JP2015131659A - Lid member, and manufacturing method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lid member that can have a sufficient adhesion preventing effect even on contents rich in milk fats and oil fats, and to provide a manufacturing method for the same.SOLUTION: A lid member is formed of a base material 1, a heat seal layer 2 and an adhesion preventing layer 3, laminated in this order, where the adhesion preventing layer 3 is formed of a modified silicone compound in which hydrophobic fine particles or fluororesin fine particles, which are fine particles with a particle diameter of 1.0 μm or less, are dispersed. The fine particles are dispersed in the modified silicone compound as a binder, which repels sufficiently contents rich in milk fats and oil fats and prevent adhesion of the contents.

Description

  The present invention relates to a lid material and a manufacturing method thereof. In particular, lids for packaging foods, beverages, pharmaceuticals, cosmetics, chemicals, etc. More specifically, lids for containers such as yogurt, jelly, pudding, syrup, retort foods such as porridge and soup, The present invention relates to a lid used for a storage container for liquids such as goods and pharmaceuticals, semi-solids, and gel substances, and a method for producing the same.

  Ordinary lids are difficult to remove due to adhesion of the contents, and often cause waste or dirt of the contents. In addition, when a fluorine material or silicone is used, although it has water repellency and adhesion prevention effects, it has poor heat sealing properties and is difficult to use as a lid material.

  In order to solve these problems, a layered product having a base material layer and a thermal adhesive layer, the thermal adhesive layer being laminated as the outermost layer on one side, and primary particles on the outermost side not adjacent to the other layer There is a cover material in which hydrophobic oxide fine particles having an average diameter of 3 to 100 nm are adhered, and the hydrophobic oxide fine particles form a porous layer having a three-dimensional network structure (Patent Document 1).

  The lid material uses hydrophobic oxide fine particles in order to develop hydrophobicity, but a sufficient adhesion preventing effect was not obtained with respect to contents containing a large amount of milk fat and oil.

Japanese Patent No. 4348401

  This invention is made | formed in view of an above-described situation, and provides the lid | cover material from which sufficient adhesion prevention effect is acquired with respect to the content with much milk fat content and fats and oils. Another object is to provide a manufacturing method thereof.

That is, the invention according to claim 1 is a lid member that thermally adheres to the opening of the container and prevents the contents from adhering to the base, the heat seal layer, and the adhesion that prevents the contents from adhering. In the lid material formed by laminating the prevention layer in this order,
The lid is characterized in that the adhesion preventing layer is made of a modified silicone compound in which hydrophobic fine particles having a particle diameter of 1.0 μm or less are dispersed.

  The invention according to claim 2 is the lid according to claim 1, wherein the surface of the adhesion preventing layer is provided with irregularities having a height difference of 5 μm or more and 100 μm or less.

Next, the invention according to claim 3 is a method for manufacturing a lid material, which includes a step of forming a heat seal layer on a substrate and a step of forming an adhesion preventing layer on the heat seal layer.
In the method for producing a lid material, the step of forming the adhesion preventing layer is a step of applying and drying a coating liquid in which hydrophobic fine particles having a particle size of 1.0 μm or less are dispersed in a modified silicone compound. is there.

According to a fourth aspect of the present invention, in the manufacturing method according to the third aspect, after the coating liquid is applied and dried, it is pressed with a plate having a plate depth of 5 μm or more and 100 μm or less to provide unevenness on the surface. This is a method for manufacturing a lid material.

  As can be seen from the examples to be described later, the lid material of the present invention constitutes an adhesion preventing layer by dispersing fine particles in a modified silicone compound. There is a sufficient adhesion prevention effect. Moreover, according to the manufacturing method of the lid | cover material of this invention, the lid | cover material can be manufactured.

Cross-sectional explanatory drawing of an example of the cover material of this invention. Cross-sectional explanatory drawing of another example of the cover material of this invention.

  The present invention is configured by laminating a heat seal layer thermally bonded to an opening of a container and an adhesion preventing layer in this order on a base material of a lid. FIG. 1 of the drawings shows a cross section thereof.

  The adhesion preventing layer 3 is formed by fixing hydrophobic fine particles having an average particle diameter of 5 to 1000 nm with a binder, and prevents adhesion of contents by a minute uneven surface based on the hydrophobic fine particles. For this reason, the adhesion prevention layer 3 needs to be arrange | positioned so that it may be exposed to the outermost surface of a cover material. In addition, since the lid material is thermally bonded to the container by the heat seal layer 2, the adhesion preventing layer 3 needs to be disposed directly on the heat seal layer 2 without any other layer. There is. In this case, the adhesion preventing layer 3 can be buried in the heat seal layer 2 and thermally bonded by disposing a lid material in the container opening and applying heat and pressure.

  In order to prevent the contents from adhering to the hydrophobic fine particles 3a, the fine particles 3a need to have a particle size of 1.0 μm or less at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method. Preferably, it is a hydrophobic fine particle with a particle diameter of 5 nm to 1.0 μm.

  As such hydrophobic fine particles 3a, for example, inorganic oxide particles surface-treated with a hydrophobic functional group can be preferably used. As the inorganic oxide particles serving as the core, silicon oxide, aluminum oxide, titanium oxide, or the like can be used.

  Examples of the surface treatment with a hydrophobic functional group include a treatment with a silane coupling agent and a treatment with a silylating agent. In this case, a hydrophobic functional group is added to the surface of the core inorganic oxide particles. It can be applied to make the surface hydrophobic.

Examples of the silane coupling agent include a dimethylsilyl silane coupling agent (chemical formula: (CH ₃ ) ₂ Si (O—R) ₂ ), a trimethylsilyl silane coupling agent (chemical formula: (CH ₃ ) ₃ SiO—R), dimethyl Polysiloxane silane coupling agent (chemical formula: (CH ₃ ) ₂ —Si—O—Si (O—R) ₃ ), dimethylsiloxane silane coupling agent, aminoalkylsilylsilane coupling agent, alkylsilylsilane coupling agent, A methacrylsilylsilane coupling agent or the like is preferable, and a trimethylsilylsilane coupling agent having a large number of methyl groups (chemical formula: CH ₃ ) is more preferable. In the chemical formula, “O—R” represents a substituent to be hydrolyzed.

Moreover, a fluorine-type silane coupling agent can also be used as a silane coupling agent. As the fluorine-based silane coupling agent, a silane coupling agent having a fluoroalkyl group (CF ₃ (CF ₂ ) n—) as a hydrophobic group can be used. For example, trifluoropropyltrialkoxysilane, heptadecafluorodecyltrialkoxysilane, and the like.

  As silylating agents, chlorotrimethylsilane, chlorotriethylsilane, trimethylsilylimidazole, hexamethyldisiloxane, N, N-dimethyltrimethylsilylamine, chlorotriisopropylsilyl, 1,3-dimethyl-1,1,3,3 -Tetraphenyldisilazane and the like can be exemplified.

  Also, fluororesin fine particles can be used as the hydrophobic fine particles 3a. Fluorine resin fine particles include polytetrafluoroethylene, polychlorotrifluoroethylene, polyhexafluoropropylene, tetrafluoroethylene-hexafluoropropylene copolymer, polyvinyl fluoride, polyvinylidene fluoride, perfluoroalkoxy resin, etc. Can be illustrated. For example, polytetrafluoroethylene marketed as a dry powder.

  Moreover, it is necessary to use a modified silicone compound as the binder 3b for fixing the hydrophobic fine particles 3a. When other resins are used as the binder, a sufficient adhesion preventing effect cannot be obtained with respect to contents containing a large amount of milk fat or oil. As the modified silicone compound, for example, polymethylhydrogen siloxane and its alkene and propylene compounds can be preferably used. The alkene and propylene compounds of polymethylhydrogensiloxane are commercially available from Goyo Paper Co., Ltd.

  Note that the adhesion preventing layer 3 is such that the hydrophobic fine particles 3a do not sink into the binder 3b and are not buried, and a part of the hydrophobic fine particles 3a is exposed on the surface, and minute irregularities based on the hydrophobic fine particles 3a. It is desirable to constitute the surface. For example, the adhesion preventing layer 3 having a ten-point average roughness Rz of 200 nm or more after the undulation is removed.

  The adhesion preventing layer 3 can be formed by dispersing hydrophobic fine particles 3a in a binder 3b to form a coating liquid, and applying and drying the coating liquid. The solvent of the coating liquid may be arbitrary. The mixing ratio of the binder 3b and the hydrophobic fine particles 3a is preferably 100: 5 to 100: 10 by weight. The thickness of the adhesion preventing layer 3 is preferably 1 to 30 μm. As the coating method, for example, roll coating, gravure coating, bar coating, kiss reverse coating, die coating, doctor blade coating, brush coating, dip coating, spray coating, spray coating and the like can be used.

  In addition, after the coating and drying, before the coating is cured, it is desirable to press the plate with a plate depth of 5 μm or more and 100 μm or less to provide unevenness on the surface. In this case, the unevenness | corrugation which the unevenness | corrugation by press of a plate and the fine unevenness | corrugation based on the microparticles | fine-particles 3a overlap is formed.

  Next, the base material 1 may be an arbitrary sheet. It may be composed of a single sheet or a sheet having a multilayer structure. For example, paper, polyethylene terephthalate, polyethylene, polypropylene, polyamide, polycarbonate, polyvinyl chloride, cellulose acetate, cellophane, aluminum foil and the like can be used. Moreover, what laminated | stacked these may be used.

  Moreover, the base material 1 may contain the vapor deposition film which provided the thin film of the metal or the metal oxide in the layer structure. Examples of the metal include silicon and aluminum. Examples of the metal oxide include silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, and magnesium oxide. In addition, as a deposition base material for forming these thin films, polyethylene terephthalate, polyethylene, polypropylene, polyamide, polycarbonate, polyvinyl chloride, cellulose acetate, cellophane, and the like can be used. And these thin films can be provided on a vapor deposition base material by vacuum processes, such as a vacuum evaporation method, sputtering method, and a plasma vapor deposition method.

  FIG. 2 shows a cross section of the lid material used in the examples described later. In this example, a laminate having a six-layer structure is used as the base material 1. That is, printing 12 is performed on polyethylene terephthalate 11, aluminum foil 14 is adhered via adhesive 13 for dry lamination, anchor coating agent 15 is applied to aluminum foil 14, and low-density polyethylene resin layer 16 is laminated. It is a laminate.

  Next, as a material of the heat seal layer 2, depending on the material of the container, polyethylene resin, ethylene-vinyl acetate copolymer resin, ionomer resin, polyvinyl acetate resin, polypropylene resin, polyvinyl chloride resin, hot melt resin, etc. Can be used.

  For example, when the sealing surface of the container is polyethylene, the material of the heat seal layer 2 is polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, a mixed resin of polyethylene and polybutene-1, You can choose from any of the polypropylene.

  When the sealing surface of the container is polypropylene, the material of the heat seal layer 2 is polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, a mixed resin of polyethylene and polybutene-1, A mixed resin of polyethylene, polybutene-1 and ethylene / butene copolymer, a mixed resin of polyethylene, polybutene-1 and propylene / butene copolymer, or polypropylene can be selected.

  When the sealing surface of the container is polystyrene, the material of the heat seal layer 2 is polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, a mixed resin of polyethylene and polybutene-1, You can choose from any of the polypropylene.

Example 1
The lid member shown in the cross-sectional view of FIG.

That is, first, a print 12 is provided on a corona-treated surface of a biaxially stretched polyethylene terephthalate film (thickness 12 μm) 11 by gravure printing using urethane-based ink. An aluminum foil 14 was laminated on the surface of the adhesive layer 13 provided by applying the type urethane adhesive 13. Then, a urethane-based anchor coat agent is applied to the surface of the aluminum foil 14 by an extrusion laminator to form an anchor coat layer 15, and then low density polyethylene (density: 0.915 g / cm ³ , MFR). 15) was extruded, a 15 μm low density polyethylene layer 16 was provided, and the substrate 1 was produced.

On the surface of the low density polyethylene layer 16 of the substrate 1, an ethylene-vinyl acetate copolymer resin hot melt was melted and applied to provide a heat seal layer 2 (application amount: 25 g / m ² ).

Next, alkene of polymethylhydrogensiloxane and a propylene compound (manufactured by Goyo Paper Industries Co., Ltd.) are used as the binder 3b of the coating solution for the adhesion preventing layer 3, and the surface is treated with a dimethylpolysiloxane silane coupling agent as the hydrophobic fine particles 3a. Treated inorganic oxide particles (particle size 50 nm) were used. Then, 5% by mass of fine particles are added to a toluene solution of a binder to form a coating solution, and this coating solution is applied onto the heat seal layer 2 to prevent adhesion layer 3 (coating amount: 5.0 g).
/ M ² ).

  Thereby, the adhesion preventing layer 3 in which the hydrophobic fine particles 3a are dispersed in the binder 3b is provided. Immediately after coating and drying, the roll surface is provided with a plate having irregularities of a grid shape and a plate depth of 50 μm, pressed from the adhesion preventing seal layer 3 side, and the plate irregularities are transferred from the surface of the adhesion preventing seal layer 3. did. The lid material of Example 1 was created as described above.

(Example 2)
Polytetrafluoroethylene fine particles (particle diameter 0.5 μm) were used as the hydrophobic fine particles 3a, and 10% by mass of these fine particles were added to a toluene solution of a binder to obtain a coating solution for the adhesion preventing layer 3. Others are the same as in the first embodiment.

(Example 3)
As the hydrophobic fine particles 3a, inorganic oxide particles (particle diameter: 1.0 μm) surface-treated with a dimethylsiloxane silane coupling agent were used. Others are the same as in the first embodiment.

Example 4
Polytetrafluoroethylene fine particles (particle diameter: 1.0 μm) were used as the hydrophobic fine particles 3a. Others are the same as in the second embodiment.

(Comparative Example 1)
As the hydrophobic fine particles 3a, inorganic oxide particles (particle diameter: 5.0 μm) surface-treated with a dimethylsiloxane silane coupling agent were used. Others are the same as in the first embodiment.

(Comparative Example 2)
Polytetrafluoroethylene fine particles (particle diameter: 5.0 μm) were used as the hydrophobic fine particles 3a. Others are the same as in the second embodiment.

(Comparative Example 3)
As the hydrophobic fine particles 3a, inorganic oxide particles (particle diameter: 2.0 μm) surface-treated with a dimethylsiloxane silane coupling agent were used. Others are the same as in the first embodiment.

(Comparative Example 4)
Polytetrafluoroethylene fine particles (particle diameter 2.0 μm) were used as the hydrophobic fine particles 3a. Others are the same as in the second embodiment.

(Comparative Example 5)
A lid was prepared in the same manner as in Example 1 except that the following coating solution was used as the coating solution for the adhesion preventing layer 3.

  That is, a modified polyolefin resin was used as the binder 3b of the coating solution for the adhesion preventing layer 3, and inorganic oxide particles (particle diameter 0.5 μm) surface-treated with a dimethylsiloxane silane coupling agent were used as the hydrophobic fine particles 3a. . Then, fine particles were added to the isopropyl alcohol solution of the binder so that the weight of the solid content would be the same weight ratio to obtain a coating solution.

(Yogurt repellent test 1)
Prepare a paper cup with a polyethylene layer on the inner surface, fill it with yogurt (plain, milk fat content 2.0%), seal the lids of the example and the comparative example to the flange part of the paper cup, After turning over, the lid material was peeled and opened, and the yogurt repellency of the lid material was evaluated. The evaluation was ◎ for those that flicked cleanly, ◯ for the lid material that had almost repelled, △ for the lid material that did not repel a little, and × for the lid material that hardly flew, and the results are shown in Table 1. Summarized.

(Yogurt repellent test 2)
The yogurt repellency 2 was evaluated in the same manner as the yogurt repellency test 1 except that plain yogurt having a milk fat content of 4.0% was used. The results are summarized in Table 1.

(Sealability test 2)
When the lid covered with a hot plate in the test for yogurt repellency was peeled and opened, its adhesion, peeling and opening were evaluated. The case where there was no problem in adhesion, peeling, and opening was evaluated as ○, and the case where there was a problem was evaluated as ×. The results are summarized in Table 1.

（考察）
実施例１〜４、比較例１〜５のいずれの蓋材においても、そのシール性には問題がなかった。

(Discussion)
In any of the lid materials of Examples 1 to 4 and Comparative Examples 1 to 5, there was no problem in the sealing property.

  In addition, Examples 1 to 4 using hydrophobic fine particles having a particle size of 50 nm to 1.0 μm had sufficient adhesion preventing properties, but hydrophobic fine particles having a particle size of 2.0 μm to 5.0 μm were used. It turned out that Comparative Examples 1-4 is inferior to this, and also that the adhesion prevention property is inferior as milk fat content in yogurt increases. From this result, it can be inferred that as the particle size of the hydrophobic fine particles becomes smaller, the adhesion preventing property to the high content of milk fat is improved. And it is enough if the particle diameter is 1.0 μm or less. This result shows that the hydrophobic fine particles are inorganic oxide particles whose surfaces are treated with a dimethylsiloxane silane coupling agent (Examples 1 and 3, Comparative Examples 1 and 3), and polytetrafluoroethylene fine particles (Examples). 2 and 4 and Comparative Examples 2 and 4), the same results were obtained, indicating that it does not depend on the material of the hydrophobic fine particles.

  Next, when Example 1 and Comparative Example 5 are compared, first, Comparative Example 5 using a modified polyolefin resin is sufficient for the low content of milk fat (milk fat content 2.0%). Although it had anti-adhesion properties, it had almost no anti-adhesion properties for the high milk fat content (milk fat content 4.0%). On the other hand, in Example 1 in which a modified silicone compound was used instead of the binder, not only the content with low milk fat (milk fat content 2.0%) but also the content with high milk fat content (milk) It had sufficient anti-adhesion properties for fat (4.0%). From this result, in order to improve the anti-adhesion property to the high milk fat content (milk fat content 4.0%), not only the particle size of the hydrophobic fine particles but also the material of the binder is important. In particular, when a modified silicone compound was used, it was confirmed that high anti-adhesion properties were exhibited.

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Heat seal layer 3 ... Adhesion prevention layer 3a ... Fine particle 3b ... Modified silicone compound

Claims (4)

A lid material that thermally adheres to the opening of the container and prevents the contents from adhering, and is formed by laminating a base material, a heat seal layer, and an adhesion prevention layer that prevents the contents from adhering in this order. In
The lid material, wherein the adhesion preventing layer is made of a modified silicone compound in which hydrophobic fine particles having a particle diameter of 1.0 μm or less are dispersed.   The lid according to claim 1, wherein the surface of the adhesion preventing layer is provided with irregularities having a height difference of 5 μm to 100 μm. In the method of manufacturing a lid material, which includes a step of forming a heat seal layer on a base material and a step of forming an adhesion preventing layer on the heat seal layer,
The step of forming the adhesion preventing layer is a step of applying and drying a coating liquid in which fine particles having a particle diameter of 1.0 μm or less and hydrophobic fine particles or fluororesin fine particles are dispersed in the modified silicone compound. A method for producing a lid material, comprising:   The manufacturing method according to claim 3, wherein the coating liquid is applied and dried, and then pressed with a plate having a plate depth of 5 μm or more and 100 μm or less to provide unevenness on the surface.

Images