JP2020050856A - Resin composition for forming liquid repellent layer, and liquid repellent film, liquid repellent laminate, packaging material and container using the same - Google Patents

Abstract

To provide a resin composition that can form a liquid repellent layer having an excellent liquid repellent property capable of sufficiently suppressing adhesion of content.SOLUTION: Provided is a resin composition for forming liquid repellent layer, containing (A) a polypropylene resin, and (B) a silylated polyolefin, and in which the (A) polypropylene resin contains (A1) a random polypropylene resin and (A2) a block polypropylene resin in a range of mass ratio (mass of (A1) random polypropylene resin/mass of (A2) block polypropylene resin) of 20/80 to 80/20.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 having excellent water resistance, oil resistance, gas barrier properties, light weight, flexibility, design, and the like are used as packaging materials for contents such as liquids, semi-solids, and gel-like 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 substances to the inner surface of the packaging material, that is, the function of suppressing the remaining inside the packaging body is required. More specifically, cover materials for containers such as yogurt, jelly and syrup, porridge, soup, curry, retort food packaging materials such as pasta sauce, liquids such as chemicals and pharmaceuticals, semi-solids, gel-like substances, etc. The contents adhere to the inner surface of the film material for storage containers, etc., and the entire contents cannot be used up. There is a demand for high liquid repellency that can suppress the need for 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. Further, Patent Document 2 proposes a packaging material having water repellency and releasability of contents using a resin layer to which spherical silicon is added as an innermost layer.

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

  As a material of 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 sealability, heat resistance, and impact resistance. However, even when the above-described silicone particles are added to the polyolefin resin in order to impart liquid repellency, aggregation of the silicone particles in the resin layer and release of the silicone particles from the resin layer are likely to occur, and The effect of suppressing the adhesion of contents to the inner surface of the material was not always sufficient.

  The present invention has been made in view of the above-mentioned problems of the related art, and a resin composition capable of forming a liquid-repellent layer having excellent liquid-repellency capable of sufficiently suppressing adhesion of contents, and 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 provides (A) a polypropylene resin and (B) a silylated polyolefin, wherein the (A) polypropylene resin comprises (A1) a random polypropylene resin and (A2) a block polypropylene. A resin composition for forming a liquid-repellent layer, comprising a resin in a mass ratio ((A1) mass of random polypropylene resin / (A2) mass of block polypropylene resin) of 20/80 to 80/20.

  According to the resin composition for forming a liquid-repellent layer, (A) a polypropylene resin is used in combination with (B) a silylated polyolefin which is a component for imparting liquid-repellency to the liquid-repellent layer, and (A) a polypropylene resin. However, by containing (A1) a random polypropylene resin and (A2) a block polypropylene resin in a mass ratio in the range of 20/80 to 80/20, an excellent liquid-repellent liquid can sufficiently suppress the adhesion of contents. A liquid-repellent layer having a property can be formed. Here, the present inventors speculate as follows about the reason that the above-mentioned effect is exerted by using (A1) a random polypropylene resin and (A2) a block polypropylene resin together in the above-mentioned mass ratio. Polypropylene resin (hereinafter also referred to as “PP”) is a hydrocarbon-based crystalline polymer, but also has an amorphous portion. On the other hand, since fats and oils contained in foods are also hydrocarbon compounds, especially when a heat treatment such as retort treatment is applied to a pouch filled with foods containing fats and oils, a low molecular weight in PP contained in a liquid repellent layer on the inner surface of the pouch is low. Amorphous parts tend to swell due to fats and oils. On the other hand, the present inventors have found that by controlling the mass ratio between (A1) random PP and (A2) block PP, it is possible to control the crystallinity and melting point of PP and to control the amount of oil swelling. Found. The present inventors have also found that by controlling the mass ratio, it is possible to control the degree of precipitation of Si in the (B) silylated polyolefin on the surface of the liquid-repellent layer when the liquid-repellent layer is formed. I found it. According to the resin composition for forming a liquid-repellent layer of the present invention, by setting the mass ratio of (A1) random PP to (A2) block PP within the above range, oil swelling of the formed liquid-repellent layer is achieved. It is possible to achieve both a reduction in the amount and an increase in the amount of Si present on the surface of the liquid repellent layer, and as a result, excellent liquid repellency can be obtained. Here, when the ratio of (A1) random PP is smaller than the mass ratio of 20/80, the crystallinity and melting point of PP become high, Si becomes difficult to deposit on the surface of the liquid repellent layer, and the liquid repellency decreases. As a result, the remaining liquid volume increases. On the other hand, when the ratio of (A1) random PP is larger than the mass ratio of 80/20, the crystallinity and melting point of PP decrease, and the oil swelling amount of the liquid-repellent layer increases. When the amount of oil swelling of the liquid-repellent layer increases, the amount of remaining liquid increases accordingly, and a large amount of oils and fats are deposited on the surface of the liquid-repellent layer. As a result, the remaining liquid amount is further increased.

  The resin composition for forming a liquid-repellent layer may further contain (C) a compatibilizing agent having (A) a part compatible with the polypropylene resin and (B) a part compatible with the silylated polyolefin. Good. By using (C) the compatibilizer, the dispersibility of the (B) silylated polyolefin is further improved, and the lyophobic property can be more efficiently imparted to the formed lyophobic layer.

  In the resin composition for forming a liquid-repellent layer, the compatibilizer (C) is selected from the group consisting of a block copolymer of propylene and ethylene and a block copolymer of ethylene and an ethylene / butylene copolymer. It may include at least one selected. By using these compatibilizers (C), the dispersibility of the (B) silylated polyolefin is further improved, and the liquid repellent layer formed can be more efficiently provided with liquid repellency.

  In the liquid repellent layer-forming resin composition, the mass ratio of the content of the (C) compatibilizer to the content of the (B) silylated polyolefin ((C) mass of the compatibilizer / (B) silylation) (Mass of polyolefin) may be 0.05 to 20. When the content ratio is within the above range, the dispersibility of the silylated polyolefin (B) is further improved, and the liquid repellent layer formed can be more efficiently provided with liquid repellency.

  The resin composition for forming a liquid repellent layer may further include (D) silicone. (D) By further including silicone, the amount of Si present on the surface of the formed liquid-repellent layer can be increased, thereby further improving the liquid-repellent property.

  The present invention also provides a liquid-repellent film provided with 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 providing the liquid-repellent layer formed using the liquid-repellent layer-forming resin composition of the present invention, it is possible to sufficiently suppress the adhesion of the contents to the liquid-repellent layer. Can be. According to the liquid repellent film, good liquid repellency can be exhibited not only for water and oil but also for oil-in-water dispersed contents such as curry and pasta sauce.

In the liquid repellent film, the liquid repellent layer may have a crystallinity represented by the following formula (I) of 45 to 55%.

  When the crystallinity of the liquid-repellent layer is within the above range, the reduction of the oil swelling of the liquid-repellent layer and the precipitation of Si on the surface of the liquid-repellent layer can be achieved in a well-balanced manner. Can be improved.

  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. Further, the liquid-repellent layer can be made thinner, and the cost can be reduced.

When the liquid-repellent film includes a resin layer other than the liquid-repellent layer, the melting point T ₁ (° C.) of the polypropylene resin (A) in the liquid-repellent layer and the liquid-repellent layer among the one or more resin layers And the melting point T ₂ (° C.) of the resin contained in the resin layer in contact with the resin layer may satisfy the relationship of T ₁ <T ₂ . By satisfying the above relationship, from the viewpoint of crystallinity, it is possible to prevent the (B) silylated polyolefin in the liquid-repellent layer from migrating to the second resin layer, and the (B) silylation on the surface of the liquid-repellent layer can be suppressed. Since the efficiency of uneven distribution or bleed-out of the polyolefin can be improved, the liquid repellency tends to 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, it is possible to sufficiently suppress the adhesion of contents to the liquid-repellent layer. Further, by laminating the liquid-repellent film with a substrate having a desired function, functions such as mechanical strength, barrier properties, and light-shielding properties can be imparted to the liquid-repellent laminate.

The liquid-repellent laminate is filled with edible oil so as to be in contact with the entire inner surface of the liquid-repellent laminate formed in a bag shape such that the liquid-repellent layer is on the inner surface, and sealed at a temperature of 121 ° C. and a pressure of 121 ° C. The amount of oil swelling per unit area of the liquid-repellent laminate after performing the heating and pressurizing treatment with steam under the conditions of 0.2 MPa and 30 minutes may be 1.0 mg / cm ² or less. . According to the liquid-repellent laminate satisfying such conditions, more excellent liquid-repellency can be obtained, and the adhesion of the contents can be more sufficiently suppressed.

  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 adhesion of contents to the liquid-repellent layer.

  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 the packaging material is used for such a purpose, adhesion of contents to the inner surface of the packaging material can be suppressed even after the heat treatment.

  The present invention further provides a container having a liquid-repellent layer formed at least on the inner surface 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, adhesion of contents to the liquid repellent layer can be sufficiently suppressed. .

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can form the lyophobic layer which has the outstanding lyophobic property which can fully suppress the adhesion of a content, the lyophobic film using the same, Laminates, packaging materials and containers 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 evaluation method of the liquid repellency of a liquid repellent laminated body. 10 is a graph showing an X-ray diffraction spectrum of a liquid-repellent layer in the liquid-repellent film obtained in Example 101. 10 is a graph showing an X-ray diffraction spectrum of a liquid-repellent layer in the liquid-repellent film obtained in Example 101α. 10 is a graph showing an X-ray diffraction spectrum of a liquid-repellent layer in the liquid-repellent film obtained in Example 101β.

  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 have the same reference characters allotted, and overlapping description will be omitted. Further, 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 includes a substrate, and a liquid-repellent film provided on the substrate, and has a structure in which a liquid-repellent layer is disposed on at least one outermost surface. It is. 1 and 2 are schematic sectional views of the liquid-repellent laminate according to the present embodiment. In the liquid-repellent laminate according to the present embodiment, like the liquid-repellent laminate 1 shown in FIG. 1, the liquid-repellent film 10 composed of the liquid-repellent layer 11 and the base material 14 It may have a laminated structure. 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 base material, like the liquid-repellent laminate 2 shown in FIG. 14 may have a structure laminated with the 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 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, the term “liquid repellency” is a concept that includes both water repellency and oil repellency. Specifically, the property of repelling liquid, semisolid, or gel aqueous or oily material It is. Examples of aqueous or oily materials include water, oil, yogurt, jelly, pudding, syrup, porridge, soup, curry, pasta sauce and other foods, hand soaps, shampoos and other detergents, pharmaceuticals, cosmetics, chemicals, and the like. . The heat sealability refers to, for example, a property that can be heat-sealed under the conditions of 100 to 200 ° C., 0.1 to 0.3 MPa, and 1 to 3 seconds. The conditions for heat sealing can be easily changed according to the conditions required for heat sealing of 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, 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, the thickness of the entire liquid-repellent laminate can be reduced.

  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.

<Liquid repellent layer forming resin composition>
The resin composition for forming a liquid-repellent layer according to one embodiment of the present invention includes (A) a polypropylene resin (hereinafter, also referred to as “component (A)”), (B) a silylated polyolefin (hereinafter, “component (B)”). ), Wherein the (A) polypropylene resin comprises (A1) a random polypropylene resin and (A2) a block polypropylene resin in a mass ratio ((A1) mass of the random polypropylene resin / (A2) block polypropylene resin). Mass) of 20/80 to 80/20. The resin composition for forming a liquid-repellent layer according to the present embodiment comprises: (A) a compatibilizer having a site compatible with the polypropylene resin (A) and a site compatible with the silylated polyolefin (B); (D) One or both of silicone may be further contained.

((A) polypropylene resin)
Examples of the polypropylene resin (PP) include homopolypropylene, block polypropylene, random polypropylene, and a copolymer of propylene and an α-olefin other than ethylene and propylene (propylene-based copolymer). Examples of the α-olefin component include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 4-methyl-1-pentene. By using such a polypropylene resin, the liquid-repellent laminate can be suitably used for a packaging material to which a heat treatment such as a hot water bath is applied, such as a retort food packaging material, and the bag-shaped packaging material is a hot water bath. It becomes easy to prevent the bag from being broken by the heat treatment.

  In the present embodiment, the polypropylene resin has a mass ratio of at least (A1) random polypropylene resin and (A2) block polypropylene resin ((A1) mass of random polypropylene resin / (A2) mass of block polypropylene resin) 20/80. ８０80/20 (0.25 to 4.0). The mass ratio is preferably 30/70 to 70/30 (0.43 to 2.3), more preferably 35/65 to 65/35 (0.54 to 1.9), The ratio is more preferably 40/60 to 60/40 (0.67 to 1.5). When the mass ratio is equal to or more than the lower limit, the crystallinity and melting point of the polypropylene resin can be sufficiently reduced, and Si is easily precipitated (segregated) on the surface of the formed liquid-repellent layer. Performance can be improved. On the other hand, when the mass ratio is equal to or less than the upper limit, the crystallinity and melting point of the polypropylene resin can be sufficiently increased, and the amount of oil swelling of the formed liquid-repellent layer can be reduced. When the oil swelling amount of the liquid-repellent layer is low, the remaining liquid amount can be reduced by that amount, and the amount of oil and fat present on the surface of the liquid-repellent layer is reduced, so that Si easily precipitates on the liquid-repellent layer surface. And the liquid repellency can be improved.

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

  The above-mentioned (A1) random polypropylene resin and (A2) block polypropylene resin can be used alone or in combination of two or more.

  The resin composition for forming a liquid-repellent layer according to this embodiment may include a polyolefin resin other than the polypropylene resin. Examples of other polyolefin resins include low-density polyethylene, medium-density polyethylene, high-density polyethylene, and ethylene-α-olefin copolymer. Examples of the α-olefin component include 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. Other than the above, the polyolefin resin may be a cyclic polyolefin such as polynorbornene. The polyolefin resin may be a linear polyolefin from the viewpoint of sealing properties and strength physical properties (such as tensile strength and impact strength), and the linear polyolefin may be linear or branched.

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

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

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

((B) silylated polyolefin)
The silylated polyolefin is a component that imparts liquid repellency to the liquid repellent layer 11. The silylated polyolefin has a polyolefin unit having a silicone site.

  Examples of the silylated polyolefin include, for example, a product manufactured by Toray Dow Corning Co., Ltd. as a PE-Si graft copolymer, an exfola manufactured by Mitsui Chemical 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, from the viewpoint of further improving the liquid repellency of the liquid repellent layer 11, a block copolymer is more preferable than a graft copolymer. This is because the block copolymer tends to be unevenly distributed or bleed out on the surface of the liquid repellent layer 11.

  The above silylated polyolefins can be used alone or in combination of two or more.

  The silylated polyolefin may have a polyolefin moiety compatible with the (A) polypropylene resin or may be incompatible (incompatible). However, when using a silylated polyolefin in which the polyolefin moiety is incompatible with the (A) polypropylene resin, it is preferable to use it in combination with the following (C) compatibilizer. When using a silylated polyolefin in which the polyolefin portion is incompatible with the (A) polypropylene resin, the choice of combinations of the materials of the (A) polypropylene resin and the (B) silylated polyolefin increases, and the number of choices depends on the purpose and application. There is an advantage that the design is possible and the liquid repellency tends to be more easily improved. Examples of the silylated polyolefin in which the polyolefin moiety is compatible with the (A) polypropylene resin include a PP-Si graft copolymer. Examples of the silylated polyolefin in which the polyolefin moiety is incompatible with the (A) polypropylene resin include: Examples include a PE-Si graft copolymer and a PE-Si block copolymer.

((C) compatibilizer)
The compatibilizer is preferably used when a silylated polyolefin whose polyolefin moiety is incompatible with the (A) polypropylene resin is used as the (B) silylated polyolefin. The compatibilizer is a component having (A) a part compatible with the polypropylene resin and (B) a part compatible with the silylated polyolefin. By using the compatibilizing agent, the compatibility between the (A) polypropylene resin and the (B) silylated polyolefin in which the polyolefin portion is incompatible with the (A) polypropylene resin can be improved.

  Examples of the site compatible with the polypropylene resin (A) include a polyolefin structure compatible with the polypropylene resin (A), and a site having the same type of polyolefin structure as the polypropylene resin (A) is preferable. That is, the (C) compatibilizer preferably has a polypropylene structure. When (A) the polypropylene resin is a copolymer composed of two or more olefins such as a propylene-α-olefin copolymer, (C) the compatibilizer is a main component of the olefins constituting the copolymer. It preferably has at least a structure obtained by polymerizing or copolymerizing an olefin of the same type as the olefin as a component.

  Examples of the site compatible with the silylated polyolefin (B) include a polyolefin structure compatible with the polyolefin site of the (B) silylated polyolefin, and have the same type of polyolefin structure as the polyolefin site of the (B) silylated polyolefin. It is preferably a site. That is, when the polyolefin moiety of the (B) silylated polyolefin has a polyethylene structure, the (C) compatibilizer preferably has a polyethylene structure. Further, when the polyolefin moiety of the silylated polyolefin (B) has a structure based on a copolymer composed of two or more olefins such as an ethylene-α-olefin copolymer and a propylene-α-olefin copolymer, (C) The compatibilizer preferably has at least a structure obtained by polymerizing or copolymerizing the same type of olefin as the main component of the olefins constituting the copolymer.

  As the compatibilizer (C), for example, a block copolymer of ethylene and propylene or a block copolymer of ethylene and ethylene / butylene copolymer can be used. When using these compatibilizers, it is preferable to use those having a polyethylene moiety as the (B) silylated polyolefin. In this case, (A) the polypropylene portion of the polypropylene resin and (C) the propylene or ethylene / butylene copolymer portion of the compatibilizer are compatible, and (B) the polyethylene portion of the silylated polyolefin and (C) the compatibilizer. Is compatible with the polyethylene moiety.

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

((D) silicone)
Silicone is a component that further improves the liquid repellency of the liquid repellent layer 11. Examples of the silicone include silicone oil, silicone resin, silicone oligomer, silicone powder and the like. Among them, silicone oil is preferable because better liquid repellency is 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.

  The content of the component (A) in the resin composition for forming a liquid-repellent layer is preferably from 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 further preferably from 60.0 to 98.0% by mass. When the content of the component (A) is equal to or more than the lower limit, good heat sealability tends to be easily obtained. On the other hand, when the content of the component (A) is equal to or less than the upper limit, the content of the component (B) and the components (C) and (D) used as needed are relatively increased. Properties tend 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 more preferable, and it is more preferable that it is 1.0-45.0 mass%, and it is still more preferable that it is 2.0-40.0 mass%. When the total content of the component (B) and the component (C) is at least the lower limit, the liquid repellency tends to be improved. On the other hand, when the total content of the components (B) and (C) is less than or equal to the above upper limit, the content of the component (A) relatively increases, so that good heat sealability tends to be easily obtained. is there.

  When the resin composition for forming a liquid-repellent layer contains the component (C), 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)) May be from 0.01 to 50, preferably from 0.04 to 30, more preferably from 0.05 to 20, and even more preferably from 0.05 to 15. When the content ratio is equal to or more than the above lower limit, the silylated polyolefin (B) can be sufficiently dispersed in the liquid-repellent layer, and a better liquid-repellency tends to be obtained. On the other hand, when the content ratio is not more than the above upper limit, it is possible to prevent the (B) silylated polyolefin from being coated with an excessive (C) compatibilizer, and to obtain better liquid repellency. Tend. Further, even when the compatibilizing agent (C) is added as the content ratio exceeds the above upper limit, the (B) silylated polyolefin does not disperse any more, and the effect of improving the liquid repellency tends not to be seen. There is.

  When the resin composition for forming a liquid-repellent layer contains the component (D), the content is preferably 0.1 to 20.0% by mass based on the total amount of the resin composition for forming a liquid-repellent layer. It is more preferably from 0.0 to 15.0% by mass, and still more preferably from 2.0 to 10.0% by mass. When the total content of the component (D) is not less than the lower limit, the liquid repellency tends to be improved. On the other hand, if the total content of the component (D) is less than or equal to the above upper limit, the content of the component (A) relatively increases, so that good heat sealability tends to be easily obtained.

  The resin composition for forming a liquid-repellent layer may contain other additives as needed, as long as the liquid-repellency 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 the above-described resin composition for forming a liquid-repellent layer.

The liquid repellent layer 11 has a degree of crystallinity represented by the following formula (I) of 45 to 55% as measured by an X-ray diffraction method at an incident angle of 0.5 ° and a measurement angle of 3 to 35 °. Is also good. The measurement of X-ray diffraction can be performed by a parallel method using CuKα radiation as an X-ray source. Further, the crystal part peak area and the amorphous part peak area can be calculated from the measured X-ray diffraction spectrum using analysis software. By performing the X-ray diffraction measurement by the parallel method at the above-described incident angle and measurement angle, it is possible to measure the degree of crystallinity near the surface of the liquid-repellent layer 11 having a large influence on the liquid-repellent property. When the crystallinity of the liquid-repellent layer 11 is 45% or more, it becomes difficult for oil to be taken into the liquid-repellent layer 11 and the amount of oil swelling can be reduced, so that the residual liquid amount can be further reduced. When the crystallinity of the liquid-repellent layer 11 is 55% or less, it is difficult to prevent Si from depositing on the surface of the liquid-repellent layer 11, so that Si is segregated on the surface and the liquid-repellency is more likely to be improved. Note that the crystallinity of the liquid-repellent layer 11 in this specification is measured before heat treatment such as retort treatment. The crystallinity of the liquid-repellent layer 11 may be measured in the state of the liquid-repellent film 10 or in the state of the liquid-repellent laminate 1. The crystallinity of the liquid-repellent layer 11 measured in the state of the liquid-repellent laminate 1 is different from that of the liquid-repellent film 10 because an additional amount of heat is applied to the liquid-repellent film 10 when the liquid-repellent laminate 1 is manufactured. The degree of crystallinity may change from the degree of crystallinity measured in each state, but the degree of crystallinity is preferably in the range of 45 to 55% in either state. The crystallinity can be measured by differential scanning calorimetry, infrared spectroscopy, or the like, in addition to the X-ray diffraction method.

  The crystallinity of the liquid-repellent layer 11 can be controlled by the composition of the (A) polypropylene resin, the amount of heat applied to the liquid-repellent layer 11, and the like. When the composition is controlled by the composition of the (A) polypropylene resin, the crystallinity of the (A2) block polypropylene resin is higher than that of the (A1) random polypropylene resin. The degree can be increased. On the other hand, as a method of controlling the amount of heat, there is a method of controlling the film forming conditions of the liquid repellent layer 11. Specific examples of the film forming conditions include a line speed, a film forming temperature, a cooling temperature, and a cooling method. For example, when controlling the cooling temperature, the crystallinity can be improved by increasing the cooling temperature and gradually cooling.

<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 sealing properties, heat resistance and impact resistance, oxygen / water vapor barrier properties, and the like. The second resin layer 12 preferably contains a heat-sealing thermoplastic resin.

  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 its esterified or ion-crosslinked product, 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 alone 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 the polyolefin resin, the same as the (A) polypropylene 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 T ₁ (° C.) of the (A) polypropylene resin in the liquid-repellent layer 11 and the melting point T ₁ (° C.) of the thermoplastic resin in the second resin layer 12 The melting point T ₂ (° C.) preferably satisfies the relationship of T ₁ <T ₂ . By satisfying the above relationship, from the viewpoint of crystallinity, it is possible to prevent the (B) silylated polyolefin in the liquid-repellent layer 11 from migrating to the second resin layer 12, and (B) to the surface of the liquid-repellent layer 11. ) Since the efficiency of uneven distribution or bleed-out of the silylated polyolefin can be improved, the liquid repellency tends to be further improved. From the same viewpoint, the melting point T ₂ are preferably higher than 1 ℃ than the melting point T _1, and more preferably 3 ° C. or more higher.

Here, the melting point T _1, the liquid-repellent layer 11 has a measurement sample, which is the melting point of which measured in the liquid repellent layer 11 (A) polypropylene resin. Similarly, the melting point T ₂ are, the second resin layer 12 has a measurement sample, which is the melting point of the resin to be measured in the second resin layer 12. Melting point T _1, when the liquid-repellent layer 11 contains two or more kinds of polypropylene resins having different melting points as polypropylene resin (A) shows a melting point of the polypropylene resin that melts at the lowest temperature in the liquid repellent layer 11 The melting point is different from the melting point measured by the polypropylene resin alone because it is affected by other polypropylene resins. Repellent layer 11 melting point _{T 2} of the of (A) the resin in the melting point _{T 1} and the second resin layer 12 of a polypropylene resin in the measurement by thermal analysis apparatus (e.g., TA7000 manufactured by Hitachi High-Tech Science) can do.

  The thickness of the second resin layer 12 can be appropriately set according to the final use of a commercial 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, further preferably 5 to 150 μm, and more preferably 10 to 100 μm. Is particularly preferred.

<Liquid repellent film 10>
The single layer of the liquid repellent layer 11 or the two layers of the liquid repellent layer 11 and the second resin layer 12 form the liquid repellent film 10 having liquid repellency. The liquid-repellent film 10 is formed so as to cover part or all of the surface of the substrate 14. Note that the liquid-repellent film 10 may be used alone without being laminated with the substrate 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.

<Base material 14>
The substrate 14 is not particularly limited as long as it is a support, and examples thereof include paper, a resin film, and a metal foil. Examples of the paper include high quality paper, special high quality paper, coated paper, art paper, cast coated paper, imitation paper, kraft paper, and the like. Examples of the resin film include polyolefin (eg, polyethylene (PE), polypropylene (PP), etc.), acid-modified polyolefin, polyester (eg, polyethylene terephthalate (PET), etc.), polyamide (PA), polyvinyl chloride (PVC), cellulose acetate, A film containing at least one kind of cellophane resin is exemplified. This film may be a stretched film or a non-stretched film. Examples of the metal foil include an aluminum foil and a 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, 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. The following are examples of the adhesive 13 used in these laminating methods.

<Adhesive 13>
The adhesive 13 is for bonding the liquid-repellent film 10 and the base 14. Examples of the adhesive 13 include a polyurethane resin obtained by reacting a main component such as a polyester polyol, a polyether polyol, an acrylic polyol, and a carbonate polyol with a bifunctional or more functional isocyanate compound. The above-mentioned various polyols can be used alone 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, other various additives and stabilizers may be blended with the above-mentioned polyurethane resin according to the performance required of the adhesive 13.

  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, followability, workability, and the like.

(Lamination method by heat treatment)
As a lamination method by heat treatment, the following methods can be roughly mentioned.
(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 substrate 14.
(3) A method in which the laminate substrate obtained by the 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 and 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 without performing extrusion lamination, an acid-modified polyolefin-based coating agent (solution type, dispersion type) is preliminarily prepared. After coating on the liquid-repellent film 14, the liquid-repellent film 10 can be laminated by heat treatment.

  It is also possible to provide an adhesive primer (anchor coat) on the base material 14, which may be made of 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, and may mix the above various curing agents and additives that can be used as the adhesive 13 as needed.

The liquid-repellent laminate according to the present embodiment has a liquid-repellent laminate formed into a bag shape such that the liquid-repellent layer is on the inner surface. The amount of oil swelling per unit area of the liquid-repellent laminate after subjecting to heat and pressure treatment with steam at 121 ° C. and a pressure of 0.2 MPa for 30 minutes is 1.0 mg / cm ² or less. preferable. When the oil swelling amount measured in this way is 1.0 mg / cm ² or less, the liquid-repellent laminate can have more excellent liquid-repellency, and the residual liquid after discharging the content is discharged. The amount can be further reduced. From the same viewpoint, the oil swelling amount is more preferably 0.95 mg / cm ² or less. On the other hand, from the viewpoint of enhancing the sliding properties of the contents, the liquid repellent layer may slightly swell with fats and oils, and the oil swelling amount may be 0.5 mg / cm ² or more.

[Packaging materials]
The packaging material according to the present embodiment is formed using the above-described liquid-repellent laminate. 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 such 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. can do. Further, in a bag-like packaging material such as a retort food packaging material, the innermost layer of the packaging material may be difficult to discharge due to blocking between the innermost layers, but according to the packaging material according to the present embodiment, In addition, the innermost liquid-repellent layers are less likely to be blocked, and the contents can be efficiently discharged.

  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 a packaging material to be subjected to a heat treatment such as a hot water bath, such as a retort food packaging material. According to the packaging material according to the present embodiment, even when the packaging material is used for such a purpose, it is possible to suppress the adhesion and remaining of the contents on the inner surface of the packaging material even after the heat treatment.

[container]
The container according to the present embodiment is a container having a liquid-repellent layer formed using the above-described resin composition for forming a liquid-repellent layer on at least an inner surface (content side). Specific examples of the container include storage containers for liquids, semi-solids, and gel-like substances such as chemicals and pharmaceuticals, and bottles for storing hand soaps and shampoos. By forming the container so 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. it can.

  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>
As the component (A), (A1) a random polypropylene resin (propylene-ethylene random copolymer, trade name “Prime Polypro”, melting point 134 ° C. (catalog value), manufactured by Prime Polymer Co., Ltd .; hereinafter abbreviated as “r-PP” And (A2) block polypropylene resin (propylene-ethylene block copolymer, trade name “Novatech”, melting point 165 to 166 ° C. (catalog value), manufactured by Nippon Polypropylene Corporation, hereinafter “b-PP” And a silylated polyethylene (PE-Si block copolymer, manufactured by Dow Corning Toray Co., Ltd .; hereinafter, may be abbreviated as “PE-Si”). Then, a resin composition for forming a liquid-repellent layer was prepared. Here, the content of each component is such that the mass ratio of r-PP to b-PP (mass of r-PP / mass of b-PP) in the component (A) is 20/80, and (A) Based on the total amount of the component (B) and the component (B), the components were adjusted so that the component (B) was 5% by mass and the balance was the component (A).

<Preparation of liquid-repellent laminate>
The resin composition for forming a liquid-repellent layer was extruded into a film using a three-layer co-extruder to obtain a liquid-repellent film having a liquid-repellent layer having a thickness of 60 μm. The obtained liquid-repellent film and a PET film having a thickness of 38 μm (trade name “Emblet”, manufactured by Unitika Ltd.) as a substrate are dried using a polyurethane-based 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 5]
The liquid-repellent layer was prepared in the same manner as in Example 1 except that the mass ratio between r-PP and b-PP in the component (A) in the resin composition for forming a liquid-repellent layer was changed as shown in Table 1. A resin composition for formation, a liquid-repellent film, and a liquid-repellent laminate were produced.

[Examples 6 to 15]
The resin composition for forming a liquid-repellent layer is further added with a block copolymer of ethylene and an ethylene / butylene copolymer (hereinafter sometimes abbreviated as “PE-Et / Bu”) as the component (C), A liquid-repellent layer-forming resin composition, a liquid-repellent film and a liquid-repellent laminate were prepared in the same manner as in Example 1 except that the content of each component was adjusted. In the resin composition for forming a liquid-repellent layer, the mass ratio of r-PP to b-PP in the component (A) and the total amount of the components (A), (B) and (C) were used as references. The content of the component (B) and the content of the component (C) were adjusted so as to have the values shown in Table 1, respectively.

[Examples 16 to 42]
The resin composition for forming a liquid-repellent layer is further added with a block copolymer of propylene and ethylene (hereinafter sometimes abbreviated as “PP-PE”) as component (C) to adjust the content of each component. A liquid-repellent layer-forming resin composition, a liquid-repellent film, and a liquid-repellent laminate were prepared in the same manner as in Example 1 except for the above. In the resin composition for forming a liquid-repellent layer, the mass ratio of r-PP to b-PP in the component (A) and the total amount of the components (A), (B) and (C) were used as references. The content of the component (B) and the content of the component (C) were adjusted so as to have the values shown in Table 1, respectively.

[Examples 43 to 51]
To the resin composition for forming a liquid-repellent layer, a silicone oil (dimethyl silicone, manufactured by Dow Corning Toray, hereinafter sometimes abbreviated as “silicone”) as the component (D) is further added, and the content of each component Was prepared in the same manner as in Example 16 except that the liquid-repellent layer was formed, and a liquid-repellent film and a liquid-repellent laminate were prepared. In the resin composition for forming a liquid-repellent layer, the mass ratio between r-PP and b-PP in the component (A), and the components (A), (B), (C) and (D) The contents of the component (B), the component (C), and the component (D) based on the total amount were adjusted to have the values shown in Table 2, respectively.

[Example 52]
<Preparation of resin composition for forming liquid repellent layer>
In the same manner as in Example 3, a resin composition for forming a liquid-repellent layer was prepared.

<Preparation of liquid-repellent laminate>
(A1) A random polypropylene resin (propylene-ethylene random copolymer, trade name “Prime PolyPro”, melting point 134 ° C. (catalog value), manufactured by Prime Polymer Co., Ltd.), which is the component (A1), as a second resin layer formation Resin composition for use. Using a three-layer co-extrusion machine, a resin composition for forming a liquid-repellent layer and a resin composition for forming a second resin layer are co-extruded into a film, and a liquid-repellent layer having a thickness of 15 μm and a second resin having a thickness of 45 μm are formed. A liquid-repellent film composed 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 Ltd.) serving as a substrate were bonded to a polyurethane-based adhesive (Mitsui Chemicals, Inc.). ) To obtain a liquid-repellent laminate.

[Examples 53 to 70]
The component (C) shown in Table 2 or the components (C) and (D) shown in Table 2 were added to the resin composition for forming a liquid-repellent layer so as to have the contents shown in the same table. In the same manner as in Example 52 except that the mass ratio between r-PP and b-PP was adjusted to be the value shown in the same table, the resin composition for forming a liquid-repellent layer and the formation of a second resin layer A resin composition for use, a liquid-repellent film, and a liquid-repellent laminate were prepared.

[Examples 71 to 75]
The mass ratio between r-PP and b-PP in the component (A) in the liquid-repellent layer-forming resin composition was changed as shown in Table 2, and as the second resin layer-forming resin composition, Example except that (A2) block polypropylene resin (propylene-ethylene block copolymer, trade name “Novatech”, melting point 165 to 166 ° C. (catalog value), manufactured by Nippon Polypropylene Co., Ltd.) as the component (A) was used. Similarly to 52, a resin composition for forming a liquid-repellent layer, a resin composition for forming a second resin layer, a liquid-repellent film, and a liquid-repellent laminate were prepared.

[Examples 76 to 119]
The components (C) shown in Tables 2 and 3 or the components (C) and (D) shown in Tables 2 and 3 were added to the resin composition for forming a liquid-repellent layer so as to have the contents shown in the same table. ) In the same manner as in Example 71 except that the mass ratio between r-PP and b-PP in the component was adjusted to be the value shown in the same table, the liquid-repellent layer-forming resin composition, A resin composition for forming a resin layer, a liquid-repellent film, and a liquid-repellent laminate were prepared.

[Comparative Example 1]
A resin composition for forming a liquid-repellent layer, a liquid-repellent film and a liquid-repellent laminate were prepared in the same manner as in Example 3, except that the component (B) was not added to the resin composition for forming a liquid-repellent layer. did.

[Comparative Examples 2 to 5]
The liquid-repellent layer was prepared in the same manner as in Example 1 except that the mass ratio between r-PP and b-PP in the component (A) in the resin composition for forming a liquid-repellent layer was changed as shown in Table 4. A resin composition for formation, a liquid-repellent film, and a liquid-repellent laminate were produced.

[Comparative Example 6]
A resin composition for forming a liquid-repellent layer, a liquid-repellent film and a liquid-repellent laminate were prepared in the same manner as in Example 8, except that the component (B) was not added to the resin composition for forming a liquid-repellent layer. did.

[Comparative Examples 7 to 10]
The liquid-repellent layer was prepared in the same manner as in Example 6, except that the mass ratio between r-PP and b-PP in the component (A) in the resin composition for forming a liquid-repellent layer was changed as shown in Table 4. A resin composition for formation, a liquid-repellent film, and a liquid-repellent laminate were produced.

[Comparative Example 11]
A resin composition for forming a liquid-repellent layer, a liquid-repellent film and a liquid-repellent laminate were prepared in the same manner as in Example 18, except that the component (B) was not added to the resin composition for forming a liquid-repellent layer. did.

[Comparative Examples 12 to 15]
The liquid-repellent layer was prepared in the same manner as in Example 16 except that the mass ratio between r-PP and b-PP in the component (A) in the resin composition for forming a liquid-repellent layer was changed as shown in Table 4. A resin composition for formation, a liquid-repellent film, and a liquid-repellent laminate were produced.

[Comparative Examples 16 to 19]
The liquid-repellent layer was prepared in the same manner as in Example 45 except that the mass ratio between r-PP and b-PP in the component (A) in the resin composition for forming a liquid-repellent layer was changed as shown in Table 4. A resin composition for formation, a liquid-repellent film, and a liquid-repellent laminate were produced.

[Comparative Examples 20 and 21]
Example 1 was repeated except that the component (B) was not added to the resin composition for forming a liquid-repellent layer, and the mass ratio between r-PP and b-PP in the component (A) was changed as shown in Table 4. A liquid-repellent layer-forming resin composition, a liquid-repellent film, and a liquid-repellent laminate were prepared in the same manner as in No. 52.

[Comparative Examples 22 to 25]
The liquid-repellent layer was prepared in the same manner as in Example 57 except that the mass ratio between r-PP and b-PP in the component (A) in the resin composition for forming a liquid-repellent layer was changed as shown in Table 4. A resin composition for formation, a liquid-repellent film, and a liquid-repellent laminate were produced.

[Comparative Examples 26 to 29]
The liquid-repellent layer was prepared in the same manner as in Example 65 except that the mass ratio between r-PP and b-PP in the component (A) in the resin composition for forming a liquid-repellent layer was changed as shown in Table 4. A resin composition for formation, a liquid-repellent film, and a liquid-repellent laminate were produced.

[Comparative Examples 30 to 33]
The liquid-repellent layer was prepared in the same manner as in Example 102 except that the mass ratio between r-PP and b-PP in the component (A) in the resin composition for forming a liquid-repellent layer was changed as shown in Table 4. A resin composition for formation, a liquid-repellent film, and a liquid-repellent laminate were produced.

[Comparative Examples 34 to 37]
The liquid-repellent layer was prepared in the same manner as in Example 114 except that the mass ratio between r-PP and b-PP in the component (A) in the resin composition for forming a liquid-repellent layer was changed as shown in Table 4. A resin composition for formation, a liquid-repellent film, and a liquid-repellent laminate were produced.

[Example 3α]
Example 3α was implemented as an example in which the degree of crystallinity of the liquid-repellent layer in Example 3 was increased. Example 3α was the same as Example 3 except that the surface temperature of the cooling roll when cooling the extruded liquid-repellent layer was increased during the formation of the liquid-repellent layer, and the liquid-repellent layer was gradually and gradually cooled. Similarly, a liquid-repellent layer-forming resin composition, a liquid-repellent film, and a liquid-repellent laminate were produced.

[Examples 8α to 119α and 101β]
Examples 8α to 119α and 101β shown in Tables 5 and 6 were performed as examples in which the crystallinity of the liquid-repellent layer was increased. These examples are different from the examples of the same number without α or β in that the lyophobic layer is cooled more slowly and slowly as in Example 3α. In Example 101β, the cooling temperature for cooling the lyophobic layer was further increased than in Example 101α, and the lyophobic layer was gradually and gradually cooled. Tables 5 and 6 also show examples having the same numbers without α or β for comparison.

Tables 1 to 6 show 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)). Tables 1 to 6 show the melting point T ₁ (° C.) of the resin as the component (A) measured in the liquid repellent layer and the melting point T ₁ (° C.) of the resin as the component (A) used in the second resin layer. The relationship with the melting point T ₂ (° C.) was shown. If the liquid-repellent layer contains r-PP and b-PP as the component (A), the melting point _{T 1} is a melting point of r-PP to melt at a lower temperature in the liquid repellent layer, b-PP From the melting point measured with r-PP alone. Melting point T ₂ of the resin in the liquid-repellent layer in the (A) melting point T ₁ and a second component of the resin layer in a thermal analyzer (Hitachi High-Tech Science Ltd., TA7000) were measured by.

[Evaluation of liquid repellency]
<Evaluation of residual liquid after retort treatment>
The liquid-repellent laminates obtained in Examples and Comparative Examples were evaluated for liquid-repellency after retort treatment by the method shown in FIG. First, two samples 100 in which the liquid-repellent laminate was cut into a length of 150 mm and a width of 138 mm were prepared. Two samples 100 are overlapped so that the respective liquid-repellent layers are on the inside, and one side of the vertical end and two sides of the horizontal end are subjected to heat sealing at 190 ° C. and 0.03 MPa for 2 sec. Under the conditions, a seal portion 51 was formed by heat sealing over a width of 10 mm, and a pouch having one side opened in a longitudinal direction was produced (see FIG. 3A). Next, 180 g of an oil-in-water dispersion liquid 54 (trade name “Boncurry Gold Medium Hot”, lipid content: 7.0 g / 180 g, manufactured by Otsuka Foods Co., Ltd.) was injected from the opening of the pouch ((b in FIG. 3). )). Thereafter, the opening was heat-sealed with a heat sealer at 190 ° C., 0.03 MPa and 2 sec over a width of 10 mm to form a seal portion 51, and the pouch was sealed (see FIG. 3 (c)).

After putting the sealed pouch into a high-temperature and high-pressure cooking sterilizer (manufactured by Hitachi Capital Co., Ltd.), it was subjected to a retort treatment at 121 ° C. for 30 minutes under high-pressure steam at a pressure of 0.2 MPa, and the sealed pouch was further heated at 100 ° C. It was baked for 5 minutes. Immediately after the above treatment, the top of the sealed pouch was cut to form a spout (see FIG. 3 (d)). Next, the pouch was turned upside down, and the spout was held at an angle of 45 ° from the horizontal plane for 10 seconds, the oil-in-water dispersion type liquid 54 was discharged into the container 56, and the discharge amount was weighed by the scale 57 ((FIG. e)). From the weighed discharge amount, the residual liquid amount (%) was determined by the following equation.
Residual liquid amount (%) = {(180−discharge amount) / 180} × 100
The measurement was performed three times, and the residual liquid was evaluated from the average residual liquid amount of the three times according to the following evaluation criteria. The evaluation results are shown in Tables 1 to 6. Tables 5 and 6 also show the value of the residual liquid amount (average residual liquid amount).
◎: Average residual liquid amount is 6.5% or less 平均: Average residual liquid amount is more than 6.5% to 8.0% or less Δ: Average residual liquid amount is more than 8.0% and 10.0% or less X: Average residual liquid amount Liquid volume exceeds 10.0%

<Appearance evaluation after retort treatment>
In the above residual liquid evaluation, the liquid discharging 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 Tables 1 to 6.
：: The liquid was repelled neatly, and the adhesion to the liquid-repellent laminate was extremely small.
：: A state of repelling liquid was observed, and adhesion to the liquid-repellent laminate was small.
Δ: Liquid repelling is observed, but attached to the liquid-repellent laminate.
×: No appearance of repelling liquid is observed.

[Measurement of oil swelling amount]
With respect to a part of the liquid-repellent laminates obtained in Examples and Comparative Examples, the amount of oil swelling was measured by the following method. First, two samples were prepared by cutting the liquid-repellent laminate to a length of 150 mm and a width of 138 mm. The two samples are stacked so that the respective liquid-repellent layers are on the inside, and one side of the vertical end and two sides of the horizontal end are subjected to heat sealing at 190 ° C., 0.03 MPa, and 2 sec. To form a seal portion by heat sealing over a width of 10 mm to produce a pouch having one end opened in the longitudinal direction. Next, 100 g of edible oil (trade name “Nisshin Salad Oil”, manufactured by Nisshin Oillio) was injected through the opening of the pouch. Thereafter, the opening was heat-sealed with a heat sealer at 190 ° C., 0.03 MPa and 2 sec over a width of 10 mm to form a seal portion, and the pouch was sealed. Sealing of the pouch was performed while evacuating so that the cooking oil was in contact with the entire inner surface of the pouch.

After putting the sealed pouch into a high-temperature and high-pressure cooking sterilizer (manufactured by Hitachi Capital Co., Ltd.), it was subjected to a retort treatment at 121 ° C. for 30 minutes with high-temperature steam under a pressure of 0.2 MPa. After the retort treatment, the edible oil filled in the pouch was discharged, the pouch was washed with a detergent, and the mass (W ₁ ) of the pouch after drying was measured. From the mass (W ₁ ) of the pouch after the retort treatment and the mass (W ₀ ) of the pouch before pouring the edible oil, the oil swelling amount per unit area (mg / mg) cm ² ).
Oil swelling amount (mg / cm ² ) = {(W ₁ −W ₀ ) / (13 × 11.8 × 2)} × 1000

[Measurement of crystallinity]
The crystallinity of the liquid-repellent layers of the liquid-repellent films obtained in Examples shown in Tables 5 and 6 was measured by X-ray diffraction. First, an X-ray diffraction spectrum was measured using an X-ray diffractometer (trade name: RINT-TTR III, manufactured by Rigaku Corporation) under the following measurement conditions. As a specific example, FIGS. 4 to 6 show the X-ray diffraction spectra of the liquid-repellent layer in the liquid-repellent films obtained in Example 101, Example 101α, and Example 101β, respectively.
<Measurement conditions>
X-ray source: CuKα ray measurement method: Parallel method Scanning Mode: 2Theta
Incident angle (fixed angle) / measuring angle: 0.5 ° / 3-35 °

From the obtained X-ray diffraction spectrum, the crystal part peak area and the amorphous part peak area were determined using powder X-ray diffraction pattern comprehensive analysis software (manufactured by Rigaku Corporation, trade name: JADE 7), and the following formula (I) was obtained. Was calculated. The results are shown in Tables 5 and 6.

  As is clear from the results shown in Tables 1 to 4, according to the liquid-repellent laminates of Examples 1 to 119, compared with the liquid-repellent laminates of Comparative Examples 1 to 37, the liquid-repellent properties were higher. It was confirmed that it could be improved. Further, as is clear from the results shown in Tables 5 and 6, it was confirmed that when the crystallinity of the liquid repellent layer was in the range of 45 to 55%, the liquid repellency could be further improved. .

1, 2 ... lyophobic laminate, 10 ... lyophobic film, 11 ... lyophobic layer, 12 ... second resin layer, 13 ... adhesive, 14 ... base material, 51 ... seal part, 54 ... oil-in-water Dispersion type liquid, 56: container, 57: scale, 100: sample for evaluating liquid repellent laminate.

Claims (14)

(A) a polypropylene resin, and (B) containing a silylated polyolefin,
The said (A) polypropylene resin is (A1) a random polypropylene resin and (A2) a block polypropylene resin in a mass ratio ((A1) mass of a random polypropylene resin / (A2) mass of a block polypropylene resin) 20 / 80-80. / 20, a resin composition for forming a liquid-repellent layer.   2. The resin composition according to claim 1, further comprising (C) a compatibilizer having a site compatible with the polypropylene resin (A) and a site compatible with the silylated polyolefin (B). 3.   The (C) compatibilizer includes at least one selected from the group consisting of a block copolymer of propylene and ethylene and a block copolymer of ethylene and ethylene / butylene copolymer. 3. The resin composition according to item 1.   The mass ratio of the content of the (C) compatibilizer to the content of the (B) silylated polyolefin (the mass of the (C) compatibilizer / the mass of the (B) silylated polyolefin) is 0.05 to 20. The resin composition according to claim 2 or 3, wherein   The resin composition according to any one of claims 1 to 4, further comprising (D) a silicone.   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 6, wherein the liquid-repellent layer has a degree of crystallinity represented by the following formula (I) of 45 to 55%.

  The liquid-repellent film according to claim 6, further comprising one or more resin layers provided on one main surface of the liquid-repellent layer. The melting point T ₁ (° C.) of the (A) polypropylene resin in the liquid repellent layer and the melting point T ₂ (° C.) of the resin contained in the resin layer in contact with the liquid repellent layer among the one or more resin layers. _but satisfies the relation of T 1 _{<T 2,} liquid repellent film according to claim 8.   A substrate, comprising the liquid-repellent film according to any one of claims 6 to 9 provided on the substrate, wherein the liquid-repellent layer is disposed on at least one outermost surface, Liquid repellent laminate. Edible oil is filled into the liquid-repellent laminate formed in a bag shape so that the liquid-repellent layer is on the inner surface so as to be in contact with the entire inner surface, and is sealed. The conditions are as follows: temperature 121 ° C., pressure 0.2 MPa, 30 minutes. in oil swell weight per unit area of the liquid repellent laminate after the heat and pressure treatment by steam, is 1.0 mg / cm ² or less, liquid repellent laminate according to claim 10.   A packaging material formed using the liquid-repellent laminate according to claim 10.   The packaging material according to claim 12, which is used for a purpose of 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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