JP2019064010A - Water-repellent laminate and manufacturing method of the water-repellent laminate - Google Patents

Abstract

To provide a water-repellent laminate having a transferable water-repellent layer with high adhesion to a base material, the water-repellent laminate having high water-repellency and adhesion-preventing properties.SOLUTION: A water-repellent laminate 10 includes a base material 11 for a water-repellent laminate, and a transferable water-repellent layer 13 fusion-bonded to the base material 11 for a water-repellent laminate. The transferable water-repellent layer 13 includes water-repellent fine particles 12. In the water-repellent laminate 10, an average particle diameter of the water-repellent fine particles 12 is 1 nm or more to 6 μm or less. A content of the water-repellent fine particles 12 in the transferable water-repellent layer 13 is 5-85 mass%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a water repellent laminate and a method for producing the water repellent laminate.

  In many commodity fields such as food, beverages, medicines and chemicals, packaging materials having various functions such as water resistance, oil resistance, gas barrier property, moisture resistance and the like have been developed according to their contents.

As a function of the packaging material, an adhesion preventing function capable of preventing adhesion of the contents having high viscosity such as liquid, semi-solid, gel-like substance to the packaging material is required.
For example, high water repellency and adhesion prevention property are required for the lid of a container containing yoghurt and the like.

  In the previous application, the applicant has proposed, as a laminate having high water repellency and adhesion prevention property, a laminate comprising a substrate and a water repellent layer containing two types of particles having different average particle sizes. There is.

The laminate proposed in the previous application can be obtained by forming a water repellent layer by applying a coating liquid for forming a water repellent layer on a substrate and drying it.
However, now, the present inventors have found it difficult to form a water repellent layer depending on the material of the base material (for example, a multilayer constitution film including a heat sealable resin film made of polyethylene etc.) Also, even if it could be formed, it was found that the adhesion to the substrate is not sufficient, whereby the use of the laminate is limited.

  The inventors of the present invention used a heat sealable resin film such as a polyethylene film as a substrate for the water repellent layer formed by transferring on a substrate using a thermal transfer sheet or the like and thermally welding it. Even in the case, it was found that the adhesion to the substrate was significantly improved.

  The present invention has been made based on such findings, and the problem to be solved is to provide a transferable water repellent layer having high adhesion to a substrate, and a water repellent laminate having high water repellency and anti-adhesion properties. It is to provide the body.

  The water repellent laminate of the present invention comprises a substrate for water repellent laminate and a transferable water repellent layer thermally welded to the substrate for water repellent laminate, and the transferable water repellent layer contains water repellent fine particles. It is characterized by

  In one embodiment, the average particle diameter of the water repellent fine particles contained in the transferable water repellent layer included in the water repellent laminate of the present invention is 1 nm or more and 6 μm or less.

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

  In one embodiment, the transferable water repellent layer provided in the water repellent laminate of the present invention further includes bead particles having a diameter of 1 μm to 50 μm.

  In one embodiment, the substrate for a water repellent laminate provided in the water repellent laminate of the present invention comprises a heat sealable resin film, and the heat sealable resin film and the transferable water repellent layer are heat-welded. There is.

The method for producing the water repellent laminate of the present invention is
Preparing a thermal transfer sheet comprising a water repellent laminate substrate, a thermal transfer sheet substrate, and a transferable water repellent layer;
The thermal transfer sheet is heated from the surface of the thermal transfer sheet on which the transferable water repellent layer is not provided, by overlapping the transferable water repellent layer provided in the thermal transfer sheet and the substrate for the water repellent laminate. And ??? transferring onto the substrate for water repellent laminate, wherein the transferable water repellent layer comprises water repellent fine particles.

  In one embodiment, the average particle diameter of the water repellent fine particles contained in the transferable water repellent layer is 1 nm or more and 6 μm or less.

  In one embodiment, the transferable water repellent layer further includes bead particles that are 1 μm or more and 50 μm or less.

  According to the present invention, since it is possible to use a substrate made of various materials (heat sealable resin film etc.), it can be used for various applications, and is a water repellent laminate having high water repellency and adhesion preventing property. It can be a body.

FIG. 1 is a schematic cross-sectional view of a water repellent laminate according to an embodiment of the present invention. FIG. 1 is a schematic cross-sectional view of a water repellent laminate according to an embodiment of the present invention.

<Water-repellent laminate>
The water repellent laminate 10 of the present invention, as shown in FIG. 1, comprises a substrate 11 for water repellent laminate and a transferable water repellent layer 13 containing water repellent fine particles 12.
In addition, as shown in FIG. 2, the transferable water repellent layer can further include bead particles 14.
Hereinafter, the configuration of each layer provided in the water repellent laminate of the present invention will be described.

<Base material for water repellent laminates>
There are no particular limitations on the substrate for the water repellent laminate, and various materials are selected according to the type of contents to be packaged, mechanical strength, chemical resistance, solvent resistance, manufacturability, etc. required in the distribution. Applicable
In the present invention, it is possible to use a heat sealable resin film and a multilayer film provided with the heat sealable film, which have been difficult to use conventionally due to the problem of adhesion with the water repellent layer, as a substrate. it can.
Examples of the heat sealable resin constituting the heat sealable resin film include polyethylene (PE), ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester co-polymer Polymers, polypropylene and the like can be mentioned.

  In addition, coated paper, printing paper, paper materials such as high quality paper and kraft paper, metal foil such as aluminum foil, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile -Butadiene-Styrene copolymer (ABS resin), polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate (PET) , Polyester resins such as polybutylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins, polyamide imide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene resins It can be used sulfide-based resins, polyether sulfone resins, polyurethane resins, acetal resins, the composed film of various resins such as cellulose resins as a substrate.

Moreover, the laminated body of the above-mentioned material can also be used as a base material for water-repellent laminated bodies. For example, a multilayer film of a heat sealable resin film such as a PE film and a PET film can be used as a water repellent laminate substrate.
The lamination can be performed by using a dry lamination method, a wet lamination method, an extrusion method or the like.

  The thickness of the water repellent laminate base material is not particularly limited, but can be 5 μm or more and 200 μm or less.

<Transferable water repellent layer>
As described later, the transferable water repellent layer provided in the water repellent laminate of the present invention is a layer which is thermally transferred from the thermal transfer sheet onto the water repellent laminate substrate and thermally welded thereto.

The transferable water repellent layer contains water repellent fine particles, and as the water repellent fine particles, oxide fine particles subjected to hydrophobization surface treatment, for example, SiO ₂ , TiO ₂ , Al ₂ O ₃ and MgO etc. may be used. it can. Further, CaCO ₃ , talc, mica, silica airgel, PTFE, PFA or the like can also be used as the water repellent fine particles.
Among them, SiO ₂ (hereinafter, sometimes referred to as hydrophobized SiO ₂ ) which has been subjected to a hydrophobized surface treatment is preferable in terms of water repellency, adhesion preventing property and cost.
The transferable water repellent layer may contain two or more water repellent fine particles.
As a method of hydrophobization surface treatment, for example, a dry method (CVD method, plasma method) or a wet method may be used.
Moreover, you may use the water-repellent microparticles | fine-particles marketed.

The average particle size of the water repellent fine particles is preferably 1 nm or more and 10 μm or less, more preferably 1 nm or more and 6 μm or less from the viewpoint of the transferability, water repellency and adhesion preventing property of the transferable water repellent layer. preferable.
The average particle size of the water repellent fine particles can be measured by a scanning electron microscope.

  The content of the water repellent fine particles in the transferable water repellent layer is preferably 5% by mass or more and 85% by mass or less, and preferably 7% by mass or more, from the viewpoint of water repellency and adhesion preventing property of the laminate of the present invention. The content is more preferably 70% by mass or less, and still more preferably 7% by mass or more and 40% by mass or less. In addition, by setting the content of the water repellent fine particles in the above numerical range, the transferability of the transferable water repellent layer from the thermal transfer sheet described later can be made favorable.

In one embodiment, the transferable water repellent layer can include bead particles having a larger average particle size than the water repellent particles.
When the transferable water repellent layer contains bead particles in addition to the water repellent fine particles, a unique uneven structure is formed on the surface, and high water repellency and adhesion prevention when transferred onto a transfer target. Show sex.

Examples of bead particles include organic resin beads and inorganic beads. As organic resin beads, acrylic resin beads, polyethylene resin beads, polystyrene resin beads, urethane resin beads, styrene-acrylic copolymer beads, polycarbonate resin beads, polyvinyl chloride beads, melamine resin beads, benzoguanamine-formaldehyde condensate beads, Examples thereof include melamine-formaldehyde condensate beads, benzoguanamine-melamine-formaldehyde condensate beads and benzoguanamine-melamine condensate beads. Further, as the inorganic beads, glass beads, silica beads, alumina silicate, talc, mica and the like can be mentioned.
Among the above-described bead particles, urethane resin beads are particularly preferable from the viewpoint of water repellency and adhesion prevention.
In addition, you may use 2 or more types of the said organic resin bead and / or inorganic bead.

  The average particle diameter of the bead particles is preferably 1 μm to 50 μm, more preferably 3 μm to 40 μm, and more preferably 5 μm to 30 μm from the viewpoint of water repellency and adhesion prevention. Is more preferred.

  The content of bead particles in the transferable water repellent layer is preferably 5% by mass or more and 85% by mass or less, from the viewpoint of transferability, water repellency and adhesion preventing property of the transferable water repellent layer, and 20% by mass. It is more preferable that it is% or more and 70 mass% or less.

As thermoplastic resins contained in the transferable water repellent layer, polyolefin resins such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, poly (meth) acrylic resin, polyester resin , Ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl methacrylate copolymer, polystyrene resin, vinyl chloride-vinyl acetate copolymer And vinyl resins, and the like.
Among these, polyester resins are preferable from the viewpoint of transferability, and it is particularly preferable to use a polyester resin and a vinyl chloride-vinyl acetate copolymer in combination.
The transferable water repellent layer may contain two or more of the above-described thermoplastic resins.

  The ratio of the content of the thermoplastic resin in the transferable water repellent layer to the total content of the water repellent fine particles and the urethane beads (the content of the thermoplastic resin / the total content of the water repellent fine particles and the urethane beads) is 2 / It is preferably 1 or more and 1/5 or less, and more preferably 1.5 / 1 or more and 1/3 or less. By making content ratio into the said numerical range, the water repellency and the adhesion prevention property of the laminated body of this invention can be improved more.

The dry coating amount of the transferable water repellent layer is preferably 0.5 g / m ² or more and 10 g / m ² or less, and more preferably 1.0 g / m ² or more and 7 g / m ² or less . Thereby, the transferability of the transferable water repellent layer, the water repellency and the adhesion preventing property of the laminate of the present invention can be improved.

<Others>
In one embodiment, the water repellent laminate of the present invention can include a vapor deposition film made of an inorganic oxide such as aluminum, silicon oxide, titanium oxide, or aluminum oxide. Thereby, the gas-barrier property and light shielding property of the water-repellent laminated body obtained can be improved.

  In one embodiment, the water repellent laminate of the present invention may be subjected to printing using a conventionally known printing ink on any layer, for example, a substrate for water repellent laminate. The printing method is also not particularly limited, and conventionally known methods such as gravure printing, flexographic printing, and screen printing can be used.

(Use)
The water repellent laminate of the present invention can be applied to various uses, for example, lids of containers filled with yoghurt etc., and formed containers filled with contents, packaging materials such as trays, tubes, pouches, etc. It can be used for production.

(Method of manufacturing water repellent laminate)
The method for producing a water repellent laminate of the present invention is
Preparing a substrate for a water repellent laminate and a thermal transfer sheet to be described later;
The thermal transfer sheet is heated from the surface of the thermal transfer sheet on which the transferable water repellent layer is not provided, by overlapping the transferable water repellent layer provided in the thermal transfer sheet and the substrate for the water repellent laminate. And ??? transfer to a substrate for water repellent laminate.
Hereinafter, each process included in the method of the present invention will be described.

(Step of preparing a substrate for water repellent laminate and a thermal transfer sheet)
The thermal transfer sheet comprises a thermal transfer sheet substrate and a transferable water repellent layer containing water repellent fine particles. In addition, the transferable water repellent layer included in the thermal transfer sheet can further include bead particles 14. The structure of the transferable water repellent layer is as described above.
In one embodiment, the thermal transfer sheet may include a release layer (not shown) between the thermal transfer sheet substrate and the transferable water repellent layer. In one embodiment, the thermal transfer sheet may be provided with a back layer on the surface of the thermal transfer sheet substrate opposite to the surface on which the transferable water repellent layer is provided.

Examples of the substrate for the thermal transfer sheet include paper materials such as coated paper, printing paper, high-quality paper and kraft paper, and examples thereof include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), Polyester-based resins such as polyethylene terephthalate-isophthalate copolymer and terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyamide-based resins such as nylon 6 and nylon 6, 6, polypropylene (PP) and polymethylpentene Polyolefin resins, polyvinyl chloride, polyvinyl alcohol (PVA), polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, vinyl resins such as polyvinyl butyral and polyvinyl pyrrolidone (PVP), polyacrylate (Meth) acrylic resins such as polymethacrylate and polymethylmethacrylate, polyimide resins such as polyimide and polyetherimide, styrenic resins, and cellophane, cellulose acetate, nitrocellulose, cellulose acetate propionate (CAP) and A film composed of a cellulose-based resin such as cellulose acetate butyrate (CAB) (hereinafter simply referred to as "resin film") or metal foil such as aluminum foil can be used.
Among these, aluminum foil and PET film, in particular, PET having an easy adhesion coat layer is preferable from the viewpoint of adhesion to the transferable water repellent layer.

Moreover, the laminated body of the above-mentioned material can also be used as a base material for thermal transfer sheets.
The laminate can be produced by using a dry lamination method, a wet lamination method, an extrusion method or the like.

  The formation of the transferable water repellent layer on the thermal transfer sheet substrate is carried out by dispersing or dissolving the above-mentioned material in water or a suitable solvent to obtain a transferable water repellent layer forming coating solution, which is used as a roll coater, reverse It can form by apply | coating and forming a coating film on the base material for thermal transfer sheets by well-known means, such as a roll coater, a gravure coater, a reverse gravure coater, a bar coater, and a rod coater, and then drying this. .

  In one embodiment, the thermal transfer sheet used for producing the water repellent laminate of the present invention can be provided with a release layer between the thermal transfer sheet substrate and the transferable water repellent layer. The release layer can contain a release agent, and as the release agent, for example, a melamine resin release agent, a silicone release agent, a fluorocarbon resin release agent, a cellulose resin release agent, urea Examples include resin-based release agents, polyolefin resin-based release agents, paraffin-based release agents, (meth) acrylic resin-based release agents, and waxes. The release layer may contain one or more of the above release agents.

  The thickness of the release layer is preferably 0.1 μm or more and 5 μm or less, more preferably 0.5 μm or more and 2 μm or less, from the viewpoint of the stability of the peeling force.

  The release layer is formed by dispersing or dissolving the above material in water or a suitable solvent to form a release layer-forming coating solution, which is used as a roll coater, reverse roll coater, gravure coater, reverse gravure coater, bar coater It can form by apply | coating and forming a coating film on the base material for thermal transfer sheets by well-known means, such as and a rod coater, and then making it dry.

In one embodiment, the thermal transfer sheet used to make the water repellent laminate of the present invention can be provided with a back layer. In one embodiment, the back layer comprises a binder resin. As the binder resin, for example, cellulose resin, styrene resin, vinyl resin, polyester resin, polyurethane resin, silicone modified urethane resin, silicone resin, fluorine modified urethane resin, (meth) acrylic resin, etc. It can be mentioned.
Among these, silicone resins, specifically, acrylic-modified silicone resins are preferable from the viewpoint of the prevention of burn-in of the thermal head and the back layer and the generation of debris.

In one embodiment, the back layer contains, as a binder resin, a two-component curable resin that is cured by combined use with an isocyanate compound or the like. Examples of such resins include polyvinyl acetal resins and polyvinyl butyral resins.
As the isocyanate compound, conventionally known isocyanate compounds can be used without particular limitation, and among them, it is desirable to use an adduct of aromatic isocyanate. As the aromatic polyisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, trans-cyclohexane-1,4-diisocyanate, xylylene diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, particularly 2,4-toluene diisocyanate, 2,6-toluene diisocyanate Alternatively, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is preferred.

In one embodiment, the back layer comprises inorganic or organic particles.
As the inorganic fine particles, for example, clay minerals such as talc and kaolin, carbonates such as calcium carbonate and magnesium carbonate, hydroxides such as aluminum hydroxide and magnesium hydroxide, sulfates such as calcium sulfate, oxides such as silica And inorganic fine particles such as graphite, nitrate and boron nitride.
Organic fine particles include organic resin fine particles made of (meth) acrylic resin, Teflon (registered trademark) resin, silicone resin, lauroyl resin, phenol resin, acetal resin, styrene resin, polyamide resin, etc., or The crosslinked resin microparticles etc. which made these react with the crosslinking agent are mentioned.

  The thickness of the back layer is preferably 0.01 μm or more and 5.0 μm or less, and more preferably 0.03 μm or more and 2 μm or less.

  The back layer is formed by dispersing or dissolving the above material in water or a suitable solvent to form a back layer-forming coating solution, which is used as a roll coater, reverse roll coater, gravure coater, reverse gravure coater, bar coater and rod. It can form by apply | coating on the base material for thermal transfer sheets by well-known means, such as a coater, to form a coating film, and then drying this.

(Transfer process)
The method according to the present invention comprises the step of transferring the transferable water repellent layer provided in the thermal transfer sheet onto the water repellent laminate substrate.

  In one embodiment, the transfer of the transferable water repellent layer is performed using a thermal head, a heat roll or the like, and specifically, a transferable water repellent layer provided to the thermal transfer sheet, and a substrate for a water repellent laminate For example, it is performed by overlapping the heat sealable resin film so as to face each other and heating the surface of the thermal transfer sheet on which the transferable water repellent layer is not provided with a thermal head.

  The heating temperature in the transfer step is preferably 120 ° C. or more and 250 ° C. or less, and more preferably 130 ° C. or more and 240 ° C. or less. By setting the heating temperature in the above-mentioned numerical range, the transferability of the transferable water repellent layer can be improved.

  The transfer speed in the transfer step 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 transfer speed within the above numerical range, the transferability of the transferable water repellent layer can be improved.

  EXAMPLES The present invention will be more specifically described by way of examples, but the present invention is not limited by these examples.

Example 1
Preparation of base material for thermal transfer sheet After dry laminating of aluminum-deposited surface of aluminum-deposited PET film on one side of printing paper (Daio Paper Co., Ltd., trade name: Ryuw coat, 55 g / m ² ), aging is performed, A substrate for a thermal transfer sheet was produced. For the dry lamination, a polyether adhesive (manufactured by Rock Paint Co., Ltd., trade name: RU 3900) was used.

Preparation of Thermal Transfer Sheet for Water-Repellent Laminate Formation A coating liquid for forming a transferable water-repellent layer is applied onto the PET surface of the above-mentioned base material for a thermal transfer sheet, and dried in a drying furnace to obtain a coating amount of 2.0 g. A transferable water repellent layer having the following composition / m ² was formed to prepare a thermal transfer sheet.
(Composition of transferable water repellent layer)
Resin component (vinyl chloride-vinyl acetate copolymer, 48 parts by mass of polyester resin, bead particles (average particle size: 20 μm, urethane resin beads) 38 parts by mass, water-repellent fine particles (average particle size: 1 to 300 nm, hydrophobic) SiO ₂ ) 14 parts by mass

Preparation of water repellent laminate As a substrate for water repellent laminate , prepare a laminate comprising a PET film of 12 μm thickness and a PE film of 50 μm thickness, and prepare as described above the PE surface of the laminate. The substrate for water repellent laminate and the thermal transfer sheet are superposed so that the transferable water repellent layer of the thermal transfer sheet faces each other, and the substrate is heated from the substrate side of the thermal transfer sheet using a thermal head The transferable water repellent layer was transferred onto the substrate. The heating temperature of the thermal head was 160 ° C., and the transfer speed was 1 m / min.

(Examples 2 to 8)
A water repellent laminate was produced in the same manner as in Example 1 except that the heating temperature of the thermal head and the transfer speed were changed to the values shown in Table 1.

(Example 9)
The heat transfer sheet and the water repellency are the same as in Example 1, except that the composition of the transferable water repellent layer is changed as follows, and the heating temperature and transfer speed of the thermal head are changed to the values shown in Table 1. A laminate was made.
(Composition of transferable water repellent layer)
Resin component (vinyl chloride-vinyl acetate copolymer, 48 parts by mass of polyester resin, bead particles (average particle size: 5 μm, urethane resin beads) 38 parts by mass, water-repellent fine particles (average particle size: 1 to 300 nm, hydrophobic) SiO ₂ ) 14 parts by mass

(Example 10)
The heat transfer sheet and the water repellency are the same as in Example 1, except that the composition of the transferable water repellent layer is changed as follows, and the heating temperature and transfer speed of the thermal head are changed to the values shown in Table 1. A laminate was made.
(Composition of transferable water repellent layer)
Resin component (vinyl chloride-vinyl acetate copolymer, 25 parts by mass of polyester resin, bead particles (average particle size: 20 μm, urethane resin beads) 35 parts by mass, water-repellent fine particles (average particle size: 1 to 300 nm, hydrophobic) SiO ₂ ) 40 parts by mass

(Example 11)
The heat transfer sheet and the water repellency are the same as in Example 1, except that the composition of the transferable water repellent layer is changed as follows, and the heating temperature and transfer speed of the thermal head are changed to the values shown in Table 1. A laminate was made.
(Composition of transferable water repellent layer)
Resin component (vinyl chloride-vinyl acetate copolymer, 25 parts by mass of polyester resin, bead particles (average particle size: 20 μm, urethane resin beads) 65 parts by mass, water-repellent fine particles (average particle size: 1 to 300 nm, hydrophobic) SiO ₂ ) 10 parts by mass

(Example 12)
A thermal transfer sheet and a water repellent laminate were produced in the same manner as in Example 1 except that the water repellent fine particles in the transferable water repellent layer were changed to Airika KT-3 (Tokuyama Co., average particle type: 3 μm).

(Comparative example 1)
An adhesive is applied to the corona surface of a PET film (Toyobo SSP Co., Ltd., trade name: T4102, thickness: 12 μm) which has been subjected to corona treatment, and a PP film (manufactured by Toray Film Co., Ltd.) After laminating the product name: ZK99S, thickness: 60 μm), it was aged to prepare a laminate.

(Comparative example 2)
A laminate comprising a PET film of 12 μm thickness and a PE film of 50 μm thickness is prepared, a coating liquid for forming a water repellent layer is applied to the PE surface of the laminate, dried, and the laminate is formed on the laminate. A water repellent layer having the following composition was formed. When the water repellent layer was rubbed by hand, the water repellent layer peeled off.
(Composition of coating liquid for water repellent layer formation)
Resin component (vinyl chloride-vinyl acetate copolymer, 48 parts by mass of polyester resin, bead particles (average particle size: 20 μm, urethane resin beads) 38 parts by mass, water-repellent fine particles (average particle size: 1 to 300 nm, hydrophobic) SiO ₂ ) 14 parts by mass

Water Repellency Test Droplets are dropped on the surface of the transferable water repellent layer provided in the water repellent laminate obtained in the Examples, and a contact angle meter manufactured by Kyowa Interface Chemical Co., Ltd. The contact angle was measured.
Moreover, it measured similarly about the contact angle of PP surface of the laminated body obtained by the comparative example 1, and a water droplet. The measurement results are summarized in Table 2.

Adhesion Prevention Test The water repellent laminate obtained in the example was inclined 45 ° so that the transferable water repellent layer was on the upper side, and yogurt (1 g) was dropped on the transfer water repellent layer. The adhesion of the yogurt to the thermal adhesive layer was visually observed and evaluated according to the following evaluation criteria.
Moreover, yoghurt was dripped similarly on PP surface of the laminated body obtained by the comparative example 1, and the adhesion prevention property was evaluated. The evaluation results are summarized in Table 2.
(Evaluation criteria)
○: There was no adhesion of yoghurt, and a good adhesion prevention was exhibited.
Fair: There was some adhesion of yogurt, but there was no problem in practical use.
X: There was much adhesion of yoghurt and there was a problem in practical use.

Seal Strength Test Two water repellent laminates obtained in Example 1 were prepared, the transferable water repellent layers were face to face, and these were heat sealed (heat seal temperature: 200 ° C., seal width 1 mm, pressure 0. 1 MPa, time: 1 second).
After heat sealing, the water repellent laminate was peeled using a tensile tester (manufactured by ORIENTEC Co., Ltd.), and the maximum strength at peeling was made the seal strength (N / 15 mm) (peeling angle 90 °, tensile speed 300 mm / min) ). The measurement results are shown in Table 2. The seal strength was similarly measured for the laminates obtained in the other examples and comparative examples. In addition, about the laminated body obtained in the comparative example 1, PP surfaces were heat-sealed.

10: water repellent laminate 11: substrate for water repellent laminate 12: water repellent fine particles 13: transferable water repellent layer 14: bead particles

Claims (8)

A substrate for water repellent laminate, and a transferable water repellent layer heat-welded to the substrate for water repellent laminate;
A water repellent laminate, wherein the transferable water repellent layer contains water repellent fine particles.   The water repellent laminate according to claim 1, wherein an average particle diameter of the water repellent fine particles is 1 nm or more and 6 μm or less.   The water repellent laminate according to claim 1 or 2, wherein a content of the water repellent fine particles in the transferable water repellent layer is 5% by mass or more and 85% by mass or less.   The water repellent laminate according to any one of claims 1 to 3, wherein the transferable water repellent layer further comprises bead particles having a diameter of 1 μm to 50 μm.   The said water-repellent laminate base material comprises a heat sealable resin film, and the heat sealable resin film and the transferable water repellent layer are heat-welded according to any one of claims 1 to 4. Water repellent laminate. It is a manufacturing method of the water repellent layered product according to any one of claims 1 to 5,
Preparing a thermal transfer sheet comprising a water repellent laminate substrate, a thermal transfer sheet substrate, and a transferable water repellent layer;
The thermal transfer sheet is heated from the surface of the thermal transfer sheet on which the transferable water repellent layer is not provided, by overlapping the transferable water repellent layer provided in the thermal transfer sheet and the substrate for the water repellent laminate. And transferring the transferable water repellent layer onto the substrate for the water repellent laminate, wherein the transferable water repellent layer comprises water repellent fine particles.   The method according to claim 6, wherein the water-repellent fine particles have an average particle size of 1 nm or more and 6 μm or less.   The method according to claim 6, wherein the transferable water repellent layer further comprises bead particles having a diameter of 1 μm to 50 μm.

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