JP7115055B2 - Liquid-repellent layer-forming resin composition, and liquid-repellent film, liquid-repellent laminate, packaging material, and container using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition for forming a liquid-repellent layer, and a liquid-repellent film, a liquid-repellent laminate, a packaging material and a container using the same.

2. Description of the Related Art Conventionally, packaging materials have been developed for many products such as foods, beverages, pharmaceuticals, and chemicals, depending on the contents of each product. In particular, as packaging materials for contents such as liquids, semi-solids, and gel substances, plastic materials are used which are excellent in water resistance, oil resistance, gas barrier properties, lightness, flexibility, and design.

In addition, as a packaging material for contents such as liquids, semi-solids, and gel-like substances, for the purpose of providing higher functionality, plastic laminates in which multiple types of plastic substrates are laminated, paper, metal foil, and inorganic materials are used. Composite laminates of materials and plastic substrates, composites obtained by treating plastic substrates with functional compositions, and the like have been proposed.

As one of the high functions described above, for example, a function to suppress adhesion of contents such as liquids, semi-solids, and gel substances to the inner surface of the packaging material, that is, to suppress the residue inside the packaging body is required. More specifically, lid materials for containers such as yogurt, jelly, and syrup; packaging materials for retort food such as porridge, soup, curry, and pasta sauce; Contents adhere to the inner surface of film materials for storage containers, and it is not possible to use up all the contents, resulting in waste. There is a demand for high liquid repellency that can suppress troublesome work.

In response to these demands, Patent Document 1, for example, proposes a water-repellent packaging material in which a silicone resin composition layer containing hydrophobic fine particles such as silicone particles is provided on the inner surface of the packaging material. Further, Patent Document 2 proposes a packaging material having a resin layer containing spherical silicon as the innermost layer and having water repellency and releasability for contents.

JP 2013-23224 A JP-A-8-337267

Polyolefin resins such as polyethylene and polypropylene are used as the material for the resin layer on the inner surface of the packaging material as a material that imparts functions such as heat sealability, heat resistance and impact resistance. However, the present inventors have found that when the above-described silicone particles are added to the polyolefin resin to impart liquid repellency, the silicone particles tend to separate from the resin layer and may migrate into the contents. This phenomenon is not limited to silicone particles, and can occur similarly when silicone other than particles is used. If the silicone migrates to the contents, there is a problem that impurities will be mixed in the contents and the function of suppressing the adhesion of the contents to the inner surface of the packaging material will not be exhibited sufficiently.

The present invention is based on the issues of the above -mentioned conventional technology, and can sufficiently suppress the transition of silicone to the contents and to suppress the adhesion of the contents. An object of the present invention is to provide a resin composition capable of forming a layer, and a liquid-repellent film, liquid-repellent laminate, packaging material and container using the same.

In order to achieve the above object, the present invention provides (A) a polyolefin resin, (B) silicone, and a site compatible with the (A) polyolefin resin and a site compatible with the (B) silicone ( C) Provide a resin composition for forming a liquid-repellent layer containing a compatibilizer.

According to the liquid-repellent layer-forming resin composition, by using (A) a polyolefin resin, (B) a silicone, and (C) a compatibilizer in combination, migration of the silicone to the contents can be sufficiently suppressed. In addition, it is possible to form a liquid-repellent layer capable of sufficiently suppressing adhesion of contents. When only (B) silicone is added to (A) polyolefin resin, (B) silicone is easily liberated from the formed liquid-repellent layer and easily migrates to the contents. On the other hand, by using (C) a compatibilizer together, the compatibility between (A) the polyolefin resin and (B) silicone can be enhanced, and the release of (B) silicone can be suppressed. The liquid layer can sufficiently suppress adhesion of the contents and sufficiently suppress migration of silicone to the contents. In addition, since (C) the compatibilizing agent has a site compatible with (B) silicone, this site can further improve the liquid repellency of the liquid repellent layer.

In the resin composition, the compatibilizing agent (C) contains a silylated polyolefin which is a graft copolymer or block copolymer of a polyolefin having the same polyolefin structure as the polyolefin resin (A) and silicone. You can stay. By including the silylated polyolefin, the formed liquid-repellent layer can more sufficiently suppress the migration of silicone to the contents, and can more sufficiently suppress the adhesion of the contents.

In the resin composition, the mass ratio of the content of the compatibilizer (C) to the content of the silicone (B) (mass of the compatibilizer (C)/mass of the silicone (B)) is 0.1. ~20. When this content ratio is within the above range, the formed liquid-repellent layer can more sufficiently suppress the migration of silicone to the contents and more sufficiently suppress the adhesion of the contents. be able to.

The present invention also provides a liquid-repellent film having a liquid-repellent layer formed using the resin composition for forming a liquid-repellent layer of the present invention. According to such a liquid-repellent film, by including the liquid-repellent layer formed using the resin composition for forming a liquid-repellent layer of the present invention, migration of silicone from the liquid-repellent layer to the contents is sufficiently suppressed. In addition, adhesion of contents to the liquid-repellent layer can be sufficiently suppressed. Moreover, the liquid-repellent film can exhibit good liquid repellency not only to water and oil, but also to oil-in-water dispersion type contents such as curry and pasta sauce.

The liquid-repellent film may further include one or more resin layers provided on one main surface of the liquid-repellent layer. By forming the liquid-repellent film into a multi-layered structure including a resin layer other than the liquid-repellent layer, it becomes possible to impart further functionality (heat resistance, impact resistance, etc.) in addition to the liquid repellency. In addition, it is possible to reduce the thickness of the liquid-repellent layer and reduce the cost.

When the liquid-repellent film has a resin layer other than the liquid-repellent layer, the melting point T1 (° C.) of the polyolefin resin (A) in the liquid-repellent layer and the liquid-repellent layer among the one or more resin layers The melting point T2 (° C.) of the resin contained in the adjacent resin layer may satisfy the relationship of T1<T2. By satisfying the above relationship, from the viewpoint of crystallinity, (B) silicone in the liquid-repellent layer can be suppressed from migrating to the second resin layer, and (B) silicone bleeds out to the surface of the liquid-repellent layer. efficiency can be improved, the liquid repellency can be further improved.

The present invention also provides a liquid-repellent laminate comprising a substrate and the liquid-repellent film of the present invention provided on the substrate, wherein the liquid-repellent layer is disposed on at least one outermost surface. provide the body According to such a liquid-repellent laminate, by providing the liquid-repellent film of the present invention, it is possible to sufficiently suppress the migration of silicone from the liquid-repellent layer of the liquid-repellent film to the contents, and Adhesion of contents to the liquid layer can be sufficiently suppressed. Further, by laminating the liquid-repellent film on a substrate having a desired function, the liquid-repellent laminate can be imparted with functions such as mechanical strength, barrier properties, and light-shielding properties.

The present invention also provides a packaging material formed using the liquid-repellent laminate of the present invention. According to such a packaging material, since it is formed using the liquid-repellent laminate of the present invention, migration of silicone from the liquid-repellent layer of the liquid-repellent laminate to the contents can be sufficiently suppressed. At the same time, adhesion of contents to the liquid-repellent layer can be sufficiently suppressed.

The packaging material may be used for applications where heat treatment at 80° C. or higher is performed. According to the packaging material according to the present embodiment, even when used for such purposes, it is possible to suppress the adhesion of the contents to the inner surface of the packaging material even after the heat treatment, and the liquid-repellent layer to the contents. migration of silicone can be suppressed.

The present invention further provides a container having, at least on its inner surface, a liquid-repellent layer formed using the resin composition of the present invention. Since such a container is provided with a liquid-repellent layer formed using the resin composition for forming a liquid-repellent layer of the present invention, migration of silicone from the liquid-repellent layer to the contents can be sufficiently suppressed. In addition, adhesion of contents to the liquid-repellent layer can be sufficiently suppressed.

According to the present invention, a resin composition capable of forming a liquid-repellent layer capable of sufficiently suppressing migration of silicone to contents and sufficiently suppressing adhesion of contents, and The used liquid-repellent film, liquid-repellent laminate, packaging material and container can be provided.

1 is a schematic cross-sectional view of a liquid-repellent laminate according to one embodiment of the present invention; FIG. 1 is a schematic cross-sectional view of a liquid-repellent laminate according to one embodiment of the present invention; FIG. It is a schematic diagram explaining the liquid-repellent evaluation method of a liquid-repellent laminated body. It is a schematic diagram explaining the liquid-repellent evaluation method of a liquid-repellent laminated body.

Preferred embodiments of the present invention will be described in detail below with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant explanations are omitted. Also, the dimensional ratios in the drawings are not limited to the illustrated ratios.

[Liquid-repellent laminate]
The liquid-repellent laminate according to the present embodiment comprises a substrate and a liquid-repellent film provided on the substrate, and has a structure in which a liquid-repellent layer is arranged on at least one outermost surface. is. 1 and 2 are schematic cross-sectional views of the liquid-repellent laminate according to this embodiment. In the liquid-repellent laminate according to the present embodiment, a liquid-repellent film 10 composed of a liquid-repellent layer 11 and a base material 14 are bonded together with an adhesive 13 interposed therebetween, like the liquid-repellent laminate 1 shown in FIG. It may have a laminated structure. Further, the liquid-repellent laminate according to the present embodiment, like the liquid-repellent laminate 2 shown in FIG. 14 may have a laminated structure with an adhesive 13 interposed therebetween. When the liquid-repellent film 10 includes the second resin layer 12 , the liquid-repellent film 10 is based on the second resin layer 12 such that the liquid-repellent layer 11 is the outermost surface of the liquid-repellent laminate 2 . It is arranged so as to face the material 14 .

<Liquid Repellent Layer 11>
The liquid repellent layer 11 is a layer having liquid repellency. The liquid-repellent layer 11 may be a layer capable of exhibiting heat-sealing properties by heating. Here, liquid repellency is a concept that includes both water repellency and oil repellency. Specifically, liquid repellency to liquid, semi-solid, or gel-like aqueous or oily materials. is. Aqueous or oily materials include water, oil, yogurt, jelly, pudding, syrup, porridge, soup, curry, foods such as pasta sauce, detergents such as hand soap and shampoo, pharmaceuticals, cosmetics, chemicals, and the like. . The heat-sealability is, for example, the property of being heat-sealable under the conditions of 100 to 200° C., 0.1 to 0.3 MPa, and 1 to 3 seconds. The heat-sealing conditions can be easily changed according to the conditions required for heat-sealing the liquid-repellent laminate.

The thickness of the liquid-repellent layer 11 is preferably 0.1 to 100 μm, more preferably 1 to 70 μm, even more preferably 3 to 50 μm, particularly preferably 5 to 30 μm. When the thickness of the liquid-repellent layer 11 is at least the above lower limit, there is a tendency that good liquid-repellency and heat-sealability can be easily obtained. On the other hand, when the thickness is equal to or less than the above upper limit, there is a tendency to suppress the migration of silicone from the liquid-repellent layer 11 to the contents, and it is possible to reduce the thickness of the liquid-repellent laminate as a whole. can.

The liquid-repellent layer 11 can be formed using a liquid-repellent layer-forming resin composition containing the following components. The resin composition for forming a liquid-repellent layer will be described below.

<Resin composition for liquid-repellent layer formation>
The resin composition for forming a liquid-repellent layer according to the present embodiment includes (A) a polyolefin resin (hereinafter also referred to as "(A) component"), (B) silicone (hereinafter also referred to as "(B) component"), and (C) a compatibilizer (hereinafter also referred to as "(C) component") having a site compatible with the (A) polyolefin resin and a site compatible with the (B) silicone.

((A) polyolefin resin)
The polyolefin resin is not particularly limited, and examples thereof include low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-α-olefin copolymer, homo-, block-, or random-polypropylene, propylene-α-olefin copolymer, and the like. . Examples of α-olefin components include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 4-methyl-1-pentene. The copolymer may be a random copolymer or a block copolymer. Besides the above, the polyolefin resin may be a cyclic polyolefin such as polynorbornene. Further, the polyolefin resin is preferably linear polyolefin from the viewpoint of sealing properties and strength physical properties (tensile strength, impact strength, etc.), and the linear polyolefin may be linear or branched.

When the liquid-repellent laminate is used as packaging materials such as retort food packaging materials that are subjected to heat treatment such as boiling in hot water, the polyolefin resin preferably contains polypropylene resin. When the polyolefin resin contains the polypropylene resin, it becomes easy to prevent the bag-shaped packaging material from breaking due to heat treatment such as boiling in hot water.

Examples of polypropylene resins include homopolypropylene, block polypropylene, random polypropylene, and copolymers of propylene and α-olefins other than ethylene and propylene as described above (propylene-based copolymers). Among these, the polypropylene resin preferably contains random polypropylene. By including random polypropylene, it becomes easy to prevent the bag-shaped packaging material from breaking due to heat, and in addition, there is a tendency that heat sealing at a low temperature in a short period of time becomes easy.

The melting point of the polyolefin resin can be appropriately adjusted depending on the end use. For example, for retort food packaging applications, the polyolefin resin preferably has a melting point of 130 to 170°C.

The polyolefin resin may be modified polyolefin modified with a predetermined acid. The modified polyolefin is obtained by graft-modifying a polyolefin with an unsaturated carboxylic acid derivative component derived from, for example, an unsaturated carboxylic acid, an acid anhydride of an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, or the like. Modified polyolefins such as hydroxyl-modified polyolefins and acrylic-modified polyolefins can also be used as polyolefin resins.

The above polyolefin resins may be used singly or in combination of two or more.

((B) silicone)
Silicone is a component that imparts liquid repellency to the liquid repellent layer 11 . Examples of silicone include silicone oil, silicone resin, silicone oligomer, and silicone powder. Among these, silicone oil is preferable because better liquid repellency can be easily obtained.

Examples of silicone oils include dimethylsilicone oil, methylphenylsilicone oil, methylhydrogensilicone oil, cyclic dimethylsilicone oil, alkyl-modified silicone oil, long-chain alkyl-modified silicone oil, and higher fatty acid-modified silicone oil.

Examples of silicone oil include products manufactured by Asahi Kasei Wacker Silicone Co., Ltd., products manufactured by Shin-Etsu Chemical Co., Ltd., products manufactured by Momentive Performance Materials, products manufactured by Dow Corning Toray Co., Ltd., and the like.

Examples of silicone resins include products manufactured by Shin-Etsu Chemical Co., Ltd., products manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and the like.

Examples of silicone oligomers include products manufactured by Shin-Etsu Chemical Co., Ltd., products manufactured by Dow Corning Toray Co., Ltd., and the like.

Examples of silicone powder include products manufactured by Shin-Etsu Chemical Co., Ltd., products manufactured by Dow Corning Toray Co., Ltd., and the like.

The above silicones can be used singly or in combination of two or more.

((C) compatibilizer)
The compatibilizer is a component having (A) a site that is compatible with the polyolefin resin and (B) a site that is compatible with the silicone. By using a compatibilizer, the compatibility between (A) the polyolefin resin and (B) the silicone can be improved.

(A) The site that is compatible with the polyolefin resin includes a polyolefin structure that is compatible with the (A) polyolefin resin. A) It is preferable that the site has the same polyolefin structure as that of the polyolefin resin. That is, when (A) the polyolefin resin is a polyethylene resin, the (C) compatibilizer preferably has a polyethylene structure, and when the (A) polyolefin resin is a polypropylene resin, the (C) compatibilizer has a polypropylene structure. It is preferred to have Further, when the (A) polyolefin resin is a copolymer consisting of two or more olefins such as an ethylene-α-olefin copolymer or a propylene-α-olefin copolymer, the (C) compatibilizer is It is preferable to have at least a structure obtained by polymerizing or copolymerizing an olefin of the same kind as the olefin constituting the main component among the olefins constituting the coalescence.

(B) The site compatible with silicone is preferably a site having a silicone structure.

From the viewpoint of further improving the compatibility between (A) the polyolefin resin and (B) the silicone, the (C) compatibilizer is a polyolefin having the same type of polyolefin structure as the (A) polyolefin resin, and a graft copolymer of the silicone. It preferably includes silylated polyolefins that are coalesced or block copolymers.

A silylated polyolefin is a polyolefin unit with a silicone moiety.

Examples of silylated polyolefins include products manufactured by Dow Corning Toray Co., Ltd. as PE-Si graft copolymers, Exfola manufactured by Mitsui Chemicals Fine Co., Ltd. as PE-Si block copolymers, and PP-Si graft copolymers. Products manufactured by Dow Corning Toray Co., Ltd., etc., can be mentioned as examples of coalescence.

As the silylated polyolefin, a graft copolymer is preferable to a block copolymer from the viewpoint of sufficiently suppressing migration of silicone from the liquid-repellent layer 11 to the contents. This is because the graft copolymer tends to bleed out from the liquid-repellent layer 11 more easily.

The above compatibilizers may be used singly or in combination of two or more.

The content of component (A) in the liquid-repellent layer-forming resin composition is preferably 50.0 to 99.9% by mass based on the total solid content of the liquid-repellent layer-forming resin composition. 0 to 99.0% by mass, more preferably 60.0 to 98.0% by mass. When the content of component (A) is at least the above lower limit, good heat-sealing properties tend to be obtained. On the other hand, if the content of the component (A) is less than the above upper limit, the content of the components (B) and (C) will be relatively increased, so that the liquid repellency tends to be easily improved.

The total content of components (B) and (C) in the liquid-repellent layer-forming resin composition is 0.1 to 50.0% by mass based on the total solid content of the liquid-repellent layer-forming resin composition. , more preferably 1.0 to 45.0% by mass, even more preferably 2.0 to 40.0% by mass. When the total content of the component (B) and the component (C) is at least the above lower limit, the liquid repellency tends to be improved. On the other hand, if the total content of the components (B) and (C) is less than the above upper limit, the content of the component (A) is relatively increased, so good heat sealability tends to be obtained. be.

In the liquid-repellent layer-forming resin composition, the mass ratio of the content of component (C) to the content of component (B) (mass of component (C)/mass of component (B)) is 0.01 to 50. , preferably 0.05 to 30, more preferably 0.1 to 20. When this content ratio is equal to or higher than the above lower limit, there is a tendency to more easily suppress migration of silicone from the liquid-repellent layer 11 to the contents. On the other hand, when the content ratio is equal to or less than the above upper limit, the amount of silicone on the surface of the liquid-repellent layer tends to increase, making it easier to obtain better liquid-repellency.

The liquid-repellent layer-forming resin composition may contain other additives, if necessary, to the extent that the liquid-repellent property is not impaired. Other additives include, for example, flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers, tackifiers, and the like.

The liquid-repellent layer 11 can be formed by forming a film from the liquid-repellent layer-forming resin composition.

<Second resin layer 12>
The second resin layer 12 is a layer provided between the liquid-repellent layer 11 and the substrate 14 in order to improve heat sealability, heat resistance, impact resistance, oxygen/water vapor barrier properties, and the like. The second resin layer 12 preferably contains a heat-sealable thermoplastic resin.

The thermoplastic resin used for the second resin layer 12 is not particularly limited, but polyolefin resin, ethylene-α,β unsaturated carboxylic acid copolymer or its esterified product or ionic crosslinked product, ethylene-vinyl acetate copolymer. or saponified products thereof, polyvinyl acetate or saponified products thereof, polycarbonate resins, thermoplastic polyester resins, ABS resins, polyacetal resins, polyamide resins, polyphenylene oxide resins, polyimide resins, polyurethane resins, polylactic acid resins, furan resins, and silicone resins etc. These thermoplastic resins can be used singly or in combination of two or more.

The thermoplastic resin used for the second resin layer 12 preferably contains a polyolefin resin, since heat sealability, heat resistance, and impact resistance are likely to be improved. The same polyolefin resin as (A) polyolefin resin used for the liquid-repellent layer 11 can be used as the polyolefin resin.

When the second resin layer 12 is in contact with the liquid-repellent layer 11, the melting point T1 (°C) of the (A) polyolefin resin in the liquid-repellent layer 11 and the melting point of the thermoplastic resin in the second resin layer 12 T2 (° C.) preferably satisfies the relationship of T1<T2. By satisfying the above relationship, from the viewpoint of crystallinity, (B) silicone in the liquid-repellent layer 11 can be suppressed from migrating to the second resin layer 12, and (B) silicone to the surface of the liquid-repellent layer 11 can be suppressed. Since the bleed-out efficiency can be improved, there is a tendency that the liquid repellency can be further improved. From the same point of view, the melting point T2 is preferably higher than the melting point T1 by 1°C or more, more preferably by 3°C or more.

The thickness of the second resin layer 12 can be appropriately set according to the end use of the product using the present liquid-repellent layer-forming resin composition. The thickness of the second resin layer 12 is, for example, preferably 0.1 to 300 μm, more preferably 1 to 200 μm, even more preferably 5 to 150 μm, and 10 to 100 μm. is particularly preferred.

<Liquid repellent film 10>
A liquid-repellent film 10 having liquid-repellency is formed by the above-described liquid-repellent layer 11 single layer or two layers of the liquid-repellent layer 11 and the second resin layer 12 . The liquid-repellent film 10 is formed so as to cover part or all of the surface of the substrate 14 . Depending on the application, the liquid-repellent film 10 may be used alone without being laminated with the base material 14 .

The liquid-repellent film 10 may further include one or more resin layers other than the liquid-repellent layer 11 and the second resin layer 12 . The composition of the other resin layer may be the same as or different from the composition of the second resin layer 12 .

<Base material 14>
The base material 14 is not particularly limited as long as it can serve as a support, and examples thereof include paper, resin film, metal foil, and the like. Examples of paper include woodfree paper, special woodfree paper, coated paper, art paper, cast-coated paper, imitation paper, and kraft paper. Examples of resin films include polyolefins (e.g., polyethylene (PE), polypropylene (PP), etc.), acid-modified polyolefins, polyesters (e.g., polyethylene terephthalate (PET), etc.), polyamides (PA), polyvinyl chloride (PVC), cellulose acetate, A film containing at least one type of cellophane resin is included. This film may be a stretched film or a non-stretched film. Examples of metal foil include aluminum foil and nickel foil. The base material 14 may be a laminate of a plurality of base materials made of different materials.

The thickness of the base material 14 is not particularly limited, and can be appropriately adjusted depending on the application.

Examples of a method for bonding the base material 14 and the liquid-repellent film 10 include, but are not limited to, a lamination method using an adhesive and a lamination method using a heat treatment, as described below.

(Lamination method with adhesive)
As a lamination method using an adhesive, various known lamination methods such as dry lamination, wet lamination, and non-solvent lamination can be used. Examples of the adhesive 13 used in these lamination methods include the following.

<Adhesive 13>
The adhesive 13 bonds the liquid-repellent film 10 and the substrate 14 together. Examples of the adhesive 13 include a polyurethane resin obtained by reacting a base material such as polyester polyol, polyether polyol, acrylic polyol, or carbonate polyol with a bifunctional or higher isocyanate compound. The various polyols mentioned above can be used singly or in combination of two or more.

For the purpose of promoting adhesion, the adhesive 13 may further contain a carbodiimide compound, an oxazoline compound, an epoxy compound, a phosphorus compound, a silane coupling agent, or the like in addition to the polyurethane resin described above.

Moreover, according to the performance required for the adhesive 13, the polyurethane resin described above may be blended with various other additives and stabilizers.

The thickness of the adhesive 13 is not particularly limited, but is preferably 1 to 10 μm, more preferably 3 to 7 μm, from the viewpoint of obtaining desired adhesive strength, conformability, workability, and the like.

(Lamination method by heat treatment)
As a lamination method by heat treatment, the following methods are roughly exemplified.
(1) A method of extrusion laminating the liquid-repellent film 10 formed in advance onto the substrate 14 together with an adhesive resin.
(2) A method of extrusion laminating a resin layer and an adhesive resin constituting the liquid-repellent film 10 onto the substrate 14 .
(3) A method of bonding the laminated base material obtained by the above method (1) or (2) by further heating and pressurizing with a hot roll.
(4) A method of storing the laminated base material obtained by the above method (1) or (2) in a high-temperature atmosphere, or passing it through a drying/baking furnace in a high-temperature atmosphere.

Examples of the adhesive resin used in the lamination method using heat treatment include acid-modified polyolefin. In the above method, the substrate 14 and the liquid-repellent film 10 are laminated by extrusion lamination. It is also possible to laminate the liquid-repellent film 10 by heat treatment after coating and forming on 14 .

In addition, it is possible to provide an adhesive primer (anchor coat) on the base material 14, and the materials thereof include polyester, polyurethane, polyallylamine, polyethyleneimine, polybutadiene, and ethylene-vinyl acetate copolymer. It is possible to use coalescence, chlorine-vinyl acetate, and the like, and if necessary, the various curing agents and additives described above that can be used as the adhesive 13 may be blended.

[Packaging material]
The packaging material according to this embodiment is formed using the liquid-repellent laminate described above. Specific examples of packaging materials include container lids for yogurt, jelly, syrup, and the like, and retort pouches for porridge, soup, curry, pasta sauce, and the like. By forming the packaging material so that the liquid-repellent layer is arranged on the inner surface (contents side) of the packaging material, it is possible to suppress the adhesion and residue of contents such as liquids, semi-solids, and gel-like substances on the inner surface of the packaging material. In addition, migration of silicone from the liquid-repellent layer to the contents can be suppressed. In addition, in a bag-shaped packaging material such as a retort food packaging material, blocking between the innermost layers of the packaging material may make it difficult to discharge the contents, but according to the packaging material according to the present embodiment, , the liquid-repellent layers, which are the innermost layers, are unlikely to block each other, and the contents can be discharged efficiently.

The packaging material may be used for applications where heat treatment at 80° C. or higher is performed. Specifically, it may be used for packaging materials such as retort food packaging materials that are subjected to heat treatment such as boiling in hot water. According to the packaging material according to the present embodiment, even when used for such purposes, it is possible to suppress the adhesion and residue of the contents on the inner surface of the packaging material even after the heat treatment, and the liquid-repellent layer separates the contents from the liquid-repellent layer. It is possible to suppress the transfer of silicone to objects.

[container]
The container according to the present embodiment is a container having at least the inner surface (on the content side) a liquid-repellent layer formed using the liquid-repellent layer-forming resin composition described above. Specific examples of containers include storage containers for liquids such as chemicals and pharmaceuticals, semi-solids, and gel-like substances, and bottles for containing hand soaps, shampoos, and the like. By forming the container so that the liquid-repellent layer is arranged on the inner surface of the container (on the content side), it is possible to suppress the adhesion and residue of contents such as liquids, semi-solids, and gel-like substances on the inner surface of the container. In addition, migration of silicone from the liquid-repellent layer to the contents can be suppressed.

EXAMPLES The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples.

[Example 1]
<Preparation of resin composition for forming liquid-repellent layer>
Linear low-density polyethylene (LLDPE, trade name “Evolue”, manufactured by Prime Polymer Co., Ltd.) as component (A), and silicone oil (dimethyl silicone, manufactured by Dow Corning Toray Co., Ltd.) as component (B), A resin composition for forming a liquid-repellent layer was prepared by mixing the component (C) with a PE-Si-PE triblock copolymer (trade name: "EXFORA", manufactured by Mitsui Chemicals & Fine Chemicals, Inc.). The content of the components is 1% by mass of component (B), 0.05% by mass of component (C), and the balance is (A ) was adjusted to be a component.

<Preparation of liquid-repellent laminate>
Using a three-layer co-extrusion machine, the liquid-repellent layer-forming resin composition was extruded into a film to obtain a liquid-repellent film having a liquid-repellent layer with a thickness of 100 μm. The resulting liquid-repellent film and a 38 μm-thick PET film (trade name “EMBRET”, manufactured by Unitika Ltd.) as a substrate were dried using a polyurethane adhesive (manufactured by Mitsui Chemicals, Inc.). It was laminated and aged at 50° C. for 5 days to obtain a liquid-repellent laminate.

[Examples 2 to 21]
The types of components (A), (B) and (C) in the liquid-repellent layer-forming resin composition, and the contents of components (B) and (C) (the content of component (A) is (remainder)) was changed as shown in Table 1 to prepare a liquid-repellent layer-forming resin composition, a liquid-repellent film, and a liquid-repellent laminate in the same manner as in Example 1.

[Example 22]
<Preparation of resin composition for forming liquid-repellent layer>
Formation of a liquid-repellent layer in the same manner as in Example 1 except that the contents of components (B) and (C) (the content of component (A) is the remainder) as shown in Table 1 A resin composition for

<Preparation of liquid-repellent laminate>
A linear low-density polyethylene (LLDPE, trade name “Evolue”, manufactured by Prime Polymer Co., Ltd.), which is the component (A), was used as the resin composition for forming the second resin layer. Using a three-layer co-extrusion machine, the liquid-repellent layer-forming resin composition and the second resin layer-forming resin composition are co-extruded to form a film, forming a liquid-repellent layer with a thickness of 15 μm and a second resin composition with a thickness of 85 μm. A liquid-repellent film consisting of a resin layer was obtained. The second resin layer of the obtained liquid-repellent film and a PET film with a thickness of 38 μm (trade name “EMBRET”, manufactured by Unitika Ltd.) as a base material are bonded together with a polyurethane adhesive (Mitsui Chemicals, Inc. (manufactured) to obtain a liquid-repellent laminate.

[Examples 23 to 45 and Comparative Examples 1 to 6]
The types of components (A), (B) and (C) in the liquid-repellent layer-forming resin composition, and the contents of components (B) and (C) (the content of component (A) is The rest of the resin for forming the liquid-repellent layer) and the type of the component (A) in the resin composition for forming the second resin layer were changed as shown in Table 1, in the same manner as in Example 1. A composition, a resin composition for forming a second resin layer, a liquid-repellent film, and a liquid-repellent laminate were prepared.

Details of each component in Table 1 are as follows. "-" in Table 1 means that the corresponding component was not used. Table 1 also shows the mass ratio of the content of component (C) to the content of component (B) in the liquid-repellent layer (mass of component (C)/mass of component (B)). Further, Table 1 shows the melting point T1 (°C) of the resin that is the component (A) used in the liquid-repellent layer and the melting point T2 (°C) of the resin that is the component (A) used in the second resin layer. shows the magnitude relationship between

[(A) polyolefin resin]
A1: Linear low-density polyethylene (LLDPE), trade name “Evolue”, melting point 116°C, manufactured by Prime Polymer Co., Ltd. A2: Propylene-ethylene random copolymer, trade name “Prime Polypro”, melting point 134°C, Co., Ltd. Prime Polymer A3: Propylene-ethylene block copolymer, trade name "Novatec", melting point 165-166°C, Japan Polypropylene Corporation A4: Linear low-density polyethylene (LLDPE), trade name "Novatec LL", melting point 122°C, manufactured by Japan Polyethylene Co., Ltd.

[(B) Silicone]
B1: Silicone oil (dimethyl silicone), Dow Corning Toray Co., Ltd. B2: Silicone oil (alkyl-modified silicone), Tanak Co., Ltd.

[(C) Compatibilizer]
C1: PE-Si-PE triblock copolymer, trade name “Exfola”, manufactured by Mitsui Chemicals Fine Co., Ltd. C2: PP-Si graft copolymer, manufactured by Dow Corning Toray Co., Ltd. C3: PE-Si graft copolymer, manufactured by Dow Corning Toray Co., Ltd.

[Evaluation of liquid repellency]
<Examples 1 to 34 and Comparative Examples 1 to 6: Liquid repellency without heat treatment>
Liquid repellency was evaluated without heat treatment by the method shown in FIG. First, a sample 100 obtained by cutting the liquid-repellent laminates obtained in Examples 1 to 34 and Comparative Examples 1 to 6 into a length of 210 mm × width of 300 mm was cut into a sample 100 of length 210 mm × width 150 mm so that the liquid-repellent layer was inside. Folded in two to size (see (a) in FIG. 3), one side of the vertical end and one side of the horizontal end (the side opposite to the folded side) were sealed with a heat sealer at 190 C., 0.03 MPa, 2 sec, and heat-sealed over a width of 10 mm to form a sealed portion 51 to produce a pouch having one side open in the longitudinal direction (see FIG. 3(b)). Next, 100 g of salad oil 52 (trade name “Nissin Salad Oil” manufactured by Nisshin OilliO Co., Ltd.) was injected from the opening of the pouch (see FIG. 3(c)). After that, the opening was heat-sealed with a heat sealer over a width of 10 mm under conditions of 190° C., 0.03 MPa, and 2 sec to form a sealed portion 51, thereby sealing the pouch (see FIG. 3(d)). A corner portion of the sealed pouch with a folded side was cut into a triangular portion measuring 3 cm long by 3 cm wide, excluding the seal portion 51, to form a spout (see FIG. 3(e)). . Hold the corner 53 diagonally from the spout, hold the pouch upside down for 30 seconds, discharge the salad oil 52 into the container 56, and weigh the discharge amount with a scale 57 (see (f) in FIG. 3). ). From the weighed discharge amount, the residual liquid amount (%) was determined by the following formula.
Remaining liquid amount (%) = {(100-discharged amount) / 100} x 100
The measurement was performed 3 times, and the liquid repellency was evaluated according to the following evaluation criteria from the average residual liquid amount of 3 times. Table 2 shows the average residual liquid amount (%) and the evaluation results of the liquid repellency.
◎: average residual liquid amount is less than 2.0% ○: average residual liquid amount is 2.0% or more and less than 2.5% △: average residual liquid amount is 2.5% or more and less than 3.0% ×: average residual liquid amount Liquid volume is 3.0% or more

<Examples 31, 35 to 45: Liquid repellency after hot water bath treatment>
The liquid repellency after the hot water bath treatment was evaluated by the method shown in FIG. First, two samples 200 were prepared by cutting the liquid-repellent laminates obtained in Examples 31 and 35 to 45 into a length of 210 mm and a width of 150 mm. Two samples 200 were stacked so that the respective liquid-repellent layers were on the inside, and one vertical edge and two horizontal edges were sealed with a heat sealer at 190° C. at 0.03 MPa for 2 seconds. The pouch was heat-sealed over a width of 10 mm under the conditions to form a sealed portion 51, and a pouch having one longitudinal end open was produced (see FIG. 4(a)). Next, 100 g of oil-in-water dispersion type liquid 54 (trade name “Bon Curry”, manufactured by Otsuka Foods Co., Ltd.) was injected from the opening of the pouch (see FIG. 4(b)). Thereafter, the opening was heat-sealed with a heat sealer over a width of 10 mm under the conditions of 190° C., 0.03 MPa, and 2 sec to form a sealed portion 51, thereby sealing the pouch (see FIG. 4(c)). After the sealed pouch was subjected to a hot water bath at 100° C. for 5 minutes, the top of the sealed pouch was immediately cut to form a spout (see FIG. 4(d)). Next, holding the seal portion 51 on the opposite side of the spout, the pouch was turned upside down and held for 30 seconds, the oil-in-water dispersion liquid 54 was discharged into the container 56, and the discharged amount was weighed by the scale 57 (Fig. 4). (e)). From the weighed discharge amount, the residual liquid amount (%) was determined by the following formula.
Remaining liquid amount (%) = {(100-discharged amount) / 100} x 100
The measurement was performed 3 times, and the liquid repellency was evaluated according to the following evaluation criteria from the average residual liquid amount of 3 times. Table 2 shows the average residual liquid amount (%) and the evaluation results of the liquid repellency.
◎: Average residual liquid amount is less than 8.0% ○: Average residual liquid amount is 8.0% or more and less than 10.0% △: Average residual liquid amount is 10.0% or more and less than 13.0% ×: Average residual liquid amount Liquid volume is 13.0% or more

[Appearance evaluation]
In the liquid repellency evaluation, the behavior of the liquid discharged from the pouch was visually observed, and the external appearance was evaluated according to the following evaluation criteria. Table 2 shows the results.
◯: Appearance of repelling the liquid, little adhesion to the liquid-repellent laminate.
Δ: Appears to repel the liquid, but adheres to the liquid-repellent laminate.
x: A state of repelling the liquid is not observed.

[Silicone migration evaluation]
The amount of Si on the surface of the liquid-repellent layer in the liquid-repellent laminate before the liquid-repellent evaluation was measured in advance by X-ray photoelectron spectroscopy (XPS). Next, the surface of the liquid-repellent layer in the liquid-repellent laminate after the liquid-repellent evaluation was wiped with isopropyl alcohol, and the amount of Si on the surface of the liquid-repellent layer was measured by XPS. Using the obtained measurement results, the transfer rate of Si from the liquid-repellent layer to the liquid in the pouch was calculated by the following calculation method.
Si migration rate (%) = [1-{Si amount (atm%) after liquid repellency evaluation/Si amount (atm%) before liquid repellency evaluation}] × 100
From the obtained Si transfer rate, the silicone transfer property was evaluated according to the following evaluation criteria. Table 2 shows the Si migration rate (%) and the evaluation results of the silicone migration property. Moreover, the measurement conditions of XPS are shown below. In Example 31, both the liquid repellency without heat treatment and the liquid repellency after the hot water bath treatment were evaluated, but the Si migration rate was the same after both liquid repellency evaluations. .
○: Si transfer rate is 5% or less △: Si transfer rate is more than 5% and 30% or less ×: Si transfer rate is more than 30% <XPS measurement conditions>
Device name: JPS-9010MX (manufactured by JEOL Ltd.)
Analysis area: 3mm x 5mm
X-ray source: MgKα rays

As is clear from the results shown in Table 2, according to the liquid repellent laminates of Examples 1 to 45, the liquid repellency was improved while suppressing the migration of silicone from the liquid repellent layer to the contents. was confirmed to be possible.

In addition, from a comparison of Examples 1 to 3 and 5 with other examples, it was found that when the mass ratio of component (C)/component (B) was 0.1 or more, Si from the liquid-repellent layer to the contents It can be seen that there is a tendency that the migration of Further, from a comparison of Examples 6 to 10 with other examples, it can be seen that liquid repellency tends to be further improved when the mass ratio of component (C)/component (B) is 20 or less. .

From the evaluation results of Examples 22 to 34, when the melting point T1 of the resin in the liquid repellent layer and the melting point T2 of the resin in the second resin layer satisfy the relationship of T1<T2, the liquid repellency tends to be further improved. It turns out that there is

From the evaluation results of Examples 31 and 35 to 45, the graft copolymers of polyolefin and silicone (C2 and C3) are higher than the block copolymer (C1) of polyolefin and silicone as the component (C). It can be seen that there is a tendency that the migration of silicone after the hot water bath treatment can be more suppressed when using .

Incidentally, when the component (C) was not added as in Comparative Examples 1 and 2, the release of silicone from the liquid-repellent layer could not be suppressed, and the migration of silicone to the contents easily occurred. It was found that good liquid repellency could not be obtained. Moreover, it was found that when the component (B) was not added as in Comparative Examples 3 to 6, the silicone did not bleed out on the surface of the liquid repellent layer, and sufficient liquid repellency was not obtained.

DESCRIPTION OF SYMBOLS 1, 2... Liquid-repellent laminated body 11... Liquid-repellent layer 12... Second resin layer 13... Adhesive 14... Base material 51... Seal part 52... Salad oil 53... Corner part 54... Oil-in-water dispersion type liquid, 56... container, 57... scale, 100, 200... sample for evaluation of liquid-repellent laminate.

Claims (15)

Liquid-repellent layer formation comprising (A) a polyolefin resin, (B) silicone, and (C) a compatibilizer having a site compatible with the (A) polyolefin resin and a site compatible with the (B) silicone A resin composition for
The (C) compatibilizer comprises a polyolefin having the same polyolefin structure as the (A) polyolefin resin and a silylated polyolefin that is a graft copolymer or block copolymer with silicone,
A resin composition for forming a liquid-repellent layer, wherein the graft copolymer is a PE-Si graft copolymer . The mass ratio of the content of the compatibilizer (C) to the content of the silicone (B) (mass of the compatibilizer (C)/mass of the silicone (B)) is 0.1 to 20. 1. The resin composition according to 1. A liquid-repellent film comprising a liquid-repellent layer formed using the resin composition according to claim 1 or 2 . For forming a liquid-repellent layer containing (A) a polyolefin resin, (B) silicone, and (C) a compatibilizer having a site compatible with the (A) polyolefin resin and a site compatible with the (B) silicone Equipped with a liquid-repellent layer formed using a resin composition,
A liquid-repellent film, wherein the liquid-repellent layer has a thickness of 0.1 to 100 μm. 5. The compatibilizing agent (C) according to claim 4, wherein the polyolefin having the same polyolefin structure as the polyolefin resin (A) and a silylated polyolefin which is a graft copolymer or block copolymer of silicone. liquid-repellent film. The mass ratio of the content of the compatibilizer (C) to the content of the silicone (B) (mass of the compatibilizer (C)/mass of the silicone (B)) is 0.1 to 20. 6. The liquid-repellent film according to 4 or 5. The liquid-repellent film according to any one of claims 3 to 6 , further comprising one or more resin layers provided on one surface of said liquid-repellent layer. The melting point T1 (°C) of the (A) polyolefin resin in the liquid-repellent layer and the melting point T2 (°C) of the resin contained in the resin layer in contact with the liquid-repellent layer among the one or more resin layers are The liquid-repellent film according to claim 7 , which satisfies the relationship of T1<T2. For forming a liquid-repellent layer containing (A) a polyolefin resin, (B) silicone, and (C) a compatibilizer having a site compatible with the (A) polyolefin resin and a site compatible with the (B) silicone A liquid-repellent film comprising a liquid-repellent layer formed using a resin composition,
Further comprising one or more resin layers provided on one surface of the liquid-repellent layer,
The melting point T1 (°C) of the (A) polyolefin resin in the liquid-repellent layer and the melting point T2 (°C) of the resin contained in the resin layer in contact with the liquid-repellent layer among the one or more resin layers are A liquid-repellent film that satisfies the relationship of T1<T2. 10. The compatibilizing agent (C) according to claim 9, wherein the polyolefin having the same polyolefin structure as the polyolefin resin (A) and a silylated polyolefin that is a graft copolymer or block copolymer with silicone. liquid-repellent film. The mass ratio of the content of the compatibilizer (C) to the content of the silicone (B) (mass of the compatibilizer (C)/mass of the silicone (B)) is 0.1 to 20. 11. The liquid-repellent film according to 9 or 10. A substrate, and the liquid-repellent film according to any one of claims 3 to 11 provided on the substrate, wherein the liquid-repellent layer is disposed on at least one outermost surface, Liquid-repellent laminate. A packaging material formed using the liquid-repellent laminate according to claim 12 . 14. The packaging material according to claim 13 , which is used for applications where heat treatment at 80[deg.] C. or higher is applied. A container having, at least on its inner surface, a liquid-repellent layer formed using the resin composition according to claim 1 or 2 .

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