JP6368331B2 - Water repellent heat seal film, water repellent heat seal structure, method for producing water repellent heat seal film, and method for producing water repellent heat seal structure - Google Patents

Description

The present invention is water-repellent heat-sealing film having both high water repellency and high heat sealable with a single layer, water repellent heat-seal structure comprising a water-repellent heat-sealing film, a method of manufacturing a water-repellent heat-sealing film, and water repellency Heat The present invention relates to a method for manufacturing a seal structure.

  Materials having both water repellency and heat sealability have been developed as packaging materials for packaging contents such as foods, beverages, pharmaceuticals, cosmetics, and chemicals.

  For example, Japanese Patent Application Laid-Open No. 2010-184454 (Patent Document 1) is a packaging material made of a laminate having at least a base material layer and a thermal adhesive layer, and the thermal adhesive layer is an outermost layer on one surface of the packaging material. Disclosed is a packaging material in which hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100 nm are adhered to the outermost surface which is laminated and the thermal adhesive layer is not adjacent to other layers.

  Japanese Patent Laying-Open No. 2011-93315 (Patent Document 2) discloses a laminate in which hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100 nm are attached to at least part of the surface of a layer containing a thermoplastic resin. To do.

  Japanese Patent Application Laid-Open No. 2011-184082 (Patent Document 3) has a cover material having at least a base material layer and a heat sealing layer, and has an adhesion preventing layer on the outer surface of the heat sealing layer, and the adhesion preventing layer is a thermoplastic resin. Disclosed is a lid for preventing adhesion of contents comprising a mixed composition of a binder and hydrophobic fine particles.

  Japanese Unexamined Patent Publication No. 2013-39930 (Patent Document 4) is a lid having at least a base material layer and a heat sealing layer, and has an adhesion preventing layer on the outer surface of the heat sealing layer, and the adhesion preventing layer is provided with water repellency. Adhesion of the contents composed of a mixture of hydrophobic wet silica particles and a thermoplastic resin binder, using hydrophobic wet silica particles with hydrophobicity on the surface of porous silica particles obtained by a wet process. A prevention lid is disclosed.

  JP 2013-75715 A (Patent Document 5) is a packaging material including a sheet-like base material and a thermal adhesive layer, and the thermal adhesive layer is laminated on at least one surface of the sheet-like base material. Disclosed is a packaging material in which water repellent particles are attached to the surface opposite to the surface where the adhesive layer is in contact with the sheet-like substrate, and two or more kinds of filler particles having different densities are contained in the thermal adhesive layer.

  Japanese Unexamined Patent Publication No. 2013-180790 (Patent Document 6) is a packaging material that is at least partially heat-sealed during use, and the packaging material includes a sheet-like base material and a heat-sealing layer, and is heat-sealed. Disclosed is a packaging material including a laminate in which a layer is disposed as an outermost layer, and resin beads and water-repellent particles are attached to part or all of the outermost surface of the heat seal layer.

JP 2010-184454 A JP 2011-93315 A JP 2011-184082 A JP 2013-39930 A JP2013-75715A JP 2013-180790 A

  Laminated bodies disclosed in JP 2011-93315 A (Patent Document 2), JP 2010-184454 A (Patent Document 1), JP 2013-75715 A (Patent Document 5), and JP 2013-180790 A. All of the packaging materials disclosed in the publication (Patent Document 6) have a multilayer structure of a heat seal layer and hydrophobic or water repellent particles adhering to a part or all of the outermost surface of the heat seal layer. ing. Moreover, as for the lid | cover material disclosed by Unexamined-Japanese-Patent No. 2011-184082 (patent document 3) and Unexamined-Japanese-Patent No. 2013-39930 (patent document 4), all are the heat sealing layer and the adhesion prevention layer arrange | positioned on the outer surface. And has a plurality of structures. That is, in any of the above patent documents, a material having a multilayer structure of a layer having heat sealing properties and a layer having water repellency has only been developed.

  From the viewpoint of simplification of the structure of the packaging material and cost reduction, there is a demand for the development of a material that combines a single layer with high water repellency and high heat sealability. However, since both the characteristics of heat sealability and water repellency are contradictory to each other in a single layer, a material having high water repellency and high heat sealability in a single layer has not been provided so far.

The present invention overcomes the above problems and is a water repellent heat seal film having a single layer of high water repellency and high heat seal properties, a water repellent heat seal agent as a raw material thereof, and a water repellent heat seal film comprising the water repellent heat seal film. It is an object of the present invention to provide a seal structure, a method for producing a water-repellent heat seal film , and a method for producing a water-repellent heat seal structure .

That is, the present invention includes the following configurations.
[1] A thermoplastic resin, a hydrophobic particle as the first particle, and a second particle having a larger average particle diameter than the hydrophobic particle, and the hydrophobic particle is 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin. 70 parts by mass or more and 110 parts by mass or less, the second particles are 20 parts by mass or more and 100 parts by mass or less, and the thermoplastic resin includes a polyester resin or a polyester resin and a vinyl chloride resin, and in 100 parts by mass of the thermoplastic resin. The content ratio of the polyester resin and the vinyl chloride resin is in the range from 100 parts by weight and 0 parts by weight to 40 parts by weight and 60 parts by weight, respectively, and is a composition for disposing on at least one main surface of the substrate. and a film of a single layer composition ratio is uniform or continuous change, and the contact angle of water on the surface 150 ° or more, the water-repellent heat with heat sealability Lumpur membrane. [2] The water-repellent heat seal film according to [1], wherein the hydrophobic particles are surface-treated with at least one silicon compound selected from the group consisting of organic siloxanes and organic silanes.

[ 3 ] A water-repellent heat seal structure comprising a base material and the water-repellent heat seal film according to the above [1] or [2] disposed on the main surface of the base material. Furthermore, the [ 4 ] base material is the water-repellent heat seal structure according to the above [ 3 ], wherein the base material is any one of a polyethylene terephthalate film and an aluminum film. Furthermore, the water repellent heat seal structure according to the above [ 3 ] or [ 4 ] for heat-sealing either [ 5 ] polystyrene film or polypropylene film.

[ 6 ] The method for producing a water-repellent heat seal film according to [1] or [2], wherein a thermoplastic resin and hydrophobic particles as the first particles are formed on the main surface of the substrate. Second particle, and 100 parts by mass of the thermoplastic resin, the hydrophobic particles are 70 parts by mass or more and 110 parts by mass or less, and the second particles are 20 parts by mass or more and 100 parts by mass or less, and are thermoplastic. The resin contains a polyester resin or a polyester resin and a vinyl acetate resin, and the content ratios of the polyester resin and the vinyl acetate resin in 100 parts by mass of the thermoplastic resin are from 100 parts by mass and 0 parts by mass to 40 parts by mass and 60 parts by mass, respectively. A step of applying at least one layer of a water-repellent heat sealant in a range up to a portion, and forming a water-repellent heat sealant into a film to form a water-repellent heat Method for producing a water-repellent heat-sealing film and forming a Le film.

[ 7 ] The method for producing a water-repellent heat seal structure according to any one of [ 3 ] to [ 5 ], wherein a thermoplastic resin and a first particle as a first particle are formed on the main surface of the substrate. Hydrophobic particles and second particles, and the hydrophobic particles are 70 parts by mass or more and 110 parts by mass or less, and the second particles are 20 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. The thermoplastic resin contains a polyester resin or a polyester resin and a vinyl acetate resin, and the content ratio of the polyester resin and the vinyl chloride resin in 100 parts by mass of the thermoplastic resin is from 40 parts by mass to 40 parts by mass, respectively. The step of applying at least one layer of the water-repellent heat sealant in a range of up to 60 parts by weight and the water-repellent heat sealant is formed on the main surface of the substrate by forming a film. Method for producing a water-repellent heat-seal structure comprising the steps of: obtaining a water-repellent heat-seal structure, the by forming a water-repellent heat-sealing film.

According to the present invention, water-repellent heat-sealing film having both high water repellency and high heat sealable with a single layer, water repellent heat-seal structure comprising a water-repellent heat-sealing film, a method of manufacturing a water-repellent heat-sealing film, and repellent A method for producing an aqueous heat seal structure can be provided.

[Embodiment 1: Water-repellent heat seal film]
The water-repellent heat seal film of the present embodiment includes a thermoplastic resin and hydrophobic particles as the first particles, and the hydrophobic particles are 55 parts by mass or more and 130 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It is the following, it is a single layer, the contact angle of water on the surface is 150 ° or more, and has heat sealability. The water repellent heat seal film of the present embodiment is a single layer and has both high water repellency and high heat seal properties.

(Thermoplastic resin)
Thermoplastic resin is a water repellent heat seal film formed on a PET (polyethylene terephthalate) film or Al (aluminum) film as a base material, and has a heat seal property with PS (polystyrene) resin or PP (polypropylene) resin. If it is, there will be no restriction | limiting in particular, A polyester resin, vinyl chloride vinyl chloride (vinyl chloride-vinyl acetate copolymer) resin, a chlorinated polypropylene resin, an acrylic resin, a polyurethane resin etc. are mentioned suitably. In addition, these resins can be used alone or in combination depending on the substrate or the heat sealing object. In particular, a polyester resin, a vinyl chloride resin, a chlorinated polypropylene resin, and a polyurethane resin are preferable because they have high heat sealability even when used alone.

(First particle)
The first particles are hydrophobic particles. Here, the hydrophobic particle means a particle in which a functional group exposed on the surface is a hydrophobic group or a functional group exposed on the surface is capped with a hydrophobic group. Such hydrophobic particles are obtained by hydrophobizing the surface of hydrophilic particles in which hydrophilic groups such as hydroxyl groups are exposed on the surface in addition to hydrophobic particles in which hydrophobic groups such as alkyl groups are exposed on the surface. Is obtained. The first particle is not particularly limited as long as it is a hydrophobic particle, and the particle itself may be a hydrophobic particle, or may be a hydrophilic particle whose surface has been subjected to a hydrophobic treatment.

  The hydrophobic particles as the first particles are preferably surface-treated with at least one silicon compound selected from the group consisting of organic siloxanes and organic silanes from the viewpoint of increasing hydrophobicity. Here, the organosiloxane refers to a silicon compound having a siloxane bond (Si—O—Si bond) whose side chain is substituted with a hydrocarbon group such as an alkyl group or a phenyl group, such as dimethylpolysiloxane, octa Preferable examples include methylcyclotetrasiloxane. Organic silanes are organic silanes which are silicon compounds in which at least a part of H bonded to Si of the silane is substituted with a hydrocarbon group such as an alkyl group, a phenyl group or the like, a halogen group, and the like. A silicon compound in which a silane is linked by a hetero group such as an NH group or an S group, for example, alkylsilanes such as trimethylsilane and octylsilane, and hexamethyldisilazane are preferable. In the hydrophobized surface treatment method, particles are dry blended. Here, dry blending refers to mixing a silicon compound that is a surface treatment agent and particles that are a surface treatment material in a gas atmosphere such as a nitrogen atmosphere. Whether the first particles are hydrophobic particles is evaluated by a methanol wettability test. Here, the methanol wettability test refers to a test for evaluating the wettability with respect to methanol from the degree of sedimentation of the first particles by adding a certain amount of first particles to methanol aqueous solutions having different concentration ratios and sufficiently shaking them. The higher the concentration of methanol required to settle the first particles, the higher the hydrophobicity.

  The average primary particle size of the hydrophobic particles as the first particles is not particularly limited, but is preferably 1 nm or more and 50 nm or less, preferably 5 nm or more and 30 nm from the viewpoint of increasing the heat sealability and water repellency of the water repellent heat seal film. The following is more preferable. Here, the average primary particle size of the first particles is measured by observation with a transmission electron microscope.

  The content ratio of the hydrophobic particles as the first particles is 55 parts by mass or more and 130 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin from the viewpoint of increasing the water repellency and heat sealability of the water-repellent heat seal film. Yes, 60 parts by mass or more and 120 parts by mass or less are preferable, 70 parts by mass or more and 110 parts by mass or less are more preferable, and 80 parts by mass or more and 100 parts by mass or less are more preferable. The content ratio of the hydrophobic particles that are the first particles can be calculated from the content of the inorganic oxide in the combustion residue (ash) when the hydrophobic particles are inorganic.

(Second particle)
The water-repellent heat seal film of the present embodiment preferably further includes second particles having a larger average particle diameter than the hydrophobic particles that are the first particles, from the viewpoint of forming irregularities on the surface and improving the water repellency. . The average particle size of the second particles is not particularly limited as long as it is larger than the average particle size of the hydrophobic particles that are the first particles, but from the viewpoint of improving water repellency by forming irregularities with an appropriate depth on the surface. 1 μm or more and 50 μm or less is preferable, and 3 μm or more and 30 μm or less is more preferable. Here, the average particle diameter of the second particles is measured by a Coulter counter.
The type of the second particles is not particularly limited, and may be an inorganic material such as nonporous silica, porous silica, or silicon, or an organic material such as an acrylic resin or a polyurethane resin. Further, the second particles may be hydrophilic particles or hydrophobic particles.

  The content ratio of the second particles is not particularly limited, but from the viewpoint of increasing the water repellency and heat sealability of the water repellent heat seal film, it is 20 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. It is preferably 30 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. The content ratio of the second particles can be calculated from the content of the inorganic oxide in the combustion residue (ash) when the second particles are inorganic.

(Single layer)
The water repellent heat seal film of the present embodiment has a single layer and has both high water repellency and high heat seal properties by having the above composition. Here, the single layer refers to a single layer having no discontinuous change in composition and composition ratio within the layer. That is, even when the water-repellent heat seal film is a multiple layer in which the water-repellent heat sealant is applied multiple times, the composition and composition ratio of those layers are changing uniformly or continuously. As a whole, it is a single layer.

(Water repellency)
The water repellency of the water repellent heat seal film of the present embodiment means that the film surface repels water, and is evaluated by the behavior of water droplets on the surface and the contact angle of water. Specifically, having water repellency means that water droplets do not remain or leave part of the surface of the water-repellent heat seal film but roll, and the contact angle of water on the surface is 150 °. That's it. Here, the behavior of water droplets on the surface is observed visually, and the contact angle of water on the surface of the membrane is measured by a contact angle meter with respect to the surface of distilled water dropped on the surface of the water-repellent heat seal membrane. The water-repellent heat seal film of this embodiment has high water repellency because water droplets roll on the surface of the water-repellent heat seal film without leaving any part thereof, and the contact angle of water on the surface is 150 ° or more.

(Heat sealability)
The heat-sealability of the water-repellent heat seal film of this embodiment is evaluated by the seal strength when the water-repellent heat seal film formed on a predetermined substrate is heat-sealed with a predetermined heat-sealing object. Specifically, a water-repellent heat seal film formed on a PET (polyethylene terephthalate) film or an Al (aluminum) film as a substrate is heat-sealed to a PS (polystyrene) film or a PP (polypropylene) film, and has a width of 15 mm. The sample is evaluated by seal strength (unit: gf / 15 mm) when peeling at a peeling angle of 90 ° and a peeling speed of 200 mm / min. The water-repellent heat seal film of this embodiment has heat seal properties when the above substrate is a PET film, the heat seal object is a PS film, the substrate is a PET film, and the heat seal object is a PP film. The sealing strength of at least one of the four types of the Al film, the heat sealing object is a PS film, the base material is an Al film, and the heat sealing object is a PP film is 150 gf / 15 mm or more, and 200 gf / 15 mm or more is preferable, 300 gf / 15 mm or more is more preferable, and 350 gf / 15 mm or more is more preferable.

[Embodiment 2: Water repellent heat sealant]
The water repellent heat sealant of the present embodiment is a water repellent heat sealant that is a raw material for the water repellent heat seal film of the first embodiment. By forming the water repellent heat sealant of this embodiment into a film, a water repellent heat seal film having both high water repellency and high heat sealability can be obtained in a single layer. Specifically, the water-repellent heat sealant of the present embodiment has the following configuration.

  From the same viewpoint as the water-repellent heat seal film of Embodiment 1, the water-repellent heat seal agent of the present embodiment includes a thermoplastic resin and hydrophobic particles as first particles, and 100 mass of the thermoplastic resin. The hydrophobic particles are 55 parts by mass or more and 130 parts by mass or less with respect to the part, and when a single-layer film is formed, the contact angle of water on the surface is 150 ° or more and has heat sealability.

  From the same viewpoint as the water-repellent heat seal film of Embodiment 1, the water-repellent heat seal agent of this embodiment may further include second particles having a larger average particle diameter than the hydrophobic particles that are the first particles. preferable. Further, the hydrophobic particles as the first particles are preferably surface-treated with at least one silicon compound selected from the group consisting of organic siloxanes and organic silanes.

  The water-repellent heat sealant of the present embodiment is the same as the water-repellent heat seal film of Embodiment 1 with respect to the types and content ratios of the thermoplastic resin, the first particles, and the second particles as the main components. That is, by forming the water-repellent heat sealant of this embodiment into a film, the types and content ratios of the thermoplastic resin, the first particles, and the second particles, which are the main components of the water-repellent heat sealant of the present embodiment, The water repellent heat seal film of Embodiment 1 having the thermoplastic resin, the first particles, and the second particles, which are main components of the same type and content ratio, is obtained. Since the types and content ratios of the thermoplastic resin, the first particles, and the second particles, which are the main components of the water-repellent heat sealant of the present embodiment, are the same as those of the water-repellent heat seal film of the first embodiment, I won't repeat it.

  The water-repellent heat sealing agent of the present embodiment is not particularly limited as long as the types and content ratios of the plastic resin, the first particles, and the second particles as the main components are the same as those of the water-repellent heat sealing film of the first embodiment. Instead, a solvent for diluting the main component may be included as a subcomponent. Depending on the type of the subcomponent and the composition ratio of the main component and the subcomponent, specific examples of the water-repellent heat sealant include hot-melt type, sealant type, and lacquer type water-repellent heat sealants. .

[Embodiment 3: Water-repellent heat seal structure]
The water-repellent heat seal structure of this embodiment includes a base material and the water-repellent heat seal film of Embodiment 1 disposed on at least one main surface side of the base material. The water-repellent heat seal structure of this embodiment is a suitable packaging material because the water-repellent heat seal film contained therein has a single layer and has both high water repellency and high heat sealability. Here, the substrate is not particularly limited as long as it is suitable for the purpose and application as a packaging material, and examples thereof include a PET film and an Al film.

[Embodiment 4: Manufacturing Method of Water Repellent Heat Seal Film]
The method for producing a water-repellent heat seal film according to this embodiment is a method for producing the water-repellent heat seal film according to Embodiment 1, and includes a thermoplastic resin and first particles on at least one main surface side of the substrate. A step of applying at least one layer of a water-repellent heat-sealing agent in which the hydrophobic particles are 55 parts by mass or more and 130 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin; Forming a water-repellent heat seal film disposed on at least one main surface side of the substrate by forming the heat sealant into a film. By the method for producing a water-repellent heat seal film of the present embodiment, a water-repellent heat seal film having a single layer having both high water repellency and high heat sealability can be obtained.

(Water repellent heat sealant application process)
The application step of the water repellent heat sealant includes a thermoplastic resin and hydrophobic particles as the first particles on at least one main surface side of the substrate, and 100 parts by mass of the thermoplastic resin, The hydrophobic particles are a step of applying at least one layer of a water-repellent heat sealant that is 55 parts by mass or more and 130 parts by mass or less. The substrate is not particularly limited as long as the water-repellent heat sealant can be applied to at least one main surface thereof, and examples thereof include a PET film and an Al film. The method for applying the water repellent heat sealant is not particularly limited, and examples thereof include brush coating, bar coater coating, spray coating, and gravure coating.

(Water repellent heat seal film forming process)
The method for forming a water-repellent heat seal film is a step of forming a water-repellent heat seal film disposed on at least one main surface side of a substrate by forming a water-repellent heat seal agent into a film. The method for forming the water repellent heat sealant into a film is not particularly limited, and examples thereof include drying.

(Example A)
1. Production of water-repellent heat seal structure A PET (polyethylene terephthalate) film having a thickness of 16 μm and an Al (aluminum) film having a thickness of 32 μm were used as the base material. Examples A-1 to A-10 include the thermoplastic resin and the first particles in the composition ratios shown in Table 1, and 1002 parts by mass of methyl ethyl ketone and ethyl acetate as solvents with respect to 100 parts by mass of the thermoplastic resin. After coating the water-repellent heat sealant containing ˜1562 parts by mass with a bar coater once, the film thickness is formed on one main surface of the substrate by heating and drying at 80 ° C. for 3 seconds to form a film. A water repellent heat seal structure in which a single layer water repellent heat seal film having a basis weight of 3 g / m ² was formed was obtained. Here, UE3500 manufactured by Unitika Ltd. was used as the polyester resin, and Solvine M5R manufactured by Nissin Chemical Industry Co., Ltd. was used as the vinyl acetate resin. As the first particles, Aerosil RY200 (fumed silica surface-treated with dimethylpolysiloxane) manufactured by Evonik was used. In Example A, the relationship between the content and average particle size of the hydrophobic particles as the first particles, and the water repellency and heat sealability was examined.

2. Evaluation of water repellency or yogurt repellency Appropriate amount of water drops or yogurt (manufactured by Snow Brand Megmilk Co., Ltd.) when one drop of tap water is dropped on the main surface of the water repellant heat seal film of the obtained water repellant heat seal structure. The water repellency or yogurt repellency was evaluated from the behavior of the yogurt droplets when dropped. Water or yogurt drops can be rolled on the surface of the water-repellent heat seal film without leaving any part, and water or yogurt drops can be left on the surface of the water-repellent heat seal film but can be rolled on. In addition, it was evaluated that a water droplet or a yogurt droplet did not roll while leaving all of it on the surface of the water-repellent heat seal film. The contact angle of water is the Kyowa interface between the water droplet and the main surface when one drop of distilled water is dropped on the main surface of the water-repellent heat seal film of the obtained water-repellent heat seal structure. It measured using the scientific FACE contact angle meter CA-X150 type | mold. The results are summarized in Table 1. The blank part of Table 1 showed that it was not evaluated.

3. Evaluation of heat sealability The obtained water-repellent heat seal structure was heat-sealed with a PS (polystyrene) sheet having a thickness of 65 μm or a PP (polypropylene) sheet having a thickness of 30 μm, and then a strip-shaped sample having a width of 15 mm was obtained. The seal strength (unit: gf / 15 mm) when the sample was peeled off at a peeling angle of 90 ° and a peeling speed of 200 mm / min was measured. Those having a measured seal strength of 150 gf / 15 mm or more were evaluated as good, and those having a seal strength of less than 150 gf / 15 mm were evaluated as defective. The results are summarized in Table 1. The blank part of Table 1 showed that it was not evaluated.

  With reference to Table 1, from Example A-1 to Example A-8, the water-repellent heat seal film is a single layer of hydrophobic particles that are the first particles from the viewpoint of having both high water repellency and high heat sealability. The content is required to be 55 parts by mass or more and 130 parts by mass or less, preferably 60 parts by mass or more and 120 parts by mass or less, and more preferably 80 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. won. Further, from Examples A-4 to A-7, the water-repellent heat seal film has a content ratio of the hydrophobic particles as the first particles of 80 parts by mass or more and 130 parts by mass with respect to 100 parts by mass of the thermoplastic resin. In a range of less than or equal to the part, the single layer had both high yogurt repellency and high heat sealability. From Example A-4, Example A-9 and Example A-10, the water-repellent heat seal film is a single layer even if the average particle diameter of the hydrophobic particles as the first particles is in the range of 7 nm to 30 nm. It had high water repellency and high heat sealability.

(Example B)
It contains the thermoplastic resin shown in Example B-1 to Example B-10 of Table 2 as the main component, the first particles and the second particles in the composition ratio of Table 2, and as a subcomponent, 100 parts by mass of the thermoplastic resin, A water repellent heat seal structure was obtained in the same manner as in Example A except that a water repellent heat sealant containing 967 to 1527 parts by mass of methyl ethyl ketone and ethyl acetate as solvents was used. The obtained water-repellent heat seal structure was evaluated in the same manner as in Example A for water repellency or yogurt repellency and heat sealability. Here, regarding the second particles, Sunsphere NP-200 or NP-30 manufactured by AGC S-Tech Co., Ltd. is used as the nonporous silica particles, and Sunsphere H-201 manufactured by AGC S-Tech Co., Ltd. is used as the porous silica particles. , KMP-602 manufactured by Shin-Etsu Chemical Co., Ltd. is used as silicon particles, Gantz Pearl GM2001 manufactured by Aika Industry Co., Ltd. is used as acrylic resin particles, and Art Pearl C400 manufactured by Negami Kogyo Co., Ltd. is used as urethane resin particles. It was. In Example B, the relationship between the content ratio, average particle diameter, type and hydrophobicity or hydrophilicity of the second particles, and the water repellency and heat sealability was examined. The results are summarized in Table 2. The blank part of Table 2 showed that it was not evaluated.

  Referring to Table 2, from Example B-1 to Example B-5, the water repellent heat seal film has a content ratio of the second particles of 20 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. Even within the range, the single layer had high water repellency and high heat sealability. Further, from Example B-3 and Example B-6, even when the average particle size of the second particles was in the range of 3 μm or more and 20 μm or less, the single layer had both high water repellency and high heat sealability. Further, from Example B-3 and Example B-7 to Example B-10, the water-repellent heat seal film has a single layer with high water repellency and high regardless of the material of the second particles, hydrophobicity or hydrophilicity. It had heat sealability.

(Example C)
As a main component, the thermoplastic resin shown in Examples C-1 to C-4 of Table 3 and the first particles and the second particles are contained in the composition ratio of Table 3, and as a subcomponent, 100 parts by mass of the thermoplastic resin, A water-repellent heat seal structure was obtained in the same manner as in Example A except that a water-repellent heat sealant containing 1178 parts by mass of methyl ethyl ketone and ethyl acetate as solvents was used. The obtained water-repellent heat seal structure was evaluated in the same manner as in Example A for water repellency or yogurt repellency and heat sealability. Here, for the hydrophobic particles as the first particles, Evonik's Aerosil RY200 is used as the surface treated with dimethylpolysiloxane, and Evonik's Aerosil RX200 is used as the surface treated with hexamethyldisilazane. Aerosil R805 manufactured by Evonik Co., Ltd. was used as the one used and surface-treated with octylsilane. In Example C, the presence or absence of a hydrophobic surface treatment with at least one silicon compound selected from the group consisting of organic siloxanes and organic silanes with respect to the hydrophilic silica as the first particles, water repellency and heat sealability I investigated the relationship with. The results are summarized in Table 3. The blank part of Table 3 showed that it was not evaluated.

  Referring to Table 3, from Example C-1 to Example C-4, the water-repellent heat seal film is a surface of at least one silicon compound selected from the group consisting of organic siloxanes and organic silanes as the first particles. By using hydrophobic treated hydrophobic particles, a single layer had both high water repellency and high heat sealability. From Example C-1 and Example C-2, the water-repellent heat seal film has a single-layer high yogurt repellency by using hydrophobic particles that have been subjected to a hydrophobic surface treatment with dimethylsiloxane or trimethylsilane as the first particles. It had high heat sealability.

(Example D)
It contains the thermoplastic resin shown in Example D-1 to Example D-9 of Table 4 as the main component, the first particles and the second particles in the composition ratio of Table 4, and as a subcomponent, 100 parts by mass of the thermoplastic resin, A water-repellent heat seal structure was obtained in the same manner as in Example A except that a water-repellent heat sealant containing 1178 parts by mass of methyl ethyl ketone and ethyl acetate as solvents was used. The obtained water-repellent heat seal structure was evaluated in the same manner as in Example A for water repellency or yogurt repellency and heat sealability. Here, regarding the thermoplastic resin, UE3500 manufactured by Unitika Co., Ltd. is used as the polyester resin, Solvine M5R manufactured by Nissin Chemical Industry Co., Ltd. is used as the vinyl chloride resin, and Harden 13LLP manufactured by Toyobo Co., Ltd. is used as the chlorinated polypropylene resin. DEGALAN P24 manufactured by Evonik was used as the acrylic resin, and XGL2200 manufactured by Sakata Inx was used as the polyurethane resin. In Example D, the relationship between the type and composition ratio of the thermoplastic resin and the water repellency and heat sealability was examined. The results are summarized in Table 4. The blank part of Table 4 showed that it was not evaluated.

  Referring to Table 4, from Example D-1 to Example D-9, the water-repellent heat seal film is made of polyester resin, vinyl chloride resin, chlorinated polypropylene resin, acrylic resin, and polyurethane resin as the thermoplastic resin. When used alone or in combination, the single layer has both high water repellency and high heat sealability. In addition, the water-repellent heat-sealing film has a high water repellency and a high heat in a single layer even when a polyester resin, a vinyl chloride resin, a chlorinated polypropylene resin, and a polyurethane resin are used as thermoplastic resins, respectively. It also had a sealing property. In addition, the water-repellent heat seal film has a high yogurt repellency with a single layer by using a polyester resin, a vinyl chloride resin, a chlorinated polypropylene resin, and an acrylic resin alone or in combination as a thermoplastic resin. It had heat sealability.

(Example E)
As a main component, it contains the thermoplastic resin, the first particles and the second particles shown in Example E-1 to Example E-3 of Table 5 in the composition ratio of Table 5, and as a subcomponent, 100 parts by mass of the thermoplastic resin, Except for using a water-repellent heat sealant containing 1178 parts by mass of methyl ethyl ketone and ethyl acetate as solvents, and having a film thickness of 1 g / m ² , 3 g / m ² or 5 g / m ² , In the same manner as in Example A, a water-repellent heat seal structure was obtained. The obtained water-repellent heat seal structure was evaluated in the same manner as in Example A for water repellency or yogurt repellency and heat sealability. In Example E, the relationship between the film thickness of the water-repellent heat seal film and the water repellency and heat sealability was examined. The results are summarized in Table 5. The blank part of Table 5 showed that it was not evaluated.

Referring to Table 5, from Example E-1 to Example E-3, the water-repellent heat seal film has a single layer and high water repellency, with a film thickness ranging from 1 g / m ^{2 to} 5 g / m ^2. It was both water-based and highly heat-sealable. Further, water-repellent heat-sealing film, the film thickness is at 3 g / m ² or more 5 g / m ² or less in the range in basis weight, was combines high water yogurt and high heat sealability a single layer.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

Claims (7)

A thermoplastic resin, hydrophobic particles as first particles, and second particles having an average particle size larger than that of the hydrophobic particles,
The hydrophobic particles are 70 parts by mass or more and 110 parts by mass or less, and the second particles are 20 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
The thermoplastic resin includes a polyester resin or the polyester resin and vinyl chloride acetate resin,
The content ratios of the polyester resin and the vinyl acetate resin in 100 parts by mass of the thermoplastic resin are ranges from 100 parts by mass and 0 parts by mass to 40 parts by mass and 60 parts by mass, respectively.
It is a single-layer film in which the composition and the composition ratio for disposing on at least one main surface of the substrate are changing uniformly or continuously,
A water repellent heat seal film having a water contact angle of 150 ° or more on the surface and having heat seal properties.   The water repellent heat seal film according to claim 1, wherein the hydrophobic particles are surface-treated with at least one silicon compound selected from the group consisting of organic siloxanes and organic silanes.   A water-repellent heat seal structure comprising the base material and the water-repellent heat seal film according to claim 1 or 2 disposed on the main surface of the base material. The water repellent heat seal structure according to claim 3 , wherein the substrate is one of a polyethylene terephthalate film and an aluminum film. The water-repellent heat seal structure according to claim 3 or 4 , for heat-sealing to either polystyrene or polypropylene. It is a manufacturing method of the water-repellent heat seal film according to claim 1 or 2,
On the main surface of the base material, the thermoplastic resin, the hydrophobic particles as the first particles, and the second particles, and with respect to 100 parts by mass of the thermoplastic resin, the hydrophobic The conductive particles are 70 parts by mass or more and 110 parts by mass or less, the second particles are 20 parts by mass or more and 100 parts by mass or less, and the thermoplastic resin contains the polyester resin or the polyester resin and the vinyl acetate resin. The content ratio of the polyester resin and the vinyl acetate resin in 100 parts by mass of the thermoplastic resin ranges from 100 parts by mass and 0 parts by mass to 40 parts by mass and 60 parts by mass, respectively. Applying at least one layer,
Forming the water-repellent heat seal film disposed on the main surface of the base material by forming the water-repellent heat seal agent into a film. A method for producing a water-repellent heat seal structure according to any one of claims 3 to 5 ,
On the main surface of the base material, the thermoplastic resin, the hydrophobic particles as the first particles, and the second particles, and with respect to 100 parts by mass of the thermoplastic resin, the hydrophobic The conductive particles are 70 parts by mass or more and 110 parts by mass or less, the second particles are 20 parts by mass or more and 100 parts by mass or less, and the thermoplastic resin contains the polyester resin or the polyester resin and the vinyl acetate resin. The content ratio of the polyester resin and the vinyl acetate resin in 100 parts by mass of the thermoplastic resin ranges from 100 parts by mass and 0 parts by mass to 40 parts by mass and 60 parts by mass, respectively. Applying at least one layer,
Forming the water-repellent heat seal structure by forming the water-repellent heat seal film formed on the main surface of the base material by forming the water-repellent heat seal agent into a film. A method for producing a water-repellent heat seal structure.