JP2019214692A - Resin composition for forming liquid-repellent layer, and liquid-repellent film, liquid-repellent laminate, packaging material and container including the same - Google Patents

Abstract

To provide a resin composition that can form a liquid-repellent layer that can sufficiently suppress migration of silicone into its contents and also sufficiently suppress the attachment of the contents.SOLUTION: A resin composition for forming a liquid-repellent layer contains (A) a polyolefin resin, (B) silicone, and a (C) compatibilizer having a site compatible with (A) polyolefin resin and a site compatible with (B) silicone.SELECTED DRAWING: Figure 1

Description

  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 corresponding to the contents of many products such as foods, beverages, pharmaceuticals, and chemicals have been developed. In particular, plastic materials excellent in water resistance, oil resistance, gas barrier properties, light weight, flexibility, design, etc. are used as packaging materials for contents such as liquids, semi-solids, and gel substances.

  In addition, as a packaging material for contents such as liquids, semi-solids, and gel-like substances, for the purpose of providing higher functionality, a plastic laminate in which a plurality of types of plastic base materials are laminated, paper, metal foil, inorganic A composite laminate of a material or the like and a plastic substrate, and a composite obtained by treating a plastic substrate with a functional composition have been proposed.

  As one of the above-mentioned high functions, for example, a function of suppressing the adhesion of contents such as liquids, semi-solids, and gel-like substances to the inner surface of the packaging material, that is, the function of suppressing the remaining inside the package is required. More specifically, containers for yogurt, jelly, syrup, etc., retort food packaging materials such as porridge, soup, curry, pasta sauce, liquids such as chemicals and pharmaceuticals, semi-solids, gels, etc. For film materials for storage containers, etc., the contents adhere to the inner surface, and the contents cannot be used up completely, resulting in waste, contamination caused by the contents, and the contents being discharged. There is a demand for high liquid repellency capable of suppressing labor.

  In response to these requirements, for example, Patent Document 1 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. Patent Document 2 proposes a packaging material having water repellency and releasability with a resin layer added with spherical silicon as the innermost layer.

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

  As a material for the resin layer on the inner surface of the packaging material, a polyolefin resin such as polyethylene or polypropylene is used as a material that imparts functions such as heat sealing properties, heat resistance, and impact resistance. However, the present inventors have found that when the above-described silicone particles are added to a polyolefin resin to impart liquid repellency, the silicone particles are easily released from the resin layer and may be transferred to the contents. This phenomenon is not limited to the silicone particles, but can also occur when silicone other than the particles is used. When the silicone is transferred to the contents, impurities are mixed into the contents, and the function of suppressing the adhesion of the contents to the inner surface of the packaging material is not sufficiently exhibited.

  The present invention has been made in view of the above-mentioned problems of the related art, and has a liquid-repellent property that can sufficiently suppress the migration of silicone to the content and sufficiently suppress the adhesion of the content. It is an object to provide a resin composition capable of forming a layer, and a liquid-repellent film, a liquid-repellent laminate, a packaging material, and a container using the same.

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

  According to the resin composition for forming a liquid-repellent layer, the use of the polyolefin resin (A), the silicone (B), and the compatibilizer (C) sufficiently suppresses migration of the silicone to the contents. And a liquid-repellent layer capable of sufficiently suppressing the adhesion of contents can be formed. When only (B) silicone is added to (A) polyolefin resin, (B) silicone is easily released from the formed liquid-repellent layer and easily transferred to the contents. On the other hand, by using (C) a compatibilizing agent in combination, the compatibility between (A) the polyolefin resin and (B) silicone can be increased, and (B) the release of silicone can be suppressed. The liquid layer can sufficiently suppress the adhesion of the content and can sufficiently suppress the transfer of silicone to the content. Further, since the compatibilizer (C) has a portion compatible with the silicone (B), the liquid repellency of the liquid repellent layer can be further improved by this portion.

  In the resin composition, the (C) compatibilizer includes a silylated polyolefin that is a graft copolymer or a block copolymer of a polyolefin having the same polyolefin structure as the (A) polyolefin resin and a silicone. You may go out. By containing the silylated polyolefin, the formed liquid-repellent layer can more sufficiently suppress the transfer of silicone to the contents and can also more sufficiently suppress the adhesion of the contents.

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

  The present invention also provides a lyophobic film provided with a lyophobic layer formed using the above-mentioned resin composition for forming a lyophobic layer of the present invention. According to such a liquid-repellent film, by providing the liquid-repellent layer formed by using the resin composition for forming a liquid-repellent layer of the present invention, the transfer of silicone from the liquid-repellent layer to the contents is sufficiently suppressed. And the adhesion of the contents to the liquid-repellent layer can be sufficiently suppressed. Moreover, according to the said liquid repellent film, favorable liquid repellency can be expressed not only with water and oil but with respect to oil-in-water-dispersed 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. When the liquid repellent film has a multilayer structure including a resin layer other than the liquid repellent layer, it is possible to impart further functionality (heat resistance, impact resistance, etc.) in addition to liquid repellency. In addition, the liquid repellent layer can be thinned, and the cost can be reduced.

  When the liquid-repellent film includes 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 contacting resin layer may satisfy the relationship of T1 <T2. By satisfying the above relationship, from the viewpoint of crystallinity, migration of (B) silicone in the liquid repellent layer to the second resin layer can be suppressed, and bleed out of (B) silicone to the surface of the liquid repellent layer. Can be improved, so that 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 body. According to such a liquid-repellent laminate, by providing the liquid-repellent film of the present invention, the migration of silicone from the liquid-repellent layer of the liquid-repellent film to the content can be sufficiently suppressed, and the liquid-repellent film can be sufficiently repelled. Adhesion of contents to the liquid layer can be sufficiently suppressed. Further, by laminating a liquid repellent film with a base material having a desired function, functions such as mechanical strength, barrier property, and light shielding property can be imparted to the liquid repellent laminate.

  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, it is possible to sufficiently suppress the transfer of silicone from the liquid-repellent layer of the liquid-repellent laminate to the contents. At the same time, adhesion of contents to the liquid repellent layer can be sufficiently suppressed.

  The above-mentioned packaging material may be used for the purpose of performing a heat treatment at 80 ° C. or higher. According to the packaging material according to the present embodiment, even when used for such a purpose, adhesion of the content to the inner surface of the packaging material can be suppressed even after the heat treatment, and the content from the liquid-repellent layer to the content can be reduced. Transfer of silicone can be suppressed.

  The present invention further provides a container having a liquid-repellent layer formed at least on the inner surface by using the resin composition of the present invention. According to such a container, since the liquid repellent layer formed using the resin composition for forming a liquid repellent layer of the present invention is provided, it is possible to sufficiently suppress the transfer of silicone from the liquid repellent layer to the contents. And the adhesion of the 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 the content and sufficiently suppressing adhesion of the content, and The used liquid-repellent film, liquid-repellent laminate, packaging material and container can be provided.

It is an outline sectional view of the lyophobic layered product concerning one embodiment of the present invention. It is an outline sectional view of the lyophobic layered product concerning one embodiment of the present invention. 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.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

[Liquid repellent laminate]
The liquid-repellent laminate according to this embodiment includes a base material and a liquid-repellent film provided on the base material, and has a structure in which the liquid-repellent layer is disposed on at least one outermost surface. It 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 this embodiment, a liquid repellent film 10 composed of a liquid repellent layer 11 and a base material 14 are interposed via an adhesive 13 as in the liquid repellent laminate 1 shown in FIG. It may have a laminated structure. In addition, the liquid repellent laminate according to the present embodiment includes a liquid repellent film 10 composed of a liquid repellent layer 11 and a second resin layer 12, and a substrate, like the liquid repellent laminate 2 shown in FIG. 14 may have a structure laminated 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 so that the liquid repellent layer 11 is the outermost surface of the liquid repellent laminate 2. It arrange | positions so that the material 14 may be opposed.

<Liquid repellent layer 11>
The liquid repellent layer 11 is a layer having liquid repellency. The liquid repellent layer 11 may be a layer that can exhibit heat sealability by heating. Here, the liquid repellency is a concept including both water repellency and oil repellency characteristics. Specifically, the liquid repellency is a characteristic of liquid repellency to a liquid, semi-solid or gel aqueous or oily material. It is. Examples of water-based or oil-based materials include water, oil, yogurt, jelly, pudding, syrup, rice cake, soup, curry, pasta sauce and other foods, hand soap, shampoo and other detergents, pharmaceuticals, cosmetics and chemicals. . The heat sealability refers to, for example, a property that can be heat-sealed under 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 from 0.1 to 100 μm, more preferably from 1 to 70 μm, further preferably from 3 to 50 μm, and particularly preferably from 5 to 30 μm. When the thickness of the liquid repellent layer 11 is equal to or more than the above lower limit value, good liquid repellency and heat sealability tend to be easily obtained. On the other hand, when the thickness is equal to or less than the upper limit, migration of silicone from the liquid-repellent layer 11 to the content tends to be easily suppressed, and the thickness of the entire liquid-repellent laminate can be reduced. it can.

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

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

((A) polyolefin resin)
The polyolefin resin is not particularly limited, and includes, for example, 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 the α-olefin component 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. In addition to the above, the polyolefin resin may be a cyclic polyolefin such as polynorbornene. The polyolefin resin is preferably a linear polyolefin from the viewpoint of sealing properties and strength properties (tensile strength, impact strength, etc.), and the linear polyolefin may be linear or branched.

  When the liquid-repellent laminate is used for a packaging material such as a retort food packaging material that is subjected to a heat treatment such as hot water bathing, the polyolefin resin preferably contains a polypropylene resin. When the polyolefin resin contains the polypropylene resin, it is easy to prevent the bag-shaped packaging material from being broken by heat treatment such as hot water.

  Examples of the polypropylene resin include homopolypropylene, block polypropylene, random polypropylene, and a copolymer of propylene and an α-olefin other than ethylene and propylene (propylene-based copolymer) as described above. Among them, the polypropylene resin preferably contains random polypropylene. By containing random polypropylene, in addition to easily preventing the bag-like packaging material from being broken by heat, heat sealing at a low temperature and in a short time tends to be easily performed.

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

  The polyolefin resin may be a 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. Moreover, modified polyolefins, such as a hydroxyl group modified polyolefin and an acrylic modified polyolefin, can also be used as polyolefin resin.

  The above-mentioned polyolefin resins can be used alone 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 the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, cyclic dimethyl silicone oil, alkyl-modified silicone oil, long-chain alkyl-modified silicone oil, and higher fatty acid-modified silicone oil.

  Examples of the 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, and products manufactured by Dow Corning Toray Co., Ltd.

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

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

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

  The above-mentioned silicones can be used alone or in combination of two or more.

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

  Examples of the (A) site compatible with the polyolefin resin include a polyolefin structure compatible with the (A) polyolefin resin, and (A) a better compatibility with the polyolefin resin is easily obtained. A) It is preferably a site having the same type of polyolefin structure as the polyolefin resin. That is, when the (A) 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 is a polypropylene structure. It is preferable to have. When the polyolefin resin (A) is a copolymer composed of two or more olefins such as an ethylene-α-olefin copolymer and a propylene-α-olefin copolymer, (C) the compatibilizing agent is as described above. It is preferable to have at least a structure obtained by polymerizing or copolymerizing the same type of olefin as the main component among the olefins constituting the union.

  (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 graft copolymer of the polyolefin having the same type of polyolefin structure as the (A) polyolefin resin and the silicone. It preferably contains a silylated polyolefin that is a coalesced or block copolymer.

  The silylated polyolefin is a polyolefin unit having a silicone site.

  Examples of the silylated polyolefin include, for example, a product manufactured by Dow Corning Toray Co., Ltd. as a PE-Si graft copolymer, an exfola manufactured by Mitsui Chemicals Fine Co., Ltd. as a PE-Si block copolymer, and a PP-Si graft copolymer. A product manufactured by Toray Dow Corning Co., Ltd. is exemplified as the combination.

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

  The above-mentioned compatibilizers can be used alone or in combination of two or more.

  The content of the component (A) in the resin composition for forming a liquid-repellent layer is preferably 50.0 to 99.9% by mass, based on the total solid content of the resin composition for forming a liquid-repellent layer. It is more preferably from 0.0 to 99.0% by mass, and still more preferably from 60.0 to 98.0% by mass. When the content of the component (A) is not less than the above lower limit value, good heat sealability tends to be obtained. On the other hand, when the content of the component (A) is less than or equal to the above upper limit, the content of the component (B) and the component (C) is relatively increased, so that the liquid repellency tends to be improved.

  The total content of the components (B) and (C) in the resin composition for forming a liquid-repellent layer is 0.1 to 50.0% by mass based on the total solid content of the resin composition for forming a liquid-repellent layer. Is preferably, more preferably 1.0 to 45.0% by mass, and even more preferably 2.0 to 40.0% by mass. When the total content of the component (B) and the component (C) is not less than the above lower limit value, the liquid repellency tends to be improved. On the other hand, if the total content of the component (B) and the component (C) is equal to or less than the above upper limit value, the content of the component (A) is relatively increased, so that good heat sealability tends to be easily obtained. is there.

  In the resin composition for forming a liquid-repellent layer, the mass ratio of the content of the component (C) to the content of the component (B) (the mass of the component (C) / the mass of the component (B)) is 0.01 to 50. And it is preferably 0.05 to 30, and more preferably 0.1 to 20. When the content ratio is equal to or greater than the lower limit, the migration of silicone from the liquid-repellent layer 11 to the contents tends to be more easily suppressed. On the other hand, if the content ratio is less than or equal to the above upper limit, the amount of silicone on the surface of the liquid repellent layer increases, and it tends to be easier to obtain better liquid repellency.

  The resin composition for forming a liquid-repellent layer may contain other additives as necessary, as long as the liquid-repellency is not impaired. Examples of other additives include flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers, and tackifiers.

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

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

  The thermoplastic resin used for the second resin layer 12 is not particularly limited, but may be a polyolefin resin, an ethylene-α, β-unsaturated carboxylic acid copolymer or an ester or ionic cross-linked product thereof, or an ethylene-vinyl acetate copolymer. Or its saponified product, polyvinyl acetate or its saponified product, polycarbonate resin, thermoplastic polyester resin, ABS resin, polyacetal resin, polyamide resin, polyphenylene oxide resin, polyimide resin, polyurethane resin, polylactic acid resin, furan resin, and silicone resin And the like. 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 because heat sealability, heat resistance and impact resistance are easily improved. As polyolefin resin, the thing similar to (A) polyolefin resin used for the liquid-repellent layer 11 can be used.

  When the second resin layer 12 is in contact with the liquid-repellent layer 11, the melting point T1 (° C.) of the polyolefin resin (A) 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 the degree of crystallinity, the migration of the (B) silicone in the liquid-repellent layer 11 to the second resin layer 12 can be suppressed, and the (B) silicone on the surface of the liquid-repellent layer 11 can be suppressed. The bleed-out efficiency can be improved, and the liquid repellency tends to be further improved. From the same viewpoint, the melting point T2 is preferably higher than the melting point T1 by 1 ° C. or more, more preferably 3 ° C. or more.

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

<Liquid repellent film 10>
The liquid repellent film 10 having liquid repellency is formed by the single layer of the liquid repellent layer 11 described above or the 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. The liquid repellent film 10 may be used alone without being laminated with the base material 14 depending on the application.

  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 layers may be the same as or different from the composition of the second resin layer 12.

<Substrate 14>
If the base material 14 is a thing used as a support body, there will be no restriction | limiting in particular, For example, paper, a resin film, metal foil, etc. are mentioned. Examples of the paper include high-quality paper, special high-quality paper, coated paper, art paper, cast-coated paper, imitation paper, and craft paper. Examples of the resin film include polyolefin (for example, polyethylene (PE), polypropylene (PP), etc.), acid-modified polyolefin, polyester (for example, polyethylene terephthalate (PET)), polyamide (PA), polyvinyl chloride (PVC), cellulose acetate, A film containing at least one kind of cellophane resin can be used. This film may be a stretched film or an unstretched film. Examples of the metal foil include aluminum foil and nickel foil. The substrate 14 may be a laminate of a plurality of substrates made of different materials.

  The thickness of the substrate 14 is not particularly limited and can be appropriately adjusted depending on the application, but is usually 1 to 500 µm, preferably 10 to 100 µm.

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

(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 laminating methods include the following.

<Adhesive 13>
The adhesive 13 bonds the liquid repellent film 10 and the base material 14 together. Examples of the adhesive 13 include a polyurethane resin obtained by allowing a bifunctional or higher functional isocyanate compound to act on a main agent such as polyester polyol, polyether polyol, acrylic polyol, and carbonate polyol. The various polyols described above can be used singly or in combination of two or more.

  The adhesive 13 may further include 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 for the purpose of promoting adhesion.

  Further, depending on the performance required of the adhesive 13, other various additives and stabilizers may be added to the polyurethane resin described above.

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

(Lamination method by heat treatment)
As a laminating method by heat treatment, the following methods can be given.
(1) A method of extruding and laminating a liquid repellent film 10 formed in advance on a substrate 14 together with an adhesive resin.
(2) A method in which a resin layer constituting the liquid-repellent film 10 and an adhesive resin are extrusion-laminated on the base material 14.
(3) A method in which the laminate substrate obtained by the above method (1) or (2) is further bonded by heating and pressing with a hot roll.
(4) A method in which the laminate substrate obtained by the method (1) or (2) is further stored in a high temperature atmosphere or passed through a drying / baking furnace in a high temperature atmosphere.

  Examples of the adhesive resin used in the lamination method by heat treatment include an acid-modified polyolefin. Further, in the above method, the base material 14 and the liquid repellent film 10 are laminated by extrusion lamination, but an acid-modified polyolefin-based coating agent (dissolving type, dispersion type) is previously applied to the base material without performing extrusion lamination. It is also possible to laminate the liquid-repellent film 10 by heat treatment after coating on 14.

  It is also possible to provide an adhesive primer (anchor coat) on the base material 14, and the material may be polyester, polyurethane, polyallylamine, polyethyleneimine, polybutadiene or ethylene-vinyl acetate copolymer. It is possible to use a coalescence, a chlorine-vinyl acetate system, or the like. If necessary, the above various curing agents and additives that can be used as the adhesive 13 may be blended.

[Packaging materials]
The packaging material according to the present embodiment is formed using the liquid repellent laminate described above. Specific examples of the packaging material include lid materials for containers such as yogurt, jelly, and syrup, and retort food packaging materials (retort pouches) such as porridge, soup, curry, and pasta sauce. By forming the packaging material so that the liquid-repellent layer is arranged on the inner surface (content side) of the packaging material, adhesion and remaining of the contents such as liquids, semi-solids, and gel substances on the inner surface of the packaging material are suppressed. And transfer 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, the innermost layers of the packaging material may be difficult to be discharged due to blocking, but according to the packaging material according to this embodiment, The liquid repellent layers that are the innermost layers are difficult to block each other, and the contents can be discharged efficiently.

  The above-mentioned packaging material may be used for the purpose of performing a heat treatment at 80 ° C. or higher. Specifically, it may be used for packaging materials that are subjected to heat treatment such as hot water baths such as retort food packaging materials. According to the packaging material according to the present embodiment, even when used for such a purpose, it is possible to suppress the adhesion and remaining of the content on the inner surface of the packaging material even after the heat treatment, and to reduce the content from the liquid repellent layer. The transfer of silicone to the product can be suppressed.

[container]
The container which concerns on this embodiment is a container which has the liquid repellent layer formed using the resin composition for liquid repellent layer formation mentioned above at least on the inner surface (content side). Specific examples of the container include storage containers for liquids such as chemicals and pharmaceuticals, semi-solids and gel substances, bottles for storing hand soaps and shampoos, and the like. By forming the container such that the liquid-repellent layer is disposed on the inner surface (content side) of the container, it is possible to prevent the contents such as liquid, semi-solid, and gel-like substances from adhering to and remaining on the inner surface of the container. In addition to the above, transfer of silicone from the liquid-repellent layer to the contents can be suppressed.

  Hereinafter, the present invention will be described more specifically 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>
A linear low-density polyethylene (LLDPE, trade name "Evolu", manufactured by Prime Polymer Co., Ltd.) as the component (A) and a silicone oil (dimethyl silicone, manufactured by Dow Corning Toray Co., Ltd.) as the component (B); A resin composition for forming a liquid-repellent layer was prepared by mixing the component (C) with a triblock copolymer of PE-Si-PE (trade name "EXFORA", manufactured by Mitsui Chemicals Fine Co., Ltd.). The content of the components is 1% by mass of the component (B), 0.05% by mass of the component (C), and the balance of (A) is based on the total amount of the components (A), (B) and (C). ) Component.

<Production of liquid repellent laminate>
Using a three-layer coextrusion machine, the liquid-repellent layer-forming resin composition was extruded to form a liquid-repellent film composed of a liquid-repellent layer having a thickness of 100 μm. The obtained liquid repellent film and a 38 μm-thick PET film (trade name “Emblet”, manufactured by Unitika Co., Ltd.) as a base material were dried using a polyurethane adhesive (manufactured by Mitsui Chemicals, Inc.). The laminate was laminated and aged at 50 ° C. for 5 days to obtain a liquid repellent laminate.

[Examples 2 to 21]
The types of the component (A), the component (B) and the component (C), and the contents of the components (B) and (C) (the content of the component (A)) 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.

[Example 22]
<Preparation of resin composition for forming liquid repellent layer>
Formation of the liquid-repellent layer in the same manner as in Example 1 except that the contents of the component (B) and the component (C) (the content of the component (A) is the rest thereof) were changed as shown in Table 1. A resin composition for use was prepared.

<Production of liquid repellent laminate>
The linear low density polyethylene (LLDPE, trade name “Evolue”, manufactured by Prime Polymer Co., Ltd.), which is the component (A), was used as the second resin layer forming resin composition. Using a three-layer coextrusion machine, the liquid repellent layer-forming resin composition and the second resin layer-forming resin composition were co-extruded to form a film having a thickness of 15 μm and a second layer having 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 38 μm-thick PET film (trade name “Emblet”, manufactured by Unitika Co., Ltd.) as a base material were combined with a polyurethane adhesive (Mitsui Chemicals, Inc.). And a liquid-repellent laminate was obtained.

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

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

[(A) Polyolefin resin]
A1: Linear low density polyethylene (LLDPE), trade name “Evolu”, 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 “Novatech”, melting point 165 to 166 ° C., Nippon Polypropylene Corporation A4: Linear low density polyethylene (LLDPE), trade name “Novatech LL”, melting point 122 ° C, manufactured by Japan Polyethylene Corporation

[(B) silicone]
B1: silicone oil (dimethyl silicone), manufactured by Dow Corning Toray B2: silicone oil (alkyl-modified silicone), manufactured by Tanac Corporation

[(C) compatibilizer]
C1: PE-Si-PE triblock copolymer, trade name "EXFORA", manufactured by Mitsui Chemical Fine Co., Ltd. C2: PP-Si graft copolymer, Toray Dow Corning Co., Ltd. C3: PE-Si Graft copolymer, manufactured by Dow Corning Toray Co., Ltd.

[Liquid repellency evaluation]
<Examples 1-34 and Comparative Examples 1-6: Liquid repellency without heat treatment>
The liquid repellency without heat treatment was evaluated by the method shown in FIG. First, the sample 100 obtained by cutting the liquid-repellent laminates obtained in Examples 1 to 34 and Comparative Examples 1 to 6 into a size of 210 mm in length and 300 mm in width was used. Fold it into two parts (see FIG. 3 (a)), and attach one side of the vertical end and one side of the horizontal end (the side opposite to the folded side) to 190 by a heat sealer. The sealing part 51 was formed by heat sealing over a width of 10 mm at a temperature of 0.03 MPa and 2 sec at a temperature of 0.03 MPa to produce a pouch having one end opened in the longitudinal direction (see FIG. 3B). Next, 100 g of salad oil 52 (trade name “Nisshin Salad Oil”, manufactured by Nisshin Oilio Co., Ltd.) was injected from the opening of the pouch (see (c) of FIG. 3). 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 seal portion 51, and the pouch was sealed (see FIG. 3D). About the corner | angular part with the side where the sealed pouch turned up, the part which becomes a triangle of 3 cm in length x 3 cm in width with the dimension except the seal part 51 was cut | disconnected, and the spout was formed (refer (e) of FIG. 3). . Hold the corner 53 on the diagonal line with the spout, hold the pouch upside down for 30 seconds, discharge the salad oil 52 into the container 56, and measure the amount discharged by the scale 57 (see (f) in FIG. 3). ). From the weighed discharge amount, the residual liquid amount (%) was determined by the following formula.
Residual liquid amount (%) = {(100-discharge amount) / 100} × 100
The measurement was performed three times, and the liquid repellency was evaluated according to the following evaluation criteria from the average residual liquid amount of three 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 Liquid volume is 3.0% or more

<Examples 31, 35 to 45: Liquid repellency after hot water treatment>
According to the method shown in FIG. 4, the liquid repellency after the water bath treatment was evaluated. First, two samples 200 were prepared by cutting the liquid-repellent laminate obtained in Examples 31 and 35 to 45 into 210 mm in length and 150 mm in width. Two samples 200 are overlapped so that each liquid repellent layer is on the inside, and one side of the longitudinal end and two sides of the lateral end are 190 ° C., 0.03 MPa, 2 sec with a heat sealer. The seal part 51 was formed by heat sealing over a width of 10 mm under conditions, and a pouch with one side opening in the longitudinal direction was produced (see FIG. 4A). Next, 100 g of an oil-in-water dispersion type liquid 54 (trade name “Boncurry”, manufactured by Otsuka Foods Co., Ltd.) was injected from the opening of the pouch (see FIG. 4B). 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 seal portion 51, and the pouch was sealed (see FIG. 4C). After the sealed pouch was subjected to a water bath treatment at 100 ° C. for 5 minutes, the top of the sealed pouch was immediately cut to form a spout (see FIG. 4D). Next, holding the seal portion 51 on the side opposite to the spout, holding the pouch upside down for 30 seconds, discharging the oil-in-water dispersed liquid 54 into the container 56, and measuring the discharged amount by the scale 57 (FIG. 4) (See (e)). From the weighed discharge amount, the residual liquid amount (%) was determined by the following formula.
Residual liquid amount (%) = {(100-discharge amount) / 100} × 100
The measurement was performed three times, and the liquid repellency was evaluated according to the following evaluation criteria from the average residual liquid amount of three 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% Δ: Average residual liquid amount is 10.0% or more and less than 13.0% ×: Average residual liquid Liquid volume is 13.0% or more

[Appearance evaluation]
In the liquid repellency evaluation, the liquid discharge behavior when the liquid was discharged from the pouch was visually observed, and the appearance was evaluated according to the following evaluation criteria. The results are shown in Table 2.
○: A state of repelling the liquid is seen, and there is little adhesion to the liquid-repellent laminate.
Δ: Although a state of repelling liquid is seen, it adheres to the liquid-repellent laminate.
X: The state which repels a liquid is not seen.

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

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

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

  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 can be further improved. It turns out that there is.

  From the evaluation results of Examples 31, 35 to 45, the graft copolymers of polyolefin and silicone (C2 and C3) were better than the case where the block copolymer (C1) of polyolefin and silicone was used as the component (C). It can be seen that there is a tendency that the transfer of the silicone after the hot water decoction treatment can be more suppressed when the water is used.

  When the component (C) was not added as in Comparative Examples 1 and 2, release of silicone from the liquid-repellent layer could not be suppressed, and the migration of silicone to the contents was easy to occur. It was found that no good liquid repellency could be obtained. In addition, when the component (B) was not added as in Comparative Examples 3 to 6, it was found that silicone did not bleed out on the surface of the liquid repellent layer, and sufficient liquid repellency was not obtained.

  1, 2 ... lyophobic laminate, 11 ... lyophobic 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 (10)

  Liquid repellent layer formation comprising (A) a polyolefin resin, (B) silicone, and (C) a compatibilizer having a site compatible with the polyolefin resin (A) and a site compatible with the silicone (B). Resin composition.   The said (C) compatibilizer contains the silylated polyolefin which is a graft copolymer or block copolymer of silicone with the polyolefin which has the same kind of polyolefin structure as the said (A) polyolefin resin, The silicone. Resin composition.   The mass ratio of the content of the (C) compatibilizer to the content of the (B) silicone (mass of the (C) compatibilizer / mass of the (B) silicone) is 0.1 to 20. 3. The resin composition according to 1 or 2.   A liquid-repellent film comprising a liquid-repellent layer formed using the resin composition according to claim 1.   The liquid repellent film according to claim 4, further comprising one or more resin layers provided on one main surface of the liquid repellent layer.   The melting point T1 (° C.) of the polyolefin resin (A) 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 as follows: The liquid-repellent film according to claim 5, which satisfies a relationship of T1 <T2.   A substrate, comprising the liquid-repellent film according to any one of claims 4 to 6 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 7.   The packaging material according to claim 8, which is used for performing a heat treatment at 80 ° C or higher. A container having at least an inner surface of a liquid repellent layer formed using the resin composition according to claim 1.

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