JP6796394B2 - Non-adhesive lid material and airtight container - Google Patents

Description

The present invention relates to a non-adhesive lid material used for articles containing water and sugar, and a closed container including the lid material and a container.

Conventionally, cup-shaped containers have been widely used as packaging containers for foodstuffs such as yogurt, milk potions, puddings, jams, gum syrups, butters, and ice creams, pharmaceuticals, and cosmetics. These cup-shaped containers are sealed by a heat-sealed lid. Therefore, it is desired that the lid material has a heat-sealing property and is non-adhesive of the contents, that is, prevents the contents from adhering to the lid material surface on the inner surface side of the packaging container. If the contents adhere to the lid material surface on the inner surface side of the packaging container, the appearance may be poor, the contents may be wasted due to the inability to use up the contents, and the fingers, clothes, or table may be soiled. There is a problem that even if information is printed on the lid material surface on the side, it cannot be visually recognized.

Therefore, in the lid material of such a cup-shaped container, the following patent documents 1 to 6 have been proposed as a lid material in which the lid material surface on the inner surface side of the packaging container is provided with non-adhesiveness of the contents.

In Patent Document 1, a lid material is a lid material in which a content adhesion prevention layer composed of a composition of wax and a filler dispersed in the wax is laminated on a heat-sealing layer, but the filler is contained in the wax. There was a concern that the heat-sealing property of the heat-sealing layer would be affected and the sealing would be unstable. In Patent Documents 2 to 4, a laminate or a lid material in which a porous layer having a three-dimensional network structure is formed by using hydrophobic oxide fine particles as an adhesion prevention layer on the outer surface of the heat-sealing layer, but adhesion prevention is provided. The heat resistance of the layer is inferior, and the adhesion prevention effect may be significantly impaired. That is, in the process of forming the adhesion prevention layer, if the heating temperature is too high or the drying time is long when the adhesion prevention layer is dried, the adhesion prevention effect is impaired, which makes process control and handling difficult. .. In Patent Document 5, the lid material uses hydrophobic wet silica for the adhesion prevention layer, but since a low melting point wax is used for the heat sealing layer, the wax melts during heat sealing, and heat sealing is performed. There was a problem of inferior sex. In Patent Document 6, the water-repellent layer is a lid in which oxide fine particles are attached to resin particles made of an olefin resin, but the water repellency is inferior, and in particular, the non-adhesiveness is insufficient for contents having low water content. Is. Further, these disclosed lid materials have a problem that the non-adhesive layer deteriorates when the contents are in contact with the contents for a long time, and the non-adhesive performance cannot be maintained.

JP-A-2009-73523 Japanese Patent No. 4348401 Japanese Unexamined Patent Publication No. 2011-93315 Japanese Unexamined Patent Publication No. 2013-32013 Japanese Patent No. 4668352 Japanese Patent No. 48878650

An object of the present invention is to provide a non-adhesive lid material having good heat-sealing strength and sufficient non-adhesiveness and durability.

The present inventor has found that the above object can be achieved by forming a non-adhesive lid material having a structure in which a heat seal layer, an anchor coat layer and a non-adhesive layer are laminated in this order on at least one surface of the base material layer. , The present invention has been completed.

That is, the present invention
(1) A non-adhesive lid material having a structure in which a heat seal layer, an anchor coat layer and a non-adhesive layer are laminated in this order on at least one side of a base material layer by a gravure printing method using a multicolor gravure printing machine. There,
The heat seal layer is a layer formed by applying a heat seal agent containing a thermoplastic resin having a glass transition point (Tg) of −50 ° C. or higher and 40 ° C. or lower.
The anchor coat layer contains an anchor coat containing a resin having a glass transition point (Tg) of 50 ° C. or higher and lower than 100 ° C., and an unevenness-imparting agent which is a resin bead having an average particle diameter in the range of 0.8 to 30 μm. It is a layer formed by applying an agent,
The non-adherent layer is Ri Sodea formed by applying a coating solution containing talc and inorganic particles subjected to hydrophobic treatment,
The coating liquid contains 0.5 to 40% by mass of the hydrophobized talc and the inorganic particles, and the hydrophobized talc and the inorganic particles are 100/0 to 5/95 by weight. nonadherent lid, characterized in der Rukoto,
(2) The resin is cellac, rosin, rosin-modified maleic acid resin, rosin-modified phenol resin, cellulose acetate, cellulose acetylpropionate, cellulose acetylbutyrate, rubber chloride, cyclized rubber, vinyl chloride, vinylidene chloride. , Polyamide resin, vinyl chloride-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, vinyl acetate resin, polyester resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated ethylene Vinyl acetate resin, ethylene vinyl acetate resin, (meth) acrylic resin, urethane resin, styrene maleic acid resin, alkyd resin, styrene resin, polyacetal resin, epoxy resin, polycarbonate resin, melamine resin, acrylonitrile resin, polysulfone resin, polyether resin , polyethersulfone resin, polyether ketone resin, and wherein the at least one selected from a thermoplastic resin of the polyimide resin (1) Symbol placement nonstick lid of
(3) The non-adhesive lid material according to (1) or (2), wherein the base material layer is at least one selected from paper, aluminum foil, plastic film or sheet .
(4) Production of a non-adhesive lid material in which a heat seal layer, an anchor coat layer and a non-adhesive layer are laminated in this order on at least one side of the base material layer by a coating step by gravure printing using a multicolor gravure printing machine. In the method
A step of forming a heat seal layer formed by applying a heat seal agent containing a thermoplastic resin having a glass transition point (Tg) of -50 ° C or higher and 40 ° C or lower, and
An anchor coating agent containing a resin having a glass transition point (Tg) of 50 ° C. or higher and lower than 100 ° C. and an unevenness-imparting agent which is a resin bead having an average particle diameter in the range of 0.8 to 30 μm is applied. The process of forming the anchor coat layer and
Including a step of applying a coating liquid containing hydrophobized talc and inorganic particles to form a non-adhesive layer.
The step of forming the heat seal layer is a coating step by gravure printing using one unit of a multicolor gravure printing machine.
The step of forming the anchor coat layer is a coating step by gravure printing using another unit of a multicolor gravure printing machine.
The step of forming the non-adhesive layer is a coating step by gravure printing using another unit different from the unit of the multicolor gravure printing machine.
The coating liquid contains 0.5 to 40% by mass of hydrophobized talc and inorganic particles, and hydrophobized talc and inorganic particles are 100/0 to 5/95 by weight. A method for producing a non-adhesive lid material, which is characterized by being
(5) The resin is cellacs, rosins, rosin-modified maleic acid resin, rosin-modified phenol resin, cellulose acetate, cellulose acetylpropionate, cellulose acetylbutyrate, rubber chloride, cyclized rubber, vinyl chloride, vinylidene chloride. , Polyamide resin, vinyl chloride-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, vinyl acetate resin, polyester resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated ethylene Vinyl acetate resin, ethylene vinyl acetate resin, (meth) acrylic resin, urethane resin, styrene maleic acid resin, alkyd resin, styrene resin, polyacetal resin, epoxy resin, polycarbonate resin, melamine resin, acrylonitrile resin, polysulfone resin, polyether resin The method for producing a non-adhesive lid material according to (4), wherein the non-adhesive lid material is at least one selected from a thermoplastic resin such as a polyether sulfone resin, a polyether ketone resin, and a polyimide resin .
(6) The method for producing a non-adhesive lid material according to (4) or (5), wherein the base material layer is at least one selected from paper, aluminum foil, a plastic film or a sheet .
( 7 ) A closed container with a thermal pressure seal comprising the non-adhesive lid material according to any one of (1) to ( 3 ) and a container.
It is about.

According to the present invention, steps such as embossing and vapor deposition to impart non-adhesiveness are not required, and even if the non-adhesive layer is thin, it has sufficient non-adhesiveness to an article that requires non-adhesiveness. A non-adhesive lid material having a structure in which a heat seal layer, an anchor coat layer and a non-adhesive layer are laminated in this order on at least one surface of a base material layer, which can be easily manufactured at low cost, and the lid material and container thereof. A closed container consisting of is provided.

Hereinafter, embodiments for carrying out the present invention will be described in detail. It should be noted that the present embodiment is only one embodiment for carrying out the present invention, the present invention is not limited to the present embodiment, and various modifications and embodiments are made without departing from the gist of the present invention. Is possible.

The non-adhesive lid material of the present invention (hereinafter, also simply referred to as “lid material”) has a structure in which a heat seal layer, an anchor coat layer and a non-adhesive layer are laminated in this order on at least one surface of a base material layer. It is preferable that the non-adhesive lid material is a layer containing talc that has been hydrophobized.

The hydrophobized talc is preferably a hydrophobized talc (hereinafter, also simply referred to as "treated talc").

The hydrophobizing treatment is not particularly limited as long as a hydrophobic group can be introduced into talc, but a silane coupling treatment, a silicone treatment, and a silazane treatment are preferable from the viewpoint of water repellency, cost, and safety. A known silane coupling agent is used for the silane coupling treatment, and the treatment of the inorganic filler such as talc is preferably a dry method or a wet method. Generally, a silane coupling agent is a silane compound having two different functional groups, an organic functional group and an alkoxy group, in one molecule, and is aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-. Aminosilane-based coupling agents such as phenylaminopropyltrimethoxysilane and N-2 (aminoethyl) aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, and glycidoxypropylmethyldiethoxy. Epoxysilane coupling agents such as silane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercaptosilane coupling agents such as mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, methyl Silane-based coupling agents such as trimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, metachloroxypropyltrimethoxysilane, imidazolesilane, and triazinesilane are used. For example, in the dry method, an inorganic filler is stirred at high speed by a stirrer, and a stock solution of a silane compound is uniformly dispersed therein for treatment. In a wet method, the inorganic filler is immersed in a dilute solution of silane. There are known ways to handle it. Silicone oil that is liquid at room temperature is used for the silicone treatment. The silicone oil is not particularly limited as long as it has a polysiloxane structure, but dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane and the like are more preferable. The treatment is preferably carried out using 1 to 5% by mass of silicone oil with respect to talc. For the treatment with silazane, organosilazanes such as hexamethyldisilazane (HMDS), hexaphenyldisilazane, dimethylaminotrimethylsilane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane Compounds are preferably used, and hexamethyldisilazane is more preferably used. For example, a method of spraying hexamethyldisilazane with talc flowing, or adding talc to an organic solvent such as alcohol or toluene, adding hexamethyldisilazane and water, and then adding water and an organic solvent. Can be produced by a method of evaporating and drying with an evaporator or the like. More specifically, HMDS-treated talc can be prepared by placing the talc in a Henschel mixer, spraying water and HMDS with stirring under a nitrogen atmosphere, heating and then cooling, and crushing with a ball mill.

Talc is a mineral composed of magnesium hydroxide and silicate, and is a type of clay mineral. Although talc itself has some hydrophobicity even if it is not treated, it is not sufficient for the water repellency and non-adhesiveness which are the subjects of the present invention, and it is necessary to perform a hydrophobic treatment. The hydrophobization treatment may be general, and may be subjected to silica treatment, silicone treatment (siloxane treatment), silazane treatment, resin treatment, fatty acid treatment, silane coupling treatment, titanate treatment, or a combined treatment thereof. Anything is acceptable. The amount to be treated is preferably 0.01 to 50% by mass, more preferably 0.05 to 30% by mass, based on talc. If it is less than 0.01% by mass, the hydrophobicity is not sufficient, and if it is more than 50% by mass, not only does it not contribute to the treatment of talc, but it becomes an impurity and inhibits water repellency. For example, the treated talc can be obtained by spraying a 10% solution of methylene chloride of silicone oil on the talc so that the silicone oil is 1 to 5% by mass and firing at 100 ° C. for 2 hours.

The non-adhesive layer containing the treated talc has the effect of improving the heat sealability.

The non-adhesive layer may contain inorganic particles such as silica, sericite, mica and kaolin. The combined use of inorganic particles has the effect of improving the stability of the coating liquid of the non-adhesive layer and improving the coating suitability. Further, it is preferable that the inorganic particles are hydrophobized. The hydrophobizing treatment of the inorganic particles can be carried out in the same manner as the hydrophobizing treatment of the talc.

There are many types of silica (silicon dioxide) such as natural products, synthetic products, crystalline and amorphous products, and among them, synthetic amorphous silica is preferable. Synthetic amorphous silica is roughly classified into wet silica and dry silica, and hydrophobic treatment such as silane coupling treatment, silicone treatment (siloxane treatment), silazane treatment, or a composite treatment thereof is performed. Anything is acceptable. Commercially available products include SIPERANT series (manufactured by EVONIK), AEROSIL series (manufactured by Nippon Aerosil Co., Ltd.), WACKER HDK series (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), Leorosil (manufactured by Tokuyama Co., Ltd.) Examples include Fuji Silicia Chemical Co., Ltd.) and Mizukasil (Mizusawa Industrial Chemicals Co., Ltd.).

The average particle size of the hydrophobized talc and the inorganic particles is preferably 50 μm or less, more preferably 0.001 to 50 μm, and more preferably 0.003 to 30 μm. Is even more preferable. If it contains 0.001 μm or less, water repellency is difficult to develop, and if it is larger than 50 μm, the abrasion resistance is inferior. The average particle size referred to here is a value measured by a laser method (MICROTRAC 9320 × 100 manufactured by Honeywell).

In the case of treated talc, it is preferably 20 μm or less, and more preferably 10 μm or less.
In the case of hydrophobized silica, it is preferably 50 μm or less, and more preferably 30 μm or less.

The content of the treated talc and the inorganic particles is preferably 100/0 to 1/99, more preferably 99/1 to 5/95, and 95/5 to 10/90 in terms of the weight ratio of the treated talc / inorganic particles. Is even more preferable. When the treated talc is less than 1, the effect of improving the heat sealability is unlikely to be exhibited. As the content of the treated talc increases, the non-adhesive layer becomes whitish. Therefore, when it is desired to ensure transparency, it is effective to adjust the weight ratio of the treated talc and the inorganic particles to the extent that the heat sealability is not impaired. Is. In addition, when a coating liquid is used, the treated talc in the coating liquid may become unstable depending on its composition, viscosity, dilution, etc., so the weight of the treated talc and the inorganic particles is not impaired in heat sealability. It is effective to adjust the ratio.

The non-adhesive layer preferably further contains alcohol and / or water. In particular, from the viewpoint of water repellency, water, methanol, ethanol, isopropyl alcohol, normal propanol and the like are preferable. These may be used alone or in combination of two or more.

Additives can be used for the non-adhesive layer, if necessary. For example, viscosity modifiers, dispersants, anti-blocking agents, waxes, fillers and the like can be mentioned. As a viscosity modifier, an inorganic compound such as silica, a resin-based thickener such as polyamide, and as a dispersant, a polymer resin dispersant, an anionic, nonionic, cationic, and amphoteric surfactants. Examples thereof include resin beads such as urethane resin, acrylic resin, nitrile resin and polystyrene resin, or a mixture thereof. Examples of the blocking inhibitor include inorganic pigments such as calcium carbonate, barium sulfate, silica, mica, montmorillonite, smectite, zeolite, and kaolinite. Examples of the wax include polyethylene, polypropylene, microcrystallin, carnauba, polytetrafluoroethylene and the like. Fillers include titanium oxide, calcium carbonate, barium sulfate, talc, zinc oxide, silica, mica, montmorillonite, smectite, zeolite, kaolinite and other inorganic pigments, polyethylene, polypropylene, microcrystallin, carnauba, polytetrafluoroethylene, etc. Waxes, urethane resins, acrylic resins, nitrile resins, resin beads such as polystyrene resins, or mixtures thereof. The average particle size of the filler is preferably in the range of 0.01 to 50 μm.
The amount of the additive added can be used within a range that does not inhibit water repellency, and the total amount of the additive is preferably 80% by mass or less, more preferably 70% by mass or less, based on the treated talc or the treated talc and the inorganic particles. If the amount of the additive is more than 80% by mass based on the treated talc or the treated talc and the inorganic particles, the water repellency is lowered.

The non-adhesive layer is preferably formed by a coating liquid containing treated talc and having coating suitability.

In the coating liquid, the amount of treated talc or treated talc and inorganic particles in the coating liquid is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and 3 to 3 to 40% by mass. It is more preferably 30% by mass. If it is less than 0.1% by mass, the water repellency of the non-adhesive layer coated with the coating liquid is difficult to develop, and if it is more than 50% by mass, the fluidity as the coating liquid is inferior, and coating by the gravure printing method is performed. Not suitable for.

Further, the film thickness of the non-adhesive layer formed by applying the coating liquid is preferably 0.01 to 50 μm, more preferably 0.01 to 30 μm. If the film thickness is smaller than 0.01 μm, water repellency is less likely to be exhibited, and if the film thickness is larger than 50 μm, it is difficult to produce by the gravure printing method.

In the non-adhesive layer formed by applying the coating liquid, the coating amount (UC) of the coating liquid is 0.02 g / m ² ≤ UC ≤ 1.5 g / m ² in terms of solid content. It is preferable, and 0.1 g / m ² ≦ UC ≦ 1 g / m ² is more preferable. If it is less than 0.02 g / m ² , water repellency is less likely to be developed, and if it is more than 1.5 g / m ² , the friction resistance of the non-adhesive layer is inferior.

The anchor coat layer preferably contains a resin having a glass transition point of 0 ° C. or higher and lower than 100 ° C. (hereinafter, also simply referred to as “Tg”), more preferably 10 ° C. or higher and 90 ° C. or lower, and more preferably 20 ° C. or higher. 80 ° C. or lower is more preferable. When Tg is lower than 0 ° C., stickiness is likely to occur, the stability of the non-adhesive layer is lowered, and the non-adhesiveness is lowered. If the temperature is 100 ° C. or higher, the heat seal strength becomes weak. In particular, when Tg is within the above range, the non-adhesive layer is stable, and the non-adhesive performance as a lid material is maintained for a long period of time without deterioration. The Tg referred to here is a value measured by differential scanning calorimetry DSC under the conditions of a sample of 5 mg, a measurement temperature of -60 to 120 ° C., and a heating rate of 20 ° C./min.

Further, it is preferable that the resin is a hydrophobic resin. Examples of the hydrophobic resin include celacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, cellulose acetate, cellulose acetylpropionate, cellulose acetylbutyrate, rubber chloride, cyclized rubber, vinyl chloride, and chloride. Vinylidene, polyamide resin, vinyl chloride-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, vinyl acetate resin, polyester resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated Ethylene vinyl acetate resin, ethylene vinyl acetate resin, (meth) acrylic resin, urethane resin, styrene maleic acid resin, alkyd resin, styrene resin, polyacetal resin, epoxy resin, polycarbonate resin, melamine resin, acrylonitrile resin, polysulfone resin, polyether It is preferably at least one selected from thermoplastic resins such as resins, polyether sulfone resins, polyether ketone resins, and polyimide resins. A type in which these resins are dissolved in a solvent, a type in which they are dissolved in an aqueous system, or an emulsion type in which acrylic emulsion, urethane emulsion, ethylene-vinyl alcohol emulsion, ethylene-vinyl acetate emulsion, polypropylene emulsion, etc. are dispersed in water. Such properties can be mentioned. Among them, chlorinated polypropylene resin, chlorinated ethylene vinyl acetate resin, ethylene vinyl acetate resin, vinylidene chloride, vinyl chloride-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, polyester resin, polyamide resin, ( Meta) Acrylic resin is more preferable.

Further, the anchor coat layer preferably contains an unevenness-imparting agent.

The unevenness-imparting agent includes inorganic pigments such as titanium oxide, calcium carbonate, barium sulfate, talc, zinc oxide, silica, mica, montmorillonite, smectite, zeolite, and kaolinite, polyethylene, polypropylene, microcrystallin, carnauba, and polytetrafluoroethylene. It is preferable that at least one selected from waxes such as waxes, urethane resins, (meth) acrylic resins, nitrile resins, polystyrene resins and the like, or mixtures thereof.

Further, it is preferable that the unevenness-imparting agent is in the form of powder or beads. Resin beads are particularly preferable, but any resin beads may be used as long as they can be mixed as an anchor coating agent and the fluidity is maintained.

The average particle size of the unevenness-imparting agent is preferably larger than 0.1 μm, more preferably in the range of 0.3 to 50 μm, and further preferably in the range of 0.8 to 30 μm. preferable. If it contains 0.1 μm or less, water repellency is difficult to develop, and if it is larger than 50 μm, the coating suitability is inferior.

By forming the anchor coat layer containing the hydrophobic resin and the unevenness-imparting agent, the hydrophobic resin layer has an uneven shape in its cross section. By further laminating a non-adhesive layer on the provided uneven hydrophobic resin layer, the three-dimensional effect of the unevenness and the hydrophobic effect of the resin itself are combined to provide good water repellency and non-adhesion. It has a great effect on sex.

The content of the hydrophobic resin and the unevenness-imparting agent is preferably 10/90 to 99.9 / 0.1 in terms of the weight ratio of the hydrophobic resin / unevenness-imparting agent. If the amount of the hydrophobic resin is less than 10, the adhesion to the base material layer is inferior, and if the amount of the unevenness-imparting agent is less than 0.1, water repellency is less likely to be developed.

The anchor coat layer preferably further contains a solvent, and dissolves or disperses the hydrophobic resin in the solvent.

As the solvent, an organic solvent type or an aqueous type usually used in gravure printing can be used. For example, organic solvents and / or water can be mentioned. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane and ethylcyclohexane, methanol, ethanol, isopropyl alcohol (IPA) and normal propyl alcohol. , 1-butanol, 2-butanol, isobutanol, tert-butanol and other alcoholic solvents, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate and the like. Solvents, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone and other ketone solvents, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Glycol ether-based solvents such as ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether and esterified products thereof can be mentioned. As the esterified product, acetates are mainly selected. For example, ethylene glycol monomethyl ether acetate and ethylene glycol are selected. Examples thereof include monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Any method may be used as long as the hydrophobic resin contained in the anchor coat layer can be dissolved.

A curing agent may be added to the anchor coat layer, if necessary. For example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4'-dicyclohexyldiisocyanate and trimethylol propane thereof. Examples thereof include polyisocyanate-based curing agents such as modified products such as trimerics, isocyanurates, bullets, and allophanates, and these can be used alone or in combination of two or more.

The anchor coat layer is preferably formed by an anchor coat agent having coating suitability containing a hydrophobic resin, an unevenness-imparting agent, and the like.

The base material layer is preferably at least one selected from paper, aluminum foil, plastic film or sheet, and a laminate having heat-sealing property thereof. The base material layer may be one in which a thermoplastic resin or the like is laminated by a method such as dry laminating, non-solvent laminating or extrusion laminating, or a method of laminating via an adhesive or the like, and these may be appropriately combined. It may be a thing. Further, a laminate having heat-sealing property can also be used as a base material layer. Examples of the method for imparting heat-sealing property include laminating known sealant films, resin coating by extrusion laminating, coating with a heat-sealing agent for coating, and the like, and a layer to which heat-sealing property is imparted by these methods. Is also called a heat seal layer. The thickness of the base material layer is not particularly limited as long as it does not interfere with printability, winding suitability, etc., but is preferably 5 to 300 μm, more preferably 6 to 250 μm.

The non-adhesive lid material of the present invention preferably contains a heat seal layer. As long as the heat-sealing layer can secure sufficient heat-sealing strength, the material thereof is, depending on the base material layer, application, composition, etc., a known sealant film is bonded, resin coating by extrusion lamination processing, and heat sealing are performed. It can be formed by appropriately selecting from the coating of the agent and the like. The heat seal layer may be formed between the base material layer and the anchor coat layer. In the case of a thermal pressure seal that seals the opening of the container with a lid material, such as a cup-shaped container such as yogurt or jelly or a portion pack such as liquid coffee cream, an anchor coat layer and a non-adhesive layer are formed on the heat seal part. You may. Of course, it is not necessary to form the anchor coat layer and the non-adhesive layer only in the heat seal portion. In the case of a surface seal (also called a heat seal) that seals the opening of a bag-shaped container such as flexible packaging with a lid material, it is necessary to prevent the formation of an anchor coat layer and a non-adhesive layer on the heat seal part. preferable. Further, the heat-sealing surface of the base material layer having heat-sealing property can also be used as the heat-sealing layer. In any case, the layer to which the heat-sealing property is imparted is referred to as a "heat-sealing layer".

Further, the thickness of the heat seal layer is not particularly limited, but from the viewpoint of heat sealability, cost, and productivity, the sealant film is 2 to 200 μm, the resin coating by extrusion laminating is 1 to 100 μm, and the hot melt adhesive. It is preferably 1 to 50 μm for coating and 0.01 to 30 μm for heat sealant coating.

Examples of the sealant film include polyolefin films such as polyethylene, polypropylene and ethylene-vinyl acetate, polystyrene films and polyacrylonitrile films, which may be stretched or unstretched, and may be of one or two types. The above may be laminated.

Examples of the resin that can be used for the resin coating and hot melt adhesive by the extrusion laminating process include polyethylene resins such as LDPE, LLDPE, and HDPE, polypropylene resins, ethylene-vinyl acetate copolymers, ionomer resins, and ethylene-acrylic acid copolymers. , Ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene and polypropylene Examples thereof include acid-modified polyolefin resins modified with maleic acid and fumaric acid, and thermoplastic resins such as polypropylene resins, and these resins may be one or more laminated.

The glass transition point of the thermoplastic resin is preferably less than 90 ° C, more preferably 80 ° C or lower, and even more preferably −50 ° C or higher and 60 ° C or lower. When Tg is lower than −50 ° C., stickiness is likely to occur, and when Tg is 90 ° C. or higher, the heat seal strength is weakened. As long as Tg is within the above range, there is no particular limitation on the resin system. The Tg referred to here is a value measured by differential scanning calorimetry DSC under the conditions of a sample of 5 mg, a measurement temperature of -60 to 120 ° C., and a heating rate of 20 ° C./min.

The heat-sealing agent preferably contains a heat-sealing resin. It may also contain a filler.

Examples of the heat-sealing resin used in the heat-sealing agent include celacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrified cotton, cellulose acetate, cellulose acetylpropionate, and cellulose acetylbuty. Rate, rubber chloride, cyclized rubber, polyamide resin, vinyl chloride-vinyl acetate copolymer, polyester resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated ethylene vinyl acetate resin, ethylene vinyl acetate Examples thereof include thermoplastic resins such as resins, (meth) acrylic resins, urethane resins, ethylene-vinyl alcohol resins, styrene maleic acid resins, caseines, and alkyd resins, and these may be used alone or in combination of two or more. .. Properties such as a type in which these resins are dissolved in a solvent, a type in which they are dissolved in an aqueous system, or an emulsion type in which acrylic emulsion, urethane emulsion, ethylene-vinyl alcohol emulsion, polyethylene emulsion, polypropylene emulsion, etc. are dispersed in water. Can be mentioned.

The glass transition point of the thermosetting resin is preferably less than 90 ° C, more preferably 80 ° C or lower, and even more preferably −50 ° C or higher and 60 ° C or lower. When Tg is lower than −50 ° C., stickiness is likely to occur, and when Tg is 90 ° C. or higher, the heat seal strength is weakened. As long as Tg is within the above range, there is no particular limitation on the resin system. The Tg referred to here is a value measured by differential scanning calorimetry DSC under the conditions of a sample of 5 mg, a measurement temperature of -60 to 120 ° C., and a heating rate of 20 ° C./min.

The filler may be, for example, inorganic pigments such as titanium oxide, calcium carbonate, barium sulfate, talc, zinc oxide, silica, mica, montmorillonite, smectite, zeolite, kaolinite, polyethylene, polypropylene, microcrystalin, carnauba, polytetrafluoro. Examples thereof include waxes such as ethylene, urethane resins, (meth) acrylic resins, nitrile resins, resins such as polystyrene resins, and mixtures thereof. Further, the filler is preferably in the form of powder or beads. Resin beads are particularly preferable, but any resin beads may be used as long as they can be mixed as a heat sealant and the fluidity is maintained.

The average particle size of the filler is preferably larger than 3 μm, more preferably in the range of 5 to 50 μm. If it contains 3 μm or less, water repellency is difficult to develop, and if it is larger than 50 μm, the coating suitability is inferior. The average particle size referred to here is a value measured by a laser method (MICROTRAC 9320 × 100 manufactured by Honeywell).

The content of the thermosetting resin and the filler in the heat-sealing agent is preferably 10/90 to 100/0 in terms of the weight ratio of the thermosetting resin / the filler. When the heat-sealing resin content is less than 10, the heat-sealing strength is weakened.

Further, the heat sealant preferably contains a solvent. Examples of solvents used include organic solvents and / or water. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane and ethylcyclohexane, methanol, ethanol, isopropyl alcohol, normal propyl alcohol, 1-. Alcohol solvents such as butanol, 2-butanol, isobutanol, tert-butanol, ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, etc. Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl Glycol ether-based solvents such as ether and propylene glycol monobutyl ether and esterified products thereof can be mentioned. As the esterified product, acetates are mainly selected. For example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and ethylene. Examples thereof include glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Any method may be used as long as the heat-sealing resin used for the heat-sealing agent can be dissolved or dispersed.

In addition, heat sealants include defoamers, antistatic agents, dispersants, surfactants, lubricants, plasticizers, leveling agents, blocking inhibitors, waxes, etc. as other additives as long as they do not affect the heat seal strength. , Can be added as appropriate.

The solid content of the heat sealant in the composition is preferably 0.1 to 90% by mass, more preferably 2 to 70% by mass, and 3 to 50% by mass in terms of coatability. Is even more preferable. If it is less than 0.1% by mass, the heat seal layer becomes thin and the strength is inferior. If it is more than 90% by mass, it is difficult to dissolve or disperse, it becomes difficult to manufacture the heat sealant itself, the viscosity becomes high, and there is a problem in coatability.

The film thickness of the heat seal layer formed by applying the heat sealant is preferably 0.01 to 30 μm. If the film thickness is smaller than 0.01 μm, water repellency is less likely to be exhibited, and if the film thickness is larger than 30 μm, it is difficult to produce by coating.

The heat seal layer formed by applying the heat sealant is a layer in which the total coating amount (HC) of the heat sealant is 0.3 g / m ² ≤ HC ≤ 10 g / m ² in terms of solid content. Is preferable, and 0.6 g / m ² ≦ HC ≦ 8 g / m ² is more preferable. If the total amount of HC is less than 0.3 g / m ² , the heat seal strength becomes weak, and if it exceeds 10 g / m ² , it becomes easier to block and the cost effectiveness is lost.

The heat-sealing layer formed by applying a heat-sealing agent containing the heat-sealing resin, filler, and the like has an uneven shape in its cross section. Good water repellency and non-adhesiveness can be obtained by forming the uneven shape.

The heat seal layer formed by applying the heat sealant may be one layer as long as the total coating amount (HC) of the heat sealant is within the above range, but may be two layers. The above can be provided, and the heat seal strength can be easily controlled. When two or more layers are provided, heat sealants having the same resin composition may be applied, but heat sealants having different resin compositions may be used and may be appropriately selected.

One or more colors of a printing ink layer (hereinafter, also simply referred to as “printing ink”) can be applied to the base material layer, and the printing ink layer is provided on the opposite surface of the non-adhesive layer or between the base material layer and the non-adhesive layer. It can also be provided. By applying a printing ink layer to the base material layer, for example, company name, product name, contents, ingredient display, scale, scale line, notification of application method and campaign, how to eat and use, date, etc. Information such as the place of origin and winning lottery can be added. It is also possible to apply an OP varnish layer on the printing ink layer.

Further, the base material layer and the heat seal layer do not have to be plain, and one or more printing ink layers can be applied to the base material layer as well.

As the printing ink layer, ordinary gravure ink can be used and can be appropriately selected depending on the base material layer. From the viewpoint of printability and versatility, gravure inks such as urethane resin, vinyl chloride-vinyl acetate copolymer resin, nitrified cotton, polyamide resin, (meth) acrylic resin, and chlorinated polypropylene resin are preferable, and these resins are one. It may be a type or a combination of two or more types of gravure ink. When using two or more colors of gravure ink, it is not necessary to use the same resin-based ink, and different resin-based inks can be used as appropriate.

As commercially available products, LG-NT, TPH, VESTA, LRC-NT, KCNT, SYNA-S, LAMEREK (all of which are manufactured by Tokyo Ink Co., Ltd.) and the like can be used.

The anchor coat layer and the non-adhesive layer are formed by applying the anchor coat agent or the coating liquid to the base material layer by a known printing or coating, spraying, dipping or the like. Examples of the coating method include a silk screen printing method, a gravure printing method, an offset printing method, a flexographic printing method, a roller coater method, a brush coating method, a spray method, and a knife jet coater method. Among them, a gravure printing method, a flexographic printing method or a silk screen printing method is preferably used from the viewpoint of high quality and productivity, and a gravure printing method using a multicolor gravure printing machine is particularly preferable. Further, with respect to the heat sealant, the heat seal layer can be formed by the above coating method. As a result, the lid material has a structure in which the heat seal layer, the anchor coat layer and the non-adhesive layer are laminated in this order on the base material layer. More specifically, after creating a laminated base material layer by the above-mentioned laminating method, a heat seal layer, an anchor coat layer and a non-adhesive layer are formed in this order by a gravure printing method, or a base material as a base material. An anchor coat layer and a non-adhesive layer may be formed on one surface of the layer by a gravure printing method, and then another base material layer may be formed on the other surface different from the anchor coat layer by the above-mentioned lamination method. Alternatively, after forming a heat seal layer by laminating a sealant film on the base material layer or resin coating by extrusion laminating, an anchor coat layer and a non-adhesive layer are applied to the surface on the heat seal layer side by a gravure printing method. It may be formed. Further, the anchor coat layer and the non-adhesive layer may be provided on both sides of the base material layer.

The formation of the anchor coat layer, the non-adhesive layer and the heat seal layer by the heat sealant is preferably performed by a gravure printing method using one or more units of a multicolor gravure printing machine. As a result, the printing ink layer, the heat seal layer, the anchor coat layer, and the non-adhesive layer can be continuously formed in-line on the base material layer, and the non-adhesive lid material can be lowered in a series of flows (1 pass). It can be easily manufactured at low cost. Further, the adhesiveness and non-adhesiveness of the non-adhesive layer and the heat seal strength can be easily controlled. Of course, it may not be possible to form continuously in-line due to restrictions such as the specifications of the gravure printing machine, printing environment, and equipment, but in this case, it is possible to form offline (outline). Further, it is preferable that the anchor coat layer is applied only to the portion where the non-adhesive layer is provided.
The adhesiveness of the non-adhesive layer means whether or not the surface having the non-adhesive layer and a part or the entire surface of the article are easily adhered to each other. Further, the non-adhesive control means that it is possible to control the difficulty of sticking the surface having the non-adhesive layer to a part surface or the entire surface of the food. In the present specification, the non-adhesive layer is interpreted as a surface having a non-adhesive layer.

Furthermore, when a non-adhesive layer is formed by gravure printing, the area ratio may be lowered or the plate may be reduced depending on the case where the non-adhesiveness is too sufficient at 100% halftone dot area ratio or the degree of non-adhesiveness to food. By adjusting the depth and the dilution ratio, the adhesion between the non-adhesive lid material and the article can be easily controlled. Furthermore, in addition to adjusting the net dot area ratio and plate depth, characters (for example, manufacturer name, brand name, product name, symbol, etc.) and patterns (for example, marks, marks, designed patterns, etc.) are "excluded". By forming (forming a part without a non-adhesive layer), the "pulled out" part adheres to the article, maintaining an appropriate adhesiveness, and also has an effect that characters and patterns stand out.

Each composition such as the anchor coating agent, the coating liquid for the non-adhesive layer, the printing ink, and the heat sealant is a hydrophobic resin, an unevenness-imparting agent, a pigment, treated talc, an inorganic particle, a heat sealant resin, various additives, and the like. Can be produced by a known method by uniformly dissolving or dispersing in a solvent. Dissolution or dispersion can be done with various stirrers or dispersions such as dissolvers, roll mills, ball mills, bead mills, sand mills, attritors, paint shakers, agitators, henshell mixers, colloid mills, pearl mills, ultrasonic homogenizers, wet jet mills, kneaders, homomixers You can use the machine. These devices may be used alone or in combination of two or more. When bubbles or coarse particles are contained in each composition, it is preferable to remove them by using a known filter, centrifuge or the like in order to deteriorate printability and print quality.

The viscosity of each of the compositions is not particularly limited as long as it does not interfere with printing. Considering the manufacturing suitability and handling of each composition, it is preferably 10 to 1,000 mPa · s at 25 ° C.

The viscosity can be measured using a commercially available viscometer such as a Brookfield viscometer.

Each of the above compositions can be coated as it is, but depending on the coating conditions and coating effect, the desired viscosity can be obtained by diluting with a diluting solvent with Zahn Cup # 3 (manufactured by Rigo Co., Ltd.). Can be adjusted and used. The viscosity in this case is preferably 10 to 40 seconds at 25 ° C.

The diluting solvent may be any one as long as it can be used by adjusting the viscosity of each of the compositions, and examples thereof include organic solvents and water, and commercially available ones can also be used. Examples of commercially available products include WA735 (alcohol-based solvent), TA52 (alcohol-based solvent), PU515 (non-toluene-based solvent), SL9155 (non-toluene-based solvent) (all of which are manufactured by Tokyo Ink Co., Ltd.). ..

The method for producing a non-adhesive lid material of the present invention has a structure in which a heat seal layer, an anchor coat layer and a non-adhesive layer are laminated in this order on at least one surface of a base material layer to form an anchor coat layer. It is preferable to include a step of applying a coating liquid containing the hydrophobized talc to form the non-adhesive layer.

The step of forming the anchor coat layer and the non-adhesive layer is preferably a step of forming on the base material layer by known printing or coating, spraying, dipping or the like, and a coating step is particularly preferable. Examples of the coating process include a forming process using silk screen printing, gravure printing, offset printing, flexographic printing, roller coater, brush coating, spraying, knife jet coater, and the like. Among them, the coating step by gravure printing, flexographic printing or silk screen printing is preferably used from the viewpoint of high quality and productivity, and the coating step by gravure printing using a multicolor gravure printing machine is particularly preferable. By these forming steps, a non-adhesive lid material having a structure in which a heat seal layer, an anchor coat layer and a non-adhesive layer are laminated in this order on at least one surface of the base material layer is obtained. More specifically, after the step of creating the laminated base material layer by the above-mentioned forming step, the anchor coat layer and the non-adhesive layer are formed in this order by gravure printing, and the non-adhesive lid material is manufactured. However, after the step of forming the anchor coat layer and the non-adhesive layer on one surface of the base material layer by gravure printing, another base material is formed on the other surface different from this by the above-mentioned forming step. The non-adhesive lid material may be produced by the step of further laminating the layers. Further, the non-adhesive lid material may be produced by a step in which non-adhesive layers can be formed on both sides of the base material layer.

Since the anchor coat layer and the non-adhesive layer can be formed in multiple layers by these steps, the adhesiveness and non-adhesiveness of the non-adhesive layer can be easily controlled. That is, the non-adhesive lid material of the present invention is inefficient because the preparation of the non-adhesive layer is a separate step in the non-adhesive lid material using the conventional embossing or plasma chemical vapor deposition method. Is a forming process by gravure printing using a multicolor gravure printing machine, so a printing ink layer, an anchor coat layer, and a non-adhesive layer can be continuously formed on the base material layer in-line, and in a series of flows ( A non-adhesive lid material can be easily produced at low cost in 1 pass). Of course, it may not be possible to form continuously in-line due to restrictions such as the specifications of the gravure printing machine, printing environment, and equipment, but in this case, it is possible to form offline (outline). Further, it is preferable that the anchor coat layer is applied only to the portion where the non-adhesive layer is provided.

For the non-adhesive lid material, the base material can be selected according to the type, form and size of the article, the container to be sealed, etc., and the size and dimensions suitable for the purpose can be cut, divided, die-cut, etc. .. The non-adhesive lid material is preferably placed at a portion where the article should not adhere to the lid material, and may be placed on the lower surface (as a laying material), the upper surface, or the side surface (may be laid around) of the article. It may be.

The non-adhesive lid material of the present invention preferably becomes a closed container by being in close contact with the container. Adhesion to the container may be carried out by human hands, but a machine such as an automatic sealing device may be used. These may be appropriately selected according to the type, form and size, quantity, sealed container, equipment, environment, etc. of the food, and may be attached or adhered with a heat seal (heat pressure seal), a surface seal, an adhesive, or the like. It may be done by a method using such as.

It is more preferable that the container is a bottomed tubular container. In this case, the non-adhesive lid material preferably covers the opening of the bottomed tubular container and is hermetically sealed, and more preferably hermetically sealed by a thermal pressure seal. As the thermal pressure sealing condition, a non-adhesive lid material is placed so as to cover the opening of the bottomed tubular container, and the temperature is 120 to 250 ° C., ² to 10 kgf / cm ² , 0.5 to ² sec. Then, the number of times of sealing 1 to 2 times may be appropriately selected.

Examples of the resin used for the container include thermoplastic resins such as polyethylene-based, polypropylene-based, polyethylene terephthalate, polyvinyl chloride, polystyrene, and polyacrylonitrile. As described above, since the heat seal layer can be made into multiple layers, the adhesion between the lid material made of a polyester base material layer such as polyethylene terephthalate and the opening of the container made of polystyrene resin can be sufficiently enhanced. In this case, "PET (base material layer of lid material) / seal layer having high affinity for PET (first heat seal layer) / seal layer having high affinity to polystyrene (second heat seal layer) / A container such as "anchor coat layer / non-adhesive layer / polystyrene (resin layer of the container)" can be easily produced.

The form of the closed container includes a two-way seal, a three-way seal, a four-way seal, a pillow seal, a standing pouch, an envelope sticker, a gusset, a fusing seal, a tube, a caramel package, an overhold, a fin seal, a manju package, a twist, a rocket, and the like. It may be in any of the well-known forms such as Tetra Pak, Gable Top, Brick, Shibori and Cup.

In the non-adhesive lid material of the present invention, the non-adhesive layer is stable and the non-adhesive performance is maintained for a long period of time without deterioration, so even in a closed container in which the non-adhesive layer and the article are always in contact with each other. Good. Further, it is not always necessary to be in contact with the article, and a closed container may be used in which a gap is provided so as not to contact the non-adhesive layer of the non-adhesive lid material and the article. As a result, even if a part or the entire surface of the article is physically in contact with the non-adhesive layer of the non-adhesive lid material due to transportation, transportation, transportation, vibration, inclination, rollover, transposition, etc. of the closed container, the said. It has the effect of preventing or reducing the adhesion of articles.

The non-adhesive lid material of the present invention will be described with reference to examples thereof, but the present invention is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The parts in Examples and Comparative Examples represent parts by weight, and% represents% by mass.

Base material layer 1
A coated paper (55 g / m ² ) is printed, OP varnish is applied to the printed surface, and a 12 μm thick aluminum-deposited polyethylene terephthalate film (abbreviation: VM-PET) is dry-laminated to form a urethane adhesive. Using (abbreviation: DL), the aluminum-deposited surface of VM-PET was bonded to the opposite surface of the printed surface, and then aged at 40 ° C. for 3 days to obtain "OP varnish / ink / paper / DL / VM-". A base material layer 1 having a structure of "PET" was produced.

Base material layer 2
Printing is applied to coated paper (55 g / m ² ), OP varnish is applied to the printed surface, and aluminum foil (abbreviation: AL) with a thickness of 9 μm is printed by the dry laminating method using a urethane adhesive. A PET film (abbreviation: PET) with a thickness of 12 μm is attached to the opposite surface of the surface using a urethane adhesive by a dry laminating method on the AL surface, and then aged at 40 ° C for 3 days. Then, the base material layer 2 having the composition of "OP varnish / ink / paper / DL / AL / DL / PET" was prepared.

[Preparation of non-adhesive layer coating liquid]
Non-adhesive layer coating liquid 1 (Example 1)
To 90 parts of ethanol, 10 parts of hydrophobized talc ¹⁾ was added with stirring to prepare a non-adhesive layer coating liquid 1.
1): A 10% solution of silicone oil (KF-96-50cs, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed on talc so as to be 3% by mass, and baked at 100 ° C. for 2 hours. Surface coated talc (average particle size 6 μm)

Non-adhesive layer coating liquid 2 (Example 2)
To 90 parts of ethanol, 8 parts of the treated talc of Example 1 and 2 parts of the hydrophobized wet silica (average particle diameter 6.2 μm, SIPERANT D10, manufactured by EVONIK) were added with stirring to add a non-adhesive layer. The coating liquid 2 was prepared.

Non-adhesive layer coating liquid 3 (Example 3)
To 90 parts of ethanol, 4 parts of the treated talc of Example 1 and 6 parts of the hydrophobized wet silica (average particle diameter 6.2 μm, SIPERANT D10, manufactured by EVONIK) were added with stirring to add a non-adhesive layer. The coating liquid 3 was prepared.

Non-adhesive layer coating liquid 4 (Example 4)
To 90 parts of ethanol, 0.5 part of the treated talc of Example 1 and 9.5 parts of hydrophobized wet silica (average particle diameter 6.2 μm, SIPERANT D10, manufactured by EVONIK) were added with stirring. , Non-adhesive layer coating liquid 4 was prepared.

Non-adhesive layer coating liquid 5 (Example 5)
To 90 parts of ethanol, 8 parts of the treated talc of Example 1 and 2 parts of wet silica (average particle diameter 6.2 μm, SIPERANT 383DS, manufactured by EVONIK) that has not been hydrophobized are added with stirring to non-hydrophobicized silica. The adhesive layer coating liquid 5 was prepared.

Non-adhesive layer coating liquid 6 (Comparative Example 1)
To 90 parts of ethanol, 10 parts of unhydrophobicized talc (average particle diameter 7 to 11 μm, JA-46R, manufactured by Asada Flour Milling Co., Ltd.) was added with stirring to add the non-adhesive layer coating liquid 6. Made.

Non-adhesive layer coating liquid 7 (Comparative Example 2)
Add 10 parts of hydrophobized dry silica (average particle size 0.2 μm, WACKER HDK H18, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) to 90 parts of ethanol with stirring, and add the non-adhesive layer coating liquid 7 Was produced.

Non-adhesive layer coating liquid 8 (Comparative Example 3)
To 90 parts of ethanol, 10 parts of hydrophobized wet silica (average particle diameter 6.2 μm, SIPERANT D10, manufactured by EVONIK) was added with stirring to prepare a non-adhesive layer coating liquid 8.

[Preparation of anchor coating agent]
Anchor coating agent 1 (Production example 1)
To 50 parts of an acrylic resin solution (solid content 30%, Tg 70 ° C.), 10 parts of acrylic resin beads (average particle diameter 10 μm) were added, and 40 parts of ethyl acetate was added with stirring to add anchor coating agent 1. Made.

Anchor coating agent 2 (Production example 2)
To 40 parts of a polyester resin solution (solid content 30%, Tg 50 ° C.), 5 parts of acrylic resin beads (average particle diameter 8 μm) were added, and 25 parts of n-propyl acetate and 30 parts of methyl ethyl ketone were added with stirring. , Anchor coating agent 2 was prepared.

Anchor coating agent 3 (Production example 3)
To 40 parts of a vinyl chloride-vinyl acetate resin solution (solid content 30%, Tg 77 ° C.), 5 parts of acrylic resin beads (average particle size 0.8 μm) were added, and while stirring, 25 parts of n-propyl acetate and methyl ethyl ketone were added. 30 parts were added to prepare an anchor coating agent 3.

[Preparation of heat sealant for coating]
Heat sealant 1 (Production example 4)
20 parts of WA735 (alcohol solvent, manufactured by Tokyo Ink Co., Ltd.) was added to 80 parts of an ethylene vinyl acetate emulsion (solid content 30%, Tg-25 ° C.) with stirring to prepare a heat sealant 1. did.

Heat sealant 2 (Production example 5)
Add 10 parts of acrylic resin beads (average particle diameter 30 μm) to 50 parts of a polyester resin solution (solid content 30%, Tg 5 ° C.), add 40 parts of n-propyl acetate with stirring, and heat sealant. 2 was prepared.

Heat sealant 3 (Production example 6)
Add 10 parts of acrylic resin beads (average particle size 30 μm) to 60 parts of an acrylic resin solution (solid content 30%, Tg 40 ° C.), and while stirring, 10 parts of ethyl acetate, 10 parts of methyl ethyl ketone, 10 parts of n-propyl acetate. A part was added to prepare a heat sealant 3.

The average particle size was measured by a laser method (MICROTRAC 9320 × 100, manufactured by Honeywell).

(Example 6)
Using a 5-color machine gravure printing machine, the first unit is the heat sealant 1 (abbreviation: HT1), the second unit is the anchor coating agent 1 (abbreviation: AC1), and the third unit is on the base material layer 1. , Non-adhesive layer coating liquid 1 (abbreviation: non-adhesive layer 1) was printed and wound up to prepare a non-adhesive lid material 1. At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 1 is TA52. It was diluted with an alcohol solvent (manufactured by Tokyo Ink Co., Ltd.), and the coating amounts were 2.5 g / m ² , 1.1 g / m ² , and 0.2 g / m ² , respectively. As a result, the non-adhesive lid material 1 became a lid material having a structure of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 1".

(Example 7)
The non-adhesive lid material 2 was produced under the same conditions as in Example 6 except that the non-adhesive layer coating liquid 1 was changed to the non-adhesive layer coating liquid 2 (abbreviation: non-adhesive layer 2). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 2 is TA52. It was diluted with (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the coating amounts were 5.0 g / m ² , 1.0 g / m ² , and 0.1 g / m ² , respectively. As a result, the non-adhesive lid material 2 became a lid material having a structure of "ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 2".

(Example 8)
The non-adhesive lid material 3 was produced under the same conditions as in Example 6 except that the non-adhesive layer coating liquid 1 was changed to the non-adhesive layer coating liquid 3 (abbreviation: non-adhesive layer 3). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 3 is TA52. Diluted with (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the coating amounts were 6.0 g / m ² , 1.1 g / m ² , and 0.2 g / m ² , respectively. As a result, the non-adhesive lid material 3 became a lid material having a structure of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 3".

(Example 9)
The non-adhesive lid material 4 was produced under the same conditions as in Example 6 except that the non-adhesive layer coating liquid 1 was changed to the non-adhesive layer coating liquid 4 (abbreviation: non-adhesive layer 4). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 4 is TA52. It was diluted with an alcohol solvent (manufactured by Tokyo Ink Co., Ltd.), and the coating amounts were 4.0 g / m ² , 1.1 g / m ² , and 0.2 g / m ² , respectively. As a result, the non-adhesive lid material 4 became a lid material having a structure of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 4".

(Example 10)
The non-adhesive lid material 5 was produced under the same conditions as in Example 6 except that the non-adhesive layer coating liquid 1 was changed to the non-adhesive layer coating liquid 5 (abbreviation: non-adhesive layer 5). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 5 is TA52. It was diluted with an alcohol solvent (manufactured by Tokyo Ink Co., Ltd.), and the coating amounts were 3.5 g / m ² , 1.1 g / m ² , and 0.2 g / m ² , respectively. As a result, the non-adhesive lid material 5 became a lid material having a structure of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 5".

(Example 11)
The non-adhesive lid material 6 was produced under the same conditions as in Example 6 except that the anchor coating agent 1 was changed to the anchor coating agent 2 (abbreviation: AC2). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 2 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 1 is TA52. It was diluted with an alcohol solvent (manufactured by Tokyo Ink Co., Ltd.), and the coating amounts were 4.0 g / m ² , 1.1 g / m ² , and 0.2 g / m ² , respectively. As a result, the non-adhesive lid material 6 became a lid material having a structure of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC2 / non-adhesive layer 1".

(Example 12)
The non-adhesive lid material 7 was produced under the same conditions as in Example 6 except that the anchor coating agent 1 was changed to the anchor coating agent 3 (abbreviation: AC3). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 3 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 1 is TA52. It was diluted with an alcohol solvent (manufactured by Tokyo Ink Co., Ltd.), and the coating amounts were 3.5 g / m ² , 1.1 g / m ² , and 0.3 g / m ² , respectively. As a result, the non-adhesive lid material 7 became a lid material having a structure of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC3 / non-adhesive layer 1".

(Example 13)
Using a 5-color machine gravure printing machine, the first unit is the heat sealant 2, the second unit is the heat sealant 3, the third unit is the anchor coat agent 1, and the fourth unit is on the base material layer 2. , The non-adhesive layer coating liquid 1 was printed and wound up to prepare a non-adhesive lid material 8. At this time, the heat sealant 2 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), the heat sealant 3 is PU515 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.). Non-toluene solvent, manufactured by Tokyo Ink Co., Ltd., non-adhesive layer coating liquid 1 was diluted with TA52 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the coating amount was 1.0 g / m. ^{It was 2} , 4.0 g / m ² , 1.0 g / m ² , and 0.5 g / m ² . As a result, the non-adhesive lid material 8 became a lid material having a structure of "OP varnish / ink / paper / DL / AL / DL / PET / HT2 / HT3 / AC1 / non-adhesive layer 1".

(Example 14)
Coated paper (55 g / m ² ) is printed with printing ink by the gravure printing method, OP varnish is applied to the printed surface, and then a urethane adhesive is used on the non-printed surface by the dry laminating method. An aluminum foil with a thickness of 15 μm is applied, and then low-density polyethylene (abbreviation: LDPE) is extruded to a thickness of 15 μm while applying an isocyanate-based primer (abbreviation: PL) on the aluminum foil. Was applied and laminated. Next, a hot melt adhesive (X40A, manufactured by Tokyo Ink Co., Ltd., abbreviation: HM) was gravure-coated on the LDPE and laminated so as to have a concentration of 25 g / m ² . As a result, a laminate having the composition of "OP varnish / ink / paper / DL / AL / PL / LDPE / HM" was produced. Further, the anchor coating agent 1 and the non-adhesive layer coating liquid 1 were sequentially coated on the coating side of the HM of the laminate with a coating machine and wound up to prepare a non-adhesive lid material 9. The anchor coating agent 1 is diluted with SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 1 is diluted with TA52 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.). It was 1.0 g / m ² and 0.6 g / m ² . As a result, the non-adhesive lid material 9 became a lid material having a structure of "OP varnish / ink / paper / DL / AL / PL / LDPE / HM / AC1 / non-adhesive layer 1".

(Comparative Example 4)
The non-adhesive lid material 10 was produced under the same conditions as in Example 6 except that the non-adhesive layer coating liquid 1 was changed to the non-adhesive layer coating liquid 6 (abbreviation: non-adhesive layer 6). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 6 is TA52. It was diluted with (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the coating amounts were 1.5 g / m ² , 1.0 g / m ² , and 0.1 g / m ² , respectively. As a result, the non-adhesive lid material 10 became a lid material having a structure of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 6".

(Comparative Example 5)
The non-adhesive lid material 11 was produced under the same conditions as in Example 6 except that the non-adhesive layer coating liquid 1 was changed to the non-adhesive layer coating liquid 7 (abbreviation: non-adhesive layer 7). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 7 is TA52. Diluted with (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the coating amounts were 3.0 g / m ² , 0.9 g / m ² , and 0.2 g / m ² , respectively. As a result, the non-adhesive lid material 11 became a lid material having a structure of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 7".

(Comparative Example 6)
The non-adhesive lid material 12 was produced under the same conditions as in Example 6 except that the non-adhesive layer coating liquid 1 was changed to the non-adhesive layer coating liquid 8 (abbreviation: non-adhesive layer 8). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 8 is TA52. It was diluted with an alcohol solvent (manufactured by Tokyo Ink Co., Ltd.), and the coating amounts were 4.0 g / m ² , 1.1 g / m ² , and 0.2 g / m ² , respectively. As a result, the non-adhesive lid material 12 became a lid material having a structure of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 8".

(Comparative Example 7)
The non-adhesive lid material 13 was produced under the same conditions as in Example 6 except that the non-adhesive layer coating liquid was not used. At this time, the heat sealant 1 is diluted with WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the anchor coating agent 1 is diluted with SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.). Was 3.0 g / m ² and 1.0 g / m ² . As a result, the non-adhesive lid material 13 became a film having the composition of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC1".

(Comparative Example 8)
The non-adhesive lid material 14 was prepared under the same conditions as in Example 13 except that the non-adhesive layer coating liquid was not used. At this time, the heat sealant 2 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), the heat sealant 3 is PU515 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.). It was diluted with a non-toluene solvent and manufactured by Tokyo Ink Co., Ltd., and the coating amounts were 1.0 g / m ² , 5.0 g / m ² and 1.0 g / m ² , respectively. As a result, the non-adhesive lid material 14 became a film having the composition of "OP varnish / ink / paper / DL / AL / DL / PET / HT2 / HT3 / AC1".

(Comparative Example 9)
Silicone resin (KF-96H-30 man cs, manufactured by Shin-Etsu Chemical Co., Ltd., abbreviation: silicone) is applied to an OPP film (abbreviation: OPP) with a thickness of 20 μm, aged at 40 ° C. for 3 days, and then non-used. An adhesive lid material 15 was produced. At this time, the film thickness of the silicone resin was 0.3 μm. As a result, the non-adhesive lid material 15 became a film having an "OPP / silicone" composition.

Non-adhesive layer coating liquid 9 (Example 15)
15 parts of the treated talc of Example 1 was added to 85 parts of ethanol with stirring to prepare a non-adhesive layer coating liquid 9.

Non-adhesive layer coating liquid 10 (Example 16)
To 90 parts of ethanol, 10 parts of hydrophobized talc ²⁾ was added with stirring to prepare a non-adhesive layer coating liquid 10.
2): A 10% solution of silicone oil (KF-96-50cs, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed on talc so as to be 3% by mass, and baked at 100 ° C. for 2 hours. Surface-coated talc (average particle size 3 μm)

Non-adhesive layer coating liquid 11 (Example 17)
15 parts of the treated talc of Example 16 was added to 85 parts of ethanol with stirring to prepare a non-adhesive layer coating liquid 11.

Non-adhesive layer coating liquid 12 (Example 18)
To 90 parts of ethanol, 4 parts of the treated talc of Example 16 and 6 parts of the hydrophobized wet silica (average particle diameter 6.2 μm, SIPERANT D10, manufactured by EVONIK) were added with stirring to add a non-adhesive layer. A coating liquid 12 was prepared.

Non-adhesive layer coating liquid 13 (Example 19)
To 90 parts of ethanol, 0.5 part of the treated talc of Example 16 and 9.5 parts of the hydrophobized wet silica (average particle diameter 6.2 μm, SIPERANT D10, manufactured by EVONIK) were added with stirring. , Non-adhesive layer coating liquid 13 was prepared.

(Example 20)
The non-adhesive lid material 16 was produced under the same conditions as in Example 6 except that the non-adhesive layer coating liquid 1 was changed to the non-adhesive layer coating liquid 9 (abbreviation: non-adhesive layer 9). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 9 is TA52. Diluted with (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the coating amounts were 3.5 g / m ² , 1.0 g / m ² , and 0.1 g / m ² , respectively. As a result, the non-adhesive lid material 16 became a lid material having a structure of "ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 9".

(Example 21)
The non-adhesive lid material 17 was produced under the same conditions as in Example 6 except that the non-adhesive layer coating liquid 1 was changed to the non-adhesive layer coating liquid 10 (abbreviation: non-adhesive layer 10). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 10 is TA52. It was diluted with (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the coating amounts were 4.0 g / m ² , 1.0 g / m ² , and 0.1 g / m ² , respectively. As a result, the non-adhesive lid material 17 became a lid material having a structure of "ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 10".

(Example 22)
The non-adhesive lid material 18 was produced under the same conditions as in Example 6 except that the non-adhesive layer coating liquid 1 was changed to the non-adhesive layer coating liquid 11 (abbreviation: non-adhesive layer 11). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 11 is TA52. It was diluted with (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the coating amounts were 4.5 g / m ² , 1.0 g / m ² , and 0.1 g / m ² , respectively. As a result, the non-adhesive lid material 18 became a lid material having a structure of "ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 11".

(Example 23)
The non-adhesive lid material 19 was produced under the same conditions as in Example 6 except that the non-adhesive layer coating liquid 1 was changed to the non-adhesive layer coating liquid 12 (abbreviation: non-adhesive layer 12). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 12 is TA52. It was diluted with (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the coating amounts were 5.0 g / m ² , 1.0 g / m ² , and 0.1 g / m ² , respectively. As a result, the non-adhesive lid material 19 became a lid material having a structure of "ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 12".

(Example 24)
The non-adhesive lid material 20 was produced under the same conditions as in Example 6 except that the non-adhesive layer coating liquid 1 was changed to the non-adhesive layer coating liquid 13 (abbreviation: non-adhesive layer 13). At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 13 is TA52. It was diluted with (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the coating amounts were 4.0 g / m ² , 1.0 g / m ² , and 0.1 g / m ² , respectively. As a result, the non-adhesive lid material 20 became a lid material having a structure of "ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 13".

(Example 25)
The non-adhesive lid material 21 was produced under the same conditions as in Example 21 except that the anchor coating agent 1 was changed to the anchor coating agent 2. At this time, the heat sealant 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 2 is SL9155 (non-toluene solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 10 is TA52. It was diluted with an alcohol solvent (manufactured by Tokyo Ink Co., Ltd.), and the coating amounts were 4.0 g / m ² , 1.1 g / m ² , and 0.2 g / m ² , respectively. As a result, the non-adhesive lid material 21 became a lid material having a structure of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC2 / non-adhesive layer 10".

The water repellency, yogurt non-adhesiveness, heat sealability, and durability of the non-adhesive lid materials of Examples 6 to 14, 20 to 25 and Comparative Examples 4 to 9 were evaluated and shown in Table 1.

<Water repellency>
The contact angle was measured for the non-adhesive layer of the non-adhesive lid material. A portable contact angle meter PCA-1 (manufactured by Kyowa Interface Science Co., Ltd.) was used for the measurement. The larger the measured value, the higher the water repellency and the better.
⊚: 130 ° or more, ◯: less than 130 °, 110 ° or more, Δ: less than 110 °, 90 ° or more, ×: less than 90 °.

<Non-adhesive yogurt>
Place a drop of yogurt (trade name: Bihidas yogurt, manufactured by Morinaga Milk Industry Co., Ltd.) on the non-adhesive layer of the non-adhesive lid material installed horizontally, and slowly lift one side of the non-adhesive lid material and tilt it. At that time, I observed the angle when the yogurt rolled down. The smaller the angle, the less yogurt adheres and the better the yogurt non-adhesiveness.
⊚: 30 ° or less, ◯: more than 30 ° and 60 ° or less, Δ: more than 60 ° and 90 ° or less, and ×: more than 90 °.

<Heat sealability>
A non-adhesive lid material and a polystyrene sheet having a thickness of 0.15 mm are heat-press sealed (ring-sealed) in a ring shape at 220 ° C. for 1 second under a load of 3 kgf / cm ² , and then the ring-sealed portion is long. A strip with a width of 15 mm was formed so as to be substantially perpendicular to the sides, and used as a sample piece. This sample piece is pulled by a universal tensile tester (RTE-1210, manufactured by Orientec Co., Ltd.) under the conditions of a peeling angle of 180 ° and a tensile speed of 300 mm / min, and the maximum load at the time of pulling and peeling is set to the sealing strength. It was measured as (g). The higher the sealing strength, the better the heat sealing property.
⊚: 400 g or more, ◯: less than 400 g, 350 g or more, Δ: less than 350 g, 300 g or more, ×: less than 300 g.

<Durability>
Put a drop of yogurt (trade name: Bihidas yogurt, manufactured by Morinaga Milk Industry Co., Ltd.) on the non-adhesive layer of the non-adhesive lid material installed in a horizontal state, cover it to prevent the yogurt from drying, and leave it for 24 hours. It was left in the refrigerator. After that, the non-adhesive lid material is taken out from the refrigerator, the cover is removed, and one side of the non-adhesive lid material is slowly lifted, and the yogurt rolls off from the non-adhesive layer of the non-adhesive lid material when tilted. The state was visually observed. The excellent durability means that even if the content is in contact with the non-adhesive layer of the non-adhesive lid material for a long time, the non-adhesive performance does not deteriorate and lasts. Therefore, the yogurt that rolls off from the non-adhesive layer of the non-adhesive lid material is considered to have excellent durability.
⊚: The yogurt rolled off and did not adhere (excellent durability), and ×: the yogurt did not roll off and adhered as it was (poor durability).

<Comprehensive evaluation>
Of the water repellency, yogurt non-adhesiveness, heat sealability, and durability, those with an evaluation result of "◎" are all evaluated as "◎", and those with an evaluation result of "◎" or "○" are comprehensive. Those with "○" as the evaluation and even one "△" were evaluated as "△", and those with even one "×" were evaluated as "×".

According to Table 1, the non-adhesive lid materials of Examples 6 to 14 and 20 to 25 have water repellency, yogurt non-adhesiveness, heat sealability, and durability as compared with the non-adhesive lid materials of Comparative Examples 4 to 9. Is clearly superior. In Comparative Example 4, which is an example of using a non-adhesive layer coating liquid containing talc (untreated talc) that has not been hydrophobized, water repellency and yogurt non-adhesiveness are inferior, and yogurt adheres to the lid material. .. Comparative Examples 5 and 6, which are examples of using the non-adhesive layer coating liquid containing no treated talc, have good water repellency, non-adhesive yogurt, and durability, but are inferior in heat sealability. Comparative Example 7, Comparative Example 8 which does not form a non-adhesive layer, and Comparative Example 9 which is an example of applying a silicone resin, which is a conventional example, have no effect on non-adhesiveness.

According to the non-adhesive lid material of the present invention, since it has sufficient non-adhesiveness and can be easily manufactured at low cost, it can be effectively used as a non-adhesive lid material to which articles do not adhere. In addition, the degree of non-adhesiveness may differ depending on the article, application, and form. In such a case, the non-adhesive lid material can be obtained by lowering the halftone dot area ratio of the gravure plate or adjusting the plate depth. Adhesion to food can be easily controlled. Further, the heat seal strength can be easily adjusted by changing the content of the treated talc. Furthermore, since it has extremely excellent durability, after filling a cup-shaped container with yogurt or the like, it is sealed with the non-adhesive lid material of the present invention, and when it is distributed as a product, it vibrates or translocates during processes such as transportation and transportation. Even if the lid material is in contact with the lid material for a long time due to rolling over, the yogurt etc. will naturally separate from the lid material and will not continue to adhere when it is placed upright. It does not look bad when the product is displayed, or there is no waste due to the contents being used up when the lid material is opened by the consumer, and there is a risk that the fingers, clothes, tables, etc. will be soiled. In addition to eliminating the problem, the lid material on the inner surface can be used to display information for customers such as campaigns, how to use goods and how to eat, which is an excellent effect. Furthermore, since it can be coated by the gravure printing method, it can be widely applied not only to food applications but also to various water-repellent lid materials for daily necessities, medical drugs, industrial materials, and packaging containers using the same.

Claims (7)

A non-adhesive lid material having a structure in which a heat seal layer, an anchor coat layer and a non-adhesive layer are laminated in this order on at least one side of the base material layer by a gravure printing method using a multicolor gravure printing machine .
The heat seal layer is a layer formed by applying a heat seal agent containing a thermoplastic resin having a glass transition point (Tg) of −50 ° C. or higher and 40 ° C. or lower.
The anchor coat layer contains an anchor coat containing a resin having a glass transition point (Tg) of 50 ° C. or higher and lower than 100 ° C., and an unevenness-imparting agent which is a resin bead having an average particle diameter in the range of 0.8 to 30 μm. It is a layer formed by applying an agent,
The non-adherent layer is Ri Sodea formed by applying a coating solution containing talc and inorganic particles subjected to hydrophobic treatment,
The coating liquid contains 0.5 to 40% by mass of the hydrophobized talc and the inorganic particles, and the hydrophobized talc and the inorganic particles are 100/0 to 5/95 by weight. nonadherent lid, characterized in der Rukoto. The resins are cellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, cellulose acetate, cellulose acetylpropionate, cellulose acetylbutyrate, rubber chloride, cyclized rubber, vinyl chloride, vinylidene chloride, and polyamide resins. , Vinyl chloride-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, vinyl acetate resin, polyester resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated ethylene vinyl acetate resin , Ethylene vinyl acetate resin, (meth) acrylic resin, urethane resin, styrene maleic acid resin, alkyd resin, styrene resin, polyacetal resin, epoxy resin, polycarbonate resin, melamine resin, acrylonitrile resin, polysulfone resin, polyether resin, polyether sulfone resins, polyether ketone resins, non-adherent cover material according to claim 1 Symbol mounting, characterized in that at least one selected from thermoplastic resins such as polyimide resin. The non-adhesive lid material according to claim 1 or 2, wherein the base material layer is at least one selected from paper, aluminum foil, plastic film or sheet. In a method for producing a non-adhesive lid material in which a heat seal layer, an anchor coat layer and a non-adhesive layer are laminated in this order by a coating step by gravure printing using a multicolor gravure printing machine on at least one side of the base material layer.
A step of forming a heat seal layer formed by applying a heat seal agent containing a thermoplastic resin having a glass transition point (Tg) of −50 ° C. or higher and 40 ° C. or lower, and
An anchor coating agent containing a resin having a glass transition point (Tg) of 50 ° C. or higher and lower than 100 ° C. and an unevenness-imparting agent which is a resin bead having an average particle diameter in the range of 0.8 to 30 μm is applied. The process of forming the anchor coat layer and
Including a step of applying a coating liquid containing hydrophobized talc and inorganic particles to form a non-adhesive layer.
The step of forming the heat seal layer is a coating step by gravure printing using one unit of a multicolor gravure printing machine.
The step of forming the anchor coat layer is a coating step by gravure printing using another unit of a multicolor gravure printing machine.
The step of forming the non-adhesive layer is a coating step by gravure printing using another unit different from the unit of the multicolor gravure printing machine.
The coating liquid contains 0.5 to 40% by mass of hydrophobized talc and inorganic particles, and hydrophobized talc and inorganic particles are 100/0 to 5/95 by weight. A method for producing a non-adhesive lid material, which is characterized by the above. The resins are cellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, cellulose acetate, cellulose acetylpropionate, cellulose acetylbutyrate, rubber chloride, cyclized rubber, vinyl chloride, vinylidene chloride, and polyamide resins. , Vinyl chloride-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, vinyl acetate resin, polyester resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated ethylene vinyl acetate resin , Ethylene vinyl acetate resin, (meth) acrylic resin, urethane resin, styrene maleic acid resin, alkyd resin, styrene resin, polyacetal resin, epoxy resin, polycarbonate resin, melamine resin, acrylonitrile resin, polysulfone resin, polyether resin, polyether The method for producing a non-adhesive lid material according to claim 4, wherein the non-adhesive lid material is at least one selected from a thermoplastic resin such as a sulfone resin, a polyether ketone resin, and a polyimide resin. The method for producing a non-adhesive lid material according to claim 4 or 5, wherein the base material layer is at least one selected from paper, aluminum foil, a plastic film or a sheet. A closed container with a thermal pressure seal comprising the non-adhesive lid material according to any one of claims 1 to 3 and a container.