JP7139824B2 - Liquid-repellent layer-forming resin composition, and liquid-repellent film, liquid-repellent laminate, packaging material, and container using the same - Google Patents

Description

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

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

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

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

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

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

Polyolefin resins such as polyethylene and polypropylene are used as the material for the resin layer on the inner surface of the packaging material as a material that imparts functions such as heat sealability, heat resistance and impact resistance. However, even when the above-described silicone particles are added to the polyolefin resin to impart liquid repellency, aggregation of the silicone particles within the resin layer and release of the silicone particles from the resin layer tend to occur, resulting in packaging problems. 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 problems of the prior art, and provides a resin composition capable of forming a liquid-repellent layer having excellent liquid repellency that can sufficiently suppress adhesion of contents, and , to provide 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 resin composition for forming a liquid-repellent layer containing (A) a polypropylene resin and (B) a silylated polyolefin, wherein the (A) polypropylene resin comprises the above A second temperature rise obtained under measurement conditions in which the following steps (1) to (5) are sequentially performed in differential scanning calorimetry using a liquid-repellent layer formed using a liquid-repellent layer-forming resin composition as a measurement sample. Provided is a resin composition for forming a liquid-repellent layer, which has two or more endothermic peaks within the range of 130 to 170° C. in its melting curve at 20° C.
(1) Heat up to 200° C. at a rate of 10° C./min as the first temperature rise.
(2) Hold at 200°C for 5 minutes.
(3) Lowering the temperature to 0°C at a temperature lowering rate of 100°C/min.
(4) Hold at 0°C for 5 minutes.
(5) Heat up to 200°C at a rate of 10°C/min as the second temperature rise.

According to the liquid-repellent layer-forming resin composition, (A) polypropylene resin and (B) silylated polyolefin, which is a component that imparts liquid repellency to the liquid-repellent layer, are used in combination, and (A) polypropylene resin However, by having two or more endothermic peaks in the range of 130 to 170 ° C. in the melting curve at the second temperature rise described above, when the liquid-repellent layer is formed, (B) the silylated polyolefin Si segregates easily on the surface of the liquid-repellent layer, and excellent liquid-repellency can be obtained that can sufficiently suppress adhesion of contents. Here, the inventors of the present invention speculate as follows about the reason why the above effects are exhibited when the polypropylene resin (A) satisfies the above conditions.

When the polypropylene resin has only one endothermic peak within the range of 130 to 170 ° C. in the melting curve at the time of the second heating, a single crystal phase is formed, and the peak temperature is as follows. properties. That is, when the peak temperature is relatively low, the degree of crystallinity of the polypropylene resin is relatively low, and Si in the silylated polyolefin (B) tends to segregate on the surface of the liquid-repellent layer when the liquid-repellent layer is formed. The amount of oil swelling into the liquid-repellent layer increases. When the amount of oil swelling in the liquid-repellent layer increases, the amount of residual liquid increases accordingly, and a large amount of oil segregates on the surface of the liquid-repellent layer. decreases, and the amount of residual liquid increases further. On the other hand, when the peak temperature is relatively high, the degree of crystallinity of the polypropylene resin is relatively high, and the amount of oil swelling of the formed liquid-repellent layer can be reduced. The liquid property is lowered and the amount of residual liquid is increased.

On the other hand, the appearance of a plurality of endothermic peaks in the melting curve during the second temperature rise means that separate crystallization has occurred in the polypropylene resin. That is, it means that a plurality of different crystal phases are formed in the polypropylene resin by cooling after the first temperature rise. As a result, intermediate properties between relatively low and relatively high peak temperatures of the polypropylene resin having only one endothermic peak within the range of 130 to 170° C. can be exhibited. As a result, it is possible to achieve both a reduction in the amount of oil swelling of the formed liquid-repellent layer 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.

The liquid-repellent layer-forming resin composition has a peak temperature of the endothermic peak on the highest temperature side within the range of 130 to 170 ° C. and an endothermic peak on the lowest temperature side in the melting curve at the time of the second temperature rise. The difference from the peak temperature may be 10°C or more. When the difference between the peak temperatures is 10° C. or more, it is possible to reduce the amount of oil swelling of the liquid-repellent layer to be formed and increase the amount of Si present on the surface of the liquid-repellent layer at a higher level. As a result, better liquid repellency can be obtained.

In the liquid-repellent layer-forming resin composition, the polypropylene resin (A) has an endothermic peak in the range of 130° C. or higher and lower than 150° C. and 150° C. or higher and 170° C. in the melting curve at the time of the second temperature rise. You may have one or more of each within the following ranges. As a result, it is possible to achieve both a reduction in the amount of oil swelling in the formed liquid-repellent layer and an increase in the amount of Si present on the surface of the liquid-repellent layer at a higher level, and as a result, obtain better liquid repellency. be able to.

In the liquid-repellent layer-forming resin composition, the polypropylene resin (A) contains a first polypropylene resin and a second polypropylene resin having a melting point higher than that of the first polypropylene resin by 10° C. or more. good too. (A) The polypropylene resin contains first and second polypropylene resins having melting points different from each other by 10°C or more, thereby reducing the amount of oil swelling of the formed liquid-repellent layer and improving the amount of Si present on the surface of the liquid-repellent layer. can be made compatible at a higher level, and as a result, more excellent liquid repellency can be obtained.

In the resin composition for forming a liquid-repellent layer, the (A) polypropylene resin is a mixture of the first polypropylene resin and the second polypropylene resin in a mass ratio (mass of the first polypropylene resin/second polypropylene Resin mass) may be contained in the range of 20/80 to 80/20. When the mass ratio of the first and second polypropylene resins is within the above range, the amount of oil swelling of the liquid-repellent layer to be formed is reduced and the amount of Si present on the surface of the liquid-repellent layer is improved at a higher level. Both can be made compatible, and as a result, more excellent liquid repellency can be obtained.

The liquid-repellent layer-forming resin composition may further contain (C) a compatibilizer having a site that is compatible with the (A) polypropylene resin and a site that is compatible with the (B) silylated polyolefin. good. By using (C) the compatibilizing agent, the dispersibility of (B) the silylated polyolefin is further improved, and the formed liquid-repellent layer can be efficiently imparted with liquid-repellent properties.

In the liquid-repellent layer-forming resin composition, 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. At least one selected may be included. By using these compatibilizers (C), the dispersibility of the silylated polyolefin (B) can be further improved, and the formed liquid-repellent layer can be provided with liquid repellency more efficiently.

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

The liquid-repellent layer-forming resin composition may further contain (D) silicone. By further containing (D) silicone, the amount of Si present on the surface of the formed liquid-repellent layer can be increased, thereby further improving the liquid-repellency.

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

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

When the liquid-repellent film is provided with 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 The melting point T ₂ (° C.) of the resin contained in the resin layer in contact with may satisfy the relationship of T ₁ <T ₂ . By satisfying the above relationship, from the viewpoint of crystallinity, the (B) silylated polyolefin in the liquid-repellent layer can be suppressed from migrating to the second resin layer, and (B) silylation on the surface of the liquid-repellent layer can be suppressed. Since the polyolefin can be unevenly distributed or the efficiency of bleeding out can be improved, there is a tendency 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 the body According to such a liquid-repellent laminate, by providing the liquid-repellent film of the present invention, adhesion of contents to the liquid-repellent layer can be sufficiently suppressed. Further, by laminating the liquid-repellent film on a substrate having a desired function, the liquid-repellent laminate can be imparted with functions such as mechanical strength, barrier properties, and light-shielding properties.

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

The packaging material may be used for applications where heat treatment at 80° C. or higher is performed. According to the packaging material according to the present embodiment, even when used for such purposes, 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, at least on its inner surface, a liquid-repellent layer formed using the resin composition of the present invention. Since such a container includes a liquid-repellent layer formed using the resin composition for forming a liquid-repellent layer of the present invention, it is possible to sufficiently suppress adhesion of contents to the liquid-repellent layer. .

According to the present invention, a resin composition capable of forming a liquid-repellent layer having excellent liquid repellency capable of sufficiently suppressing adhesion of contents, a liquid-repellent film using the same, and a liquid-repellent Laminates, packaging and containers can be provided.

1 is a schematic cross-sectional view of a liquid-repellent laminate according to one embodiment of the present invention; FIG. 1 is a schematic cross-sectional view of a liquid-repellent laminate according to one embodiment of the present invention; FIG. It is a schematic diagram explaining the liquid-repellent evaluation method of a liquid-repellent laminated body. 3 is a diagram showing a melting curve of the liquid-repellent layer obtained in Example 1 at the second temperature rise. FIG. FIG. 10 is a diagram showing a melting curve of the liquid-repellent layer obtained in Example 2 at the second temperature rise. FIG. 10 is a diagram showing a melting curve of the liquid-repellent layer obtained in Example 3 at the second temperature rise. FIG. 10 is a diagram showing a melting curve of the liquid-repellent layer obtained in Comparative Example 2 at the second temperature rise. FIG. 10 is a diagram showing a melting curve of the liquid-repellent layer obtained in Comparative Example 3 at the second temperature rise.

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

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

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

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

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

<Resin composition for liquid-repellent layer formation>
The resin composition for forming a liquid-repellent layer according to one embodiment of the present invention includes (A) a polypropylene resin (hereinafter also referred to as "(A) component"), (B) a silylated polyolefin (hereinafter referred to as "(B) component ”). Then, the (A) polypropylene resin is obtained by performing the following steps (1) to (5) in differential scanning calorimetry using a liquid-repellent layer formed using the liquid-repellent layer-forming resin composition as a measurement sample. The melting curve at the second temperature rise obtained under the successive measurement conditions has two or more endothermic peaks within the range of 130 to 170°C.
(1) Heat up to 200° C. at a rate of 10° C./min as the first temperature rise.
(2) Hold at 200°C for 5 minutes.
(3) Lowering the temperature to 0°C at a temperature lowering rate of 100°C/min.
(4) Hold at 0°C for 5 minutes.
(5) Heat up to 200°C at a rate of 10°C/min as the second temperature rise.

The resin composition for forming a liquid-repellent layer according to the present embodiment includes (C) a compatibilizer having a site compatible with the (A) polypropylene resin and a site compatible with the (B) silylated polyolefin, and (D) One or both of silicones may be further contained.

((A) polypropylene resin)
Polypropylene resins (PP) include homopolypropylene, block polypropylene, random polypropylene, and copolymers of propylene and α-olefins other than ethylene and propylene (propylene-based copolymers). Examples of α-olefin components 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 packaging materials such as retort food packaging materials that are subjected to heat treatment such as hot water bathing. It becomes easy to prevent bag breakage by heat treatment such as.

In the present embodiment, the polypropylene resin has two or more endothermic peaks within the range of 130 to 170° C. in the melting curve during the second heating measured under the conditions described above. The appearance of multiple endothermic peaks in the melting curve during the second temperature rise means that separate crystallization has occurred in the polypropylene resin. Examples of the method of causing separate crystallization include a method of blending different crystalline polypropylene resins. Thereby, different crystal phases can be formed by cooling after the first temperature rise. More specifically, a method of blending a random polypropylene resin and a block polypropylene resin, a method of blending a random polypropylene resin and a homopolypropylene resin, a method of blending two or more random polypropylene resins having different melting points, and a method of blending two or more random polypropylene resins having different melting points. A method of blending two or more kinds of block polypropylene resins, and the like.

The polypropylene resin preferably includes a first polypropylene resin and a second polypropylene resin having a melting point higher than that of the first polypropylene resin by 10° C. or more. The melting point difference between the second polypropylene resin and the first polypropylene resin is more preferably 15° C. or higher, still more preferably 20° C. or higher, particularly preferably 25° C. or higher, and 30° C. or higher. is highly preferred. When the melting point difference is equal to or greater than the above lower limit, it is possible to achieve both a reduction in the amount of oil swelling in the liquid-repellent layer to be formed and an increase in the amount of Si present on the surface of the liquid-repellent layer at a higher level. , more excellent liquid repellency can be obtained. When the polypropylene resin contains three or more kinds of polypropylene resins, the melting point difference between the polypropylene resin with the highest melting point and the polypropylene resin with the lowest melting point should be within the above range.

In the polypropylene resin, the mass ratio of the first polypropylene resin and the second polypropylene resin (mass of the first polypropylene resin/mass of the second polypropylene resin) is 20/80 to 80/20 (0.25 to 4.0). The above mass ratio is more preferably 30/70 to 70/30 (0.43 to 2.3), more preferably 35/65 to 65/35 (0.54 to 1.9). , 40/60 to 60/40 (0.67 to 1.5). When the mass ratio is equal to or higher than the above lower limit, Si can be more easily segregated on the surface of the formed liquid-repellent layer, and the liquid-repellent property can be further improved. On the other hand, when the mass ratio is equal to or less than the above upper limit, it is possible to further reduce the amount of oil swelling of the formed liquid-repellent layer. When the amount of oil swelling in the liquid-repellent layer is low, the amount of residual liquid can be reduced accordingly, and the amount of oil on the surface of the liquid-repellent layer is reduced, so Si segregates more easily on the surface of the liquid-repellent layer. and the liquid repellency can be further improved.

Here, the first polypropylene resin is preferably a random polypropylene resin, and the second polypropylene resin is preferably a block polypropylene resin. Whether the polypropylene resin includes random polypropylene resin and block polypropylene resin can be confirmed, for example, by analyzing the formed liquid-repellent layer by infrared spectroscopy (IR).

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

The above random polypropylene resin and block polypropylene resin may be used alone or in combination of two or more.

The number of endothermic peaks observed in the range of 130 to 170° C. in the melting curve during the second heating is two or more, but may be three or more. Further, the number of endothermic peaks may be 5 or less, or 4 or less. When the number of endothermic peaks is within the above range, the formed liquid-repellent layer can have good liquid repellency.

In the melting curve at the time of the second heating, the difference between the peak temperature of the endothermic peak on the highest side and the peak temperature of the endothermic peak on the lowest side within the range of 130 to 170 ° C. is 10 ° C. or more. It is preferably 15° C. or higher, and even more preferably 20° C. or higher. When the difference between the peak temperatures is equal to or greater than the above lower limit, it is possible to achieve both a reduction in the amount of oil swelling in the formed liquid-repellent layer and an increase in the amount of Si present on the surface of the liquid-repellent layer at a higher level. , and as a result, better liquid repellency can be obtained.

It is preferable that the melting curve during the second temperature rise has one or more endothermic peaks in the range of 130°C or higher and lower than 150°C and in the range of 150°C or higher and 170°C or lower. As a result, it is possible to achieve both a reduction in the amount of oil swelling in the formed liquid-repellent layer and an increase in the amount of Si present on the surface of the liquid-repellent layer at a higher level, and as a result, obtain better liquid repellency. be able to.

Differential scanning calorimetry (DSC) can be performed according to JIS K7121-1987, except that the heating and cooling conditions are performed under the conditions (1) to (5) above. A liquid-repellent layer obtained by forming a film of a liquid-repellent layer-forming resin composition can be used as a measurement sample (test piece).

The liquid-repellent layer-forming resin composition according to the present embodiment may contain a polyolefin resin other than the polypropylene resin. Other polyolefin resins include, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, and ethylene-α-olefin copolymers. Examples of α-olefin components 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. Besides 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 sealability and strength properties (tensile strength, impact strength, etc.), and the linear polyolefin may be linear or branched.

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

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

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

((B) silylated polyolefin)
The silylated polyolefin is a component that imparts liquid repellency to the liquid repellent layer 11 . A silylated polyolefin is a polyolefin unit with a silicone moiety.

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

From the viewpoint of further improving the liquid repellency of the liquid repellent layer 11, the silylated polyolefin is preferably a block copolymer rather 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 silylated polyolefins mentioned above can be used singly or in combination of two or more.

The silylated polyolefin may or may not be compatible (incompatible) with the (A) polypropylene resin at the polyolefin site. However, when using a silylated polyolefin whose polyolefin moiety is incompatible with (A) the polypropylene resin, it is preferable to use the following (C) compatibilizer together. In addition, when using a silylated polyolefin in which the polyolefin part is incompatible with (A) polypropylene resin, there are more options for combining materials of (A) polypropylene resin and (B) silylated polyolefin, and depending on the purpose and application There is an advantage that the design is possible and the liquid repellency tends to be improved more easily. Examples of the silylated polyolefin whose polyolefin part is compatible with the (A) polypropylene resin include PP-Si graft copolymers, and examples of the silylated polyolefin whose polyolefin part is incompatible with the (A) polypropylene resin include: Examples include PE-Si graft copolymers and PE-Si block copolymers.

((C) compatibilizer)
A 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 site that is compatible with (A) the polypropylene resin and a site that is compatible with the (B) silylated polyolefin. By using a compatibilizing agent, the compatibility between (A) polypropylene resin and (B) silylated polyolefin whose polyolefin moiety is incompatible with (A) polypropylene resin can be improved.

The (A) site compatible with the polypropylene resin includes a polyolefin structure compatible with the (A) polypropylene resin, and is preferably a site having the same polyolefin structure as the (A) polypropylene resin. That is, (C) the compatibilizer preferably has a polypropylene structure. Further, when the (A) polypropylene resin is a copolymer composed of two or more olefins such as a propylene-α-olefin copolymer, the (C) compatibilizer is mainly It preferably has at least a structure obtained by polymerizing or copolymerizing the same kind of olefin as the component olefin.

(B) The site that is compatible with the silylated polyolefin includes a polyolefin structure that is compatible with the polyolefin site of the (B) silylated polyolefin, and has the same polyolefin structure as the polyolefin site of the (B) silylated polyolefin. A site is preferred. That is, when the polyolefin portion of (B) the silylated polyolefin has a polyethylene structure, the (C) compatibilizer preferably has a polyethylene structure. In addition, when the polyolefin moiety of (B) the silylated polyolefin has a structure based on a copolymer consisting of two or more olefins such as an ethylene-α-olefin copolymer and a propylene-α-olefin copolymer, (C) The compatibilizing agent preferably has at least a structure obtained by polymerizing or copolymerizing an olefin of the same kind as the olefin constituting the main component among the olefins constituting the copolymer.

As the (C) compatibilizer, for example, a block copolymer of ethylene and propylene or a block copolymer of ethylene and an ethylene/butylene copolymer can be used. When these compatibilizers are used, it is preferable to use those having polyethylene moieties 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 compatible with the polyethylene portion of

The above compatibilizers may be used singly 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 silicone include silicone oil, silicone resin, silicone oligomer, and silicone powder. Among these, silicone oil is preferable because better liquid repellency can be easily obtained.

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

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

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

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

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

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

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

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

When the liquid-repellent layer-forming resin composition contains component (C), the mass ratio of the content of component (C) to the content of component (B) (mass of component (C)/mass of component (B)) may be 0.01 to 50, preferably 0.04 to 30, more preferably 0.05 to 20, even more preferably 0.05 to 15. If the content ratio is at least the above lower limit, the (B) silylated polyolefin can be sufficiently dispersed in the liquid-repellent layer, and there is a tendency that better liquid repellency can be obtained. On the other hand, when the content ratio is equal to or less than the above upper limit, it is possible to prevent the (B) silylated polyolefin from being coated with an excessive amount of the compatibilizer (C), thereby obtaining better liquid repellency. Tend. In addition, when the content ratio exceeds the above upper limit, even if (C) compatibilizer is added, (B) silylated polyolefin will not be dispersed any more, and the effect of improving liquid repellency will not be seen. There is

When the liquid-repellent layer-forming resin composition contains component (D), the content thereof is preferably 0.1 to 20.0% by mass based on the total amount of the liquid-repellent layer-forming resin composition. 0 to 15.0% by mass, and even more preferably 2.0 to 10.0% by mass. When the total content of component (D) is at least the above lower limit, liquid repellency tends to be improved. On the other hand, if the total content of the component (D) is less than the above upper limit, the content of the component (A) is relatively increased, so that good heat-sealability tends to be obtained.

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

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

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

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

The thermoplastic resin used for the second resin layer 12 preferably contains a polyolefin resin, since heat sealability, heat resistance, and impact resistance are likely to be improved. As the polyolefin resin, the same one 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 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, the (B) silylated polyolefin in the liquid-repellent layer 11 can be suppressed from migrating to the second resin layer 12 from the viewpoint of crystallinity, and the (B) to the surface of the liquid-repellent layer 11 can be suppressed. ) Since the uneven distribution or bleeding out efficiency of the silylated polyolefin can be improved, the liquid repellency tends to be further improved. From the same point of view, the melting point T2 is preferably higher _than the melting point T1 by ₁ °C or more, more preferably by 3°C or more.

Here, the melting point T1 is the melting point of the ( _A ) polypropylene resin measured in the liquid-repellent layer 11 using the liquid-repellent layer 11 as a measurement sample. Similarly, the melting point T2 is the melting point of the resin measured in the _second resin layer 12 using the second resin layer 12 as a measurement sample. The melting point T1 indicates the melting _point of the polypropylene resin that melts at the lowest temperature in the liquid-repellent layer 11 when the liquid-repellent layer 11 contains two or more polypropylene resins having different melting points as the (A) polypropylene resin. , and is affected by other polypropylene resins, etc., so it differs from the melting point measured for polypropylene resin alone. The melting point T1 of the (A) polypropylene resin in the liquid-repellent layer ₁₁ and the melting point T2 of the resin in the _second resin layer 12 are measured by a thermal analyzer (for example, TA7000 manufactured by Hitachi High-Tech Science Co., Ltd.). can do.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the liquid-repellent laminate according to the present embodiment, the liquid-repellent laminate is formed in the shape of a bag so that the liquid-repellent layer is on the inner surface. The amount of oil swelling per unit area of the liquid-repellent laminate is 1.0 mg/cm ² or less after being subjected to heat and pressure treatment with water vapor under conditions of 121° C., pressure of 0.2 MPa, and 30 minutes. 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 the contents are discharged. The amount can be further reduced. From the same point of view, the oil swelling amount is more preferably 0.95 mg/cm ² or less. On the other hand, the liquid-repellent layer may swell to some extent with oils and fats from the viewpoint of improving the slideability of the contents, and the oil swelling amount may be 0.5 mg/cm ² or more.

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

The packaging material may be used for applications where heat treatment at 80° C. or higher is performed. Specifically, it may be used for packaging materials such as retort food packaging materials that are subjected to heat treatment such as boiling in hot water. According to the packaging material according to the present embodiment, even when used for such purposes, it is possible to prevent the contents from adhering or remaining 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 at least the inner surface (on the content side) a liquid-repellent layer formed using the liquid-repellent layer-forming resin composition described above. Specific examples of containers include storage containers for liquids such as chemicals and pharmaceuticals, semi-solids, and gel-like substances, and bottles for containing hand soaps, shampoos, and the like. By forming the container so that the liquid-repellent layer is arranged on the inner surface of the container (on the content side), it is possible to suppress the adhesion and residue of contents such as liquids, semi-solids, and gel-like substances on the inner surface of the container. can.

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

[Example 1]
<Preparation of resin composition for forming liquid-repellent layer>
As component (A), (A1) 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 "Novatec", melting point 165-166 ° C. (catalog value), manufactured by Japan Polypropylene Corporation, hereinafter "b-PP" (sometimes abbreviated as )) and (B) component silylated polyethylene (PE-Si block copolymer, manufactured by Dow Corning Toray Co., Ltd., hereinafter sometimes abbreviated as “PE-Si”) are mixed. 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 and b-PP in component (A) (mass of r-PP/mass of b-PP) is 20/80, and (A ) component and (B) component were adjusted so that the component (B) was 5% by mass and the balance was the component (A).

<Preparation of liquid-repellent laminate>
Using a three-layer co-extrusion machine, the liquid-repellent layer-forming resin composition was extruded into a film to obtain a liquid-repellent film having a liquid-repellent layer with a thickness of 60 μm. The resulting liquid-repellent film and a 38 μm-thick PET film (trade name “EMBRET”, manufactured by Unitika Ltd.) as a substrate were dried using a polyurethane adhesive (manufactured by Mitsui Chemicals, Inc.). It was laminated and aged at 50° C. for 5 days to obtain a liquid-repellent laminate.

[Examples 2-3]
A liquid-repellent layer was prepared in the same manner as in Example 1, except that the mass ratio of r-PP and b-PP in the component (A) in the liquid-repellent layer-forming resin composition was changed as shown in Table 1. A forming resin composition, a liquid-repellent film, and a liquid-repellent laminate were prepared.

[Example 4]
Silicone oil (dimethyl silicone, manufactured by Dow Corning Toray Co., Ltd., hereinafter sometimes abbreviated as “silicone”) as component (D) is further added to the liquid-repellent layer-forming resin composition, and the content of each component is 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 2, except that the was adjusted. In the liquid-repellent layer-forming resin composition, the contents of components (B) and (D) based on the total amount of components (A), (B) and (D) are the values shown in Table 1. was adjusted to be

[Examples 5-16 and 18-20]
A block copolymer of ethylene and an ethylene-butylene copolymer (hereinafter sometimes abbreviated as "PE-Et/Bu") or propylene, which is the component (C), is added to the liquid-repellent layer-forming resin composition. A liquid-repellent layer-forming resin was prepared in the same manner as in Example 1, except that a block copolymer with ethylene (hereinafter sometimes abbreviated as "PP-PE") was further added and the content of each component was adjusted. A composition, a liquid-repellent film and a liquid-repellent laminate were produced. In the liquid-repellent layer-forming resin composition, the mass ratio of r-PP and b-PP in component (A), the type of component (C), and components (A), (B), and (C) The contents of component (B) and component (C) based on the total amount of components were adjusted to the values shown in Table 1, respectively.

[Example 17]
A block copolymer of propylene and ethylene (PP-PE) as component (C) and a silicone oil (silicone) as component (D) are further added to the liquid-repellent layer-forming resin composition. A resin composition for forming a liquid-repellent layer, a liquid-repellent film, and a liquid-repellent laminate were produced in the same manner as in Example 2, except that the contents of the components were adjusted. In the liquid-repellent layer-forming resin composition, the amount of component (B), component (C) and component (D) based on the total amount of component (A), component (B), component (C) and component (D) The contents were adjusted to the values shown in Table 1, respectively.

[Example 21]
<Preparation of resin composition for forming liquid-repellent layer>
Example 1, except that a block copolymer of propylene and ethylene (PP-PE), which is the component (C), was further added to the liquid-repellent layer-forming resin composition, and the content of each component was adjusted. Similarly, a resin composition for forming a liquid-repellent layer was prepared. In the liquid-repellent layer-forming resin composition, the contents of components (B) and (C) based on the total amount of components (A), (B) and (C) are the values shown in Table 2. was adjusted to be

<Preparation of liquid-repellent laminate>
The (A1) random polypropylene resin (r-PP), which is the component (A), was used as the resin composition for forming the second resin layer. Using a three-layer co-extrusion machine, the liquid-repellent layer-forming resin composition and the second resin layer-forming resin composition are co-extruded to form a film, forming a liquid-repellent layer with a thickness of 15 μm and a second resin composition with a thickness of 45 μm. A liquid-repellent film consisting of a resin layer was obtained. The second resin layer of the obtained liquid-repellent film and a PET film with a thickness of 38 μm (trade name “EMBRET”, manufactured by Unitika Ltd.) as a base material are bonded together with a polyurethane adhesive (Mitsui Chemicals, Inc. (manufactured) to obtain a liquid-repellent laminate.

[Examples 22 to 30]
The mass ratio of r-PP and b-PP in component (A) and the contents of components (B) and (C) in the liquid-repellent layer-forming resin composition were adjusted to the values shown in Table 2. A liquid-repellent layer-forming resin composition, a second resin layer-forming resin composition, a liquid-repellent film, and a liquid-repellent laminate were produced in the same manner as in Example 21 except for the adjustments.

[Example 31]
A block copolymer (PE-Et/Bu) of ethylene and an ethylene-butylene copolymer is used as the (C) component in the liquid-repellent layer-forming resin composition, and the second resin layer-forming resin composition ( A) A resin composition for forming a liquid-repellent layer, a resin composition for forming a second resin layer, a resin composition for forming a second resin layer, and A liquid-repellent film and a liquid-repellent laminate were produced.

[Example 32]
A resin composition for forming a liquid-repellent layer was prepared in the same manner as in Example 21, except that block polypropylene resin (b-PP), which is component (A), was used as the second resin layer-forming resin composition. , a resin composition for forming a second resin layer, a liquid-repellent film, and a liquid-repellent laminate were prepared.

[Examples 33-41]
The mass ratio of r-PP and b-PP in component (A) and the contents of components (B) and (C) in the liquid-repellent layer-forming resin composition were adjusted to the values shown in Table 2. A liquid-repellent layer-forming resin composition, a second resin layer-forming resin composition, a liquid-repellent film, and a liquid-repellent laminate were produced in the same manner as in Example 32 except for the adjustments.

[Comparative Example 1]
A liquid-repellent layer-forming resin composition and a second resin layer-forming resin composition were prepared in the same manner as in Example 24, except that the components (B) and (C) were not added to the liquid-repellent layer-forming resin composition. A resin composition, a liquid-repellent film and a liquid-repellent laminate were produced.

[Comparative Example 2]
In the same manner as in Example 21, except that r-PP was used alone as the component (A) in the liquid-repellent layer-forming resin composition, and component (C) was not added to the liquid-repellent layer-forming resin composition. , a liquid-repellent layer-forming resin composition, a second resin layer-forming resin composition, a liquid-repellent film, and a liquid-repellent laminate were prepared.

[Comparative Example 3]
In the same manner as in Example 21, except that b-PP was used alone as the component (A) in the liquid-repellent layer-forming resin composition, and component (C) was not added to the liquid-repellent layer-forming resin composition. , a liquid-repellent layer-forming resin composition, a second resin layer-forming resin composition, a liquid-repellent film, and a liquid-repellent laminate were prepared.

Tables 1 and 2 show the mass ratio of the content of component (C) to the content of component (B) in the liquid-repellent layer (mass of component (C)/mass of component (B)). Tables 1 and 2 also show the melting point T ₁ (° C.) of the resin as component (A) measured in the liquid-repellent layer, and the melting point of the resin as component (A) used in the second resin layer. The magnitude relationship with the melting point T ₂ (°C) is shown. When the liquid-repellent layer contains r-PP and b-PP as the (A) component, the melting point T1 indicates the melting point of r-PP which melts at _a lower temperature in the liquid-repellent layer, but b-PP It differs from the melting point measured for r-PP alone. The melting point T1 of the component (A) in the liquid-repellent layer and the melting point T2 of the resin in the _second resin layer _were measured with a thermal analyzer (TA7000, manufactured by Hitachi High-Tech Science Co., Ltd.).

[Differential scanning calorimetry (DSC)]
Differential scanning calorimetry (DSC) was performed in accordance with JIS K7121-1987 using the liquid-repellent layers of the liquid-repellent films prepared in Examples and Comparative Examples as measurement samples. DSC 6220 and SII EXTAR 6000 manufactured by Hitachi High-Tech Science Co., Ltd. (formerly SII Nanotechnology Co., Ltd.) were used as measuring instruments. The measurement conditions were such that the following steps (1) to (5) were performed sequentially.
(1) Heat up to 200° C. at a rate of 10° C./min as the first temperature rise.
(2) Hold at 200°C for 5 minutes.
(3) Lowering the temperature to 0°C at a temperature lowering rate of 100°C/min.
(4) Hold at 0°C for 5 minutes.
(5) Heat up to 200°C at a rate of 10°C/min as the second temperature rise.

The number of endothermic peaks present in the range of 130 to 170° C. and the peak temperature were determined from the melting curve at the time of the second heating obtained in the above measurement. The results are shown in Tables 1 and 2. 4 to 8 show the melting curves of the liquid-repellent layers of Examples 1 to 3 and Comparative Examples 2 to 3 at the second temperature rise.

[Evaluation of liquid repellency]
<Residual liquid evaluation 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 were prepared by cutting the liquid-repellent laminate into a size of 150 mm long and 138 mm wide. Two samples 100 are stacked so that the liquid-repellent layer of each is on the inside, and one side of the longitudinal end and two sides of the lateral end are sealed with a heat sealer at 190° C., 0.03 MPa, 2 sec. The pouch was heat-sealed over a width of 10 mm under conditions to form a sealed portion 51, and a pouch having one longitudinal end open was produced (see FIG. 3(a)). Next, 180 g of the oil-in-water dispersion type liquid 54 (trade name “Boncurry Gold Medium Spicy”, lipid content 7.0 g / 180 g, manufactured by Otsuka Foods Co., Ltd.) was injected from the opening of the pouch (Fig. 3 (b )). After that, the opening was heat-sealed over a width of 10 mm with a heat sealer under the conditions of 190° C., 0.03 MPa, and 2 sec to form a sealed portion 51, thereby sealing the pouch (see FIG. 3(c)).

After the sealed pouch is put into a high-temperature and high-pressure cooking sterilizer (manufactured by Hitachi Capital Co., Ltd.), retort treatment is performed at 121 ° C. for 30 minutes with high-temperature steam at a pressure of 0.2 MPa, and the sealed pouch is heated at 100 ° C. It was boiled in hot water for 5 minutes. Immediately after the above treatment, the top of the sealed pouch was cut to form a spout (see Figure 3(d)). Next, the pouch was turned upside down, and the spout was held at an angle of 45° from the horizontal surface for 10 seconds, the oil-in-water dispersion liquid 54 was discharged into the container 56, and the discharge amount was weighed by the scale 57 (( e)). From the weighed discharge amount, the residual liquid amount (%) was determined by the following formula.
Remaining liquid amount (%) = {( 180 - discharge amount) / 180 } x 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. Evaluation results are shown in Tables 1 and 2.
◎: Average residual liquid amount is less than 6.5% ○: Average residual liquid amount is 6.5% or more and less than 8.0% △: Average residual liquid amount is 8.0% or more and less than 10.0% ×: Average residual liquid amount Liquid volume is 10.0% or more

<Appearance evaluation after retort treatment>
In the above residual liquid evaluation, the liquid discharge behavior was visually observed when the liquid was discharged from the pouch, and the external appearance was evaluated according to the following evaluation criteria. The results are shown in Tables 1 and 2.
⊚: Appearance of repelling the liquid cleanly, and very little adhesion to the liquid-repellent laminate.
◯: Appearance of repelling the liquid, little adhesion to the liquid-repellent laminate.
Δ: Appears to repel the liquid, but adheres to the liquid-repellent laminate.
x: A state of repelling the liquid is not observed.

As is clear from the results shown in Tables 1 and 2, according to the liquid-repellent laminates of Examples 1-41, compared with the liquid-repellent laminates of Comparative Examples 1-3, the liquid repellency is improved. confirmed that it can be improved.

DESCRIPTION OF SYMBOLS 1, 2... Liquid-repellent laminated body 10... Liquid-repellent film 11... Liquid-repellent 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 evaluation of liquid-repellent laminate.

Claims (14)

A resin composition for forming a liquid-repellent layer containing (A) a polypropylene resin and (B) a silylated polyolefin having a silicone moiety in a polyolefin unit ,
The (A) polypropylene resin is a first polypropylene resin and a second polypropylene resin having a melting point higher than the first polypropylene resin by 10 ° C. or more, in a mass ratio (mass of the first polypropylene resin / second mass of polypropylene resin) in the range of 20/80 to 80/20,
The first polypropylene resin is a random polypropylene resin, the second polypropylene resin is a block polypropylene resin,
The (B) silylated polyolefin is a PE-Si graft copolymer, a PE-Si block copolymer, or a PP-Si graft copolymer,
The content of the (A) polypropylene resin is 50.0 to 95.0% by mass based on the total solid content of the liquid-repellent layer-forming resin composition,
The following steps (1) to (5) are sequentially performed in differential scanning calorimetry using a liquid-repellent layer formed of the polypropylene resin (A) using the liquid-repellent layer-forming resin composition as a measurement sample. A resin composition for forming a liquid-repellent layer, which has two or more endothermic peaks within the range of 130 to 170° C. in the melting curve at the second temperature rise obtained under the measurement conditions.
(1) Heat up to 200° C. at a rate of 10° C./min as the first temperature rise.
(2) Hold at 200°C for 5 minutes.
(3) Lowering the temperature to 0°C at a temperature lowering rate of 100°C/min.
(4) Hold at 0°C for 5 minutes.
(5) Heat up to 200°C at a rate of 10°C/min as the second temperature rise. In the melting curve during the second heating, the difference between the peak temperature of the endothermic peak on the highest side and the peak temperature of the endothermic peak on the lowest side within the range of 130 to 170 ° C. is 10 ° C. or more. , The resin composition of claim 1. The (A) polypropylene resin has one or more endothermic peaks in the range of 130 ° C. or higher and lower than 150 ° C. and in the range of 150 ° C. or higher and 170 ° C. or lower in the melting curve at the time of the second temperature rise. The resin composition according to claim 1 or 2. 4. The compatibilizer according to any one of claims 1 to 3 , further comprising (C) a compatibilizer having a site compatible with the (A) polypropylene resin and a site compatible with the (B) silylated polyolefin. Resin composition. 5. The compatibilizing agent (C) comprises at least one selected from the group consisting of a block copolymer of propylene and ethylene and a block copolymer of ethylene and an ethylene - butylene copolymer. The resin composition according to . The mass ratio of the content of the compatibilizer (C) to the content of the silylated polyolefin (B) (mass of the compatibilizer (C)/mass of the silylated polyolefin (B)) is 0.05 to 20. A resin composition according to claim 4 or 5 . (D) The resin composition according to any one of claims 1 to 6 , further comprising silicone. A liquid-repellent film comprising a liquid-repellent layer formed using the resin composition according to any one of claims 1 to 7 . 9. The liquid-repellent film according to claim 8 , further comprising one or more resin layers provided on one main surface of said 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 satisfies the relationship T ₁ <T ₂ . A substrate, and the liquid-repellent film according to any one of claims 8 to 10 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 11 . 13. The packaging material according to claim 12 , which is used for applications that require heat treatment at 80[deg.] C. or higher. A container having, at least on its inner surface, a liquid-repellent layer formed using the resin composition according to any one of claims 1 to 7 .

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