JP6534850B2 - Non-adhesive lid and closed container - Google Patents

Description

  The present invention relates to a non-adhesive lid material used for an article containing water and sugar and a sealed container comprising the lid material and a container.

  Conventionally, cup-shaped containers are widely used as packaging containers for food products such as yogurt, milk portion, pudding, jam, gum syrup, butter, ice cream, medicines, cosmetics and the like. These cup-like containers are sealed by a lid which is heat sealed. Therefore, such a lid is desired to have heat sealability and to prevent nonadhesion of the contents, that is, to prevent the contents from adhering to the lid surface of the inner surface of the packaging container. If the contents adhere to the lid surface of the inner side of the packaging container, the appearance may be poor, waste may be caused by the inability to use the contents, and it may cause stains on fingers, clothes, or a table. There is a problem that even if information etc. is printed on the side of the lid material, it can not be viewed.

  Then, the following patent documents 1-6 have been proposed about the lid material which gave non-adhesivity of the contents to the lid material side of the inner surface side of a packaging container in the lid material of such a cup-like container.

  In Patent Document 1, a lid is obtained by laminating a content adhesion preventing layer consisting of a composition of a wax and a filler dispersed in the wax on a heat sealing layer, but the filler in the wax In addition, there is a concern that the heat sealability of the heat sealable layer is affected by the dispersion, and the seal tends to be unstable. In Patent Documents 2 to 4, although it is a laminated body or a lid member in which a porous layer having a three-dimensional network structure is formed on the outer surface of a heat sealing layer using hydrophobic oxide fine particles as an adhesion preventing layer The heat resistance of the layer is inferior, and the adhesion preventing effect may be significantly impaired. That is, in the step of forming the adhesion prevention layer, the adhesion prevention effect is impaired if the heating temperature is too high or the drying time is prolonged when the adhesion prevention layer is dried, so process control and handling are difficult. . In patent document 5, although it is a lid material which used hydrophobic wet silica for adhesion prevention layer, since wax of low melting point is used for heat sealing layer, wax melts at the time of heat sealing, and heat sealing is carried out. There was a problem that sex was inferior. In Patent Document 6, although the lid is a lid in which the oxide fine particles are attached to resin particles composed of an olefin resin in the water repellent layer, it is inferior in water repellency, and in particular, it is insufficient nonadhesion It is. In addition, these disclosed lid materials have a problem that when the contents are in contact for a long time, the non-adhesion layer is deteriorated and the non-adhesion performance can not be maintained.

JP, 2009-73523, A Patent No. 4348401 gazette JP, 2011-93315, A JP, 2013-32013, A Patent No. 4686352 Patent No. 4878650

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

  The inventors have found that the above object can be achieved by using a non-adhesive lid material having a configuration in which a heat seal layer, an anchor coat layer and a non-adhesion layer are laminated in this order on at least one side of a substrate layer. The present invention has been completed.

That is, the present invention
(1) A non-adhesive lid material having a configuration in which a heat seal layer, an anchor coat layer and a non-adhesion layer are laminated in this order on at least one side of a base material layer,
The anchor coat layer contains a hydrophobic resin having a glass transition point (Tg) of 50 ° C. or more and less than 100 ° C. , and an unevenness imparting agent which is a resin bead having an average particle diameter of 0.8 to 30 μm. Sodea is,
The hydrophobic resin is 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 At least one selected from resin and (meth) acrylic resin,
The non-adhesive lid material, wherein the heat seal layer is a layer containing a thermoplastic resin having a glass transition point (Tg) of -50 ° C. or more and 30 ° C. or less and containing no filler.
(2) The non-adhesive lid according to ( 1 ), wherein the base material layer is at least one selected from paper, aluminum foil, plastic film or sheet.
(3) the non-adherent layer and the anchor coat layer is, according to, characterized in that a layer formed by coating by a gravure printing method using a multi-color gravure printing machine (1) or (2) Non-adhesive lid,
(4) A method of manufacturing a non-adhesive lid material having a configuration in which a heat seal layer, an anchor coat layer and a non-adhesion layer are laminated in this order on at least one side of a base material layer,
Apply an anchor coating agent containing a hydrophobic resin having a glass transition point (Tg) of 50 ° C. or more and less than 100 ° C., and an unevenness imparting agent which is a resin bead having an average particle diameter of 0.8 to 30 μm. Forming the anchor coat layer;
Applying a coating liquid containing hydrophobized inorganic particles to form the non-adhesive layer;
The hydrophobic resin is 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 At least one selected from resin and (meth) acrylic resin,
The method for producing a non-adhesive lid material, wherein the heat seal layer contains a thermoplastic resin having a glass transition point (Tg) of -50 ° C. or more and 30 ° C. or less, and does not contain a filler .
(5) The method for producing a non-adhesive lid according to (4), wherein the base material layer is at least one selected from paper, aluminum foil, plastic film or sheet .
(6) The step of forming the anchor coat layer is a coating step by gravure printing using one unit of a multicolor gravure printing machine,
The non-adhesive property according to (4) or (5), wherein the step of forming the non-adhesive layer is a coating step by gravure printing using another unit of the multicolor gravure printer. Method of manufacturing lid material ,
(7) A closed container comprising the non-adhesive lid according to any one of (1) to ( 3 ) and a container,
It is about

  According to the present invention, steps such as embossing and deposition processing for imparting non-adhesion are unnecessary, and even if the non-adhesion layer is thin, it has sufficient non-adhesion to an article requiring non-adhesion. And a non-adhesive lid 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 substrate layer, which can be easily manufactured at low cost A sealed container is provided.

  Hereinafter, modes for carrying out the present invention will be described in detail. The present embodiment is only one mode for carrying out the present invention, and the present invention is not limited to the present embodiment, and various modifications and embodiments can be made without departing from the scope of the present invention. Is possible.

  The non-adhesive lid of the present invention (hereinafter, also simply referred to as "lid") 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 substrate layer. It is preferable that it is a non-adhesive lid material, and the anchor coat layer is a layer containing a resin having a glass transition point (Tg) of 0 ° C. or more and less than 100 ° C., and an unevenness imparting agent.

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

  Furthermore, it is preferable that the resin is a hydrophobic resin. Examples of hydrophobic resins include shellacs, rosins, rosin modified maleic acid resins, rosin modified phenolic resins, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, chlorinated rubber, chlorinated rubber, cyclized rubber, vinyl chloride, chlorinated Vinylidene, polyamide resin, vinyl chloride-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, vinyl acetate- (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, ethylene-vinyl alcohol resin, styrene maleic acid resin, alkyd resin, styrene resin, polyaceta resin Is preferably at least one selected from thermoplastic resins such as epoxy resin, epoxy resin, polycarbonate resin, melamine resin, acrylonitrile resin, polysulfone resin, polyether resin, polyether sulfone resin, polyether ketone resin, polyimide resin, etc. . These resins are dissolved in a solvent, dissolved in water, or dispersed in water, such as acrylic emulsions, urethane emulsions, ethylene-vinyl alcohol emulsions, ethylene-vinyl acetate emulsions, polypropylene emulsions, etc. And other properties. 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 preferred.

  Moreover, it is preferable that the said anchor coat layer contains an uneven | corrugated imparting agent.

  The said unevenness imparting agent is titanium oxide, calcium carbonate, barium sulfate, talc, zinc oxide, silica, mica, montmorillonite, smectite, zeolite, inorganic pigments such as kaolinite, polyethylene, polypropylene, microcrystalline, carnauba, polytetrafluoroethylene It is preferable that it is at least one selected from waxes such as, urethane resins, acrylic resins, nitrile resins, resins such as polystyrene resins, or mixtures thereof.

  Furthermore, it is preferable that the said concavo-convex imparting agent is powdery or bead-like. Although resin beads are particularly preferable, any resin beads may be used as long as they can be mixed as an anchor coating agent and can maintain fluidity.

  The average particle diameter 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. When the particle size is 0.1 μm or less, the water repellency is difficult to be expressed, and when it is larger than 50 μm, the coating suitability is poor.

  By forming an anchor coat layer containing a hydrophobic resin and an unevenness imparting agent, it becomes an uneven hydrophobic resin layer in the cross section. By further laminating a non-adhesion layer on the provided uneven hydrophobic resin layer, the steric effect of the uneven surface and the hydrophobic effect of the resin itself are combined to provide good water repellency and non-adhesion. Sex has a big effect.

  The content of the hydrophobic resin and the unevenness imparting agent is preferably 10/90 to 99.9 / 0.1 in the weight ratio of the hydrophobic resin / the unevenness imparting agent. When the amount of the hydrophobic resin is less than 10, the adhesion to the substrate layer is poor, and when the amount of the unevenness imparting agent is less than 0.1, the water repellency is hardly expressed.

  The anchor coat layer preferably further contains a solvent, and the hydrophobic resin is dissolved or dispersed in the solvent.

  The solvent may be an organic solvent type or an aqueous type generally used in gravure printing. 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 Alcohol solvents such as 1-butanol, 2-butanol, isobutanol, tert-butanol, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, esters of tert-butyl acetate, etc. Solvents, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, ketone solvents such as cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Glycol ether solvents such as glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like, and their esterified products are mentioned. Acetates selected from the group consisting of ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol Such as chromatography monoethyl ether acetate. Any may be used as long as the hydrophobic resin contained in the anchor coat layer can be dissolved.

  A hardening agent can also be added to the above-mentioned anchor coat layer if needed. For example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4'-dicyclohexyl diisocyanate and trimethylolpropane thereof Polyisocyanate-based curing agents such as trimers, isocyanurate bodies, burette bodies, modified bodies such as allophanate bodies and the like can be mentioned, and these can be used alone or in combination of two or more.

  The anchor coat layer is preferably formed of an anchor coat agent having a coating suitability containing a hydrophobic resin, a roughening agent and the like.

  The non-adhesive layer preferably contains hydrophobicized inorganic particles.

  The hydrophobized inorganic particles are preferably at least one selected from silica, talc, sericite, mica, kaolin, or a mixture thereof subjected to hydrophobization. Among them, hydrophobically treated silica and talc (hereinafter, also simply referred to as “treated silica” and “treated talc”, respectively) are more preferable.

  The hydrophobic treatment of the inorganic particles is not particularly limited as long as a hydrophobic group can be introduced into the inorganic particles, but from the viewpoint of water repellency, cost and safety, silane coupling treatment, silicone treatment and silazane treatment are preferable. A well-known silane coupling agent is used for a silane coupling process, and the process to an inorganic filler, such as a silica and a talc, the process by a dry method or a wet method is preferable. In general, a silane coupling agent is a silane compound having two different functional groups of an organic functional group and an alkoxy group in one molecule, and aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N- Aminosilane coupling agents such as phenylaminopropyltrimethoxysilane, N-2 (aminoethyl) aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxy Epoxy silane coupling agents such as silane, glycidyl butyl trimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyl trie Mercaptosilane-based coupling agents such as toxisilane, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, silane-based coupling agents such as imidazole silane and triazine silane, and the like are used. For example, a dry method is known in which inorganic particles are stirred at high speed with a stirrer, and a stock solution of a silane compound is uniformly dispersed and treated there. In a wet method, inorganic particles are immersed in a dilute solution of silane. Methods of processing are known. For the silicone treatment, silicone oil which is liquid at normal temperature is used. 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 weight of silicone oil, based on talc. Organosilazanes such as hexamethyldisilazane (HMDS), hexaphenyldisilazane, dimethylaminotrimethylsilane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane for silazane treatment The compounds are preferably used, and hexamethyldisilazane is more preferably used. For example, a method of spraying hexamethyldisilazane in a state in which inorganic particles such as silica and talc are made to flow, silica, talc and the like in an organic solvent such as alcohol and toluene, and further hexamethyldisilazane and water After the addition, it can be produced by a method of evaporating and drying water and an organic solvent with an evaporator. More specifically, HMDS-treated inorganic particles are prepared by placing inorganic particles in a Henschel mixer, spraying water and HMDS while stirring under a nitrogen atmosphere, heating and cooling, and crushing with a ball mill. it can.

  Silica (silicon dioxide) is abundant in natural products, synthetic products, or crystalline or amorphous, among which synthetic amorphous silica is preferred. Synthetic amorphous silica is roughly classified into wet method silica and dry method silica, but it has been subjected to hydrophobic treatment such as silane coupling treatment, silicone treatment (siloxane treatment), silazane treatment or composite treatment of these. For example. As a commercially available product, SIPERNAT series (manufactured by EVONIK), AEROSIL series (manufactured by Nippon Aerosil Co., Ltd.), WACKER HDK series (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), Reoroseal (manufactured by Tokuyama Co., Ltd.), Silo Hobik (manufactured by Tokuyama) Fuji Silysia Chemical Co., Ltd. product, Mizukasil (Mizusawa Chemical Industry Co., Ltd. product), etc. are mentioned.

  Talc is a mineral consisting of magnesium hydroxide and silicate and is a kind of clay mineral. Talc itself, although untreated, has some degree of hydrophobicity, but is not sufficient for the water repellency and nonadhesion of the object of the present invention, and it is necessary to carry out a hydrophobic treatment. Hydrophobization treatment may be general, and may be treated with silica treatment, silicone treatment (siloxane treatment), silazane treatment, resin treatment, fatty acid treatment, silane coupling treatment, titanate treatment, or a composite treatment of these. For example. The treatment amount is preferably 0.01 to 50% by weight, and more preferably 0.05 to 30% by weight with respect to talc. If it is less than 0.01% by weight, the hydrophobicity is not sufficient, and if it is more than 50% by weight, it not only does not contribute to the treatment of talc but it becomes an impurity to inhibit water repellency. For example, the treated talc is obtained by spraying a 10% solution of silicone oil in methylene chloride to the talc so as to be 1 to 5% by weight of the silicone oil and calcining at 100 ° C. for 2 hours.

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

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

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

The non-adhesion layer can use an additive as needed. For example, viscosity modifiers, dispersants, antiblocking agents, waxes, fillers and the like can be mentioned. As viscosity modifiers, inorganic compounds such as silica, resin-based thickeners such as polyamide, as dispersants, polymeric resin dispersants, surfactants such as anionic, nonionic, cationic and amphoteric, Resin beads, such as a urethane resin, an acrylic resin, a nitrile resin, a polystyrene resin, or these mixtures etc. are mentioned. Antiblocking agents include inorganic pigments such as calcium carbonate, barium sulfate, silica, mica, montmorillonite, smectite, zeolite, kaolinite and the like. Examples of the wax include polyethylene, polypropylene, microcrystalline, carnauba, polytetrafluoroethylene and the like. As the filler, titanium oxide, calcium carbonate, barium sulfate, talc, zinc oxide, silica, mica, montmorillonite, smectite, zeolite, inorganic pigments such as kaolinite, polyethylene, polypropylene, microcrystalline, carnauba, polytetrafluoroethylene etc. Resin beads such as waxes, urethane resins, acrylic resins, nitrile resins and polystyrene resins, or mixtures thereof. The average particle size of the filler is preferably in the range of 0.01 to 50 μm.
The additive amount of the additive can be used in the range not to inhibit the water repellency, and the total amount of the additive is preferably 80% by weight or less, more preferably 70% by weight or less based on the hydrophobically treated inorganic particles. If the additive is more than 80% by weight with respect to the hydrophobized inorganic particles, the water repellency is reduced.

  The non-adhesion layer is preferably formed of a coating liquid having a coating suitability including a hydrophobicized inorganic particle or the like.

  The amount of hydrophobized inorganic particles in the coating liquid is preferably 0.1 to 50% by weight, and more preferably 1 to 40% by weight, in the coating liquid. More preferably, it is in weight percent. If the amount is less than 0.1% by weight, the water repellence of the non-adhesion layer coated with the coating liquid is difficult to be expressed, and if it is more than 50% by weight, the fluidity as the coating liquid is inferior and coating by the gravure printing method Not suitable for

  Furthermore, it is preferable that it is 0.01-50 micrometers, and, as for the film thickness of the non-adhesion layer formed by coating the said coating liquid, it is more preferable that it is 0.01-30 micrometers. If the film thickness is less than 0.01 μm, it is difficult to express water repellency, and if the film thickness is more than 50 μm, it is difficult to prepare by the gravure printing method.

In the non-adhesion layer formed by applying the coating solution, the coating amount (UC) of the coating solution is 0.02 g / m ² ≦ UC ≦ 1.5 g / m ² in solid content. It is preferable that 0.1 g / m ² ≦ UC ≦ 1.0 g / m ² is more preferable. When the amount is less than 0.02 g / m ² , the water repellency is difficult to be expressed, and when the amount is more than 1.5 g / m ² , the abrasion resistance of the nonadherent layer is inferior.

The substrate layer is preferably at least one selected from paper, an aluminum foil, a plastic film or sheet, and a laminate having heat sealability with them. The base material layer may be formed by laminating a thermoplastic resin or the like by a method such as dry lamination, non-solvent lamination or extrusion lamination, or a method of bonding through an adhesive or the like. It may be one. Moreover, the laminated body provided with heat sealability can also be used as a base material layer. Examples of methods for imparting heat sealability include laminating of known sealant films, resin coating by extrusion lamination, coating of a heat seal agent for coating, and the like, and layers provided with heat sealability by these methods Is also called a heat seal layer. The thickness of the substrate layer is not particularly limited as long as there is no problem in printability, winding-up ability and the like, but it is preferably 5 to 300 μm, and more preferably 6 to 250 μm.
The abrasion resistance of the deposited layer is poor.

  The non-adhesive lid of the present invention preferably comprises a heat seal layer. If the heat seal layer can ensure sufficient heat seal strength, the material thereof is a laminate of a known sealant film, resin coating by extrusion lamination, heat seal, etc., depending on the substrate layer, application, constitution, etc. It can be selected appropriately from the coating of the agent and the like. A heat seal layer may be formed between the base layer and the anchor coat layer. In the case of a heat and pressure seal where the opening of the container is sealed with a lid like a cup-shaped container such as yogurt or jelly or a portion pack such as liquid coffee cream, an anchor coat layer and a nonadherent layer are formed on the heat seal. May be Of course, it is not necessary to form the anchor coat layer and the non-adhesive layer only at the heat seal portion. In the case of a face seal (also referred to as heat seal etc.) in which the opening of a bag-like container such as a soft package is sealed with a lid, do not form an anchor coat layer and a nonadherent layer on the heat seal. preferable. Moreover, the heat seal surface of the base material layer which has heat sealability can also be used as a heat seal layer. In any case, the layer to which heat sealability is imparted is referred to as "heat seal layer".

  Furthermore, 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 lamination is 1 to 100 μm, and the hot melt adhesive is used. The coating thickness is preferably 1 to 50 μm, and the heat sealing agent coating is preferably 0.01 to 30 μm.

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

  Examples of resins usable for resin coating and hot melt adhesive by extrusion lamination 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 And acid-modified polyolefin resins modified with maleic acid, fumaric acid, etc., and thermoplastic resins such as polystyrene resins. These resins may be laminated one or two or more.

  The glass transition point of the thermoplastic resin is preferably less than 90 ° C., more preferably 80 ° C. or less, and still more preferably −50 ° C. or more and 60 ° C. or less. When the Tg is lower than -50 ° C, stickiness tends to occur, and when the temperature is 90 ° C or higher, the heat seal strength becomes weak. If Tg is in the said range, there is no restriction | limiting in particular of a resin system. Tg here is a value measured by differential scanning calorimetry DSC under the conditions of 5 mg of sample, a measurement temperature of -60 to 120 ° C., and a temperature rising rate of 20 ° C./min.

  The heat seal agent preferably contains a heat sealable resin. It may also contain a filler.

  Examples of the heat sealable resin used for the heat seal agent include, for example, shellacs, rosins, rosin modified maleic acid resin, rosin modified phenolic resin, cotton nitrate, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate Rate, chlorinated rubber, 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 Thermoplastic resins such as resin, (meth) acrylic resin, urethane resin, ethylene-vinyl alcohol resin, styrene maleic acid resin, casein, alkyd resin, etc. may be mentioned, and one or more of these may be used in combination. . Properties of these resins dissolved in a solvent, dissolved in water, or dispersed in water such as acrylic emulsion, urethane emulsion, ethylene-vinyl alcohol emulsion, polyethylene emulsion, polypropylene emulsion, etc. Can be mentioned.

  The glass transition temperature of the heat sealable resin is preferably less than 90 ° C, more preferably 80 ° C or less, and still more preferably -50 ° C or more and 60 ° C or less. When the Tg is lower than -50 ° C, stickiness tends to occur, and when the temperature is 90 ° C or higher, the heat seal strength becomes weak. If Tg is in the said range, there is no restriction | limiting in particular of a resin system. Tg here is a value measured by differential scanning calorimetry DSC under the conditions of 5 mg of sample, a measurement temperature of -60 to 120 ° C., and a temperature rising rate of 20 ° C./min.

  Examples of the filler include titanium oxide, calcium carbonate, barium sulfate, talc, zinc oxide, silica, mica, montmorillonite, smectite, zeolite, inorganic pigments such as kaolinite, polyethylene, polypropylene, microcrystalline, carnauba and polytetrafluoroethylene. Examples thereof include waxes such as ethylene, urethane resins, (meth) acrylic resins, nitrile resins, resins such as polystyrene resins, and mixtures thereof. Furthermore, the filler is preferably in the form of powder or beads. Particularly preferable is resin beads, but any resin beads may be used as long as they can be mixed as a heat sealing agent and maintain fluidity.

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

  The content of the heat sealable resin component and the filler in the heat seal agent is preferably 10/90 to 100/0 in the weight ratio of the heat sealable resin component / filler. If the heat sealable resin content is less than 10, the heat seal strength becomes weak.

  Furthermore, the heat sealing agent 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, and ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethy Glycol ether solvents such as ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like and esterified products thereof are mentioned, and esterified products are mainly acetate Are selected, for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Etc. Le acetate. Any may be used as long as the heat sealable resin used for the heat seal agent can be dissolved or dispersed.

  Furthermore, the heat sealing agent may be added to the heat sealing strength of the antifoaming agent, the antistatic agent, the dispersant, the surfactant, the lubricant, the plasticizer, the leveling agent, the antiblocking agent, the wax and the like as other additives. And can be added as appropriate.

  The heat seal agent preferably has a solid content in the composition of 0.1 to 90% by weight in terms of coating suitability, more preferably 2 to 70% by weight, and 3 to 50% by weight. Is more preferred. If it is less than 0.1% by weight, the heat seal layer becomes thin and the strength is poor. When it is more than 90% by weight, it is difficult to dissolve or disperse, the production of the heat sealing agent itself becomes difficult, the viscosity becomes high, and there is a problem in the coatability.

  It is preferable that the film thickness of the heat sealing layer formed by coating the said heat sealing agent shall be 0.01-30 micrometers. If the film thickness is smaller than 0.01 μm, the water repellency is difficult to express, and if the film thickness is larger than 30 μm, the preparation by coating is difficult.

In the heat seal layer formed by applying the heat seal agent, the total coating amount (HC) of the heat seal agent is a layer having a solid content of 0.3 g / m ² ≦ HC ≦ 10 g / m ² Is preferable, and it is more preferable that 0.6 g / m ² ≦ HC ≦ 8 g / m ² . If the total amount of HC is less than 0.3 g / m ² , the heat seal strength is weakened, and if it exceeds 10 g / m ² , cost-effectiveness is lost in addition to easy blocking.

  The heat seal layer formed by applying the heat seal agent containing the heat sealable resin, the filler and the like becomes uneven in its cross section. By being uneven, good water repellency and non-adhesion can be obtained.

  The heat seal layer formed by applying the heat seal agent may be a single layer, as long as the total coating amount (HC) of the heat seal agent falls within the above range. It is also possible to provide more than one, which makes it easy to control the heat seal strength. When providing two or more layers, although the heat sealing agent of the same resin composition may be coated, it may be a heat sealing agent of a different resin composition, and can be selected suitably.

  A printing ink layer (hereinafter, also simply referred to as "printing ink") can be applied to the base layer in one or more colors, and the printing ink layer is formed between the non-adhering layer and the opposite surface of the non-adhering layer It can also be provided. By applying a printing ink layer to the substrate layer, for example, company name, product name, contents, component indication, scale, scale lines, notification of application method or campaign, eating method or using method, date, Information such as origin, winning ticket, etc. can be given. An OP varnish layer can also be coated on the printing ink layer.

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

  A normal gravure ink can be used as the printing ink layer, and can be appropriately selected according to the base material layer. From the viewpoint of printability and versatility, gravure inks such as urethane resin, vinyl chloride-vinyl acetate copolymer resin, nitrifying cotton, polyamide resin, (meth) acrylic resin, and chlorinated polypropylene resin are preferable, and these resins are preferred. It may be a gravure ink of a combination of two or more types. Moreover, when using two or more colors of gravure ink, it is not necessary to be the ink of the same resin system, and the ink of another resin system can also be used suitably.

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

  The anchor coat layer and the non-adhesion layer are formed by applying the anchor coat agent or the coating liquid to the base material layer by a known method such as printing, application, spraying, or immersion. The coating method may, for example, be a silk screen printing method, a gravure printing method, an offset printing method, a flexo printing method, a roller coater method, a brush coating method, a spray method or a knife jet coater method. Among them, a gravure printing method, a flexographic printing method or a silk screen printing method is preferably used in view of high quality and productivity, and a gravure printing method using a multicolor gravure printing machine is particularly preferable. Moreover, a heat seal layer can be formed also with a heat sealing agent by the said application method. It is set as the cover material which has the structure which the heat seal layer, the anchor coat layer, and the non-adhesion layer were laminated | stacked in this order to the said base material layer by these. More specifically, a base material layer is formed by the above-described lamination method, and then a heat seal layer, an anchor coat layer and a non-adhesion layer are formed in this order by a gravure printing method, or a base material serving as a base. The anchor coat layer and the non-adherent layer may be formed on one side of the layer by gravure printing, and another base layer may be formed on the other side different from this by the above-described lamination method. Alternatively, after forming a heat seal layer by laminating a sealant film on a base material layer, resin coating by extrusion lamination, etc., the anchor coat layer and the nonadherent layer are formed on the heat seal layer side by gravure printing. You may form. The anchor coat layer and the nonadherent layer may be provided on both sides of the substrate layer.

The formation of the heat seal layer by the anchor coat layer, the non-adhesion layer and the heat seal agent is preferably performed by a gravure printing method using one or more units of a multicolor gravure printer. This makes it possible to form the printing ink layer, the heat seal layer, the anchor coat layer, and the non-adhesion layer continuously on the substrate layer in-line, and reduce the non-adhesive lid material in a series of flows (1 pass). It can be easily manufactured at cost. In addition, control of adhesion and non-adhesion of the non-adhesion layer and control of heat seal strength can be easily performed. Of course, there are cases where continuous formation can not be performed inline due to the restrictions of the specifications of the gravure printing machine, the printing environment, equipment, etc. In this case, the formation can be performed offline (outline). Moreover, it is preferable to apply | coat an anchor coat layer only to the part which provides a nonadhesion layer.
The adhesion of the nonadherent layer means whether the surface having the nonadherent layer and a part or the entire surface of the article are easily stuck. The nonadherent control means that the adhesion between the surface having the nonadherent layer and the part or whole surface of the food can be controlled. In the present specification, the non-adhesive layer is meant to be interpreted as a surface having the non-adhesive layer.

  Furthermore, when a non-adhesion layer is formed by gravure printing, the 100% dot area ratio may lower the area ratio if the non-adhesion is too high or the demand for the non-adhesion to food, or the plate By adjusting the depth or adjusting the dilution rate, the adhesion between the non-adhesive lid and the article can be easily controlled. Furthermore, in addition to adjustment of dot area ratio and plate depth, letters (eg, maker name, brand name, product name, symbols etc.) and patterns (eg, marks, marks, designed designs etc.) etc. are "dropped" By forming a portion (without forming a non-adhesion layer), the "punched" portion adheres to the article, and while maintaining appropriate adhesion, there is also an effect that characters, patterns, etc. stand out.

  Each composition such as the above-mentioned anchor coating agent, coating liquid for non-adhesion layer, printing ink, heat seal agent, hydrophobic resin, unevenness imparting agent, pigment, hydrophobically treated inorganic particles, heat sealable resin, various additives It can be produced by a known method by dissolving or dispersing uniformly in a solvent. Dissolution or dispersion can be performed with various stirrers or dispersions such as dissolver, roll mill, ball mill, bead mill, sand mill, attritor, paint shaker, agitator, Henschel mixer, colloid mill, pearl mill, ultrasonic homogenizer, wet jet mill, kneader, homo mixer, etc. Machine can be used. These devices may be used alone or in combination of two or more. When air bubbles or coarse particles are contained in each composition, it is preferable to remove them using a known filter, centrifuge or the like in order to reduce printability and print quality.

  The viscosity of each of the above compositions is not particularly limited as long as it does not affect printing. It is preferable that it is 10-1,000 mPa * s at 25 degreeC, when the manufacture aptitude of each composition, handling, etc. are considered.

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

  Each composition described above can be coated as it is, but depending on the coating conditions and the coating effect, the desired viscosity can be obtained by diluting with a dilution solvent with Zahn cup # 3 (manufactured by Rikasha Co., Ltd.) It can be adjusted to use. The viscosity in this case is preferably 10 to 40 seconds at 25 ° C.

  The dilution solvent may be any one as long as it can be used by adjusting the viscosity of each composition, and examples thereof include organic solvents and water, and commercially available ones can also be used. Commercially available products include WA 735 (alcohol solvents), TA 52 (alcohol solvents), PU 515 (non-toluene solvents), SL 9155 (non-toluene solvents) (all manufactured by Tokyo Ink Co., Ltd.), etc. .

  The method for producing a non-adhesive lid according to the present invention has a configuration 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 substrate layer, and is 0 ° C or more and less than 100 ° C. A step of applying an anchor coat agent containing a resin having a glass transition point (Tg) and a concavo-convex imparting agent to form the anchor coat layer, and a coating liquid containing hydrophobized inorganic particles It is preferable to include the process of apply | coating and forming the said non-adhesion layer.

  The step of forming the anchor coat layer and the non-adhesion layer is preferably a step of forming the base layer by known printing or coating, spraying, dipping or the like, and particularly preferably the coating step. Examples of the application process include formation processes using silk screen printing, gravure printing, offset printing, flexo printing, roller coater, brush coating, spray, knife jet coater and the like. Among them, a coating process by gravure printing, flexographic printing or silk screen printing is preferably used in view of high quality and productivity, and in particular, a coating process by gravure printing using a multicolor gravure printing machine is preferable. A heat-seal layer, an anchor coat layer, and a non-adhesion layer are laminated in this order on at least one surface of the base material layer by these forming steps to obtain a non-adhesive lid material. More specifically, after the step of forming the base material layer laminated by the forming step described above, a step of forming the anchor coat layer and the non-adhesion layer in this order by gravure printing is performed to manufacture a non-adhesive lid material. After the step of forming the anchor coat layer and the nonadherent layer by gravure printing on one surface of the base substrate layer, another substrate may be formed by the above-mentioned forming step. The step of further laminating the layers may produce a non-stick lid. Moreover, you may manufacture a non-adhesive lid material by the process which can form a non-adhesion layer in both surfaces of a base material layer.

  By these steps, the anchor coat layer and the non-adhesion layer can be formed in multiple layers, so that the adhesion and non-adhesion properties of the non-adhesion layer can be easily controlled. That is, in the non-adhesive lid material using the conventional embossing and plasma chemical vapor deposition method, the non-adhesive lid material of the present invention is against the fact that the preparation of the non-adhesive layer becomes a separate step and is inefficient. Is a forming process by gravure printing using a multicolor gravure printer, so it is possible to form a printing ink layer, an anchor coat layer, and a non-adhesion layer continuously on the substrate layer inline, and a series of streams ( Non-adhesive lid material can be easily manufactured at low cost in one pass. Of course, there are cases where continuous formation can not be performed inline due to the restrictions of the specifications of the gravure printing machine, the printing environment, equipment, etc. In this case, the formation can be performed offline (outline). Moreover, it is preferable to apply | coat an anchor coat layer only to the part which provides a nonadhesion layer.

  For the non-adhesive lid material, the base material can be selected depending on the type, shape and size of the article, the container to be sealed, etc., and cutting such as cutting, dividing, die-cutting can be performed to the size and size according to the purpose. . The placement position of the non-adhesive lid material is preferably a portion where the article should not adhere to the lid material, and either the lower surface (as a spreader), the upper surface or the side surface (may be provided circumferentially) of the article. It may be

  It is preferable that the non-adhesive lid material of the present invention becomes a closed container by being in close contact with the container. The close contact with the container may be performed through the hand of a person, but a machine such as an automatic sealing device may be used. These may be selected as appropriate depending on the type, shape, size, number of food, container to be sealed, equipment, environment, etc., and heat seal (heat pressure seal), face seal, adhesion with adhesive or the like, or adhesion It may be performed by a method using

More preferably, the container is a bottomed cylindrical container. In this case, it is preferable that the non-adhesive lid cover the opening of the bottomed cylindrical container and be sealed, and more preferably be sealed by a heat and pressure seal. As the heat and pressure sealing conditions, a non-adhesive lid material is placed so as to cover the opening of the bottomed cylindrical container, and the range of 120 to 250 ° C., ² to 10 kgf / cm ² , 0.5 to ² sec Then, the number of times of sealing may be appropriately selected once or twice.

  Examples of the resin used for the container include thermoplastic resins such as polyethylene resins, polypropylene resins, polyethylene terephthalate, polyvinyl chloride, polystyrene, and polyacrylonitrile. As described above, since the heat seal layer can be multi-layered, the adhesion between the lid made of a polyester base 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 to PET (first heat seal layer) / seal layer having high affinity to polystyrene (second heat seal layer) / A container such as anchor coat layer / non-adhesion layer / polystyrene (resin layer of container) can be easily produced.

  The form of the sealed container is a two-sided seal, a three-sided seal, a four-sided seal, a pillow seal, a standing pouch, an envelope sticking, a gusset, a blowout seal, a tube, a caramel package, an overhold, a fin seal, a bun package, a twist, a rocket, It may be in any of known forms such as a tetra pack, a gable top, a brick, a shibori, and a cup.

  The non-adhesive lid of the present invention is a sealed container in which the non-adhesive layer and the article are always in contact, because the non-adhesive layer is stable and the non-adhesive performance is maintained for a long time without deterioration. Good. Further, the container does not necessarily have to be in contact with the article, and it may be a sealed container provided with a gap to such an extent that the non-adhesion layer of the non-adhesive lid and the article do not contact. As a result, even if the partial or whole surface of the article physically contacts the non-adherent layer of the non-adhesive lid material by transport, transport, transport, vibration, inclination, rollover, displacement, etc. of the closed container, There is an effect that adhesion of the article can be prevented or reduced.

  The non-adhesive lid of the present invention will be described by way of examples, but is not limited thereto.

  EXAMPLES The present invention will be more specifically described below by showing Examples and Comparative Examples, but the present invention is not limited thereto. In Examples and Comparative Examples, parts represent parts by weight and% represents weight%.

Base layer 1
The coated paper (55 g / m ² ) is printed, and the printing surface is coated with OP varnish, and a 12 μm thick aluminum-deposited polyethylene terephthalate film (abbreviation: VM-PET) is urethane-based adhesive by dry lamination method. (Abbreviation: DL), after bonding the aluminum deposition side of VM-PET to the opposite side of the printing side, it is aged for 3 days at 40 ° C, “OP varnish / ink / paper / DL / VM- The base material layer 1 of the structure of "PET" was produced.

Base layer 2
The coated paper (55 g / m ² ) is printed, and the printing surface is coated with OP varnish, and a 9 μm thick aluminum foil (abbreviation: AL) is printed by a dry lamination method using a urethane adhesive. After bonding a 12 μm-thick PET film to the opposite side of the surface by using a urethane adhesive by dry lamination method to the AL surface, it is aged at 40 ° C for 3 days, The base material layer 2 of the structure of / ink / paper / DL / AL / DL / PET was produced.

[Preparation of anchor coating agent]
Anchor coat agent 1 (Example 1)
10 parts of an acrylic resin bead (average particle diameter 10 μm) is added to 50 parts of a vinylidene chloride resin solution (solid content 30%, Tg 55 ° C.), 40 parts of n-propyl acetate is added while stirring, and anchor coating is performed. Agent 1 was prepared.

Anchor coat agent 2 (Example 2)
To 60 parts of an acrylic resin solution (solid content 30%, Tg 60 ° C.), add 10 parts of acrylic resin beads (average particle diameter 10 μm), and while stirring, 10 parts of ethyl acetate, 10 parts of methyl ethyl ketone and 10 parts of isopropyl alcohol An anchor coat agent 2 was prepared by adding.

Anchor coat agent 3 (Example 3)
5 parts of acrylic resin beads (average particle diameter 8 μm) are added to 40 parts of polyester resin based solution (solid content 30%, Tg 50 ° C.), and 25 parts of n-propyl acetate and 30 parts of methyl ethyl ketone are added while stirring , And anchor coating agent 3 were produced.

Anchor coat agent 4 (Example 4)
5 parts of acrylic resin beads (average particle diameter 0.8 μm) are added to 40 parts of a vinyl chloride-vinyl acetate resin system solution (solid content 30%, Tg 77 ° C.), and 25 parts of n-propyl acetate, methyl ethyl ketone while stirring An anchor coat agent 4 was prepared by adding 30 parts.

Anchor coat agent 5 (comparative example 1)
20 parts of ethyl acetate, 10 parts of methyl ethyl ketone, and 10 parts of isopropyl alcohol were added to 60 parts of an acrylic resin system solution (solid content: 30%, Tg 60 ° C.) while stirring, to prepare anchor coating agent 5.

Anchor coat agent 6 (comparative example 2)
5 parts of acrylic resin beads (average particle diameter 8 μm) are added to 40 parts of polyester resin based solution (solid content 30%, Tg-30 ° C.), and 25 parts of n-propyl acetate and 30 parts of methyl ethyl ketone are added while stirring Then, anchor coating agent 6 was produced.

[Preparation of non-adhesion layer coating solution]
Non-adherent layer coating solution 1 (Production Example 1)
To 90 parts of ethanol, 10 parts of hydrophobized dry silica (average particle diameter 0.2 μm, WACKER HDK H18, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) is added while stirring, and non-adhesion layer coating liquid 1 is added. Made.

Non-adhesion layer coating solution 2 (Production Example 2)
10 parts of wet method silica (average particle diameter 6.2 μm, SIPERNAT D10, manufactured by EVONIK) having been hydrophobized was added to 90 parts of ethanol while stirring to prepare a non-adhesion layer coating solution 2.

Non-adhesion layer coating solution 3 (Production Example 3)
10 parts of hydrophobized talc ¹⁾ was added to 90 parts of ethanol while stirring to prepare a non-adhesion layer coating liquid 3.
1): A solution of 10% solution of silicone oil (KF-96-50cs, Shin-Etsu Chemical Co., Ltd.) in 10% methylene chloride is sprayed to 3% by weight of talc, and calcinated at 100 ° C. for 2 hours, Surface-coated talc (average particle size 6 μm)

Non-adhesion layer coating solution 4 (Production Example 4)
Add 8 parts of hydrophobized talc and 2 parts of non-hydrophobicized wet silica (average particle diameter 6.2 μm, SIPERNAT 383DS, manufactured by EVONIK) to 90 parts of ethanol while stirring and do not adhere Layer coating solution 4 was prepared.

[Preparation of heat sealing agent for coating]
Heat Sealant 1 (Production Example 5)
To 80 parts of ethylene vinyl acetate emulsion (solid content 30%, Tg-25 ° C), add 20 parts of WA 735 (alcohol solvent, Tokyo Ink Co., Ltd.) while stirring to prepare the heat sealing agent 1 did.

Heat Sealant 2 (Production Example 6)
To 50 parts of a polyester resin solution (solid content 30%, Tg 5 ° C.), 10 parts of an acrylic resin bead (average particle diameter 30 μm) is added and 40 parts of n-propyl acetate is added while stirring to obtain a heat sealing agent 2 was produced.

Heat Sealing Agent 3 (Production Example 7)
To 60 parts of an acrylic resin solution (solid content 30%, Tg 30 ° C.), add 10 parts of acrylic resin beads (average particle diameter 30 μm), and while stirring, 10 parts of ethyl acetate, 10 parts of methyl ethyl ketone, n-propyl acetate 10 The heat sealing agent 3 was produced by adding parts.

(Example 5)
The heat seal agent 1 (abbreviation: HT1) in the first unit, the anchor coat agent 1 (abbreviation: AC1) in the second unit, and the third unit in the base layer 1 using a five-color gravure printing machine Non-adhesion layer coating liquid 1 (abbreviation: non-adhesion layer 1) was printed and wound up to prepare a non-adherent lid 1. At this time, the heat sealing agent 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 1 is TA52. at (an alcohol-based solvent, manufactured by Tokyo ink Co.) was diluted, each coating ^{weight, 3.0g / m 2, 0.9g /} m 2, was 0.1 g / ^{m 2.} Thereby, the non-adhesive lid 1 became a lid of the configuration of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 1".

(Example 6)
Non-adhesive lid 2 was produced under the same conditions as Example 5 except that anchor coating agent 1 was changed to anchor coating agent 2 (abbreviation: AC2). At this time, the heat sealing agent 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 2 is SL9155 (non-toluene-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 1 is TA52. It diluted with (alcohol solvent, Tokyo Ink Co., Ltd. product), and the coating amount was 3.2 g / m < ² >, 1.0 g / m < ² >, 0.15 g / m < ² >, respectively. Thereby, the non-adhesive lid 2 became a lid of the configuration of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC2 / non-adhesive layer 1".

(Example 7)
Non-adhesive lid 3 was produced under the same conditions as Example 5 except that anchor coating agent 1 was changed to anchor coating agent 3 (abbreviation: AC3). At this time, the heat sealing agent 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 3 is SL9155 (non-toluene-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 1 is TA52. at (an alcohol-based solvent, manufactured by Tokyo ink Co.) was diluted, each coating ^{weight, 4.0g / m 2, 1.1g /} m 2, was 0.2 g / ^{m 2.} Thereby, the non-adhesive lid 3 became a lid of the configuration of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC3 / non-adhesive layer 1".

(Example 8)
The non-adhesive lid 4 was produced under the same conditions as Example 5 except that the anchor coat agent 1 was changed to the anchor coat agent 4 (abbreviation: AC4). At this time, the heat sealing agent 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 4 is SL9155 (non-toluene-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 1 is TA52. at (an alcohol-based solvent, manufactured by Tokyo ink Co.) was diluted, each coating ^{weight, 3.5g / m 2, 1.1g /} m 2, was 0.2 g / ^{m 2.} Thereby, the non-adhesive lid 4 became a lid of the configuration of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC4 / non-adhesive layer 1".

(Example 9)
A non-adhesive lid 5 was produced under the same conditions as in Example 5 except that the non-adhesive layer coating solution 1 was changed to a non-adhesive layer coating solution 2 (abbreviation: non-adhesive layer 2). At this time, the heat sealing agent 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesion layer coating liquid 2 is TA52. at (an alcohol-based solvent, manufactured by Tokyo ink Co.) was diluted, each coating ^{weight, 4.0g / m 2, 1.1g /} m 2, was 0.2 g / ^{m 2.} Thereby, the non-adhesive lid 5 became a lid of the configuration of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 2".

(Example 10)
The non-adhesive lid 6 was produced under the same conditions as in Example 5 except that the non-adhesive layer coating solution 1 was changed to the non-adhesive layer coating solution 3 (abbreviation: non-adhesive layer 3). At this time, the heat sealing agent 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesion layer coating liquid 3 is TA52. at (an alcohol-based solvent, manufactured by Tokyo ink Co.) was diluted, each coating ^{weight, 2.5g / m 2, 1.1g /} m 2, was 0.2 g / ^{m 2.} Thereby, the non-adhesive lid 6 became a lid of the configuration of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 3".

(Example 11)
The non-adhesive lid 7 was produced under the same conditions as in Example 5 except that the non-adhesive layer coating solution 1 was changed to the non-adhesive layer coating solution 4 (abbreviation: non-adhesive layer 4). At this time, the heat sealing agent 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 1 is SL9155 (non-toluene-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesion layer coating liquid 4 is TA52. at (an alcohol-based solvent, manufactured by Tokyo ink Co.) was diluted, each coating ^{weight, 3.5g / m 2, 1.1g /} m 2, was 0.2 g / ^{m 2.} Thereby, the non-adhesive lid 7 became a lid of the configuration of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC1 / non-adhesive layer 4".

(Example 12)
Using a five-color gravure printing machine, the first unit, the heat sealing agent 2, the second unit, the heat sealing agent 3, the third unit, the anchor coating agent 1, the fourth unit on the base layer 2 The non-adhesive layer coating solution 1 was printed and wound up to prepare a non-adhesive lid 8. At this time, heat seal agent 2 is SL9155 (non-toluene type solvent, manufactured by Tokyo Ink Co., Ltd.), heat seal agent 3 is PU515 (non-toluene type solvent, manufactured by Tokyo Ink Co., Ltd.), anchor coat agent 1 is SL9155 ( The non-toluene solvent, Tokyo Ink Co., Ltd., and non-adhesion layer coating solution 1 were diluted with TA 52 (alcohol solvent, Tokyo Ink Co., Ltd.), and the coating amount was 1.0 g / m, respectively. ² , 4.0 g / m ² , 1.0 g / m ² and 0.5 g / m ² . As a result, the non-adhesive lid 8 became a lid of the configuration of "OP varnish / ink / paper / DL / AL / DL / PET / HT2 / HT3 / AC1 / non-adhesive layer 1".

(Example 13)
The coated paper (55 g / m ² ) is printed with a printing ink by gravure printing, and further coated with an OP varnish on the printing surface, then using a urethane adhesive on the non-printing surface by a dry lamination method. While laminating an aluminum foil with a thickness of 15 μm, and then applying an isocyanate primer (abbreviation: PL) on the aluminum foil, extruding and laminating a low density polyethylene (abbreviation: LDPE) to a film thickness of 15 μm. Applied and laminated. Next, a hot melt adhesive (X40A, manufactured by Tokyo Ink Co., Ltd., abbreviation: HM) was gravure coated on LDPE and laminated to 25 g / m ² . Thus, a laminate having a configuration of “OP varnish / ink / paper / DL / AL / PL / LDPE / HM” was produced. Furthermore, the anchor coating agent 1 and the non-adhesion layer coating liquid 1 were sequentially coated on the coated side of the laminate with the coating machine using a coating machine, and wound up to prepare a non-adherent lid member 9. The anchor coating agent 1 is diluted with SL9155 (non-toluene type solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesion layer coating liquid 1 is diluted with TA52 (alcohol solvent, manufactured by Tokyo Ink Co., Ltd.). It was 1.0 g / m ² and 0.3 g / m ² . Thereby, the non-adhesive lid 9 became a lid of the configuration of "OP varnish / ink / paper / DL / AL / PL / LDPE / HM / AC1 / non-adhesive layer 1".

(Comparative example 3)
Non-adhesive lid 10 was produced under the same conditions as Example 5 except that anchor coating agent 1 was changed to anchor coating agent 5 (abbreviation: AC5). At this time, the heat sealing agent 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 5 is SL9155 (non-toluene-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 1 is TA52. at (an alcohol-based solvent, manufactured by Tokyo ink Co.) was diluted, each coating ^{weight, 3.0g / m 2, 1.0g /} m 2, was 0.1 g / ^{m 2.} Thereby, the non-adhesive lid 10 became a lid of the configuration of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC5 / non-adhesive layer 1".

(Comparative example 4)
Non-adhesive lid 11 was produced under the same conditions as Example 5 except that anchor coating agent 1 was changed to anchor coating agent 6 (abbreviation: AC6). At this time, the heat sealing agent 1 is WA735 (alcohol-based solvent, manufactured by Tokyo Ink Co., Ltd.), the anchor coating agent 6 is SL9155 (non-toluene-based solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesive layer coating liquid 1 is TA52. at (an alcohol-based solvent, manufactured by Tokyo ink Co.) was diluted, each coating ^{weight, 5.0g / m 2, 1.0g /} m 2, was 0.1 g / ^{m 2.} Thereby, the non-adhesive lid 11 became a lid of the configuration of "OP varnish / ink / paper / DL / VM-PET / HT1 / AC6 / non-adhesive layer 1".

(Comparative example 5)
The non-adhesive lid 12 was produced under the same conditions as Example 5 except that the anchor coating agent was not used. At this time, the heat sealing agent 1 is diluted with WA 735 (alcohol solvent, manufactured by Tokyo Ink Co., Ltd.), and the non-adhesion layer coating liquid 1 is diluted with TA 52 (alcohol solvent, manufactured by Tokyo Ink Co., Ltd.), and coated. The amount was 3.5 g / m ² , 0.1 g / m ² . Thereby, the non-adhesive lid 12 became a film of the configuration of "OP varnish / ink / paper / DL / VM-PET / HT1 / non-adhesive layer 1".

(Comparative example 6)
The non-adhesive lid 13 was produced under the same conditions as in Example 12 except that the anchor coating agent was not used. At this time, the heat sealing agent 2 is SL9155 (non-toluene type solvent, manufactured by Tokyo Ink Co., Ltd.), the heat sealing agent 3 is PU 515 (non toluene type solvent, manufactured by Tokyo Ink Co., Ltd.), the non-adhesion layer coating liquid 1 is TA52 at (an alcohol-based solvent, Tokyo ink Co., Ltd.) was diluted, each coating ^{weight, 1.0g / m 2, 5.0g /} m 2, was 0.5 g / ^{m 2.} Thereby, the non-adhesive lid 13 became a film of the configuration of "OP varnish / ink / paper / DL / AL / DL / PET / HT2 / HT3 / non-adhesive layer 1".

(Comparative example 7)
A silicone resin (KF-96H-30 Man cs, Shin-Etsu Chemical Co., Ltd. product, abbreviation: silicone) is applied to a 20 μm thick OPP film (abbreviation: OPP) and aged for 3 days at 40 ° C. An adhesive lid 14 was produced. At this time, the film thickness of the silicone resin was 0.3 μm. Thereby, the non-adhesive lid 14 became a film of the configuration of “OPP / silicone”.

  With respect to the non-adhesive lid materials of Examples 5 to 13 and Comparative Examples 3 to 7, the water repellency, the non-growing property to yogurt, the heat sealability, and the durability were evaluated, and are shown in Table 1.

<Water repellant>
The contact angle was measured for the non-stick layer of the non-stick lid. For measurement, a portable contact angle meter PCA-1 (manufactured by Kyowa Interface Science Co., Ltd.) was used. 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, x: less than 90 °.

Yogurt non-adherence
Place 1 drop of yoghurt (trade name: Hadidas Yogurt, manufactured by Morinaga Milk Industry Co., Ltd.) on the non-adhering layer of the non-adhesive lid placed horizontally, lift one side of the non-adhesive lid slowly and lean At that time, the angle at which the yoghurt rolled off was observed. The smaller the angle, the less the yogurt adheres and the better the yogurt non-adhesion.
◎: 30 ° or less, :: 30 ° to 60 ° or less, Δ: 60 ° to 90 ° or less, x: 90 ° or more.

<Heat sealability>
The ring seal portion is long after heat sealing (ring sealing) in a ring shape at 220 ° C. for 1 second under a load of 3 kgf / cm ^{2 with} a non-adhesive lid and a polystyrene sheet having a thickness of 0.15 mm. It was made into a strip shape of 15 mm width so that it might become substantially perpendicular to a side, and it was set as the sample piece. This sample piece is pulled with a universal tensile tester (RTE-1210, manufactured by Orientec Co., Ltd.) at a peeling angle of 180 ° and a tensile speed of 300 mm / min, and the maximum load at peeling is sealed. It was measured as (g). The higher the seal strength, the better the heat sealability.
◎: 300 g or more, :: less than 300 g 100 g or more, Δ: less than 100 g 50 g or more, x: less than 50 g.

<Durability>
Place a drop of yoghurt (trade name: Hadidas Yogurt, manufactured by Morinaga Milk Industry Co., Ltd.) on the non-adhering layer of the non-adhesive lid material installed horizontally, cover it to prevent the yogurt from drying, and leave it for 24 hours It stood still in the refrigerator. After that, take out the non-adhesive lid from inside the refrigerator, remove the cover, and slowly lift one side of the non-adhesive lid, and when it is tilted, yoghurt rolls off from the non-adhesive layer of the non-adhesive lid. The appearance was observed visually. The term "excellent in durability" means that even when the content is in contact with the non-adhesive layer of the non-adhesive lid material for a long time, deterioration of the non-adhesive performance does not occur and continues. Therefore, the thing in which the yogurt rolls down from the non-adhesion layer of the non-adhesive lid material made durability excellent.
◎: Yogurt was rolling off, no adhesion (excellent durability), x: yogurt was not rolling off, and was evaluated as it was (as durability is poor).

<Overall evaluation>
Of the water repellency, yogurt nonadhesion, heat sealability, and durability, all those with an evaluation result of "o" are "o" as an overall evaluation, and those with an evaluation result of either "o" or "o" are general. The evaluations were "○", and those with one or more "Δ" were evaluated as "Δ" as the comprehensive evaluation, and those with one or more "×" were "X" as the comprehensive evaluation.

  According to Table 1, the non-adhesive lids of Examples 5 to 13 are superior to the non-adhesive lids of Comparative Examples 3 to 7 in water repellency, yogurt non-adhesiveness, heat sealability, and durability. It is clear. In Comparative Example 3 which is an example using an anchor coating agent which does not contain an unevenness imparting agent, the water repellency and the non-adhesion property of yogurt are inferior, and the yogurt adheres to the lid material. With regard to durability as well, since yoghurt adheres to the non-adhered layer of the lid material in the first place, it will continue to adhere as it is even when it is in contact for a long time. Comparative Example 4, which is an example using an anchor coating agent containing a hydrophobic resin having a low glass transition temperature, although having some water repellency, has poor non-adhering properties to yogurt as in Comparative Example 3, and has poor durability. Further, Comparative Examples 5 and 6, which are examples not including an anchor coat layer, are inferior in water repellency and non-adherence to yogurt as in Comparative Example 3, and yogurt adheres to the lid material. The comparative example 7 which is an example which apply | coated the silicone resin which is a prior art example is completely ineffective in non-adhesiveness.

  According to the non-adhesive lid 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 to which an article does not adhere. In addition, depending on the product, application, and form, the nonadhesion requirement may differ, and in such a case, the nonadherent lid material by lowering the dot area ratio of the gravure plate or adjusting the plate depth. You can easily control the adhesion between food and food. In addition, since the container is very durable, the cup-like container is filled with yogurt or the like, sealed with the non-adhesive lid material of the present invention, and circulated as a product, vibration or displacement during transport, transportation, etc. Even if yoghurt comes in contact with the lid material for a long time due to overturning etc., then when yoghurt etc. is placed directly, yoghurt etc. naturally separates from the lid material and does not continue to adhere, There is no risk of deterioration in appearance when the product is displayed, etc. or there is no risk of waste due to being able to use up the contents when the cover material is opened by the consumer, or contamination of fingers, clothes, or tables etc. As a result, the lid on the inner surface can be used for displaying a campaign, how to use the food, how to eat it, information for customers, etc. Furthermore, since it can be coated by a gravure printing method, it can be widely applied not only to food applications, but also to various water-repellent lid materials for daily use applications, medical pharmaceutical applications, industrial materials applications, etc.

Claims (7)

A non-adhesive lid material having a configuration in which a heat seal layer, an anchor coat layer and a non-adhesion layer are laminated in this order on at least one side of a base material layer,
The anchor coat layer contains a hydrophobic resin having a glass transition point (Tg) of 50 ° C. or more and less than 100 ° C. , and an unevenness imparting agent which is a resin bead having an average particle diameter of 0.8 to 30 μm. Sodea is,
The hydrophobic resin is 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 At least one selected from resin and (meth) acrylic resin,
The non-adhesive lid material , wherein the heat seal layer is a layer containing a thermoplastic resin having a glass transition point (Tg) of -50 ° C to 30 ° C and not containing a filler . The non-adhesive lid according to claim 1, wherein the base material layer is at least one selected from paper, aluminum foil, plastic film or sheet. The non-adhesive lid material according to claim 1 or 2, wherein the anchor coat layer and the non-adhesive layer are layers formed by coating according to a gravure printing method using a multicolor gravure printing machine. . In a method of manufacturing a non-adhesive lid having a configuration in which a heat seal layer, an anchor coat layer and a non-adhesion layer are laminated in this order on at least one side of a substrate layer,
Apply an anchor coating agent containing a hydrophobic resin having a glass transition point (Tg) of 50 ° C. or more and less than 100 ° C., and an unevenness imparting agent which is a resin bead having an average particle diameter of 0.8 to 30 μm. Forming the anchor coat layer;
Applying a coating liquid containing hydrophobized inorganic particles to form the non-adhesive layer;
The hydrophobic resin is 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 At least one selected from resin and (meth) acrylic resin,
The method for producing a non-adhesive lid material, wherein the heat seal layer contains a thermoplastic resin having a glass transition point (Tg) of -50 ° C or more and 30 ° C or less and does not contain a filler. The said base material layer is at least one chosen from paper, aluminum foil, a plastic film, or a sheet, The manufacturing method of the non-adhesive lid material of Claim 4 characterized by the above-mentioned. The step of forming the anchor coat layer is a coating step by gravure printing using one unit of a multicolor gravure printing machine,
The non-adhesive lid material according to claim 4 or 5, wherein the step of forming the non-adhesive layer is a coating step by gravure printing using another unit of the multicolor gravure printer. Manufacturing method. A closed container comprising the non-adhesive lid according to any one of claims 1 to 3 and a container.