JP2019171807A - Laminate for forming water-repellent laminate film, water-repellent laminate film, and method for producing the same - Google Patents

Abstract

To provide a laminate for forming a water-repellent laminate film that can be used for preparing a water-repellent laminate film having extremely high water repellency and attachment prevention properties, and a water-repellent laminate film.SOLUTION: A laminate for forming water-repellent laminate film has a shaped base material, water-repellent layer and peeling base material. The water-repellent layer contains water-repellent fine particles and resin materials and causes cohesive peeling when a peeling base material is peeled.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate for forming a water-repellent laminated film, a water-repellent laminated film, and a method for producing the same.

  In many product fields such as foods, beverages, pharmaceuticals, and chemicals, packaging materials having various functions such as water resistance, oil resistance, gas barrier properties, moisture resistance and the like have been developed depending on the contents.

The packaging material is required to have an adhesion preventing function capable of preventing adhesion of a highly viscous content such as a liquid, a semi-solid, or a gel substance to the packaging material.
For example, a lid for a container containing yogurt or the like is required to have high water repellency and adhesion prevention.

  In the previous application, the present applicant has proposed a water-repellent laminate comprising a base material, a thermal adhesive layer, and a water-repellent layer having water-repellent fine particles attached to the surface thereof.

JP 2017-024740 A

  The present inventors have surprisingly found that the release group of a laminate for forming a water-repellent laminate film comprising a shaped substrate, a water-repellent layer containing water-repellent fine particles and a resin material, and a release substrate. At the same time as the material is peeled off, the water-repellent layer is agglomerated and peeled to form a concavo-convex structure caused by the water-repellent fine particles and a fine concavo-convex structure caused by the agglomerated and peeled water-repellent layer on the surface of the water-repellent layer. It was found that a water-repellent laminated film having excellent water repellency and anti-adhesion properties can be obtained by combining uneven structures resulting from shaping.

  The present invention has been made based on the above findings, and the problem to be solved is for forming a water-repellent laminated film that can be used for producing a water-repellent laminated film having extremely high water repellency and adhesion prevention. It is providing a laminated body and a water-repellent laminated film.

  The laminate for forming a water-repellent laminated film of the present invention comprises a shaped substrate, a water-repellent layer and a release substrate, the water-repellent layer contains water-repellent fine particles and a resin material, and peels off the release substrate. It is characterized by causing cohesive peeling when it is performed.

  In one embodiment, the average particle diameter of the water-repellent fine particles is 1 nm or more and 100 nm or less.

  In one embodiment, the content of the water-repellent fine particles in the water-repellent layer is 5% by mass or more and 85% by mass or less.

  In one embodiment, the water repellent layer comprises bead particles having an average particle diameter of 1 μm or more and 50 μm or less.

  In one embodiment, the water repellent layer includes a polyolefin resin and / or an unsaturated carboxylic acid-modified polyolefin resin as a resin material.

In one embodiment, the water repellent layer has a thickness of 0.5 g / m ² or more and 10 g / m ² or less.

  In one embodiment, the laminate for forming a water-repellent laminated film of the present invention includes a heat-sealable extruded resin layer between a base material and a water-repellent layer.

  The water-repellent laminated film of the present invention is obtained by peeling the release substrate from the laminate for forming a water-repellent laminated film.

  In one embodiment, the arithmetic surface roughness Ra of the water repellent layer is 10 μm or more and 200 μm or less.

  The method for producing a water-repellent laminated film of the present invention comprises a step of preparing a substrate and a release substrate, and a water-repellent layer-forming coating solution is applied to one surface of the release substrate, dried, and water-repellent Forming a layer and obtaining a laminate, heating and pressurizing the substrate and the laminate so that the substrate and the water-repellent layer are in contact with each other, forming the layer, and peeling the release substrate And a step of performing.

  The method for producing a water-repellent laminated film of the present invention comprises a step of preparing a substrate and a release substrate, and a water-repellent layer-forming coating solution is applied to one surface of the release substrate, dried, and water-repellent A step of forming a layer to obtain a laminate, a step of melt-extruding a resin material that melts or softens by heat and develops adhesion between the substrate and the laminate, a substrate, a resin material, and It includes a step of pressurizing and laminating the laminate, and a step of shaping, and a step of peeling the release substrate.

  According to the method of the present invention, it is possible to provide a water-repellent laminate film-forming laminate and a water-repellent laminate film that can be used to produce a water-repellent laminate film having extremely high water repellency and adhesion prevention properties.

FIG. 1 is a schematic cross-sectional view showing an embodiment of a laminate for forming a water-repellent laminated film of the present invention. FIG. 2 is a schematic diagram for producing a water-repellent laminated film using the water-repellent laminated film-forming laminate. FIG. 3 is a schematic cross-sectional view showing an embodiment of the water-repellent laminated film-forming laminate of the present invention. FIG. 4 is a schematic cross-sectional view of a container according to an embodiment of the present invention. FIG. 5 is a schematic view of a laminate manufacturing apparatus for forming a water-repellent laminate film. FIG. 6 is a schematic view of a laminate manufacturing apparatus for forming a water-repellent laminate film. FIG. 7 is a schematic view of a laminate manufacturing apparatus for forming a water-repellent laminate film. FIG. 8 shows the surface of the water-repellent laminated film produced by the water-repellent laminated film-forming laminate obtained in Example 1-1 at a magnification of 1000 times with a scanning electron microscope (SU3500, manufactured by Hitachi High-Technologies Corporation). It is an enlarged photo.

(Laminated body for forming water-repellent laminated film)
The laminate 10 for forming a water-repellent laminated film of the present invention includes a shaped substrate 11, a water-repellent layer 12 containing water-repellent fine particles 13, and a release substrate 14 (see FIG. 1).
By peeling off the release substrate 14 included in the water-repellent laminated film forming laminate, the water-repellent layer 12 is agglomerated and peeled, and the surface of the water-repellent layer 12 is agglomerated and peeled off due to the water-repellent fine particles 13. A water repellent laminated film 15 in which a fine uneven structure resulting from the water repellent layer 12 is formed is obtained (see FIG. 2). Furthermore, the water-repellent laminated film has a concavo-convex structure resulting from shaping, and the water-repellent laminated film having these concavo-convex structures can significantly improve water repellency and anti-adhesion properties. it can.
Moreover, the laminated body for water-repellent laminated film formation of this invention may be equipped with the heat-sealable extruded resin layer 16 between a base material and a water-repellent layer (refer FIG. 3).

  The form of shaping applied to the water-repellent laminated film-forming laminate is not particularly limited as long as the release substrate side surface of the water-repellent layer has a concavo-convex structure by shaping, as shown in FIG. Further, the substrate surface may not be shaped. Moreover, although not shown in figure, the base material surface may be shaped and the peeling base material surface may not be shaped, and the base material surface and the peeling base material surface may be both shaped.

  The shape of shaping is not particularly limited, and for example, a concavo-convex structure of a lattice shape or a honeycomb shape can be used.

  The depth of the concavo-convex structure formed on the shaped side surface of the laminate for forming a water-repellent laminated film (for example, the release substrate 14 in FIG. 1) is preferably 10 μm or more and 200 μm or less, preferably 30 μm or more. More preferably, it is 100 μm or less. Thereby, the water repellency and adhesion prevention property of a water repellent laminated film can be improved more.

The peeling force between the water repellent layer and the peeling substrate is preferably 0.1 N / 15 mm or more and 20 N / 15 mm or less, and more preferably 1 N / 15 mm or more and 10 N / 15 mm or less. By setting the peeling force between the water-repellent layer and the release substrate within the above numerical range, cohesive peeling in the water-repellent layer can be favorably caused.
Further, the peeling force between the base material or the heat-sealable extruded resin layer and the water-repellent layer is more preferably 1 N / 15 mm or more and 3 N / 15 mm or more.
In the present invention, the peeling force between these layers can be measured by a tensile tester (manufactured by Orientec).

  Hereafter, each layer with which the laminated body for water-repellent laminated film formation of this invention is provided is demonstrated in detail.

(Base material)
Examples of substrates include paper substrates such as fine paper, art paper, coated paper, resin coated paper, cast coated paper, paperboard, synthetic paper and impregnated paper, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene Polyester resins such as naphthalate (PEN), 1,4-polycyclohexylenedimethylene terephthalate, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyamide resins such as nylon 6 and nylon 6,6, low density polyethylene (LDPE, density of less than 0.925g / cm ^3), linear low density polyethylene (LLDPE, density less than 0.925g / cm ^3), medium density polyethylene (MDPE, density 0.925~0.944g / cm ³ ), High density polyethylene (HDPE, density 0. 0). 945 g / cm ³ or more), polyolefin resins such as polypropylene (PP) and polymethylpentene, polyvinyl chloride, polyvinyl alcohol (PVA), polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral and polyvinyl pyrrolidone ( PVP) and other vinyl resins, polyacrylate, polymethacrylate and polymethyl methacrylate (meth) acrylic resins, polyimide and polyetherimide and other polyimide resins, cellophane, cellulose acetate, nitrocellulose, cellulose acetate pro Cellulose resins such as pionate (CAP) and cellulose acetate butyrate (CAB), polystyrene resins such as polystyrene (PS), polycarbonate resins, and ionomer resins Etc. (hereinafter simply referred to as “resin film”).
The film may be unstretched, uniaxially stretched, or biaxially stretched.

Moreover, the laminated body of an above-described material can be used as a base material. For example, a laminate of a biaxially stretched PET film and an unstretched LLDPE film, unstretched LDPE film, or unstretched PP film has durability and heat seal properties, and is suitable for lidding and packaging applications It can be set as the laminated body for laminated film formation.
In this case, the water repellent layer is preferably formed on an unstretched LLDPE film, an unstretched LDPE film, or an unstretched PP film.

  The substrate surface is preferably subjected to surface treatment such as corona discharge treatment, chemical treatment, and ozone treatment. Thereby, the adhesiveness of a base material and the adjacent layer can be improved more.

  The base material may be printed using a conventionally known printing ink. The printing method is not particularly limited, and conventionally known methods such as gravure printing, flexographic printing, and screen printing can be used.

  Although it is preferable to change suitably the thickness of a base material according to the use of the laminated body for water-repellent laminated film formation, it can be 5 micrometers or more and 200 micrometers or less, for example.

(Water repellent layer)
The water-repellent layer includes water-repellent fine particles and a resin material, and is a layer that causes agglomeration and peeling when the peeling substrate is peeled, and a fine hairy uneven structure is formed by this agglomeration and peeling.

As the water-repellent fine particles, oxide fine particles subjected to a hydrophobic surface treatment, for example, SiO ₂ , TiO ₂ , Al ₂ O _3, MgO, and the like can be used. Among these, SiO ₂ is preferable from the viewpoint of cost. These may be used alone or in combination of one or more. As a method for hydrophobizing surface treatment, for example, a dry method (CVD method, plasma method) or a wet method may be used.

The average primary particle diameter (average primary particle diameter) of the water repellent fine particles is preferably 1 nm or more and 100 nm or less, and more preferably 3 nm or more and 90 nm or less. By making the average particle diameter of the water-repellent fine particles within the above numerical range, the water-repellent and anti-adhesion properties of the water-repellent laminated film can be further improved.
In the present invention, the average particle diameter of the water-repellent fine particles can be measured with a scanning electron microscope.

  The content of the water-repellent fine particles in the water-repellent layer is preferably 5% by mass or more and 85% by mass or less, and more preferably 20% by mass or more and 70% by mass or less. By setting the content of the water-repellent fine particles within the above numerical range, the water-repellent and anti-adhesion properties of the water-repellent laminated film can be further improved.

  Further, the water repellent layer preferably comprises bead particles having an average particle diameter of 1 μm or more and 50 μm or less. When the water repellent layer contains the bead particles, the water repellency and adhesion preventing property of the water repellent laminated film can be further improved, and the water repellent fine particles can be prevented from sliding off. More preferably, the average particle diameter of the bead particles is 5 μm or more and 30 μm or less.

  Organic beads and inorganic beads can be used as the bead particles, and styrene beads, polyethylene terephthalate beads, polysulfone beads, polytetrafluoroethylene beads, polyvinyl chloride can be used as the organic resin beads. And inorganic resin beads include glass beads, silica beads, alumina silicate, talc, mica, and the like.

  The content of the bead particles in the water repellent layer is preferably 5% by mass or more and 85% by mass or less, and more preferably 20% by mass or more and 70% by mass or less. By setting the content of the bead particles within the above numerical range, the water repellency and adhesion preventing property of the water repellent laminated film can be further improved.

The water repellent layer includes a resin material. Examples of the resin material include polyester resins, polyamide resins, polyolefin resins, vinyl resins, (meth) acrylic resins, polypolyimide resins, cellulose resins, and polystyrene. Resin, polycarbonate resin, and those modified with these unsaturated carboxylic acids.
Among these, since the adhesiveness with the base material or the heat-sealable extruded resin layer is high and cohesive peeling can be generated satisfactorily, a polyolefin-based resin is preferable, and an LLDPE film, LDPE, and PP are more preferable. More preferred are those modified with an unsaturated carboxylic acid.
In the present invention, the unsaturated carboxylic acid-modified polyolefin resin refers to a reaction of an unsaturated carboxylic acid or a derivative thereof with a copolymer of an α-olefin and a polyolefin resin with the unsaturated carboxylic acid or the derivative thereof. Refers to the resin obtained.
An unsaturated carboxylic acid is a compound having one or more unsaturated bonds and one or more carboxyl groups in one molecule, such as (meth) acrylic acid, ethacrylic acid and Examples thereof include unsaturated monocarboxylic acids such as crotonic acid, unsaturated dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid.
Examples of the unsaturated carboxylic acid derivatives include chlorides, amides, esters and anhydrides of the acids described above. In the case of unsaturated dicarboxylic acids, half derivatives such as half esters and half amides are also included.
Examples of the acid ester include methyl ester, ethyl ester, propyl ester, and dimethylaminoethyl ester.

  The content of the resin material in the water repellent layer is preferably 15% by mass or more and 95% by mass or less, and more preferably 30% by mass or more and 70% by mass or less. By making the content of the resin material within the above numerical range, it is possible to prevent the water-repellent fine particles from sliding off and to further improve the water repellency and anti-adhesion properties of the water-repellent laminated film.

  The water repellent layer is a curing agent, a silane coupling agent, a plasticizer, an ultraviolet stabilizer, a coloring inhibitor, a matting agent, a deodorant, a flame retardant, a weathering agent, an electrification, as long as the characteristics of the present invention are not impaired. Various additives such as an inhibitor, a yarn friction reducing agent, a slip agent, a release agent, an antioxidant, and an ion exchange agent can be included.

The arithmetic surface roughness Ra of the water-repellent layer after peeling the release substrate is preferably 10 μm or more and 200 μm or less, and more preferably 30 μm or more and 100 μm or less. By setting the arithmetic surface roughness Ra of the water repellent layer within the above numerical range, the water repellency and anti-adhesion properties of the water repellent laminated film can be further improved.
In the present invention, the arithmetic surface roughness Ra can be measured by a surface roughness meter (Mitutoyo surftest SJ-310, manufactured by Mitutoyo Corporation) in accordance with JIS B 0601 (issued in 1994).

  The depth of the concavo-convex structure due to shaping formed on the surface of the water-repellent layer after peeling the release substrate is preferably 10 μm or more and 200 μm or less, and more preferably 30 μm or more and 100 μm or less. preferable. Thereby, the water repellency and adhesion prevention property of a water repellent laminated film can be improved more.

  The depth of the concavo-convex structure caused by the bead particles and the water-repellent fine particles formed on the surface of the water-repellent layer after peeling the release substrate is preferably 0.01 μm or more and 50 μm or less, and 0.05 μm or more , 30 μm or less is preferable. Thereby, the water repellency and adhesion prevention property of a water repellent laminated film can be improved more.

  The depth of the concavo-convex structure resulting from cohesive peeling formed on the surface of the water-repellent layer after peeling the release substrate is preferably 0.001 μm or more and 10 μm or less, and 0.01 μm or more and 5 μm or less. More preferably. Thereby, the water repellency and adhesion prevention property of a water repellent laminated film can be improved more.

The thickness of the water repellent layer is preferably 0.5 g / m ² or more and 10 g / m ² or less, more preferably 1 g / m ² or more and 5 g / m ² or less. By making the thickness of the water-repellent layer within the above numerical range, the water-repellent fine particles can be prevented from slipping and the water-repellent laminated film can be further improved in water repellency and adhesion prevention.

(Peeling substrate)
As the release substrate, as long as it can ensure adhesion with the water-repellent layer to the extent that it can cause cohesive peeling of the water-repellent layer instead of peeling at the interface with the water-repellent layer, The resin film can be used without any particular limitation, and for example, the resin film can be used.

  The thickness of a peeling base material is not specifically limited, For example, it can be set as 5 micrometers or more and 50 micrometers or less.

(Heat sealable extruded resin layer)
The laminate for forming a water-repellent laminated film of the present invention may be provided with a heat-sealable extruded resin layer between the substrate and the water-repellent layer, whereby a water-repellent laminated film suitable for packaging applications. It can be set as the laminated body for formation.

The heat-sealable extruded resin layer can contain a resin material that melts or softens by heat and exhibits adhesive properties. For example, polyvinyl acetate, PVB, ethylene-vinyl acetate copolymer, and vinyl chloride-vinyl acetate copolymer. Such as vinyl resins such as polymers, polyolefin resins such as LLDPE, LDPE and PP, polyester resins such as PET and PBT, polyamide resins, polyimide resins, polyacrylates, polymethacrylates and polymethylmethacrylates ( Examples thereof include cellulose resins such as (meth) acrylic resins and cellulose diastases, and polyurethane resins.
Among the above, from the viewpoint of heat sealability, polyolefin resins are preferable, and LLDPE, LDPE, and PP are more preferable.
Moreover, from the viewpoint of improving the adhesion with the water-repellent layer, the heat-sealable extruded resin layer preferably contains the same resin material as that contained in the water-repellent layer. For example, when the water-repellent layer contains a polyolefin resin, the heat-sealable extruded resin layer also preferably contains a polyolefin resin.

  The content of the resin material in the heat-sealable extruded resin layer is preferably 50% by mass or more and 999% by mass or less, and more preferably 60% by mass or more and 95% by mass or less. By setting the content of the resin material in the heat-sealable extruded resin layer within the above numerical range, the heat-sealability of the heat-sealable extruded resin layer can be improved. Moreover, adhesiveness with a water repellent layer can be improved.

  Moreover, the heat-sealable extruded resin layer can contain the above-mentioned additives as long as the characteristics of the present invention are not impaired.

(Water repellent laminated film)
The water-repellent laminated film is obtained by peeling the release substrate from the above-mentioned laminate for forming a water-repellent laminated film, and includes a substrate and a water-repellent layer that has undergone cohesive peeling. Moreover, you may provide the heat-sealable extruded resin layer between the base material and the water-repellent layer.

  The water-repellent laminated film of the present invention can be used, for example, as a lid material for yogurt containers or a packaging material.

(container)
As shown in FIG. 4, the container 17 of the present invention includes a lid 18 made of a water-repellent laminated film and a container body 19, and includes a heat-sealable extruded resin layer 16 provided in the lid, and a container body 19. Are heat sealed. In addition, when a lid | cover material is not provided with the heat-sealable extruded resin layer and is provided with the film which has heat-sealability as a base material, you may heat-seal this film and a container main body.

  The container body may be made of polystyrene, polypropylene, polyethylene, paper or the like. Among these, polystyrene is more preferable because of good moldability.

  The shape of the container body is not particularly limited, and may be a cup shape or a bottomed cylindrical shape shown in FIG.

  The contents that can be filled in the container are not particularly limited, and examples thereof include foods such as pudding, yogurt, and jelly, and non-food products such as shampoo and body soap.

(Method for producing laminate for forming water-repellent laminated film)
In one embodiment, the method for producing a water-repellent laminate film-forming laminate of the present invention comprises:
Preparing a substrate and a release substrate;
Applying a water-repellent layer-forming coating liquid on one surface of the release substrate, drying, forming a water-repellent layer, and obtaining a laminate;
A step of heating and pressurizing and laminating the substrate and the laminate so that the substrate and the water-repellent layer are in contact with each other.

(Process for preparing base material and release base material)
A base material and a peeling base material may be produced by a conventionally known film forming method such as an inflation method or a T-die method, or commercially available materials may be used.

(Step of obtaining a laminate)
The method of the present invention includes a step of applying a water-repellent laminate-forming coating solution onto a release substrate and drying to form a water-repellent layer to obtain a laminate comprising the release substrate and the water-repellent layer. .
The method for applying the water repellent layer forming coating liquid onto the release substrate is not particularly limited. For example, as shown in FIG. 5, the release substrate supply roller provided in the laminate manufacturing apparatus 20 for forming a water repellent laminate film. The water-repellent layer-forming coating solution can be applied to the release substrate 22 delivered from 21 using the spray coat device 23.
Instead of the spray coating apparatus, a slot die for applying the coating liquid onto the peeling substrate or a knife coating apparatus for applying the coating liquid onto the peeling substrate with a knife can be used from the die head.

  In another embodiment, as shown in FIG. 6, a water repellent layer forming coating solution is filled in a bath 24 provided in the water repellent laminated film forming laminate manufacturing apparatus 20, and a release substrate supply roller is provided. A water repellent layer-forming coating solution can be applied to the surface of the release substrate 22 fed from 21 by a gravure roll 25. In one embodiment, the water-repellent laminate manufacturing apparatus may include a doctor blade that adjusts the amount of adhesive applied (not shown).

The water-repellent layer-forming coating solution can be prepared by dispersing or dissolving the above-mentioned water-repellent fine particles and the like in water or a suitable solvent.
When the water-repellent laminated film is used for producing a lid material for a yogurt container or a packaging material filled with food, the water-repellent layer is in contact with the food. Therefore, the water repellent layer is preferably a water-based coating film, and the above material is preferably dispersed or dissolved in water.
A mixed solution of water and methyl acetate, ethyl acetate, butyl acetate, toluene, xylene, methanol, ethanol, isopropanol, isobutyl alcohol, methyl ethyl ketone, or the like can also be used.

  The water repellent layer-forming coating solution applied to the release substrate can be dried by passing it through a drying furnace or the like or by applying hot air to form a water repellent layer.

(Lamination and shaping process)
In one embodiment, the lamination and shaping of the base material 26 and the laminated body 27 by pressure heating are performed by passing between heating rolls 28 having at least one surface shaped as shown in FIG. Is called. The lamination is performed such that the substrate and the water repellent layer are in contact with each other. When the substrate is a laminated film including a resin film having heat sealability, the resin film, the water repellent layer, Is done to touch.
Further, the base material 26 is sent out from the base material supply roller 29.

In one embodiment, the surface of a shaped roll (hereinafter simply referred to as a shaped roll) has a concavo-convex structure such as a lattice or honeycomb.
The depth of the concavo-convex structure is preferably 10 μm or more and 200 μm or less, and more preferably 30 μm or more and 100 μm or less. By setting the depth of the concavo-convex structure on the surface of the shaping roll to be within the above numerical range, it is possible to obtain a concavo-convex structure with high adhesion prevention.
For example, the shaping roll is provided with grooves having a depth of 10 μm or more and 200 μm or less, a width of 10 μm or more and 200 μm or less on the surface thereof in a lattice shape with an interval of 10 μm or more and 200 μm or less.
Further, for example, the shaping roll has a concavo-convex structure having a depth of 10 μm or more and 200 μm or less, and a side of 10 μm or more and 100 μm or less in a honeycomb shape on the surface.

  The arithmetic surface roughness Ra of the shaping roll is preferably 10 μm or more and 200 μm or less, and more preferably 30 μm or more and 100 μm or less. By setting the arithmetic surface roughness Ra of the shaping roll within the above numerical range, a concavo-convex structure having a high adhesion preventing property can be obtained.

  The passage speed between the heating roll of the substrate and the laminate is preferably 1 m / min or more and 200 m / min or less, more preferably 2 m / min or more and 180 m / min or less. By setting the passage speed within the above numerical range, it is possible to further improve the adhesion between the substrate and the laminate while maintaining high productivity.

  The heating temperature in this step is preferably 120 ° C. or higher and 250 ° C. or lower, and more preferably 130 ° C. or higher and 240 ° C. or lower. By making heating temperature into the said numerical range, the adhesiveness of a base material and a laminated body can be improved more.

  The laminate 30 for forming a water-repellent laminated film is wound up by a winding roll 31.

Other Embodiments The method for producing a water-repellent laminate film-forming laminate of the present invention comprises:
Preparing a substrate and a release substrate;
Applying a water-repellent layer-forming coating liquid on one surface of the release substrate, drying, forming a water-repellent layer, and obtaining a laminate;
A step of melting and extruding a resin material that is melted or softened by the heat described above between the base material and the laminate, and exhibits adhesiveness;
Pressurizing, laminating and shaping, and
including.

(Process for preparing base material and release base material)
Since this process is described above, the description is omitted here.

(Step of obtaining a laminate)
Since this process is described above, the description is omitted here.

(Process to melt extrude resin material)
The method of the present invention includes a step of melt-extruding a resin material that is melted or softened by the heat described above and exhibits adhesiveness between the base material and the laminate.

(Lamination and shaping process)
The method of the present invention includes a step of laminating and shaping the base material 26, the resin material 32, and the laminated body 27 by passing at least one surface between the cooling roll 33 and the nip roll 34. Included (see FIG. 7). In this step, the heat-sealable extruded resin layer is simultaneously formed between the substrate and the laminate.
The lamination is performed so that the heat-sealable extruded resin layer and the water-repellent layer are adjacent to each other.

  The shaped cooling roll and / or nip roll surface can have the same structure as the shaped roll described above.

  The passing speed between rolls of the base material, the resin material, and the laminate is preferably 1 m / min or more and 200 m / min or less, and more preferably 2 m / min or more and 180 m / min or less. By setting the passage speed within the above numerical range, it is possible to further improve the adhesion while maintaining high productivity.

  Examples The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1-1
A PET film having a thickness of 12 μm (manufactured by Toyobo Co., Ltd., Espet (registered trademark) E5100) was prepared as a peeling substrate, and a PET film having a thickness of 12 μm (manufactured by Toyobo Co., Ltd., Espet Co., Ltd.) was prepared as the substrate. (Registered trademark) E5100) and a 50 μm thick LLDPE film (manufactured by Mitsui Chemical Tosero Co., Ltd., TUX-TCS) are bonded together with a dry laminate adhesive (manufactured by Rock Paint Co., Ltd., RU77T / H7). A laminate was produced.

On one surface of the release substrate, a water repellent layer forming coating solution having the following composition was applied and dried so that the coating amount after drying was 2.0 g / m ² to form a water repellent layer. .
(Coating liquid composition for water repellent layer formation)
Unsaturated carboxylic acid-modified polyethylene 10 parts by mass Water-repellent fine particles 5 parts by mass (hydrophobic SiO ₂ , average particle diameter 1 to 100 nm)
-5 parts by mass of bead particles (SiO ₂ , average particle diameter of 1 μm to 30 μm)
・ Isopropanol (IPA) 40 mass parts ・ Water 40 mass parts

A laminate comprising a release substrate and a water-repellent layer and the substrate were passed between a roll having a flat surface and a shaping roll, and bonded to obtain a laminate for forming a water-repellent laminate film.
Passing between the rolls was performed such that the laminate of the release substrate and the water repellent layer was on the shaping roll side, and the substrate was on the roll side having a flat surface, and the water repellent layer and the LLDPE film were in contact with each other. .
On the surface of the shaping roll, grooves having a depth of 50 μm and a width of 50 μm were provided so as to form a lattice pattern at intervals of 50 μm.

  According to JIS B 0601 (issued in 1994), the surface roughness meter (Mitutoyo Surftest SJ-310, manufactured by Mitutoyo Corporation) is used as the arithmetic average roughness Ra of the release substrate of the laminate for forming a water-repellent laminated film. And are shown in Table 1. In the following examples and comparative examples, the arithmetic surface roughness Ra of the release substrate of the laminate for forming a water-repellent laminated film was also measured and shown in Tables 1 and 2.

  The release substrate included in the laminate for forming a water-repellent laminated film produced as described above was peeled off to obtain a water-repellent laminated film. When the surface was observed with a scanning electron microscope (SU3500, manufactured by Hitachi High-Technologies Corporation) at a magnification of 1000 times, the water-repellent layer was agglomerated and peeled, and fine hairy irregularities were formed on the surface of the water-repellent fine particles and bead particles. Was observed (see FIG. 8).

  The arithmetic average roughness Ra of the water-repellent layer in which the cohesive peeling occurred was measured and shown in Table 1. Also in the following examples and comparative examples, the release substrate was similarly peeled, and the arithmetic surface roughness Ra of the water-repellent layer was measured and shown in Tables 1 and 2.

Example 1-2
A water-repellent laminate film-forming laminate and a water-repellent laminate film were produced in the same manner as in Example 1-1 except that the composition of the water-repellent laminate-forming coating solution was changed as follows.
(Coating liquid composition for water repellent layer formation)
Unsaturated carboxylic acid-modified polypropylene 10 parts by massWater-repellent fine particles 10 parts by mass (hydrophobic SiO ₂ , average particle diameter 1 to 100 nm)
・ IPA 40 mass parts ・ Water 40 mass parts

Example 1-3
The base material is 12 μm thick PET film (Toyobo Co., Ltd., Espet (registered trademark) E5100) and CPP film (Toray Film Processing Co., Ltd., ZK99S) are bonded together by dry lamination adhesiveness. The laminate for forming a water-repellent laminate film and the water-repellent laminate are the same as in Example 1-1 except that the composition of the coating solution for forming the water-repellent laminate is changed as follows. A film was prepared. Bonding was performed between the water repellent layer and the CPP film.
(Coating liquid composition for water repellent layer formation)
Unsaturated carboxylic acid-modified polypropylene 10 parts by massWater-repellent fine particles 10 parts by mass (hydrophobic SiO ₂ , average particle diameter 1 to 100 nm)
・ IPA 40 mass parts ・ Water 40 mass parts

Example 1-4
Passing between a roll having a flat surface and a shaping roll so that the laminate comprising the release substrate and the water repellent layer has a flat surface, and the substrate is on the shaping roll side A water-repellent laminate film-forming laminate and a water-repellent laminate film were produced in the same manner as in Example 1-1, except for the above.

Example 1-5
The water repellent laminated film forming laminate and the water repellent laminated film are the same as in Example 1-1 except that the shaping roll is changed to a shaping roll having a honeycomb structure with a piece of 50 μm on the surface and a depth of 50 μm. Was made.

Example 1-6
The water repellent laminated film forming laminate and the water repellent were the same as in Example 1-1 except that the shaping roll was changed to a lattice shaped shaping roll having a depth of 5 μm and a width of 50 μm and a spacing of 50 μm. A laminated film was produced.

Comparative Example 1-1
A water-repellent laminate film-forming laminate and a water-repellent laminate film were produced in the same manner as in Example 1-1 except that the composition of the water-repellent laminate-forming coating solution was changed as follows.
(Coating liquid composition for water repellent layer formation)
-Unsaturated carboxylic acid-modified polyethylene 20 parts by mass-IPA 40 parts by mass-Water 40 parts by mass

Example 2-1
A PET film having a thickness of 12 μm (manufactured by Toyobo Co., Ltd., Espet (registered trademark) E5100) was prepared as a peeling substrate. A water repellent layer was formed by applying and drying a water repellent layer forming coating solution having the following composition on one surface of the release substrate so that the coating amount after drying was 2.0 g / m ² .
(Coating liquid composition for water repellent layer formation)
Unsaturated carboxylic acid-modified polyethylene 10 parts by mass Water-repellent fine particles 5 parts by mass (hydrophobic SiO ₂ , average particle diameter 1 to 100 nm)
-5 parts by mass of bead particles (SiO ₂ , average particle diameter of 1 μm to 30 μm)
・ Isopropanol (IPA) 40 mass parts ・ Water 40 mass parts

  In addition, as a base material, a PET film having a thickness of 12 μm (Toyobo Co., Ltd., Espet (registered trademark) E5100) and a LLDPE film having a thickness of 50 μm (manufactured by Mitsui Chemicals Tosero Co., Ltd., TUX-TCS) Then, a laminated body bonded by dry laminate adhesiveness was produced.

As described above, the laminate of the release substrate and the water-repellent layer, and the LLDPE film of the substrate, and LLDPE (manufactured by Nippon Polypro Co., Ltd., Novatec (registered trademark) LC600A) between them are thickened. Extrusion was carried out so as to be 20 μm, and the sheet was passed between a shaping nip roll and a cooling roll, and bonded to obtain a laminate for forming a water-repellent laminated film.
Passing between the rolls was performed such that the laminate of the release substrate and the water repellent layer was on the shaping nip roll side and the substrate was on the cooling roll side, and the water repellent layer and the LLDPE film were in contact.
On the surface of the shaping nip roll, grooves having a depth of 50 μm and a width of 50 μm were provided so as to form a lattice at intervals of 50 μm.

Example 2-2
The same as Example 2-1 except that the LLDPE used for bonding the water repellent layer and the LLDPE film was changed to a linear LLDPE (Sumitomo Chemical Co., Ltd., Sumikasen (registered trademark) Hiα CW8003). Thus, a laminate for forming a water-repellent laminate film was produced.

Example 2-3
The base material is 12 μm thick PET film (Toyobo Co., Ltd., Espet (registered trademark) E5100) and CPP film (Toray Film Processing Co., Ltd., ZK99S) are bonded together by dry lamination adhesiveness. The laminate was changed to polypropylene (F329RA, manufactured by Prime Polymer Co., Ltd.) for bonding the water-repellent layer and the CPP film, and the composition of the water-repellent laminate-forming coating solution was changed as follows: A water-repellent laminate film-forming laminate and a water-repellent laminate film were produced in the same manner as in Example 2-1, except that the above changes were made. Bonding was performed between the water repellent layer and the CPP film.
(Coating liquid composition for water repellent layer formation)
Unsaturated carboxylic acid-modified polypropylene 10 parts by massWater-repellent fine particles 10 parts by mass (hydrophobic SiO ₂ , average particle diameter 1 to 100 nm)
・ IPA 40 mass parts ・ Water 40 mass parts

Example 2-4
Implemented except that the shaping nip roll was changed to a nip roll having a normal flat surface, and the cooling roll was changed to a shaping cooling roll provided with a 50 μm deep, 50 μm wide groove in a grid pattern at 50 μm intervals. In the same manner as in Example 2-1, a laminate for forming a water-repellent laminated film was produced.

Example 2-5
The water repellent laminated film forming laminate and the water repellent laminated film were the same as in Example 2-1, except that the shaped nip roll was changed to a shaped nip roll having a honeycomb structure with a piece of 50 μm on the surface and a depth of 50 μm. Was made.

Comparative Example 2-1
A water-repellent laminate film-forming laminate and a water-repellent laminate film were produced in the same manner as in Example 2-1, except that the composition of the water-repellent laminate-forming coating solution was changed as follows.
(Coating liquid composition for water repellent layer formation)
-Unsaturated carboxylic acid-modified polyethylene 20 parts by mass-IPA 40 parts by mass-Water 40 parts by mass

Water repellent test Water drops were dropped on the water repellent layer provided in the water repellent laminated films obtained in the above examples and comparative examples, and a water repellent layer and water drops were measured using a contact angle meter manufactured by Kyowa Interface Chemical Co., Ltd. The contact angle of was measured. The measurement results are summarized in Tables 1 and 2.

The water-repellent layer film obtained by the adhesion prevention test example was inclined 45 ° so that the water-repellent layer provided on the film was on top, and yoghurt (1 g) was hung on the water-repellent layer. The adhesion of yogurt to the water repellent layer was visually observed and evaluated according to the following evaluation criteria. The measurement results are summarized in Tables 1 and 2.
(Evaluation criteria)
○: There was no adhesion of yogurt, and good adhesion prevention was demonstrated.
X: There was much adhesion of yogurt and there was a problem in practical use.

Peel strength test In the laminate for forming a water-repellent laminated film obtained in Example 1-1, the peel strength (1) between the base material and the water-repellent layer using a tensile tester (Orientec). The cohesive peel strength (2) of the water repellent layer and the peel strength (3) between the water repellent layer and the release substrate were measured (N / 15 mm) (peel angle 90 °, pulling speed 50 mm / min). The maximum strength at the time of peeling was defined as the peeling strength. The measurement results are summarized in Tables 1 and 2. For the water-repellent laminated films obtained in other examples and comparative examples, the sealing strength was measured in the same manner.

Seal strength test Two water-repellent laminated films obtained by Example 1-1 were prepared, and the water-repellent layers were faced to each other and heat-sealed (heat seal temperature: 160 ° C. (in the case of polyethylene) 200 ° C. ( In the case of polypropylene)), seal width 1 mm, pressure 0.1 MPa, time: 1 second).
After heat sealing, the water-repellent laminated film was peeled off using a tensile tester (Orientec Co., Ltd.), and the maximum strength at the time of peeling was taken as the sealing strength (N / 15 mm) (peeling angle 90 °, pulling speed 300 mm / min) ). The measurement results are summarized in Tables 1 and 2. For the water-repellent laminated films obtained in other examples and comparative examples, the sealing strength was measured in the same manner.

10: laminate for forming water-repellent laminated film, 10: substrate, 12: water-repellent layer, 13: water-repellent fine particles, 14: release substrate, 15: water-repellent laminated film, 16: heat-sealable extruded resin layer 17 : Container, 18: Lid, 19: Container body, 20: Laminate manufacturing apparatus for forming a water-repellent laminated film, 21: Peeling substrate supply roller, 22: Peeling substrate, 23: Spray coating device, 24: Bath, 25: Gravure roll, 26: Substrate, 27: Laminate, 28: Heating roll, 29: Substrate supply roller, 30: Laminate for forming water-repellent laminated film, 31: Winding roll, 32: Resin material, 33 : Cooling roll, 34: Nip roll

Claims (11)

A shaped substrate, a water repellent layer and a release substrate are provided,
The water-repellent layer-containing laminate for forming a water-repellent laminated film, wherein the water-repellent layer contains water-repellent fine particles and a resin material, and causes cohesive peeling when peeling the release substrate.   The laminate for forming a water-repellent laminated film according to claim 1, wherein the water-repellent fine particles have an average particle diameter of 1 nm or more and 100 nm or less.   The laminate for forming a water-repellent laminated film according to claim 1 or 2, wherein the content of the water-repellent fine particles in the water-repellent layer is 5% by mass or more and 85% by mass or less.   The laminate for forming a water-repellent laminated film according to any one of claims 1 to 3, wherein the water-repellent layer comprises bead particles having an average particle diameter of 1 µm or more and 50 µm or less.   The water-repellent laminated film-forming laminate according to any one of claims 1 to 4, wherein the water-repellent layer contains a polyolefin resin and / or an unsaturated carboxylic acid-modified polyolefin resin as a resin material. The laminate for forming a water-repellent laminated film according to any one of claims 1 to 5, wherein the water-repellent layer has a thickness of 0.5 g / m ² or more and 10 g / m ² or less.   The laminate for forming a water-repellent laminated film according to any one of claims 1 to 6, further comprising a heat-sealable extruded resin layer between the substrate and the water-repellent layer.   The water-repellent laminated film obtained by peeling the said peeling base material from the laminated body for water-repellent laminated film formation as described in any one of Claims 1-7.   The water repellent laminated film according to claim 8, wherein the water repellent layer has an arithmetic surface roughness Ra of 10 μm or more and 200 μm or less. Preparing a substrate and a release substrate;
Applying a water-repellent layer forming coating solution on one surface of the release substrate, drying, forming a water-repellent layer, and obtaining a laminate;
The substrate and the laminate are heated and pressurized so that the substrate and the water-repellent layer are in contact with each other, laminated and shaped, and
Peeling the release substrate;
A method for producing a water-repellent laminated film. Preparing a substrate and a release substrate;
Applying a water-repellent layer forming coating solution on one surface of the release substrate, drying, forming a water-repellent layer, and obtaining a laminate;
A step of melting and extruding a resin material that melts or softens by heat and develops an adhesive between the base material and the laminate, and
Pressurizing, laminating and shaping the substrate, the resin material and the laminate; and
Peeling the release substrate;
A method for producing a water-repellent laminated film.