WO2017204258A1

WO2017204258A1 - Water repellent laminate for cover materials, cover material and container

Info

Publication number: WO2017204258A1
Application number: PCT/JP2017/019411
Authority: WO
Inventors: 翔三結城; 山田　新
Original assignee: 大日本印刷株式会社
Priority date: 2016-05-25
Filing date: 2017-05-24
Publication date: 2017-11-30

Abstract

[Problem] To provide a water repellent laminate for cover materials, which has high water repellency, adhesion prevention properties and heat sealability. [Solution] A water repellent laminate for cover materials according to the present invention comprises a base and a thermal bonding layer arranged on the base, and is characterized in that the thermal bonding layer contains a thermoplastic resin, water repellent fine particles, and bead particles which have a larger average particle diameter than the water repellent fine particles.

Description

Water repellent laminate for lid, lid and container

The present invention relates to a water-repellent laminate for a lid, a lid and a container.

In many product fields such as food, beverages, pharmaceuticals, and chemicals, packaging materials have been developed for each content. In particular, plastic materials that are excellent in water resistance, oil resistance, gas barrier properties, moisture resistance, light weight, flexibility, and design properties as packaging materials for packaging viscous contents such as liquids, semi-solids, and gel substances Is used to protect the contents required for packaging materials.

As a function of the packaging material, there is a demand for an adhesion preventing function capable of preventing adhesion of the highly viscous content such as liquid, semi-solid, and gel substance to the packaging material.

For example, it has been proposed to provide an adhesion preventing layer comprising hydrophobic fine particles and a thermoplastic binder resin on one side of a substrate (see Patent Document 1).

Japanese Patent No. 5490574

However, the lid material proposed in Patent Document 1 is provided with a thermal bonding layer and an adhesion preventing layer, and has a problem in that the number of manufacturing steps is large and the manufacturing cost increases. In addition, depending on the type of solvent used when forming the adhesion preventing layer, there is a problem that it reacts with the resin contained in the thermal adhesive layer, causing a decrease in heat sealability and a decrease in water repellency. .

The present invention has been made in order to solve the above-described problems, and is a water-repellent laminate for a lid that can be manufactured with a smaller number of steps and has high water repellency, adhesion prevention, and heat sealability. Its purpose is to provide.

The water-repellent laminate for a lid according to the present invention includes a base material and a thermal adhesive layer on the base material, and the thermal adhesive layer has an average particle diameter larger than that of the thermoplastic resin, the water-repellent microparticles, and the water-repellent microparticles. It is characterized by comprising large bead particles.

In the above aspect, the average particle diameter of the water-repellent fine particles is preferably 1 nm or more and 300 nm or less.

In the above aspect, the average particle diameter of the bead particles is preferably 1 μm or more and 50 μm or less.

In the above aspect, the content of the water-repellent fine particles in the thermal adhesive layer is preferably 5 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin contained in the thermal adhesive layer.

In the above aspect, the ratio of the thermoplastic resin content in the thermal adhesive layer to the water repellent fine particles and the bead particle content is preferably 2: 1 to 1: 5 on a mass basis.

In the above embodiment, it is preferable that the Si element concentration on the surface of the thermal adhesive layer measured by X-ray photoelectron spectroscopy is 17% or more.

In the above aspect, the water-repellent fine particles are preferably SiO ₂ subjected to a hydrophobic surface treatment.

In the said aspect, it is preferable that the specific surface area of the surface on the opposite side to the said base material side of a heat bonding layer is 1.0 m < ² > / g or more.

The lid material of the present invention is characterized by comprising the above laminate.

The container of the present invention comprises the above-described lid material and a container body, and is characterized in that the thermal adhesive layer of the lid material and the container body are heat-sealed.

The method for producing the laminate of the present invention is as follows.
Preparing a substrate;
Applying a thermal adhesive layer coating liquid containing thermoplastic resin, water-repellent fine particles and bead particles having an average particle diameter larger than that of the water-repellent fine particles on a substrate;
Including a step of drying the applied thermal adhesive layer coating solution,
In the drying step, the amount of heat applied to the thermal adhesive layer coating solution is 0.5 KJ / m ² or more and 5.5 KJ / m ² or less.

The container according to the present invention includes a lid member and a container body, and the heat bonding layer of the lid member and the container body are heat-sealed.

According to the present invention, it is possible to provide a water-repellent laminate for a lid material having high water repellency, adhesion prevention and heat sealability. Moreover, according to this invention, the water-repellent laminated body for lid | cover materials which has high abrasion resistance in which water-repellent fine particles do not slide off by friction can be provided.

It is a cross-sectional schematic diagram of the water-repellent laminated body for lid | cover materials by one Embodiment of this invention. It is a cross-sectional schematic diagram of the container by one Embodiment of this invention.

<Water-repellent laminate for lid>
Embodiments of the present invention will be described with reference to the drawings. FIG. 1 shows a schematic cross-sectional view of a water-repellent laminate for a lid according to an embodiment of the present invention. In one embodiment, the lid water-repellent laminate 10 includes a base material 11 and a thermal adhesive layer 12 including water-repellent fine particles 13 and bead particles 14.
Hereinafter, each layer which comprises the water-repellent laminated body for lid | cover materials by this invention is demonstrated.

(Base material)
Use as the base material paper such as coated paper, printing paper, high-quality paper and kraft paper, films made of resin such as polyester such as polypropylene, polyamide and polyethylene terephthalate (PET), or metal foil such as aluminum foil Can do.
Moreover, it is preferable that a base material is provided with the vapor deposition film which consists of inorganic oxides, such as aluminum, silicon oxide, titanium oxide, and aluminum oxide. Thereby, the function as a barrier layer with respect to oxygen and water vapor | steam can be provided to a base material. Moreover, since the light-shielding property of a base material can be improved, it is preferable that a base material is provided with a vapor deposition film.
Moreover, you may use the laminated material of an above-described paper material and a film as a base material. The lamination method is not particularly limited, and a dry lamination method, a wet lamination method, a heat lamination method, or the like can be used.

Also, the substrate can be subjected to surface treatment such as corona discharge treatment, chemical treatment, ozone treatment, etc., as desired. Thereby, the adhesiveness of a base material and the adjacent layer can be improved.

The substrate may be subjected to printing 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.

The thickness of the substrate is not particularly limited, but can be, for example, 5 μm or more and 200 μm or less.

(Thermal adhesive layer)
The thermal adhesive layer of the present invention comprises thermoplastic resin, water-repellent fine particles and bead particles having an average particle size larger than that of the water-repellent fine particles.
By including two types of particles having different sizes, the thermal adhesive layer has a unique concavo-convex structure formed on the surface of the thermal adhesive layer, and remarkably improves the adhesion prevention and water repellency of viscous contents. Can do.
In addition, since it comprises bead particles having an average particle diameter larger than that of the water-repellent fine particles, it is possible to improve the scratch resistance of the thermal adhesive layer and to prevent the water-repellent fine particles from sliding off due to friction.

The thermoplastic resin contained in the thermal adhesive layer includes polyolefin resins such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, and polypropylene, poly (meth) acrylic resin, polyester resin, ionomer resin, and ethylene. -Vinyl resins such as acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl methacrylate copolymer, polystyrene resin, vinyl chloride-vinyl acetate copolymer, etc. Can be mentioned.
Among these, when the container is made of polystyrene, an acrylic resin and a vinyl chloride-vinyl acetate copolymer are particularly preferable.
The thermal adhesive layer may contain two or more kinds of the thermoplastic resins described above.

As the water-repellent fine particles contained in the heat-adhesive layer, oxide fine particles having been subjected to a hydrophobic surface treatment, such as SiO ₂ , TiO ₂ , Al ₂ O ₃ and MgO can be used. Also, CaCO ₃ , talc, mica, etc. can be used as the water-repellent fine particles.
Among these, from the viewpoint of adhesion prevention, water repellency, and cost, SiO ₂ subjected to a hydrophobic surface treatment (hereinafter sometimes referred to as hydrophobic SiO ₂ ) is preferable.
The thermal adhesive layer may contain two or more types of water-repellent fine particles.
As a method for hydrophobizing surface treatment, for example, a dry method (CVD method, plasma method) or a wet method may be used.
Commercially available water-repellent fine particles may be used.

The average particle diameter of the water-repellent fine particles is preferably 1 nm or more and 300 nm or less, more preferably 1 nm or more and 200 nm or less, and further preferably 1 nm or more and 100 nm or less. By setting the average particle diameter of the water-repellent fine particles in the above numerical range, it is possible to further improve adhesion prevention and water repellency while maintaining the heat-sealing property of the heat-adhesive layer.
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 thermal adhesive 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 making the content of the water-repellent fine particles in the above numerical range, it is possible to further improve the anti-adhesion property and the water repellency while maintaining the heat sealability of the heat-adhesive layer.
The content of the water-repellent fine particles in the thermal adhesive layer is preferably 5 parts by mass or more and 500 parts by mass or less, more preferably 20 parts by mass or more and 200 parts by mass with respect to 100 parts by mass of the thermoplastic resin contained in the thermal adhesive layer. More preferably, it is 70 parts by mass or more and 170 parts by mass or less.

Examples of the bead particles contained in the thermal adhesive layer include organic resin beads or inorganic beads. Organic resin beads include 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 include melamine-formaldehyde condensate beads, benzoguanamine-melamine-formaldehyde condensate beads, and benzoguanamine-melamine condensate beads. Examples of inorganic beads include glass beads, silica beads, alumina silicate, talc, and mica. Two or more kinds of the above organic resin beads and / or inorganic beads may be used.

The average particle diameter of the bead particles is preferably 1 μm or more and 50 μm or less, more preferably 3 μm or more and 30 μm or less, and further preferably 5 μm or more and 20 μm or less. By making the average particle diameter of the bead particles in the above numerical range, it is possible to further improve the adhesion preventing property and the water repellency while maintaining the heat sealing property of the heat bonding layer. Furthermore, the scratch resistance of the thermal adhesive layer can be improved, and the water-repellent fine particles can be prevented from falling off due to friction.

The content of the bead particles in the heat bonding 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 in the above numerical range, it is possible to further improve adhesion prevention and water repellency while maintaining the heat sealability of the thermal adhesive layer. Furthermore, the scratch resistance of the thermal adhesive layer can be improved.

The ratio of the thermoplastic resin content to the water repellent fine particle and bead particle content in the thermal adhesive layer is preferably 2: 1 to 1: 5 on a mass basis, and preferably 1.5: 1 to 1. : 3 is more preferable. Thereby, the adhesion preventing property and water repellency of the thermal adhesive layer can be further improved.

The content ratio between the water-repellent fine particles and the bead particles in the heat-adhesive layer is preferably 10: 1 to 1:10, more preferably 8: 3 to 3: 8 on a mass basis. Thereby, the adhesion preventing property and water repellency of the thermal adhesive layer can be further improved.

The element concentration of Si on the surface of the thermal bonding layer is preferably 17 atomic% or more, more preferably 20 atomic% or more and 50 atomic% or less, and further preferably 21 atomic% or more and 40 atomic% or less.
By setting the Si element concentration on the surface of the thermal adhesive layer within the above numerical range, the water repellency and the anti-adhesion property can be improved while maintaining the heat sealability of the thermal adhesive layer.
The Si element concentration on the surface of the thermal adhesive layer is not limited to this, but the type and amount of constituent materials such as thermoplastic resin, water-repellent fine particles, bead particles, the thickness of the thermal adhesive layer, thermal adhesiveness, etc. It can be adjusted by changing the amount of heat applied when forming the layer.
In the present invention, the elemental concentration of Si on the surface of the thermal adhesive layer was measured using an X-ray electron spectroscopic analyzer under the following conditions.
(Measurement condition)
X-ray source: Mg Kα ray (1253.6 eV)
・ X-ray output: 300W (12kV, 25mA)

Moreover, the specific surface area of the surface opposite to the base material side of the thermal adhesive layer, that is, the surface in contact with the contents when used as a lid member, is preferably 1.0 m ² / g or more, and 2.0 m ^2. / G or more is more preferable.
The specific surface area is preferably 20.0 m ² / g or less.
By setting the specific surface area of the surface in contact with the content within the above numerical range, the adhesion prevention and water repellency of the viscous content can be significantly improved.
The specific surface area of the thermal adhesive layer can be adjusted by adjusting the ratio of the water-repellent fine particles and bead particles contained in the thermal adhesive layer coating liquid and the thickness of the thermal adhesive layer.
In the present invention, the specific surface area can be measured by a BET method in accordance with JIS K 6221.

(Other layers)
The laminate of the present invention may have one or more other layers between the base material and the thermal adhesive layer. Examples of other layers include a barrier layer, a printing layer, and an anchor layer.

As the barrier layer, for example, a metal foil can be used, and more specifically, an aluminum foil, a stainless steel foil, a titanium foil and the like can be mentioned. Aluminum foil is preferred from the viewpoints of gas barrier properties that prevent transmission of oxygen gas, water vapor, and the like, and light shielding properties that prevent transmission of visible light, ultraviolet light, and the like.

A printing layer is a layer provided in order to provide design properties, such as a character, information, a pattern, and a design, to a laminated body. A printing layer can be formed using a conventionally well-known pigment and dye, The formation method is not specifically limited.
For example, titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue titanium yellow, carbon black and other inorganic pigments, isoindolinone yellow, hansa yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, indanthrene blue RS And organic pigments such as aniline black, metal pigments made of metal powders such as aluminum and brass, pearl pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate, and fluorescent pigments.

The anchor layer is a layer that functions to improve adhesion between the base material and the thermal adhesive layer and to prevent the water-repellent fine particles and bead particles contained in the thermal adhesive layer from sliding off.
The anchor layer can contain a (meth) acrylic resin, a urethane resin, a polyester resin, a cellulose resin, a vinyl resin, or a copolymer of these resins (for example, an acrylic polyester resin).
Curing agents, silane coupling agents, plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, slip agents, mold release Various additives such as an agent, an antioxidant and an ion exchange agent may be included.

(Method for producing water-repellent laminate)
The method for producing a water-repellent laminate of the present invention comprises a step of preparing a base material and a step of forming a thermal adhesive layer on the base material.
Hereafter, each process which comprises the method of this invention is demonstrated.

(Process for preparing the base material)
A commercially available substrate may be used, and a film made of a resin may be produced by a conventionally known method such as a T-die method or an inflation method.
Moreover, it is preferable to perform surface treatments such as corona discharge treatment, chemical treatment, and ozone treatment on the substrate. Thereby, the adhesiveness of a base material and the layer adjacent to a base material can be improved.

(Process for forming a thermal adhesive layer)
The thermal adhesive layer is coated on a base material by a known method such as a bar coating method using a thermoplastic resin, water-repellent fine particles, bead particles having an average particle size larger than the water-repellent fine particles and an organic solvent. It can be formed by drying.
Examples of the organic solvent include methyl acetate, ethyl acetate, propyl acetate, acetone, methyl ethyl ketone, methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, tetrahydrofuran, difuran, and the like, and one or more of these can be contained. .

The coating amount after drying of the coating liquid 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. When the coating amount after drying of the coating liquid is within the above numerical range, adhesion prevention and water repellency can be further improved while maintaining the heat sealability of the laminate.

In the drying of the applied coating liquid, the amount of heat applied is, 0.5kJ / ^{m 2} or more, preferably 5.5kJ / ^{m 2} or less, 1.5 kJ / ^{m 2} or more, 4.5kJ / ^{m 2} or less It is more preferable that it is 2.0 kJ / m ² or more and 4.0 kJ / m ² or less. By setting the amount of heat applied to the formation of the heat-adhesive layer within the above numerical range, the water-repellent fine particles and the bead particles appear appropriately on the surface of the heat-adhesive layer, and the water repellency and adhesion preventing property can be further improved.
In particular, when SiO ₂ is used as the water-repellent fine particles, the element concentration of Si on the surface of the thermal adhesive layer can be set to a preferable numerical range, and the water repellency and adhesion preventing property can be improved.
The amount of heat can be adjusted by controlling the temperature in the drying furnace and the drying time.

(Cover material)
The lid material according to the present invention can be produced using the above-mentioned laminate, and is preferably used as a lid material for a viscous content such as a liquid, a semi-solid, or a gel substance, for example, a yogurt packaging container. Can do.

(container)
A container 20 according to the present invention includes a lid 21 made of a water-repellent laminate for a lid as shown in FIG. 3 and a container body 22, and includes a thermal adhesive layer 12 for the lid, a container body 22, Is heat sealed. More specifically, the opening 23 of the container body 22 and the heat bonding layer 12 of the lid material are heat sealed.
The method of heat sealing is not particularly limited, and can be performed by using a conventionally known method such as bar sealing, high frequency sealing or ultrasonic sealing.

The container body can 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 items such as shampoo and body soap.

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
Fabrication of base material Corona surface of PET film (trade name: E5100, thickness: 12 μm, manufactured by Toyobo Espet Co., Ltd.) with corona treatment applied to one side, polyester adhesive (trade name, manufactured by Rock Paint Co., Ltd.) : RU-004) was applied, and AL foil (Toyo Aluminum Co., Ltd., trade name: 1N30, thickness: 7 μm) was laminated, followed by aging to prepare a substrate.

Preparation of water-repellent laminate for lid material 100 parts by weight of Inomiya Chemical WRD-2 was mixed with a diluent solvent consisting of 50 parts by weight of toluene, 30 parts by weight of methyl ethyl ketone, and 20 parts by weight of ethyl acetate. Got.
The ink WRD-2 contains 50 parts by mass of toluene, 30 parts by mass of methyl ethyl ketone and 20 parts by mass of ethyl acetate as a solvent, and contains vinyl chloride-vinyl acetate copolymer as a thermoplastic resin, and water-repellent fine particles. Includes hydrophobic SiO ₂ (average particle size of 1 to 100 nm), and beads particles include SiO ₂ (average particle size of 1 to 30 nm).
The content ratio of the thermoplastic resin to the water-repellent fine particles and bead particles (thermoplastic resin: water-repellent fine particles + bead particles) was 1: 1 (mass ratio).

The coating solution prepared as described above was applied to the AL foil side of the base material by a bar coating method so that the coating amount after drying was 1.0 g / m ^2, and was 100 ° C. in a drying furnace. And dried for 3 seconds to prepare a water-repellent laminate for a lid. In addition, Miyabar # 3 (Daiichi Rika Co., Ltd.) was used for application | coating of a coating liquid.

Example 1-2
A water-repellent laminate for a lid material in the same manner as in Example 1-1 except that the ink WRD-2 was applied so that the coating amount after drying was 2.0 g / m ² without mixing the dilution solvent. Was made.

(Example 1-3)
In the same manner as in Example 1-2, except that the dilution solvent was not mixed, and ink WRD-2 was applied using Miyabar # 8 so that the coating amount after drying was 3.0 g / m ^2. A water-repellent laminate for a material was produced.

(Example 1-4)
In the same manner as in Example 1-2, except that the dilution solvent was not mixed and the ink WRD-2 was applied using a Myber # 12 so that the coating amount after drying was 4.0 g / m ^2. A water-repellent laminate for a material was produced.

Example 2-1
Fabrication of substrate A pattern is printed by gravure printing using printing ink (manufactured by DIC, trade name: Cias HR) on one side of printing paper (trade name: Ryuo Coat, 55 g / m ² , manufactured by Daio Paper Co., Ltd.). gave. An aluminum-deposited PET film was dry-laminated on the non-printing surface of the printing paper, and then aging was performed to prepare a substrate. A polyether adhesive (trade name: RU3900, manufactured by Rock Paint Co., Ltd.) was used for dry lamination.

Preparation of water-repellent laminate for lid material 60 parts by mass of a solution obtained by diluting EVONIK heat sealant (VP4174E) with ethyl acetate was mixed with 200 parts by mass of Inomiya Chemical WRD-4. A working solution was obtained.
Ink WRD-4 contains acrylic resin and polyester resin as thermoplastic resins, hydrophobic SiO ₂ (average particle diameter of 1 to 100 nm) as water-repellent fine particles, and as bead particles. SiO ₂ (average particle size 1-30 μm) is included.
The content ratio of the thermoplastic resin to the water-repellent fine particles and bead particles (thermoplastic resin: water-repellent fine particles + bead particles) was 1: 1 (mass ratio).

The coating solution prepared as described above is applied to the PET film side by a bar coating method so that the coating amount after drying is 4 g / m ² and dried at 100 ° C. for 3 seconds in a drying furnace. Then, a water-repellent laminate for a lid material was produced. In addition, Miyabar # 12 was used for application | coating of a coating liquid.

(Example 2-2)
Made by EVONIK, Inc. so that the content ratio of the thermoplastic resin, the water-repellent fine particles and the bead particles in the coating solution for the thermal adhesive layer is 1: 1.5. A water-repellent laminate for a lid was produced in the same manner as in Example 2-1, except that the amount of the heat sealant (VP4174E) was changed.

(Example 2-3)
EVONIK's heat so that the content ratio of the thermoplastic resin and the water-repellent fine particles and bead particles in the coating solution for the thermal adhesive layer is thermoplastic resin: water-repellent fine particles + bead particles = 1: 2. A water-repellent laminate for a lid material was produced in the same manner as in Example 2-1, except that the mixing amount of the sealing agent (VP4174E) was changed.

(Example 2-4)
EVONIK's heat so that the content ratio of the thermoplastic resin to the water-repellent fine particles and bead particles in the coating solution for the heat-bonding layer is thermoplastic resin: water-repellent fine particles + bead particles = 1: 3. A water-repellent laminate for a lid material was produced in the same manner as in Example 2-1, except that the mixing amount of the sealing agent (VP4174E) was changed.

(Comparative Example 2-1)
A water-repellent laminate for a lid material was produced in the same manner as in Example 2-1, except that the water-repellent fine particles were not included in the coating solution for the thermal adhesive layer.

(Comparative Example 2-2)
A water-repellent laminate for a lid material was produced in the same manner as in Example 2-1, except that the bead particles were not included in the coating solution for the thermal adhesive layer.

(Comparative Example 2-3)
A water-repellent laminate for a lid material was produced in the same manner as in Example 2-1, except that the water-repellent fine particles and bead particles were not included in the coating solution for the thermal adhesive layer.

Example 3-1
Fabrication of substrate A pattern is printed by gravure printing using printing ink (manufactured by DIC, trade name: Cias HR) on one side of printing paper (trade name: Ryuo Coat, 55 g / m ² , manufactured by Daio Paper Co., Ltd.). gave. After the aluminum vapor-deposited surface of the aluminum vapor-deposited PET film was dry-laminated on the non-printing surface of the printing paper, aging was performed to produce a substrate. A polyether adhesive (trade name: RU3900, manufactured by Rock Paint Co., Ltd.) was used for dry lamination.

Preparation of water-repellent laminate for lid material 50 parts by weight of a solution prepared by mixing toluene, MEK, and ethyl acetate in a ratio of 5: 4: 1 to 50 parts by weight of ink WRD-1 manufactured by Sasamiya Chemical Co., Ltd. A coating solution was obtained.
The ink WRD-1 contains an olefin resin and vinyl chloride-vinyl acetate copolymer as the thermoplastic resin, and hydrophobic SiO ₂ (average particle diameter of 1 to 100 nm) as the water-repellent fine particles. As the bead particles, SiO ₂ (average particle diameter of 1 to 30 μm) is included.
The content ratio of the thermoplastic resin to the water-repellent fine particles and bead particles (thermoplastic resin: water-repellent fine particles + bead particles) was 1: 1 (mass ratio).

The coating solution prepared as described above was applied to the PET film side by a bar coating method so that the coating amount after drying was 1.5 g / m ^2, and then at 100 ° C. for 3 seconds in a drying furnace. It dried and produced the water-repellent laminated body for lid | cover materials. In addition, Miyabar # 8 was used for application | coating of a coating liquid.

(Example 3-2)
A water-repellent laminate for a lid was produced in the same manner as in Example 3-1 except that the coating amount after drying was 2.0 g / m ² .

(Example 3-3)
A water-repellent laminate for a lid was prepared in the same manner as in (Example 3-1) except that the coating amount after drying was 2.5 g / m ² .

<Performance evaluation of water-repellent laminate for lid>
Sealing strength test The heat-adhesive layer provided in the water-repellent laminate for lid materials obtained in Examples and Comparative Examples was heat-sealed to a polystyrene sheet (heat-sealing temperature: 210 ° C., sealing width 2 mm, pressure 0.3 MPa, time) : 0.8 seconds). After heat sealing, the water-repellent laminate for the lid is peeled off using a tensile tester (Orientec Co., Ltd.), and the maximum strength at the time of peeling is taken as the sealing strength (N / 15 mm) (peeling angle 180 °, tensile speed 300 mm / min). The measurement results are shown in Tables 1, 2 and 3.

Using a water repellency test contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd.), the contact angle between the thermal adhesive layer and water droplets provided in the water repellent laminate for lid materials obtained in Examples and Comparative Examples was measured. The measurement results are shown in Tables 1, 2 and 3. In addition, about the thing with high water repellency so that a droplet could be bounced and a measurement could not be performed, it was set to 150 degrees or more.

Adhesion prevention test The water-repellent laminates for lids obtained in Examples and Comparative Examples were inclined 45 ° so that the thermal adhesive layer was on top, and yogurt (1 g) was hung on the thermal adhesive layer. The adhesion of the yogurt to the heat bonding layer was visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1, 2 and 3.
○: There was no adhesion of yogurt, and good adhesion prevention was demonstrated.
(Triangle | delta): Although yogurt adhered a little, there was no problem practically.
X: There was much adhesion of yogurt and there was a problem in practical use.

The surface of the heat-bonding layer of the water-repellent laminate for lids obtained in the scratch resistance test examples and comparative examples was rubbed 10 times using a manual tape pressing roll (manufactured by Tester Sangyo Co., Ltd.) (Load 2) .5 kg). Thereafter, water droplets were dropped on the surface of the thermal adhesive layer, and the sliding property was visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1, 2 and 3.
○: The water-repellent fine particles did not slide down and exhibited good water repellency.
Δ: The water-repellent fine particles slipped slightly, but exhibited water repellency with no practical problem.
X: Many water-repellent fine particles slipped, and there was a problem in practical use.

Example 4-1
Preparation of base material Print pattern (made by Daio Paper Co., Ltd., trade name: Ryuoh Coat, 55 g / m ² ) on one side with printing ink (DIC, trade name: Cias HR), and a pattern by gravure printing gave. After the aluminum vapor-deposited surface of the aluminum vapor-deposited PET film was dry laminated on the non-printing surface of the printing paper, aging was performed to produce a substrate. A polyether adhesive (trade name: RU3900, manufactured by Rock Paint Co., Ltd.) was used for dry lamination.

Preparation of water-repellent laminate for lid material An ink WRD-1 manufactured by Sasamiya Chemical Co., Ltd. having the following composition as a coating solution for a thermal adhesive layer was applied onto a PET surface by a bar coating method to give a coating amount of 2. It was applied so as to be 0 g / m ² and dried in a drying furnace to form a thermal adhesive layer, and a water-repellent laminate for a lid material was produced. In the drying furnace, a heat amount of 1.0 kJ / m ² was applied to the applied ink WRD-1.
The Si element concentration on the surface of the heat-adhesive layer of the obtained water repellent laminate for lids was measured under the following measurement conditions using an X-ray electron spectrometer, and found to be 28.8 atomic%.
(Measurement condition)
X-ray source: Mg Kα ray (1253.6 eV)
-X-ray output: 300 W (12 kV, 25 mA)
(Composition of ink WRD-1)
Resin component (vinyl chloride-vinyl acetate copolymer, olefin resin) 7 parts by mass Bead particle (average particle size: 1 to 30 nm, SiO ₂ ) 1 part by mass Water-repellent fine particles (average particle size: 1 to 100 nm, Hydrophobic SiO ₂ )
5 parts by mass, toluene 40 parts by mass, methyl ethyl ketone 30 parts by mass, ethyl acetate 10 parts by mass

(Examples 4-2 to 5-8 and Comparative Example 4-1)
A water-repellent laminate for a lid material was produced in the same manner as in Example 4-1, except that the amount of heat applied in the drying furnace was changed to the value shown in Table 4.

<Performance evaluation of water-repellent laminate for lid>
Sealing strength test The heat-adhesive layer provided in the water-repellent laminate for lid materials obtained in Examples and Comparative Examples was heat-sealed to a polystyrene sheet (heat-sealing temperature: 210 ° C., sealing width 2 mm, pressure 0.3 MPa, time) : 0.8 seconds). After heat sealing, the water-repellent laminate for the lid is peeled off using a tensile tester (Orientec Co., Ltd.), and the maximum strength at the time of peeling is taken as the sealing strength (N / 15 mm) (peeling angle 180 °, tensile speed 300 mm / min). Table 4 shows the measurement results.

Using a water repellency test contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd.), the contact angle between the heat-bonding layer and water droplets provided in the water-repellent laminates for lids obtained in the examples and comparative examples was measured, and 150 ° or more Was evaluated as ○, and less than 150 ° was evaluated as ×. Table 4 shows the measurement results.

Adhesion prevention test The water-repellent laminates for lids obtained in Examples and Comparative Examples were inclined 45 ° so that the thermal adhesive layer was on top, and yogurt (1 g) was hung on the thermal adhesive layer. The adhesion of the yogurt to the heat bonding layer was visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 4. In addition, Binidas BB536 aloe yogurt manufactured by Morinaga Milk Industry Co., Ltd. was used.
○: There was no adhesion of yogurt, and good adhesion prevention was demonstrated.
(Triangle | delta): Although yogurt adhered a little, there was no problem practically.
X: There was much adhesion of yogurt and there was a problem in practical use.

The surface of the heat-bonding layer of the water-repellent laminate for lids obtained in the abrasion resistance test examples and comparative examples was rubbed 10 times using a manual tape pressing roll (manufactured by Tester Sangyo Co., Ltd.) (Load 2) .5 kg). Thereafter, water droplets were dropped on the surface of the thermal adhesive layer, and the sliding property was visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 4.
○: The water-repellent fine particles did not slide down and exhibited good water repellency.
Δ: The water-repellent fine particles slipped slightly, but exhibited water repellency with no practical problem.
X: Many water-repellent fine particles slipped, and there was a problem in practical use.

Example 5-1
Preparation of base material An aluminum-deposited PET film having a thickness of 12 μm (manufactured by Toray Film Processing Co., Ltd., trade name: BRPET1312) was prepared.

Preparation of water-repellent laminate for lid material An ink WRD-5T manufactured by Sasamiya Chemical Co., Ltd. having the following composition was applied to the non-deposited side of an aluminum-deposited PET film by a bar coating method, and the coating amount after drying was 1.5 g / m. ² was applied and dried in a drying oven at 100 ° C. for 3 seconds to form a heat-adhesive layer, thereby producing a water-repellent laminate for a lid. In addition, Miyabar # 12 (made by Daiichi Rika Co., Ltd.) was used for application | coating of a coating liquid.
It was 1.2 m < ² > / g when the specific surface area of the surface on the opposite side to the base material side of a heat bonding layer was measured by BET method based on JISK6221. The content ratio of the thermoplastic resin and the water-repellent fine particles and the bead particles was 1: 1.4 on a mass basis.
(Composition of ink WRD-5T)
・ Resin component (vinyl chloride-vinyl acetate copolymer and polyester resin)
7 parts by mass / water-repellent fine particles (hydrophobic SiO ₂ , average particle diameter 1 to 100 nm) 4 parts by mass / bead particles (SiO ₂ , average particle diameter 1 to 30 μm) 5.5 parts by mass / toluene 40 parts by mass / methyl ethyl ketone 30 10 parts by mass of ethyl acetate

(Example 2)
A laminate was produced in the same manner as in Example 1 except that the coating amount after drying of the ink WRD-5T was changed to 2.0 g / m ² .
As in Example 1, the specific surface area of the thermal adhesive layer was measured and found to be 2.5 m ² / g.

(Example 3)
A laminate was produced in the same manner as in Example 1 except that the coating amount after drying of the ink WRD-5T was changed to 2.5 g / m ² .
As in Example 1, the specific surface area of the thermal adhesive layer was measured and found to be 3.9 m ² / g.

Example 4
A laminate was produced in the same manner as in Example 1 except that the coating amount after drying of the ink WRD-5T was changed to 3.0 g / m ² .
As in Example 1, the specific surface area of the thermal adhesive layer was measured and found to be 4.6 m ² / g.

(Comparative Example 1)
A laminate was produced in the same manner as in Example 1 except that the coating amount after drying of the ink WRD-5T was changed to 1.0 g / m ² . As in Example 1, the specific surface area of the thermal adhesive layer was measured and found to be 0.5 m ² / g.

<Performance evaluation of water-repellent laminate for lid>
Sealing strength test The heat-adhesive layer provided in the water-repellent laminate for lid materials obtained in Examples and Comparative Examples was heat-sealed to a polystyrene sheet (heat-sealing temperature: 210 ° C., sealing width 2 mm, pressure 0.3 MPa, time) : 0.8 seconds). After heat sealing, the water-repellent laminate for the lid is peeled off using a tensile tester (Orientec Co., Ltd.), and the maximum strength at the time of peeling is taken as the sealing strength (N / 15 mm) (peeling angle 180 °, tensile speed 300 mm / min). The measurement results are shown in Table 1.

Using a water repellency test contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd.), the contact angle between the heat-bonding layer and water droplets provided in the water-repellent laminates for lids obtained in the examples and comparative examples was measured, and 150 ° or more Was evaluated as ○, and less than 150 ° was evaluated as ×. The measurement results are shown in Table 1.

Adhesion prevention test The water-repellent laminates for lids obtained in Examples and Comparative Examples were inclined 45 ° so that the thermal adhesive layer was on top, and yogurt (1 g) was hung on the thermal adhesive layer. The adhesion of the yogurt to the heat bonding layer was visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.
○: There was no adhesion of yogurt, and good adhesion prevention was demonstrated.
(Triangle | delta): Although yogurt adhered a little, there was no problem practically.
X: There was much adhesion of yogurt and there was a problem in practical use.

The surface of the heat-bonding layer of the water-repellent laminate for lids obtained in the abrasion resistance test examples and comparative examples was rubbed 10 times using a manual tape pressing roll (manufactured by Tester Sangyo Co., Ltd.) (Load 2) .5 kg). Thereafter, water droplets were dropped on the surface of the thermal adhesive layer, and the sliding property was visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.
○: The water-repellent fine particles did not slide down and exhibited good water repellency.
Δ: The water-repellent fine particles slipped slightly, but exhibited water repellency with no practical problem.
X: Many water-repellent fine particles slipped, and there was a problem in practical use.
-: Water repellency was low in the initial state, and the test was not performed.

10: Water-repellent laminate for cover material 11: Base material 12: Thermal adhesive layer 13: Water-repellent fine particles 14: Bead particles 20: Container 21: Cover material 22: Container body 23: Opening

Claims

Comprising a base material and a thermal adhesive layer on the base material;
The water-repellent laminate for a lid material, wherein the thermal adhesive layer comprises a thermoplastic resin, water-repellent fine particles, and bead particles having an average particle diameter larger than that of the water-repellent fine particles.
The laminate according to claim 1, wherein the water-repellent fine particles have an average particle diameter of 1 nm or more and 300 nm or less.
The laminate according to claim 1 or 2, wherein an average particle size of the bead particles is 1 µm or more and 50 µm or less.
The content of the water-repellent fine particles in the thermal adhesive layer is 5 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin contained in the thermal adhesive layer. The laminate according to claim 1.
The ratio of the content of the thermoplastic resin in the thermal adhesive layer and the content of the water-repellent fine particles and the bead particles is 2: 1 to 1: 5 on a mass basis. The laminated body as described in any one.
The laminate according to any one of claims 1 to 5, wherein the Si element concentration on the surface of the thermal adhesion layer measured by X-ray photoelectron spectroscopy is 17% or more.
The laminate according to any one of claims 1 to 6, wherein the water-repellent fine particles are SiO 2 subjected to a hydrophobic surface treatment.
The laminate according to any one of claims 1 to 7, wherein a specific surface area of the surface opposite to the substrate side of the thermal adhesive layer is 1.0 m 2 / g or more.
A lid material comprising the laminate according to any one of claims 1 to 8.
A lid material according to claim 9 and a container body,
A container in which the thermal adhesive layer of the lid and the container body are heat-sealed.
A method for producing a laminate according to any one of claims 1 to 8,
Preparing a substrate;
Applying a coating solution for a thermal adhesive layer containing thermoplastic resin, water-repellent fine particles and bead particles having an average particle diameter larger than that of the water-repellent fine particles on the substrate;
Including a step of drying the applied thermal adhesive layer coating solution,
In the drying step, the amount of heat applied to the thermal adhesive layer coating solution is 0.5 kJ / m 2 or more and 5.5 kJ / m 2 or less.