JP2017196864A - Water-repellent laminate for lid material, lid material and container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repellent laminate for lid material that can prevent the movement of fine particles included in an attachment-resistant layer, and has improved attachment resistance and water repellency.SOLUTION: A water-repellent laminate for lid material has a base material, a heat adhesion layer, and an attachment-resistant layer, in the stated order. The heat adhesion layer contains thermoplastic resin and fine particles. The attachment-resistant layer contains thermoplastic resin, water-repellent fine particles, and beads particles having an average particle size larger than that of the water-repellent fine particles.SELECTED DRAWING: Figure 1

Description

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

  In many commodity fields such as foods, beverages, pharmaceuticals, and chemicals, packaging materials corresponding to their contents have been developed. 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 contents having high viscosity such as liquid, semi-solid, and gel substance to the packaging material.

  For example, it has been proposed to provide a thermal adhesive layer and 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 includes a solvent contained in the adhesion preventing layer coating liquid when the hydrophobic fine particles contained in the adhesion preventing layer form the adhesion preventing layer on the thermal adhesion layer. Due to the reaction with the thermal adhesive layer, and by heating the thermal adhesive layer and the anti-adhesion layer when heat-sealing the lid, it will move relatively to the thermal adhesive layer side, thus preventing sufficient adhesion It has been newly found that it cannot exhibit the properties and water repellency.

  The present invention has been made to solve the above-described new problem, and can prevent the movement of fine particles contained in the anti-adhesion layer, and has a higher anti-adhesion property and water repellency. The object is to provide an aqueous laminate.

  The water-repellent laminate for a lid material of the present invention comprises a base material, a thermal adhesive layer, and an adhesion prevention layer in this order, and the thermal adhesion layer contains a thermoplastic resin and fine particles, thereby preventing adhesion. The layer is characterized by comprising a thermoplastic resin, water-repellent fine particles and bead particles having an average particle diameter larger than that of the water-repellent fine particles.

  In the said aspect, it is preferable that the average particle diameter of water-repellent fine particles is 1 nm or more and 300 nm or less.

  In the said aspect, it is preferable that the average particle diameter of a bead particle is 1 micrometer or more and 50 micrometers or less.

  In the said aspect, it is preferable that ratio of content of the thermoplastic resin in an adhesion prevention layer and content of water-repellent fine particles and bead particles is 2: 1 to 1: 5 on a mass basis.

  In the said aspect, it is preferable that ratio of the content of the thermoplastic resin in a thermoadhesion layer and content of microparticles | fine-particles is 4: 1 to 1: 2.

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

  The container of the present invention includes the above-described lid material and a container body, and the heat bonding layer of the lid material and the container body are heat-sealed.

  ADVANTAGE OF THE INVENTION According to this invention, the movement of the microparticles | fine-particles contained in an adhesion prevention layer can be prevented, and the water-repellent laminated body for lid | cover materials which has higher adhesion prevention property and water repellency can be provided. 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 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 thru | or 3 shows the cross-sectional schematic diagram of the water-repellent laminated body for lid | cover materials by embodiment of this invention. In one embodiment, the lid water-repellent laminate 10 includes a base material 11, a thermal adhesive layer 13 including fine particles 12, and an adhesion preventing layer 16 including water-repellent fine particles 14 and bead particles 15. Prepare. Hereinafter, each layer which comprises the water-repellent laminated body for lid | cover materials by this invention is demonstrated.

(Base material)
The base material is a paper material such as coated paper, printing paper, high-quality paper and kraft paper, a film made of a resin such as polyester such as polypropylene, polyamide and polyethylene terephthalate (PET), or a metal such as aluminum foil. Metal foil can be used. In addition, since the substrate can function as a barrier layer against oxygen and water vapor, it is preferable to deposit an inorganic oxide such as aluminum, silicon oxide, titanium oxide, or aluminum oxide on a paper material or film. . Moreover, since the light-shielding property of a base material can be improved, it is preferable. 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.

  Further, the heat bonding layer laminated surface of the base material can be subjected to a surface treatment such as corona discharge treatment, chemical treatment, ozone treatment, etc. if desired.

  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 the thickness of a base material is not specifically limited, For example, it can be 5 micrometers or more and 200 micrometers or less.

(Anti-adhesion layer)
The water-repellent laminate for a lid according to the present invention comprises an adhesion preventing layer comprising a 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 outermost surface. As described above, since the adhesion preventing layer contains two types of particles having different sizes, a unique uneven structure is formed on the surface, and the adhesion preventing property and water repellency of the viscous content can be significantly improved. it can. 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 adhesion prevention 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.

As the water-repellent fine particles contained in the adhesion preventing 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, SiO ₂ is preferable from the viewpoint of cost.
The adhesion preventing 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.

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 making the average particle diameter of the water-repellent fine particles in the above numerical range, the adhesion prevention property and the water repellency of the adhesion preventing layer can be further improved.
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 adhesion preventing 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, the adhesion prevention property and the water repellency of the adhesion preventing layer can be further improved.

  Examples of the bead particles contained in the adhesion preventing layer include organic resin beads or inorganic beads. Organic resin beads include acrylic resin beads, polyethylene resin beads, polystyrene resin beads, styrene-acrylic copolymer beads, polycarbonate resin beads, polyvinyl chloride beads, melamine resin beads, benzoguanamine-formaldehyde condensate beads, and melamine-formaldehyde condensation beads. Body beads, benzoguanamine-melamine-formaldehyde condensate beads, benzoguanamine-melamine condensate beads, and the like. Examples of inorganic beads include glass beads, silica beads, alumina silicate, talc, mica and the like. Among these, silica beads are more preferable from the viewpoint of stability and cost. Two or more kinds of the above organic resin beads and / or inorganic beads may be used.

  The average particle size 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, the adhesion prevention property and water repellency of the adhesion prevention layer can be further improved. Furthermore, the abrasion resistance of the adhesion preventing layer can be improved, and slippage due to friction of the water repellent fine particles can be prevented.

  The content of the bead particles in the adhesion preventing 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 bead particles in the above numerical range, the adhesion preventing property and water repellency of the adhesion preventing layer can be further improved. Furthermore, the scratch resistance of the adhesion preventing layer can be improved.

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

The adhesion preventing layer can be formed by applying and drying a coating solution for an adhesion preventing layer comprising the above-described material on a substrate by a known method such as a bar coating method.
The coating amount after drying of the coating solution for the adhesion preventing layer is preferably 0.5 g / m ² or more and 10 g / m ² or less, and 1.0 g / m ² or more and 7 g / m ² or less. More preferred. When the coating amount after drying of the adhesion preventing layer is within the above numerical range, adhesion preventing property and water repellency can be further improved while maintaining the heat sealability of the laminate.

(Thermal adhesive layer)
The water-repellent laminate for a lid according to the present invention comprises a thermal adhesive layer containing a thermoplastic resin and fine particles between a base material and an adhesion preventing layer. When the thermal adhesive layer contains fine particles, the solvent contained in the anti-adhesion layer coating solution used when forming the anti-adhesion layer on the thermal adhesive layer may react with the thermal adhesive layer, When heat-sealing the water-repellent laminate for a lid, the water-repellent fine particles and the bead particles contained in the adhesion-preventing layer are relatively placed on the substrate and the heat-adhesive layer side by heating the heat-adhesive layer and the adhesion-preventing layer. It can be prevented from moving and becoming unable to exhibit sufficient adhesion prevention and water repellency.

  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 average particle size of the fine particles contained in the thermal adhesive layer is preferably 1 nm or more and 50 μm or less, and preferably 1 nm or more and 30 μm or less.
As the fine particles, the above-mentioned water-repellent fine particles and bead particles can be used, and the water-repellent fine particles and the bead particles may be used in combination.

  The content of fine particles in the heat bonding layer is preferably 20% by mass or more and 80% by mass or less, and more preferably 40% by mass or more and 60% by mass or less. By setting the content of the fine particles in the above numerical range, it is possible to prevent the water-repellent fine particles and the bead particles from moving in and from the adhesion preventing layer while maintaining the heat sealability of the heat bonding layer.

  The ratio between the content of the thermoplastic resin and the content of the fine particles in the heat-adhesive layer is preferably changed as appropriate depending on the type of fine particles used, the average particle size, and the like. The ratio is preferably 1: 2, more preferably 2: 1 to 1: 1. While maintaining the heat sealability of the thermal adhesive layer, the movement of the water-repellent fine particles and the bead particles in and from the adhesion preventing layer can be prevented.

The thermal adhesive layer can be formed by applying and drying a thermal adhesive layer coating liquid comprising the above-described material on a substrate by a known method such as a bar coating method.
The coating amount after drying of the thermal adhesive layer coating solution is preferably 0.5 g / m ² or more and 10 g / m ² or less, and 1.0 g / m ² or more and 7 g / m ² or less. More preferred. If the coating amount after drying of the heat-adhesive layer is within the above numerical range, the movement of water-repellent fine particles and bead particles in and from the anti-adhesion layer is prevented while maintaining the heat sealability of the laminate. Can do.

(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)
As shown in FIG. 4, the container 20 according to the present invention includes a lid 21 made of a water-repellent laminate for a lid, and a container body 22, and includes a thermal adhesive layer 16 of the lid, a container body 22, Is heat sealed. More specifically, the opening 23 of the container body 22 and the heat bonding layer 16 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 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.

  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
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 As coating liquid for thermal adhesive layer, ink WRD-3 manufactured by Sasamiya Chemical (polyester resin as acrylic resin, acrylic resin, hydrophobic SiO ₂ as water-repellent fine particles (average particle diameter) 1 to 100 nm), containing SiO ₂ (average particle diameter 1 to 30 μm) as bead particles, thermoplastic resin: water-repellent fine particles + bead particles = 1: 1.4) on the aluminum vapor-deposited PET film side by a bar coating method Then, coating was performed so that the coating amount after drying was 4 g / m ^2, and drying was performed at 100 ° C. for 3 seconds in a drying furnace to form a thermal adhesive layer. In addition, Miyabar # 12 (made by Daiichi Rika Co., Ltd.) was used for application | coating of a coating liquid.

Ink WRD-3 was applied onto the thermal adhesive layer as an anti-adhesion layer coating solution so that the coating amount after drying would be 4 g / m ² and dried at 100 ° C. for 3 seconds in a drying oven to prevent adhesion. A layer was formed to obtain a water-repellent laminate for a lid. In addition, Miyabar # 12 was used for application | coating of a coating liquid.

(Example 2)
Except for adding heat sealing agent VP4311E (thermoplastic resin content: 20 parts by mass) manufactured by EVONIK to the thermal adhesive layer coating solution and changing the thermoplastic resin: water-repellent fine particles + bead particles to 1: 1. In the same manner as in Example 1, a laminate was obtained.

(Example 3)
A laminate in the same manner as in Example 1 except that EVONIK heat sealant VP4311E was added to the thermal adhesive layer coating solution and the thermoplastic resin: water-repellent fine particles + bead particles were changed to 1: 0.5. Got.

(Comparative Example 1)
A laminate was obtained in the same manner as in Example 1 except that the coating solution for the thermal adhesive layer was changed to EVONIK heat sealant VP4311E.

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

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

<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 laminate for lid materials obtained in Examples and Comparative Examples was measured and evaluated as follows. Evaluation was made according to the criteria. The measurement results are shown in Tables 1 and 2.
○: The contact angle was 150 ° or more.
X: The contact angle was less than 150 °.

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 and 2.
○: 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 and 2.
○: 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.

DESCRIPTION OF SYMBOLS 10: Water-repellent laminated body for lid | cover material 11: Base material 12: Fine particle 13: Thermal adhesive layer 14: Water-repellent fine particle 15: Bead particle | grain 16: Adhesion prevention layer 20: Container 21: Lid material 22: Container main body 23: Opening part

Claims (7)

A base material, a thermal adhesive layer, and an adhesion preventing layer are provided in this order,
The thermal adhesive layer comprises a thermoplastic resin and fine particles;
The water-repellent laminate for a lid material, wherein the adhesion preventing 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 an average particle diameter of the water-repellent fine particles is 1 nm or more and 300 nm or less.   The layered product according to claim 1 or 2 whose average particle diameter of said bead particles is 1 micrometer or more and 50 micrometers or less.   The ratio of the content of the thermoplastic resin in the adhesion preventing 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 ratio of the content of the thermoplastic resin in the thermal adhesive layer and the content of the fine particles is 4: 1 to 1: 2 on a mass basis, according to any one of claims 1 to 4. Laminated body.   The cover material which consists of a laminated body as described in any one of Claims 1-5. A lid material according to claim 6 and a container body,
The container, wherein the thermal adhesive layer of the lid member and the container main body are heat-sealed.

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