material and the container main body (the inner surface thereof) is not sufficient, the inner surface of the container main body can be subjected to an anchor coat treatment, a plumer coat treatment or the like.

  The method for laminating the inner surface of the container body and the material for forming irregularities is not limited, and for example, a known method such as a dry laminating method, an extrusion laminating method, a wet laminating method, a heat laminating method, or roll coating can be employed.

  When making the unevenness forming material function as a thermal adhesive layer, a known thermal adhesive material can be employed. For example, in addition to a known sealant film, a layer formed of an adhesive such as a lacquer type adhesive, an easy peel adhesive, or a hot melt adhesive can be employed. That is, in this embodiment, the unevenness forming material includes a known thermal adhesive containing a resin component. When forming a hot melt layer, after applying the hot melt adhesive in a molten state, if the hydrophobic oxide fine particles are applied before cooling and solidifying, the hydrophobic oxide fine particles are allowed to adhere to the thermal adhesive layer as they are. Therefore, continuous production of the container of this embodiment is facilitated.

  As the filler particles, filler particles containing at least one of an organic component and an inorganic component can be employed. Examples of inorganic components include 1) metals such as aluminum, copper, iron, titanium, silver, and calcium, or alloys or intermetallic compounds containing these metals, and 2) silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, iron oxide, and the like. Oxides, 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 can be suitably used.

  Examples of organic components include acrylic resins, urethane resins, melamine resins, amino resins, epoxy resins, polyethylene resins, polystyrene resins, polypropylene resins, polyester resins, cellulose resins, vinyl chloride resins, and polyvinyl resins. Organic polymer components (or resin components) such as alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, polyacrylonitrile, and polyamide can be suitably used.

  As the filler particles in this embodiment, particles containing both an inorganic component and an organic component can be used in addition to particles made of an inorganic component or particles made of an organic component. Among these, it is particularly preferable to use at least one of acrylic resin particles, hydrophilic silica particles, calcium phosphate particles, carbon powder, calcined calcium particles, uncalcined calcium particles, calcium stearate particles, and the like.

  The average particle diameter of the packed particles (by a laser diffraction particle size distribution analyzer) is preferably about 0.5 to 100 μm, more preferably 1 to 50 μm, and most preferably 5 to 30 μm. If it is less than 0.5 μm, it may be unsuitable in terms of handleability, the above-described formation of irregularities, and the like. On the other hand, when it exceeds 100 μm, it may be unsuitable in terms of dropping off of the packed particles, dispersibility, and the like.

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

  The content of the filler particles in the unevenness forming material can be appropriately changed according to the type of resin component or filler particles, desired physical properties, etc., but generally 1 to 80% by weight based on the solid content weight is preferable, It is more preferably 2 to 70% by weight, particularly preferably 3 to 50% by weight.

  The method for containing the filler particles is not particularly limited, and generally includes a method of blending the filler particles into the material for forming unevenness or its starting material. Therefore, in general, the filler particles may be dispersed in a composition containing 1) a resin component and / or a monomer or oligomer constituting the resin component, and 2) a solvent, 3) a crosslinking agent, etc. as necessary. .

2. Method for Producing Container The non-adhesive container of the present invention is a process in which hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100 nm are attached to at least a part of or the entire surface of the container body that contacts the contents (attachment process). It can obtain suitably by the manufacturing method containing.

  As a container main body, a well-known container is employable as mentioned above. The method for carrying out the adhering step on the container body is not particularly limited. For example, known methods such as dipping, brush coating, roll coating, and electrostatic powder coating can be employed. In the case of dipping, brushing or roll coating, the adhesion step can be carried out by a method of drying after forming a coating film on the container body using a dispersion in which hydrophobic oxide fine particles are dispersed in a solvent. . The solvent in this case is not limited, and in addition to water, for example, ethanol, isopropyl alcohol, cyclohexane, toluene, acetone, propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, normal pentane, normal hexane, hexyl alcohol, etc. An organic solvent can be appropriately selected. Among these, a poor solvent that does not contain a good solvent is preferable, and it is desirable to use ethanol that does not contain a good solvent from the viewpoints of environment and hygiene. The solvent may be used in combination with a trace amount of a dispersant, a colorant, an anti-settling agent, a viscosity modifier, and the like within a range that does not impair the effects of the present invention. The dispersion amount of the hydrophobic oxide fine particles with respect to the solvent is usually about 10 to 100 g / L. When drying, either natural drying or forced drying (heat drying) may be used, but industrially forced drying is preferable. The drying temperature is not particularly limited depending on the material of the container, but it is usually preferably 250 ° C. or lower, particularly 120 to 200 ° C. from the viewpoint of maintaining non-adhesiveness.

  In the manufacturing method of this invention, a container main body can also be heated during the said adhesion process and / or after an adhesion process. By heating the container body, the adhesion force (fixing force) of the hydrophobic oxide fine particles to the container body can be further increased. The heating temperature in this case is not particularly limited, but is usually about 120 to 200 ° C.

  In the production method of the present invention, prior to the step of attaching the hydrophobic oxide fine particles, the step of forming irregularities on the surface of the surface to which the hydrophobic oxide fine particles adhere (or the step of roughening the surface) ) (Unevenness forming step) may be included.

  Examples of the unevenness forming step include 1) a method of providing unevenness on the adhesion surface itself, 2) a method of applying a liquid or semi-solid unevenness forming material or its starting material in layers on the adhesion surface, 3) Examples thereof include a method of laminating a previously formed sheet-like unevenness forming material on the adhesion surface, and 4) a method of laminating a resin sheet having irregularities on the adhesion surface.

  As the method 1), for example, fine unevenness can be imparted to the surface of the adhesion surface by a mechanical method such as sandblasting or polishing.

  As the method of 2) and 3), a material for forming irregularities or a starting material thereof is used in advance on a portion to which hydrophobic oxide fine particles are adhered in a non-adhesive container, and in-mold molding, coating, thermal spraying, spraying, and transfer are performed in advance. A step of forming the unevenness forming material in layers by a method such as fitting, bonding, or the like may be included. In the case of using the starting material, the film may be cured by, for example, heating, ultraviolet irradiation or the like after forming the film of the starting material. Thereafter, by carrying out the above-described adhesion step, hydrophobic oxide fine particles can be adhered to the formed portion. Thereby, the non-adhesion container which can maintain favorable water repellency and non-adhesion more effectively can be provided. What is necessary is just to use the same thing as the above as an uneven | corrugated material or its starting material.

  As the method of 4), instead of the material for forming unevenness, an embossed resin film, a resin film having a surface shape formed into unevenness, and the like are attached to the portion where the hydrophobic oxide fine particles of the non-adhesive container are attached. What is necessary is just to laminate. When a resin film is employed, the same type of resin as the material for forming irregularities can be used. If necessary, aluminum foil or other materials can be laminated and used. A publicly known method can be adopted for each lamination method. For example, a dry laminating method, a coextrusion method, a roll coating, a heat laminating method and the like can be appropriately employed.

  In the present invention, the place where the uneven state is formed is not limited. For example, it may be only a portion to which the hydrophobic oxide fine particles are attached, may include a portion to which the hydrophobic oxide fine particles are not attached, or may be the entire inner surface of the container or the entire surface of the container.

  The features of the present invention will be described more specifically with reference to the following examples and comparative examples. However, the scope of the present invention is not limited to the examples.

Example 1
A coating solution was prepared by dispersing 50 g of hydrophobic oxide fine particles (product name “AEROSIL R812S” manufactured by Evonik Degussa, BET specific surface area: 220 m ² / g, primary particle average diameter: 7 nm) in 1000 mL of ethanol. A commercially available polypropylene container (flange width of about 3 mm, flange outer diameter of about 70 mm, height of about 110 mm, and internal volume of about 200 cc) was immersed in this coating solution. The adhesion amount of the coating liquid was 0.5 g / m ² in terms of weight after drying (= solid content adhesion amount). After the immersion treatment, a sample (container) was obtained by evaporating ethanol with a warm air of 25 ° C. × 30 seconds (drying treatment).

Example 2
A coating solution was prepared by dispersing 50 g of hydrophobic oxide fine particles (product name “AEROSIL R812S” manufactured by Evonik Degussa, BET specific surface area: 220 m ² / g, primary particle average diameter: 7 nm) in 1000 mL of ethanol. In this coating solution, a commercially available flanged paper / polyethylene container (with a flange width of 3 mm, a flange outer diameter of 70 mm, a height of about 55 mm, an internal volume of about 130 cm ³ and a thickness of about 300 μm coated with 100 μm of polyethylene) Soaked inside the container). The adhesion amount of the coating liquid was 0.5 g / m ² in terms of weight after drying (= solid content adhesion amount). After the immersion treatment, a sample (container) was obtained by evaporating ethanol with 25 ° C. warm air.

Example 3
A coating solution was prepared by dispersing 50 g of hydrophobic oxide fine particles (product name “AEROSIL R812S” manufactured by Evonik Degussa, BET specific surface area: 220 m ² / g, primary particle average diameter: 7 nm) in 1000 mL of ethanol. A commercially available polystyrene container (flange width: about 3 mm, flange outer diameter: about 88 mm, height: about 63 mm, internal volume: about 176 cc) was immersed in this coating solution. The adhesion amount of the coating liquid was 0.5 g / m ² in terms of weight after drying (= solid content adhesion amount). After the immersion treatment, a sample (container) was obtained by evaporating ethanol with 25 ° C. warm air.

Comparative Example 1
The commercially available polypropylene container used in Example 1 was used as a sample as it was.

Comparative Example 2
The commercially available paper / polyethylene container used in Example 2 was used as a sample as it was.

Comparative Example 3
The commercially available polystyrene container used in Example 3 was used as a sample as it was.

Test example 1
<Observation of porous layer made of hydrophobic oxide fine particles>
In the containers of Examples 1 to 3, the structure of the layer made of hydrophobic oxide fine particles was observed by FE-SEM. As a result, a porous layer having a three-dimensional network structure formed of hydrophobic oxide fine particles was observed.

<Contact angle>
The bottom inner surface of each container of Examples 1 to 3 was used as a test piece (test surface), and the contact angle of pure water was determined using a contact angle measuring device (solid-liquid interface analyzer “Drop Master 300” manufactured by Kyowa Interface Science Co., Ltd.). When measured, all were 150 degree | times or more.

<Adhesion test>
The weight (A) of each container of Examples 1 to 3 and Comparative Examples 1 to 3 is measured in advance, and then 100 g of commercially available yogurt (product name “Delicious Caspian Sea” soft yogurt, manufactured by Glico Dairy Co., Ltd.) After each filling, the container is turned upside down for 10 seconds (the opening is in the ground direction), the contents are discharged, and the container is returned to the top (= opening is in the top direction). The weight (B) was measured. By calculating B-A, the amount of yogurt adhered was determined. The measurement results for n = 10 are shown in Table 1.

  As is apparent from the results in Table 1, in the conventional product (comparative example), about 6 to 16% of the filling amount remains attached to the container, whereas in the example, the filling amount is about 1% or less. It turns out that it reduces (it hardly adheres). The container of the present invention has a contact angle of pure water of 150 ° or more, and has excellent content non-adhesiveness not found in conventional containers.

Example 4
A sample (container) was obtained in the same manner as in Example 1 except that the drying treatment after the immersion treatment was hot air of 140 ° C. × 30 seconds.

Example 5
A sample (container) was obtained in the same manner as in Example 1, except that the drying treatment after the immersion treatment was hot air of 160 ° C. × 30 seconds.

Test example 2
<Sustainability improvement test>
The weight (A) of each container of Example 1, Example 4 and Example 5 was measured in advance, and then 100 g of commercially available yogurt (product name “Delicious Caspian Sea” soft yogurt, manufactured by Glico Dairy Co., Ltd.) After each filling, the coating liquid used in Example 1 was dried and applied to the surface of the heat-bonding layer of the laminate cover material composed of 40 μm thick aluminum foil + the heat-bonding layer, and 0.5 g / m ^{2 by} weight was applied. A package was obtained by thermally bonding to the end face (flange, etc.) of the opening of each container. Each package is subjected to a vibration tester (BF-30U manufactured by IDEX Co., Ltd.) for 1 minute, 30 Hz (30 vertical vibrations per minute), 2.2 mm amplitude (vertical direction), and acceleration of about 40 G. After oscillating under conditions, the lid material is unsealed (no yogurt adhered to the lid material), each container is turned upside down for 10 seconds (the opening is in the direction of the ground), and the contents are discharged. The weight (B) of the container was measured in a state where the top and bottom of the container was returned (= the state where the opening was in the top direction). By calculating B-A, the amount of yogurt adhered was determined. The measurement results for n = 10 are shown in Table 2.

  As is clear from the results in Table 2, it can be seen that the non-adhesive sustaining effect (durability) is further improved by applying heat treatment after adhering the hydrophobic oxide fine particles.

Example 6
One surface of paper (basis weight 50 g / m ² ) and an aluminum-deposited surface of a polyethylene terephthalate film (thickness 16 μm, also referred to as an aluminum-deposited PET film) on which aluminum is deposited are bonded to a polyurethane-based dry laminate adhesive (weight 3 after drying). .5 g / m ² ), and bonded by a dry laminating method. Further, a heat seal lacquer (acrylic resin solid content: 100 parts by weight, acrylic resin beads (average particle diameter: 15 μm), 5 parts by weight, solvent (toluene + MEK mixed solvent), 40 parts by weight was blended on the other surface of the aluminum vapor-deposited PET film. After drying, 3 g / m ^{2 was} applied by weight and dried. (Drying conditions are 150 ° C. × 10 seconds) Further, 50 g of hydrophobic oxide fine particles (product name “AEROSIL R812S” manufactured by Evonik Degussa, BET specific surface area: 220 m ² / g, primary particle average diameter: 7 nm) in 1000 mL of ethanol A coating solution is prepared by dispersing, and the coating solution is applied to the application surface of the heat seal lacquer by a bar coating method so that the weight is 0.3 g / m ² after drying, and then dried at 100 ° C. for about 10 seconds. Ethanol was evaporated to obtain a laminate for containers.

Example 7
A container laminate was obtained in the same manner as in Example 6 except that the average particle diameter of the acrylic resin beads was 20 μm and the blending amount of the acrylic resin beads in the heat seal lacquer was 8 parts by weight.

Example 8
One surface of a polyethylene terephthalate film (also referred to as PET film) having a thickness of 12 μm and one surface of an aluminum foil having a thickness of 15 μm are dry-laminated using an adhesive for polyurethane-based dry laminating (weight after drying: 3.5 g / m ² ). Pasted together. Furthermore, the other side of the PET film and one side of a 35 μm thick sealant film (formed by blending 5 parts by weight of acrylic resin beads (average particle size 30 μm) with 100 parts by weight of a blended resin solid content of polyethylene and polybutene), Were bonded by a dry laminating method using an adhesive for polyurethane dry laminating (weight after drying: 3.5 g / m ² ). Furthermore, 50 g of hydrophobic oxide fine particles (product name “AEROSIL R812S” manufactured by Evonik Degussa, BET specific surface area: 220 m ² / g, primary particle average diameter: 7 nm) are dispersed in 1000 mL of ethanol to prepare a coating solution. After coating the coating liquid on the other surface of the sealant film by a bar coating method so that the weight is 0.3 g / m ² after drying, the coating liquid is dried at 100 ° C. for about 10 seconds, the ethanol is evaporated, Obtained.

Example 9
A container laminate was obtained in the same manner as in Example 8 except that the amount of the acrylic resin beads was 10 parts by weight.

Example 10
A container laminate was obtained in the same manner as in Example 8 except that the blending amount of the acrylic resin beads was 20 parts by weight.

Example 11
One surface of a 15 μm thick aluminum foil (1N30, soft foil) and one surface of a polyethylene terephthalate film (also referred to as a PET film) having a thickness of 12 μm using a polyurethane dry laminate adhesive (weight after drying: 3.5 g / m ² ) Pasted together. Subsequently, the other surface of the aluminum foil was subjected to an anchor coat (main component: polyester resin; abbreviated as AC) treatment, and a low density polyethylene resin (abbreviated as LDPE) was extruded and laminated to a film thickness of 20 μm after drying. did. Further, a gravure hot melt coating was performed on the low density polyethylene so that the hot melt agent (35 parts by weight of wax, 35 parts by weight of rosin and 30 parts by weight of ethylene-vinyl acetate copolymer) was dried to a weight of 22 g / m ² . At this time, a large number of concavities and convexities are formed on the surface of the hot melt by continuously providing a number of cells each having a size of about 760 μm × width of about 760 μm × depth of about 150 μm on the surface of the gravure plate (gravure roll). )did. Subsequently, 50 g of hydrophobic oxide fine particles (product name “AEROSIL R812S” manufactured by Evonik Degussa, BET specific surface area: 220 m ² / g, primary particle average diameter: 7 nm) are dispersed in 1000 mL of ethanol to prepare a coating solution, This coating solution is applied to the hot melt coating surface by a bar coating method so that the weight after drying is 0.3 g / m ² , and then dried at 100 ° C. for about 10 seconds to evaporate ethanol, and the laminate for containers Got.

Example 12
The coating amount of the hot melt agent (35 parts by weight of wax, 35 parts by weight of rosin and 30 parts by weight of ethylene-vinyl acetate copolymer) was dried to a weight of 20 g / m ² and the surface of the gravure plate (gravure roll) A container laminate was obtained in the same manner as in Example 11, except that the cell size per cell was about 425 μm long × about 425 μm wide × about 160 μm deep.

Comparative Example 4
One surface of a polyethylene terephthalate film (also referred to as PET film) having a thickness of 12 μm and one surface of an aluminum foil having a thickness of 15 μm are dry-laminated using an adhesive for polyurethane-based dry laminating (weight after drying: 3.5 g / m ² ). Pasted together. Furthermore, the other surface of the PET film and one surface of a 35 μm-thick sealant film (made of a blended resin of polyethylene and polybutene) were coated with an adhesive for polyurethane-based dry lamination (weight after drying: 3.5 g / m ² ). The laminated body for containers was obtained by using and laminating by the dry laminating method.

Test example 3
<Adhesion test 2>
Using the container laminates of Examples 6 to 12 and Comparative Example 4, a four-side sealed bag-like container (with one side unsealed) having a width of 100 × 200 mm was prepared, and a commercially available yogurt (product name “delicious Caspian Sea” was prepared. "Soft yogurt, manufactured by Glico Dairy Co., Ltd.) 100g each, after standing for 1 hour, when the yogurt was dropped out of the container upside down, all the yogurt in the bag-like container of the example could be discharged. However, the yogurt adhered to almost the entire surface of the bag-like container of the comparative example and could not be completely discharged.

<Measurement of surface roughness, etc.>
Ten point average roughness Rz, cross-section curve maximum height Rmax, Pc of the adhesion surface of the hydrophobic oxide fine particles of the container laminates of Examples 6 to 12 and the sealant film surface of the container laminate of Comparative Example 4 (Peak count) was measured using a contact-type surface roughness meter (product name “SURFCOM1400D-12” manufactured by Tokyo Seimitsu Co., Ltd.). The ten-point average roughness Rz and the cross-section curve maximum height Rmax are defined in JIS B0601 (-1982). However, Rz and Rmax in the arbitrary X-axis direction on the measurement surface and in the Y-axis direction perpendicular to the X-axis were measured for each sample, and arithmetically averaged values were adopted. Further, the number of convex portions in the minute uneven state was calculated using the above-described formula 1. However, the value read directly from the cross-sectional curve was adopted as the value of Pc in Comparative Example 4. These results are shown in Table 3.

<Abrasion resistance test>
The adhesion surface of the hydrophobic oxide fine particles of the container laminates of Examples 6 to 12 and the sealant film surface of the container laminate of Comparative Example 4 were used as test surfaces, respectively. According to JIS K 5701-1), an abrasion resistance test was performed under the conditions of 100/500 reciprocations, a load of 200 g, and a mating material: chrome plating surface. After the abrasion resistance test, each test surface is fixed to a horizontal flat table with a clip, and a commercially available yogurt (product name “Delicious Caspian Sea” soft yogurt, 1 drop manufactured by Glico Dairy Co., Ltd .: approx. 0.4 g) is in close range. When the yogurt droplets fell down, the test was accepted. When the plate was tilted 90 degrees, it dropped and did not fall down. The results are shown in Table 3.

  As is apparent from the results in Table 3, it can be seen that good results can be obtained in the abrasion resistance test by imparting a certain uneven state to the adhesion surface. That is, it can be seen that non-adhesiveness is effectively maintained in the container of the present invention.

Claims (10)

A container for containing contents, and a coating made of a material for forming irregularities including filler particles and a resin component is applied to at least part or all of the surface of the container that comes into contact with the contents, Hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100 nm are attached on the surface, and the hydrophobic oxide fine particles form a porous layer having a three-dimensional network structure,
A non-adhesive container having a ten-point average roughness Rz of 7 to 500 μm and a cross-sectional curve maximum height Rmax of 12 to 1000 μm on the surface to which the hydrophobic oxide fine particles adhere . The non-adhesive container according to claim 1, wherein the adhesion amount of the hydrophobic oxide fine particles is 0.01 to 10 g / m ² . The non-adhesive container according to claim 1 or 2, wherein the content of the filler particles in the unevenness forming material is 1 to 80% by weight based on the weight of the solid content. The non-adhesive container according to any one of claims 1 to 3, wherein the hydrophobic oxide fine particles have a specific surface area of 50 to 300 m ² / g by BET method. The non-adhesive container according to any one of claims 1 to 4 , wherein the surface to which the hydrophobic oxide fine particles adhere is in a minute uneven state, and the number of convex portions is 50 to 100,000 / cm ² . The non-adhesive container according to claim 1 , wherein the hydrophobic oxide fine particles are hydrophobic silica. The non-adhesive container according to claim 6 , wherein the hydrophobic silica has a trimethylsilyl group on a surface thereof. The non-adhesive container according to any one of claims 1 to 7 , wherein the average particle diameter of the filled particles is 0.5 to 100 µm. A product in which the non-adhesive container according to claim 1 is filled with contents, and the contents are sealed with a lid. A method for producing a container for containing contents, wherein 1) a liquid or semi-solid unevenness forming material or a starting material thereof is applied in a layered manner on a surface to which hydrophobic oxide fine particles are adhered. A step of forming a concavo-convex surface having a point average roughness Rz of 7 to 500 μm and a cross-sectional curve maximum height Rmax of 12 to 1000 μm; 2) an average primary particle diameter of 3 to 3 on the concavo-convex surface; A method for producing a non-adhesive container, comprising a step of adhering 100 nm hydrophobic oxide fine particles.