JP2009069302A - Wraparound label and container with the label attached thereto - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wraparound label having biodegradability, excellent gas barrier performance and easily separable. <P>SOLUTION: The wraparound label wrapped around the outer peripheral surface of a drum part of a container includes: a base material film 10; and an alkali-soluble thermosensitive adhesive layer 20 provided at least on both ends of the label, wherein the base material film is a gas barrier film obtained by providing a gas barrier layer 15 on a biodegradable film 11, and the alkali-soluble thermosensitive adhesive layer is soluble in an aqueous solution with an alkali concentration of 1.5 w/w% at 85°C°-90C° for 15 minutes. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a body-wound label to be wound around and attached to the outer peripheral surface of the body portion, a container with a body-wound label around which the body-wound label is wound, and more specifically, excellent in gas barrier properties, biodegradability, excellent in alkali treatment, and disposal The present invention relates to a body-wound label that facilitates material processing, and a container with a body-wound label to which the body-wound label is attached.

  2. Description of the Related Art Conventionally, a label printed with a trade name, a pattern, or the like is wound around an outer periphery of a container body and used as a container for liquids such as soft drinks. As such labels, various synthetic resin films such as polypropylene film, polyester film, polystyrene film and the like are widely used because they are excellent in water resistance, durability and inexpensiveness. Usage development is underway. Here, the biodegradable plastic generally has almost the same physical properties as ordinary plastic, but after use, it is a polymer that is rapidly degraded by microorganisms when discarded in the natural environment such as soil or water. A compound.

  As a body-wound label using such a biodegradable plastic, a biodegradable pressure-sensitive adhesive label body formed by laminating a pressure-sensitive adhesive base film made of a biodegradable polymer layer and a pressure-sensitive adhesive layer, and paper and / or non-biodegradable A release sheet in which a release agent layer is formed on a release sheet substrate made of an adhesive polymer, and the biodegradable pressure-sensitive adhesive label body and the release sheet peel from the pressure-sensitive adhesive layer of the biodegradable pressure-sensitive adhesive label body There is a biodegradable pressure-sensitive adhesive label that is laminated so as to be in contact with the release agent layer of the sheet (Patent Document 1). The biodegradable pressure-sensitive adhesive label may cause global warming due to carbon dioxide if incinerated after use, and may destroy the natural environment or the ecosystem in the soil if discarded in the soil. When the plastic substrate is separated and collected from the label main body, it is made in view of the fact that the separate collection of the plastic substrate is expensive and inferior in marketability. As a biodegradable polymer, a linear polyester of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, a lactic acid biodegradable polymer obtained by ring-opening polymerization of lactide, a natural polymer such as starch, polysaccharide, chitin, etc. And biodegradable polycaprolactone obtained by ring-opening polymerization of ε-caprolactone, polylactic acid, and the like are disclosed. The biodegradable pressure-sensitive adhesive label is formed by forming a release agent layer on a release sheet such as paper and laminating a pressure-sensitive adhesive layer and a pressure-sensitive adhesive label base material thereon, and the pressure-sensitive adhesive label base material is the biodegradable material. It is composed of a polymer.

  On the other hand, there is a cylindrical shrink label using a biodegradable plastic. It consists of a biodegradable film that is uniaxially or biaxially stretched and has a sealing property with a solvent, so it is formed as a cylindrical shrink label by a center seal with a solvent, and the circumferential direction of this cylindrical shrink label coincides with the direction of heat shrinkage. It is the made biodegradable shrink label (patent document 2). A polylactic acid film is disclosed as a biodegradable film, and dioxolane, cyclohexane, etc. are disclosed as a center seal solvent.

  On the other hand, according to the Recycling Law “Independent Design Guidelines for Type 2 Designated PET Bottles” by the PET Bottle Recycling Promotion Council, when immersed in a cleaning solution of 1.5 w / w% alkali concentration for 15 minutes at 85 ° C. to 90 ° C. The label is peeled off and the adhesive is required not to remain in the bottle. This is to obtain a high-purity raw material without leaving impurities such as labels and paste in the pulverized product during container recycling.

There is also a body-wound label for the purpose of peelability by such an alkaline solution (Patent Document 3). In Patent Document 3, an alkali-soluble heat-sensitive adhesive layer is formed on at least both ends of the back surface of a label substrate made of a degradable stretched film, and the label and the container are bonded via the alkali-soluble heat-sensitive adhesive layer. It is a body-wound label that winds the label in the circumferential direction of the adhesive on the label peeling surface on the container side after immersion for 15 minutes at 85 ° C. to 90 ° C. in an aqueous solution having an alkali concentration of 1.5 w / w%. The residue can be removed.
JP-A-7-44103 JP 2006-58647 A JP 2005-263294 A

  However, biodegradable plastics inherently have the property of being naturally decomposable by microorganisms, and may have poor oxygen barrier properties, water vapor barrier properties, heat resistance, and impact resistance. For this reason, it is difficult to use for products that require long-term storage. Although the said patent document 1, patent document 2, and patent document 3 disclose a biodegradable plastic, there is no description regarding gas barrier properties, such as oxygen barrier property and water vapor | steam barrier property.

  On the other hand, it is necessary to secure an adhesive strength that does not peel from the container in the distribution process and a peel strength that can be easily detached from the container after use. If a gas barrier layer is simply laminated on a biodegradable film, if the gas barrier layer is thick, the amount of biodegradable plastic used for the entire label is reduced, and the biodegradable characteristics may not be fully exhibited. In addition, as a result of increasing the thickness of the gas barrier layer, the weight of the entire label increases, and it is necessary to increase the amount of adhesive used in order to avoid detachment of the label from the container. Separation may be difficult.

  In addition, biodegradable films are inferior in heat resistance and impact resistance as described above, so they may not be suitable for laminating gas barrier layers. Even if they can be laminated, if they are inferior in mechanical strength, they are attached to containers. The peeled label may peel off during the distribution process. This is also the case with the body-wrapped label described in Patent Document 3, and even if a gas barrier layer is simply laminated on the biodegradable film, the predetermined adhesive strength may not be ensured, whereas if the adhesive strength can be ensured, In some cases, it is inferior in decomposability with an alkaline solution. In order to make a self-winding label that conforms to the above-mentioned voluntary design guidelines of the recycling law, it is required that the adhesive be soluble under specified conditions. However, the gas barrier properties sufficient for maintaining quality, biodegradability after disposal, and labels in the distribution process It is not easy to ensure adhesive strength and satisfy the alkali treatment appropriateness at the time of disposal.

  In addition, the pressure-sensitive adhesive used in the body-wrapped label of Patent Document 1 requires an off-line coating process when coated on a base material, and also has release properties (separator) because it has adhesiveness at room temperature. This is disadvantageous in terms of economy, and there is a demand for disposal of release paper (separator), which is one of the environmental problems.

  Further, as in Patent Document 2, a container formed by externally fitting a cylindrical label on a container performs a process of covering the label material intermittently, so that the operation rate is lowered or a shift occurs when the label material is covered. In some cases, the correct labeling may not be performed on the appropriate part of the container. On the other hand, it is convenient if the label can be directly attached to the container without forming a cylindrical label in advance. However, an adhesive method using a cold glue adhesive such as casein glue or an adhesive label is applied to a glass bottle such as a beer bottle. This is a method of wearing, and the adhesive sticks out and floats easily, and the adhesion time is long.

  In addition, the biodegradable plastic film may be inferior in adhesion to the printing ink and the pressure-sensitive adhesive as compared with non-biodegradable plastic films such as polyester and polypropylene. It is common to print letters, figures, symbols, designs, etc. on the body-wound label for decoration, shading, and content display, but biodegradable plastic film is used as the base film for the body-wound label Then, when the used label is peeled from the container by hand, the resin component and the adhesive component of the printing ink remain on the container side, which may impair biodegradability.

  In view of such a current situation, the present invention provides a body-wound label that has biodegradability, is excellent in gas barrier properties, and can be easily peeled off.

  The present invention also provides a body-wrapped label that can be wound around and mounted on the outer peripheral surface of the body of the container without forming the label into a cylindrical shape.

  Another object of the present invention is to provide a container to which the above-mentioned body-wound label is attached.

  As a result of detailed examination of the body-wound label that is wound around and mounted on the outer peripheral surface of the body of the container, the present inventor made a gas barrier film in which a gas barrier layer is provided on a biodegradable film as a base film, and an alkali-soluble heat-sensitive adhesive. By providing an agent layer, it ensures a stable label adhesive strength that does not detach in the distribution process, and can be easily peeled off by alkali treatment after use, by using a specific biodegradable film The present inventors have found that gas barrier properties can be secured without reducing biodegradability, and have completed the present invention.

  In addition, even when the container is made of biodegradable plastic and is inferior in gas barrier property, the gas barrier property of the container can be improved by covering it with a body-wrapped label having excellent gas barrier property. The present inventors have found that a container excellent in the storage performance of contents can be provided simply by coating the film.

  That is, the present invention is a body-wound label that is wound around and mounted on the outer peripheral surface of a body portion of a container, and comprises a base film and an alkali-soluble heat-sensitive adhesive layer provided at least at both ends of the label, A gas barrier film in which a gas barrier layer is provided on a biodegradable film, and the alkali-soluble heat-sensitive adhesive layer is dissolved in an aqueous solution having an alkali concentration of 1.5 w / w% at 85 ° C. to 90 ° C. for 15 minutes. Provide a label.

  The present invention also provides a container with a body-wound label in which the body-wound label is attached to the container.

  The body-wound label of the present invention uses a biodegradable plastic as a base film, so that even if it is incinerated, it does not damage the incinerator, and it is easy to dispose of waste without generating harmful gases. Excellent. Moreover, if the container is inferior in gas barrier properties, the gas barrier properties can be easily provided. Moreover, it is possible to ensure an adhesive strength that does not cause the labels to peel off during the distribution process.

  Since the present invention has an alkali-soluble heat-sensitive adhesive layer, the label can be easily peeled off by using an alkaline solution after use, and the container is excellent in recyclability.

  Since the body-wound label of the present invention can be wound around a container and attached, the process of forming the label into a cylindrical shape is not required, the production process can be simplified, and the cost can be reduced. In addition, the use of release paper (separator) is not required, and less waste is required, which is environmentally friendly. The adhesive layer can be coated on the label in the printing process of the base film, and the productivity is excellent.

  Moreover, according to the body-wound label of the present invention, since the adhesive strength between the base film / printing ink resin and the adhesive strength between the base film / adhesive layer is excellent, the label has an adhesive strength that does not peel off during distribution. There is adhesive strength that does not peel even if the attached container is submerged, and it has easy peelability that can be easily peeled off by hand after use, printing ink resin on the surface of the container after peeling the label, No adhesive remains and is excellent in biodegradability.

The body-wrapped label of the present invention is a body-wrapped label that is wound around and mounted on the outer peripheral surface of the body of the container, and includes a base film and an alkali-soluble heat-sensitive adhesive layer provided at least at both ends of the label. A gas barrier film in which a gas barrier layer is provided on a biodegradable film. The gas barrier layer may be formed by forming an inorganic oxide vapor-deposited film. Furthermore, the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ , R ² represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M And a gas barrier composition obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by formula (II)), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A gas barrier coating film may be provided. This is because it is excellent in biodegradability and gas barrier properties, has printability, and can form an alkali-soluble heat-sensitive adhesive layer.

  Moreover, the alkali-soluble heat-sensitive adhesive layer used for the body-wound label of the present invention may be an alkali-soluble delayed tack adhesive mainly composed of an ethylene-vinyl acetate copolymer resin. According to the alkali-soluble heat-sensitive adhesive, the label does not come off in the distribution process, and after use, an alkaline aqueous solution can be used to easily peel between the label and the label and between the container and the label.

  In the body-wrapped label of the present invention, a printing layer may be laminated on the inner side of the base film.

  Hereinafter, the body-wound label and the container with the body-wound label of the present invention will be described.

(1) Structure of body-wound label FIG. 1 shows a preferred embodiment of the body-wound label of the present invention. The body-wound label of the present invention has an attachment part (W) for attaching to a container. FIG. 1 shows a base film (10) composed of a biodegradable film (11) and a gas barrier layer (15), and an alkali-soluble heat-sensitive adhesive layer (20). This is an embodiment in which the alkali-soluble heat-sensitive adhesive layer (20) is formed only on the attachment part (W).

  Moreover, the aspect which has a design printing layer (30) is shown in FIG. In FIG. 2, the attached portion (W) is not provided with the print layer (30), and the alkali-soluble heat-sensitive adhesive layer (20) is formed inside the label of the base film (10). . However, the alkali-soluble heat-sensitive adhesive layer (20) may be formed on the printing layer.

  FIG. 3 shows an embodiment having a primer layer (40) on the label surface of the base film (10) of the body-wound label of FIG. In addition, the biodegradable film and gas barrier layer which comprise a base film (10) are not limited to a single layer, All may be a lamination | stacking of 2 or more.

  In the present invention, the size of the body-wound label can be appropriately selected according to the size of the container to be attached. Similarly, the size of the attachment part to which the adhesive is applied can be appropriately selected according to the usage mode of the label attachment device, for example.

  In the present invention, the alkali-soluble heat-sensitive adhesive layer is formed at least at the start and end portions inside the body-wrapped label, but the alkali-soluble heat-sensitive adhesive layer is limited to the start and end portions of the body-wrap label. It is not a thing. Accordingly, the alkali-soluble heat-sensitive adhesive layer may be formed on the entire inner surface of the body-wrapped label, or the alkali-soluble heat-sensitive adhesive layer may be formed in a frame shape over the entire inner periphery of the body-wrapped label. Further, the alkali-soluble heat-sensitive adhesive layer at the start end of the body-wrapped label and the alkali-soluble heat-sensitive adhesive layer at the end need not have the same shape.

  The body-wrapped label of the present invention is not limited to an adherend. As long as it can be bonded with an alkali-soluble heat-sensitive adhesive, it can be applied to containers made of various materials such as metals and synthetic resins, and its use is not limited. This is because the wound label after use has biodegradability and is excellent in environmental conservation. Therefore, the types of items stored in the container are not limited. Soft drinks, condiments, sake (Japanese sake, barley liquor, sparkling wine, wine, shochu, distilled liquor, etc.), cooking oil, cosmetic containers, toiletries, It can be suitably used as a wound label used for containers such as a dehumidifier container, a detergent container, an ampule bottle, an energy drink, an eye drop container, a medicine container, and a dessert.

(2) Base film The base film constituting the body-wound label of the present invention is a gas barrier film in which a gas barrier layer is provided on a biodegradable film. The surface of the base film may be subjected to conventional surface treatment such as corona discharge treatment, plasma treatment, flame treatment, and acid treatment in order to improve printability.

(I) Biodegradable film The biodegradable film constituting the base film has biodegradability and strength sufficient to provide a vapor-deposited film of inorganic oxide or a gas barrier coating film. It is a film that can withstand the conditions for forming a vapor deposition film of an object and can be well maintained without impairing the properties of the vapor deposition film of an inorganic oxide, and has a mechanical strength as a body wound label, and an alkali-soluble heat-sensitive adhesive layer It is limited to what can form.

  In general, the biodegradable material constituting the biodegradable film has a property that can be degraded by microorganisms, and has a high microorganism production system such as polyhydroxybutyrate and poly (hydroxybutyrate / hydroxyhexanoate). Molecule, cellulose acetate, natural polymer such as chitosan / cellulose / starch, esterified starch, poly-L-lactide (poly-L-lactic acid), (polylactic acid / polybutylene succinate) block copolymer, poly ( There are chemical synthetic polymers such as ethylene terephthalate / succinate) and polyvinyl alcohol, and any of them can be suitably used. In particular, (co) polymers of lactic acid, butyric acid, lactide, such as poly-L-lactide (poly-L-lactic acid), and modified products thereof, ring-opening (co) polymers of lactones, such as poly-ε-caprolactone, and the like Modified products, succinate polymers such as polybutylene succinate / polyethylene succinate and aliphatic polyester films such as modified products thereof are suitable because they are easily available and have excellent heat resistance and mechanical strength.

  The polylactic acid comprising the above poly-L-lactide includes glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxy-n-butyric acid, 2 as copolymerization components without departing from the spirit of the present invention. -Bifunctional aliphatic hydroxycarboxylic acids such as hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-methyllactic acid and 2-hydroxycaproic acid, and lactones such as caprolactone, butyrolactone and valerolactone Other hydroxycarboxylic acid units may be included. Further, as an additive, a chain extender and, if necessary, a heat stabilizer, a light stabilizer, a light absorber, a lubricant, a plasticizer, an inorganic filler, a colorant, a pigment, and the like may be added. Examples of the polymerization method for the resin include polymerization by a method such as dehydration condensation polymerization and ring-opening polymerization.

  The biodegradable film is preferably a film obtained by stretching a biodegradable plastic as a film raw material uniaxially or biaxially. This is because heat shrinkability can be imparted by stretching. One or more of the above plastics are used to form a single layer using an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, or other film forming methods, or Multi-layered film by co-extrusion using two or more kinds of resin, or formed by mixing two or more kinds of plastics, and stretched uniaxially or biaxially by tenter method or tubular method A biodegradable film can be obtained. For example, a biaxially stretched film composed mainly of an aliphatic polyester such as a polylactic acid-based polymer is biaxially formed by a roll method, a tenter method, a tubular method, etc. after cooling a sheet-like material extruded from a T-die or the like. It can manufacture by the method of extending | stretching.

  In addition, the heat shrinkage rate in this invention is a heat shrinkage rate by 100 degreeC hot water, Comprising: The heat shrinkage rate of an extending | stretching direction shall follow a following formula. Therefore, in the case of a longitudinally uniaxially stretched film, since the shrinking direction is the film flow direction, the thermal shrinkage rate in the flow direction is 5 to 85%, and in the case of a laterally uniaxially stretched film, the film shrinks in the film width direction. The heat shrinkage ratio in the film width direction is 5 to 85%. In the case of a biaxially stretched film, for example, there are a sequential biaxial stretching method and a simultaneous biaxial stretching method. The stretching conditions are appropriately selected in the range of 5 to 85% in the vertical direction and 5 to 85% in the horizontal direction.

本発明において、生分解性フィルムの膜厚としては、６〜１００μｍ、より好ましくは、９〜５０μｍが好ましい。この範囲であれば、胴巻きラベルとしての剛性や強度を確保しうるからである。

In the present invention, the thickness of the biodegradable film is preferably 6 to 100 μm, more preferably 9 to 50 μm. This is because within this range, rigidity and strength as a body-wound label can be secured.

  The biodegradable film may be a commercial product. For example, as a biodegradable film produced by polymerizing lactic acid, it is produced by polymerizing lactic acid obtained by fermenting starch or saccharides made from corn or the like. “Ecology” manufactured by Mitsubishi Plastics Co., Ltd. can be preferably used.

  Furthermore, as the biodegradable film used in the present invention, a composite sheet obtained by laminating a nonwoven fabric made of a polylactic acid resin obtained from corn starch may be used. Examples of the biodegradable nonwoven fabric include “Hybon” sold by Tokyo Medical Co., Ltd. Moreover, it is good also as a composite sheet which laminated | stacked the foam biodegradable film formed by foam-molding by using a polylactic acid resin as a foaming agent using a raw material and various crosslinking agents. The base film can impart heat insulation to the label by laminating a foam biodegradable film or a biodegradable nonwoven fabric on the biodegradable stretched film.

(Ii) Gas barrier layer The base film of the present invention includes a gas barrier layer provided on a biodegradable film. As the gas area layer, those capable of reducing oxygen permeability and water vapor permeability can be widely used from the viewpoint of ensuring the quality of the contents. Aluminum foil or the like also has gas barrier properties, but aluminum ash remains during incineration and is not decomposed by microorganisms. For this reason, in the present invention, a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are carbon atoms) on the inorganic oxide vapor-deposited film or the inorganic oxide vapor-deposited film. The organic group of the number 1-8 is represented, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M. A gas barrier coating film comprising a gas barrier composition comprising at least one or more alkoxides represented, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further obtained by polycondensation by a sol-gel method It is preferable to use a gas barrier layer or the like provided with. The gas barrier coating film forms a strong three-dimensional network composite polymer layer by the chemical reaction between polyvinyl alcohol resin or ethylene / vinyl alcohol copolymer and one or more alkoxides. It acts synergistically with the inorganic oxide vapor-deposited film, has an excellent gas barrier property to block the permeation of oxygen, water vapor, etc., and has excellent hot water resistance. In addition, since it is excellent in gas-barrier property, it can prepare in a thin layer and does not inhibit the biodegradability of a base film.

(Ii-1) Inorganic oxide vapor-deposited film As the inorganic oxide vapor-deposited film, for example, a chemical vapor deposition method, a physical vapor deposition method, or a combination thereof, from one layer of an inorganic oxide vapor-deposited film. It can be manufactured by forming a single layer film or a multilayer film or a composite film composed of two or more layers.

  Examples of the chemical vapor deposition method include chemical vapor deposition methods such as plasma chemical vapor deposition method, low temperature plasma chemical vapor deposition method, thermal chemical vapor deposition method, and photochemical vapor deposition method (Chemical Vapor Deposition method), CVD method). Specifically, on one side of the biodegradable film, a monomer gas for vapor deposition such as an organosilicon compound is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen is supplied. An oxygen oxide vapor or the like can be used as a gas, and a vapor deposition film of an inorganic oxide such as silicon oxide can be formed using a low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like.

  In the above, as a low temperature plasma generator, generators, such as high frequency plasma, pulse wave plasma, and microwave plasma, can be used, for example. In view of obtaining highly active and stable plasma, it is preferable to use a high-frequency plasma generator.

  An example of a method for forming a vapor-deposited film of an inorganic oxide by the low temperature plasma chemical vapor deposition method will be described with reference to FIG. 4 which is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus.

  In the present invention, the biodegradable film 201 is fed out from the unwinding roll 223 disposed in the vacuum chamber 222 of the plasma chemical vapor deposition apparatus 221, and the biodegradable film 201 is further passed through the auxiliary roll 224 to a predetermined state. At the speed of cooling / conveying on the circumferential surface of the electrode drum 225. On the other hand, a gas mixture for vapor deposition is prepared by supplying vapor deposition monomer gas such as oxygen gas, inert gas, organosilicon compound, etc. from the gas supply devices 226, 227 and the raw material volatilization supply device 228, etc. Is introduced into the vacuum chamber 222 through the raw material supply nozzle 229. The vapor deposition mixed gas composition is supplied onto the biodegradable film 201 transported on the cooling / electrode drum 225 circumferential surface, and plasma is generated and irradiated by glow discharge plasma 230 to irradiate inorganic oxide such as silicon oxide. The deposited film of the object is formed into a film. Next, when the biodegradable film 201 on which a vapor-deposited film of inorganic oxide such as silicon oxide is formed is wound around the take-up roll 234 via the auxiliary roll 233, the vapor deposition of the inorganic oxide by the plasma chemical vapor deposition method is performed. A film can be formed. A predetermined power is applied to the cooling / electrode drum 225 from a power source 231 disposed outside the vacuum chamber 222, and a magnet 232 is disposed in the vicinity of the cooling / electrode drum 225 to promote plasma generation. Has been. Since a predetermined voltage is applied from the power source to the cooling / electrode drum in this way, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. The glow discharge plasma is derived from one or more gas components in the mixed gas. When the biodegradable film is conveyed at a constant speed in this state, the glow discharge plasma causes the cooling / electrode drum peripheral surface to be cooled. A vapor deposition film of an inorganic oxide such as silicon oxide can be formed on the biodegradable film. In FIG. 4, reference numeral 235 represents a vacuum pump.

In the present invention, the vacuum chamber is depressurized by a vacuum pump and adjusted to a vacuum degree of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a vacuum degree of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is preferable to do.

The raw material volatilization supply device volatilizes the organic silicon compound as the raw material, mixes it with oxygen gas, inert gas, etc. supplied from the gas supply device, and introduces this mixed gas into the vacuum chamber through the raw material supply nozzle. . At this time, the content of the organosilicon compound in the mixed gas is preferably 1 to 40%, the oxygen gas content is 10 to 70%, and the inert gas content is preferably 10 to 60%. For example, the mixing ratio of organosilicon compound: oxygen gas: inert gas can be about 1: 6: 5 to 1:17:14. Note that the degree of vacuum in the vacuum chamber when supplying the organosilicon compound, the inert gas, the oxygen gas, and the like is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to It is preferably 1 × 10 ⁻² Torr, and the transport speed of the biodegradable film is 10 to 300 m / min, preferably 50 to 150 m / min. Formation of a vapor-deposited film of an inorganic oxide such as silicon oxide obtained in this way is formed on a biodegradable film in the form of a thin film in the form of SiO _x while oxidizing the plasma source gas with oxygen gas. Therefore, the deposited inorganic oxide vapor deposition film such as silicon oxide is a dense continuous layer having a small gap and rich in flexibility. Therefore, the barrier property of the vapor deposition film of inorganic oxide such as silicon oxide is Compared with a deposited film of an inorganic oxide such as silicon oxide formed by a conventional vacuum deposition method or the like, a sufficiently high barrier property can be obtained with a thin film thickness. In addition, since the surface of the biodegradable film is cleaned by SiO _X plasma, and polar groups, free radicals, etc. are generated on the surface of the biodegradable film, a deposited film of inorganic oxide such as silicon oxide is formed. The close adhesion with the biodegradable film is high. Further, the degree of vacuum when forming a continuous film of an inorganic oxide such as silicon oxide is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Since the vacuum degree when forming a deposited film of an inorganic oxide such as silicon oxide by a conventional vacuum vapor deposition method is lower than 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, It is possible to shorten the vacuum state setting time at the time of replacing the original film of the degradable film, and the degree of vacuum is easily stabilized and the film forming process is also stabilized.

In the present invention, a vapor deposition film of silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas, and the reaction product is It is tightly bonded to one surface of a biodegradable film to form a dense, flexible thin film and is usually represented by the general formula SiO _x (where X represents a number from 0 to 2). It is a continuous thin film mainly composed of silicon oxide. The silicon oxide vapor deposition film is a silicon oxide vapor deposition represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) in terms of transparency and barrier properties. A thin film mainly composed of a film is preferable. The value of X varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself is yellow. The transparency becomes worse.

In the present invention, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further contains at least one compound of carbon, hydrogen, silicon or oxygen, or a compound composed of two or more elements by chemical bonding or the like. It consists of a vapor deposition film. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the silicon oxide vapor deposition film can be varied by changing the conditions of the vapor deposition process. At this time, the content of the above-mentioned compound in the deposited film of silicon oxide is 0.1 to 50%, preferably 5 to 20%. When the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the deposited silicon oxide film become insufficient, and scratches, cracks, etc. are likely to occur due to bending, and high barrier properties are achieved. On the other hand, it may be difficult to maintain stably, and if it exceeds 50%, the barrier property may be lowered.

  Further, in the present invention, in the silicon oxide vapor-deposited film, it is preferable that the content of the above compound decreases in the depth direction from the surface of the silicon oxide vapor-deposited film. As a result, the impact resistance and the like are enhanced by the above-mentioned compound and the like on the surface of the vapor-deposited film of silicon oxide, and on the other hand, the content of the above-mentioned compound is small at the interface with the biodegradable film. The tight adhesion with the deposited film becomes strong.

  In the present invention, the silicon oxide vapor deposition film is formed using a surface analyzer such as an X-ray photoelectron spectrometer (XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), or the like. The above-mentioned physical properties can be confirmed by performing analysis such as ion etching in the vertical direction and performing elemental analysis of the deposited film of silicon oxide.

  In the present invention, the thickness of the silicon oxide vapor-deposited film is preferably about 50 to 4000 mm, more preferably 100 to 1000 mm. If it is thicker than 4000 mm, cracks or the like may occur in the film. On the other hand, if it is less than 50 mm, it may be difficult to achieve a barrier effect. The film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. As a means for changing the film thickness of the silicon oxide vapor deposition film, a method of increasing the volume velocity of the vapor deposition film, that is, a method of increasing the amount of monomer gas and oxygen gas, a method of slowing the vapor deposition rate, etc. be able to.

  In the present invention, the inorganic oxide vapor-deposited film may be not only one layer of the inorganic oxide vapor-deposited film but also a multilayer film in which two or more layers are laminated, and one or two materials are used. It is also possible to form a vapor-deposited film of an inorganic oxide that is used as a mixture of seeds or more and mixed with different materials.

  In the present invention, as a monomer gas for vapor deposition of an organic silicon compound or the like that forms a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyl Trimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane , Methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. Among these, it is particularly preferable to use 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material because of its handleability and the characteristics of the formed continuous film. In the above, as the inert gas, for example, argon gas, helium gas, or the like can be used.

  On the other hand, in the present invention, an inorganic oxide vapor-deposited film can also be formed by physical vapor deposition. As such a physical vapor deposition method, for example, an inorganic oxide can be formed by a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, an ion plating method, or an ion cluster beam method. A vapor deposition film can be formed.

  Specifically, a metal or metal oxide is used as a raw material, this is heated and vaporized, and this is vapor deposited on one of the biodegradable films, or a metal or metal oxide as a raw material. Vapor deposition using an oxidation reaction deposition method in which oxygen is introduced and oxidized to deposit on one of the biodegradable films, and a plasma-assisted oxidation reaction deposition method in which the oxidation reaction is supported by plasma. Can be formed. In addition, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used. A method of forming a thin film of an inorganic oxide by physical vapor deposition will be described with reference to FIG. 5 showing a schematic configuration diagram showing an example of a take-up vacuum deposition apparatus.

  First, the biodegradable film 201 fed out from the unwinding roll 243 in the vacuum chamber 242 of the wind-up type vacuum vapor deposition apparatus 241 is guided to the cooled coating drum 246 through the guide rolls 244 and 245. On the biodegradable film 201 guided on the cooled coating drum 246, a vapor deposition source 248 heated by a crucible 247, for example, metal aluminum or aluminum oxide is evaporated, and if necessary. Then, an oxygen gas or the like is ejected from the oxygen gas outlet 249, and an inorganic oxide vapor deposition film such as aluminum oxide is formed through the masks 250 and 250 while supplying the oxygen gas. For example, when the biodegradable film 201 on which a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed is sent out through the guide rolls 251 and 252 and wound around the take-up roll 253, the inorganic oxide formed by physical vapor deposition is used. A vapor deposition film can be formed. In addition, using the above-described winding-type vacuum vapor deposition apparatus, first, a first-layer inorganic oxide vapor-deposited film is formed, and then an inorganic oxide vapor-deposited film is further formed thereon, or A vacuum evaporation apparatus may be connected in series, and an inorganic oxide vapor deposition film may be continuously formed to form an inorganic oxide vapor deposition film composed of a multilayer film of two or more layers.

The vapor deposition film of metal or inorganic oxide may basically be a thin film on which a metal oxide is deposited, for example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca). , Vapor deposition films of metal oxides such as potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) Can be used. Preferably, a vapor-deposited film of a metal oxide such as silicon (Si) or aluminum (Al) can be used. Therefore, the metal oxide vapor deposition film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, and the like, for example, SiO _x , AlO _x , MgO. MO _X (in the formula, M represents a metal element, the value of X is in the range respectively of a metal element different.) as _X, etc. represented by.

  In addition, as the range of the value of X, silicon (Si) exceeds 0 and 2 or less, aluminum (Al) exceeds 0 and 1.5 or less, magnesium (Mg) exceeds 0 and 1 or less, calcium (Ca ) Is greater than 0 and less than or equal to 1, potassium (K) is greater than 0 and less than or equal to 0.5, tin (Sn) is greater than 0 and less than or equal to 2, sodium (Na) is greater than 0 and less than or equal to 0.5, and boron (B) is 0 to 1, 5 or less, Titanium (Ti) is more than 0 to 2 or less, Lead (Pb) is more than 0 to 1 or less, Zirconium (Zr) is more than 0 to 2 or less, Yttrium (Y) is more than 0 to 1 .5 or less. In the above, when X = 0, it is a complete metal, and the upper limit of the range of X is a completely oxidized value. Generally, examples other than silicon (Si) and aluminum (Al) are poor. Therefore, in the present invention, silicon or aluminum is preferable as M. In this case, the value of X is 1.0 to 2.0 for silicon (Si) and 0.5 to 1.5 for aluminum (Al). It is a range. In addition, although the film thickness of the vapor deposition film | membrane of an inorganic oxide changes with kinds etc. of the metal to be used or a metal oxide, it can select arbitrarily within the range of 50-2000 mm, for example, Preferably, it is 100-1000 mm. it can. In addition, as the inorganic oxide vapor deposition film, the metal or metal oxide to be used is used in one kind or a mixture of two or more kinds to constitute a vapor deposition film of an inorganic oxide mixed with different materials. You can also.

  Further, in the present invention, for example, a composite film composed of two or more vapor-deposited films of different kinds of inorganic oxides can be formed by using both physical vapor deposition and chemical vapor deposition.

  As a composite film composed of two or more layers of the above-mentioned different types of inorganic oxide vapor-deposited films, first, on a biodegradable film, a chemical vapor deposition method is used to provide a dense and flexible film with relatively cracking. An inorganic oxide vapor deposition film capable of preventing generation is provided, and then an inorganic oxide vapor deposition film formed by physical vapor deposition is provided on the inorganic oxide vapor deposition film to form a composite film composed of two or more layers. It is preferable to constitute a vapor-deposited film of inorganic oxide consisting of Contrary to the above, on the biodegradable film, an inorganic oxide vapor-deposited film is first formed by physical vapor deposition, and then dense and flexible by chemical vapor deposition. It is also possible to provide an inorganic oxide vapor-deposited film composed of a composite film composed of two or more layers by providing an inorganic oxide vapor-deposited film that can relatively prevent the occurrence of cracks.

(Ii-2) Gas Barrier Coating Film The gas barrier layer used in the present invention preferably has a gas barrier coating film in addition to the inorganic oxide vapor deposition film. The gas barrier coating film has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n Represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.), a polyvinyl alcohol-based resin and / or ethylene. A coating film comprising a gas barrier composition comprising a vinyl alcohol copolymer and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent; The composition is coated on the vapor-deposited film of the inorganic oxide on the biodegradable film to provide a coating film, and it is 10 seconds to 20 ° C. to 180 ° C. and a temperature equal to or lower than the melting point of the biodegradable film. It can be formed by heat treatment for 10 minutes.

  Further, the gas barrier composition is coated on the inorganic oxide vapor-deposited film on the biodegradable film, and two or more coating films are laminated, and the biodegradable film has a temperature of 20 ° C. to 180 ° C. A composite polymer layer in which two or more gas barrier coating films are laminated may be formed by heat treatment at a temperature not higher than the melting point of 10 seconds to 10 minutes.

As the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , at least one of alkoxide partial hydrolyzate and alkoxide hydrolysis condensate can be used. The partial hydrolyzate is not limited to the one in which all of the alkoxy groups are hydrolyzed, and may be one in which one or more are hydrolyzed, or a mixture thereof, and further a hydrolysis condensate. As a dimer or more of a partially hydrolyzed alkoxide, specifically, a dimer or hexamer may be used.

In the general formula R ¹ _n M (OR ² ) _m , R ¹ is an alkyl group having 1 to 8, preferably 1 to 5, more preferably 1 to 4 carbon atoms which may have a branch. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group, etc. Can be mentioned.

In the general formula R ¹ _n M (OR ² ) _m , R ² is an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 5, and particularly preferably 1 to 4 which may have a branch. Yes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and the like. When a plurality of (OR ² ) are present in the same molecule, (OR ² ) may be the same or different.

Examples of the metal atom represented by M in the general formula R ¹ _n M (OR ² ) _m include silicon, zirconium, titanium, aluminum, and the like.

In the present invention, silicon is preferable. In this case, as an alkoxide that can be preferably used in the present invention, when n = 0 in the general formula R ¹ _n M (OR ² ) _m , the general formula Si (ORa) ₄ (wherein Ra is Represents an alkyl group having 1 to 5 carbon atoms). In the above, Ra includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. Specific examples of such an alkoxysilane include tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si ( OC ₄ H ₉₎ can be exemplified ₄ like.

In the case where n is 1 or more, the general formula RbnSi (ORc) _4-m (wherein m represents an integer of 1, 2, 3 and Rb and Rc are a methyl group, an ethyl group, An alkylalkoxysilane represented by n-propyl group, n-butyl group, etc.) can be used. Examples of such an alkylalkoxysilane include methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OC ₂ H ₅ ) ₃ , dimethyldimethoxysilane (CH ₃ ) ₂ Si (OCH). _{3) 2,} dimethyl diethoxy silane _{(CH 3) 2 Si (OC} 2 H 5) 2, may use other like. In the present invention, the above alkoxysilane, alkylalkoxysilane and the like may be used alone or in combination of two or more.

  In the present invention, a polycondensation product of the above alkoxysilane can also be used, and specifically, for example, polytetramethoxysilane, polytetraemethoxysilane, and the like can be used.

In the present invention, a zirconium alkoxide in which M is Zr can also be suitably used as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m . For example, tetramethoxyzirconium Zr (OCH ₃ ) ₄ , tetraethoxyzirconium Zr (OC ₂ H ₅ ) ₄ , tetra ipropoxyzirconium Zr (iso-OC ₃ H ₇ ) ₄ , tetra n butoxyzirconium Zr (OC ₄ H ₉ ) ₄ , etc. can be exemplified.

Further, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , a titanium alkoxide in which M is Ti can be preferably used. For example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetra Examples include ethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (iso-OC ₃ H ₇ ) ₄ , tetra-n-butoxytitanium Ti (OC ₄ H ₉ ) ₄ , and others.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , an aluminum alkoxide in which M is Al can be used. For example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum _{Al (OC 2 H 5) 4} , tetraisopropoxy aluminum _{Al (is0-OC 3 H 7} ) 4, tetra-n-butoxy aluminum _{Al (OC 4 H 9) 4} , may use other like.

  In the present invention, two or more of the alkoxides may be used in combination. For example, when alkoxysilane and zirconium alkoxide are mixed and used, the toughness, heat resistance and the like of the resulting gas barrier film can be improved, and a decrease in the retort resistance of the film during stretching can be avoided. Under the present circumstances, the usage-amount of a zirconium alkoxide is the range of 10 mass parts or less with respect to 100 mass parts of said alkoxysilanes. When the amount exceeds 10 parts by mass, the formed gas barrier coating film tends to gel, and the brittleness of the film increases, and the gas barrier coating film tends to peel off when the biodegradable film is coated. Therefore, it is not preferable.

  In addition, when alkoxysilane and titanium alkoxide are mixed and used, the thermal conductivity of the resulting gas barrier coating film is lowered, and the heat resistance is remarkably improved. Under the present circumstances, the usage-amount of a titanium alkoxide is the range of 5 mass parts or less with respect to 100 mass parts of said alkoxysilane. When the amount exceeds 5 parts by mass, the brittleness of the formed gas barrier coating film becomes large, and when the biodegradable film is coated, the gas barrier coating film may be easily peeled off.

  As the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer used in the present invention, a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer can be used alone, respectively, or polyvinyl alcohol A single resin and an ethylene / vinyl alcohol copolymer can be used in combination. In the present invention, physical properties such as gas barrier properties, water resistance, weather resistance, and the like can be remarkably improved by using a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer.

  When the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is polyvinyl alcohol resin: ethylene / vinyl alcohol copolymer = 10: 0. It is preferable that the position is from 05 to 10: 6.

  The content of the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by mass, preferably 20 to 200 parts by mass with respect to 100 parts by mass of the total amount of the alkoxide. The blending ratio of When it exceeds 500 parts by mass, the brittleness of the gas barrier coating film becomes large, and the water resistance and weather resistance of the resulting barrier film may be lowered. On the other hand, if it is less than 5 parts by mass, the gas barrier property may be lowered.

  In the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, as the polyvinyl alcohol resin, one obtained by saponifying polyvinyl acetate can be generally used. Polyvinyl alcohol resins include partially saponified polyvinyl alcohol resins in which several tens of percent of acetate groups remain, completely saponified polyvinyl alcohols in which no acetate groups remain, and modified polyvinyl alcohol resins in which OH groups have been modified. Well, not particularly limited. Examples of such a polyvinyl alcohol resin include “RS-110 (degree of saponification = 99%, degree of polymerization = 1,000)” manufactured by Kuraray Co., Ltd., and “Kuraray Poval LM-20SO ( “Saponification degree = 40%, polymerization degree = 2,000)”, “GOHSENOL NM-14 (degree of saponification = 99%, polymerization degree = 1,400)” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Can do.

  As the ethylene / vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer can be used. For example, it is not particularly limited, and includes a partially saponified product in which several tens mol% of acetic acid groups remain to a complete saponified product in which only several mol% of acetic acid groups remain or no acetic acid groups remain. However, it is preferable to use a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. In addition, the content of the repeating unit derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. It is preferable. Examples of such an ethylene / vinyl alcohol copolymer include “Eval EP-F101 (ethylene content; 32 mol%)” manufactured by Kuraray Co., Ltd., “Soarnol D2908 (ethylene content; 29 mol) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.” %) "And the like.

The gas barrier composition used in the present invention has the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M is Represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) And a gas barrier obtained by polycondensation by the sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. Composition. In preparing the gas barrier composition, a silane coupling agent or the like may be added.

  As the silane coupling agent that can be suitably used in the present invention, known organic reactive group-containing organoalkoxysilanes can be widely used. For example, an organoalkoxysilane having an epoxy group is suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3,4-epoxy). (Cyclohexyl) ethyltrimethoxysilane or the like can be used. Such silane coupling agents may be used alone or in combination of two or more. In addition, the usage-amount of a silane coupling agent exists in the range of 1-20 mass parts with respect to 100 mass parts of said alkoxysilanes. If 20 parts by mass or more is used, the gas barrier coating film to be formed has increased rigidity and brittleness, and the insulation and workability of the gas barrier coating film may be lowered.

  The sol-gel catalyst is a catalyst mainly used as a polycondensation catalyst, and a basic substance such as tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. For example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc. can be used. In the present invention, N, N-dimethylbenzylamine is particularly preferred. The usage-amount is 0.01-1.0 mass part per 100 mass parts of total amounts of an alkoxide and a silane coupling agent.

  The “acid” used in the gas barrier composition is mainly used as a catalyst for hydrolysis of an alkoxide, a silane coupling agent or the like in the sol-gel method. For example, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, organic acids such as acetic acid and tartaric acid, and the like can be used. The amount of the acid used is preferably 0.001 to 0.05 mol based on the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety).

  Furthermore, in the gas barrier composition, water can be used in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, relative to 1 mol of the total molar amount of the alkoxide. When the amount of water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally crosslinked to form a porous polymer having a low density, Such a porous polymer cannot improve the gas barrier property of the gas barrier film. Moreover, when the amount of the water is less than 0.8 mol, the hydrolysis reaction may hardly proceed.

  Furthermore, as an organic solvent used in said gas-barrier composition, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used, for example. The polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably handled in a state of being dissolved in a coating solution containing the alkoxide, silane coupling agent, or the like. It can be selected appropriately. For example, when a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in combination, it is preferable to use n-butanol. An ethylene / vinyl alcohol copolymer solubilized in a solvent can also be used. For example, trade name “Soarnol” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be preferably used. The amount of the organic solvent used is usually 30 to 500 with respect to 100 mass of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel catalyst. Part by mass.

  In the present invention, the gas barrier film can be produced by the following method.

  First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel catalyst, an acid, water, an organic solvent, and, if necessary, a metal alkoxide Etc. are mixed to prepare a gas barrier composition. By mixing, the gas barrier composition (coating liquid) starts and proceeds with a polycondensation reaction.

  Next, the gas barrier composition is applied onto the vapor-deposited film of the inorganic oxide on the biodegradable film by a conventional method and dried. By this drying step, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer further proceeds, and a coating film is formed. . On the first coating film, the above coating operation may be further repeated to form a plurality of coating films composed of two or more layers.

  Next, the biodegradable film coated with the gas barrier composition is 20 ° C. to 180 ° C. and a temperature below the melting point of the biodegradable film, preferably 50 ° C. to 160 ° C. for 10 seconds to 10 seconds. Heat for minutes. This makes it possible to produce a barrier film in which one or more gas barrier coating films of the gas barrier composition are formed on the inorganic oxide vapor-deposited film.

  A barrier film obtained by using an ethylene / vinyl alcohol copolymer alone or both a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer is excellent in gas barrier properties after hydrothermal treatment. On the other hand, when a barrier film is produced using only a polyvinyl alcohol-based resin, a first coating film is formed by previously applying a gas barrier composition using a polyvinyl alcohol-based resin, On the coating film, a gas barrier composition containing an ethylene / vinyl alcohol copolymer is applied to form a second coating film, and when these composite layers are formed, the gas barrier properties after hydrothermal treatment It is possible to produce a barrier film with improved resistance.

  Further, a coating film is formed by the gas barrier composition containing the ethylene / vinyl alcohol copolymer, or the gas barrier composition containing a combination of the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer is applied. Even if a film is formed and a plurality of these films are laminated, it becomes an effective means for improving the gas barrier property of the barrier film according to the present invention.

  The production method of the gas barrier film used in the present invention will be described in more detail using alkoxysilane as the alkoxide.

  The alkoxysilane and metal alkoxide blended as the gas barrier composition are hydrolyzed by the added water. During the hydrolysis, the acid acts as a hydrolysis catalyst. Next, protons are taken from the hydroxyl groups generated by the hydrolysis by the action of the sol-gel catalyst, and the hydrolysis products are dehydrated and polycondensed. At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group.

  In addition, the opening of the epoxy group also occurs due to the action of the base catalyst, generating a hydroxyl group. In addition, a polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds. In the reaction system, polyvinyl alcohol resin, ethylene / vinyl alcohol copolymer, or polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer are present, so polyvinyl alcohol resin and ethylene / vinyl alcohol copolymer are present. Reaction with the hydroxyl group of the polymer also occurs. In addition, the polycondensate to be generated includes, for example, an inorganic part composed of a bond such as Si—O—Si, Si—O—Zr, Si—O—Ti, and the like, and an organic part resulting from the silane coupling agent. It is a composite polymer containing.

  In the above reaction, for example, a linear polymer having a partial structural formula represented by the following formula (III) and further having a portion derived from a silane coupling agent is first formed.

このポリマーは、ＯＲ基（エトキシ基などのアルコキシ基）が、直鎖状のポリマーから分岐した形で有する。このＯＲ基は、存在する酸が触媒となって加水分解されてＯＨ基となり、ゾルゲル法触媒（塩基触媒）の働きにより、まず、ＯＨ基が、脱プロトン化し、次いで、重縮合が進行する。すなわち、このＯＨ基が、下記の式（Ｉ）に示されるポリビニルアルコール系樹脂、または、下記の式（ＩＩ）に示されるエチレン・ビニルアルコール共重合体と重縮合反応し、Ｓｉ−Ｏ−Ｓｉ結合を有する、例えば、下記の式（ＩＶ）に示される複合ポリマー、あるいは、下記の式（Ｖ）及び（ＶＩ）に示される共重合した複合ポリマーを生じると考えられる。

This polymer has an OR group (an alkoxy group such as an ethoxy group) branched from a linear polymer. The OR group is hydrolyzed to become an OH group using an existing acid as a catalyst, and the OH group is first deprotonated by the action of a sol-gel catalyst (base catalyst), and then polycondensation proceeds. That is, this OH group undergoes a polycondensation reaction with a polyvinyl alcohol-based resin represented by the following formula (I) or an ethylene / vinyl alcohol copolymer represented by the following formula (II) to form Si—O—Si. For example, it is considered that a composite polymer represented by the following formula (IV) or a copolymerized composite polymer represented by the following formulas (V) and (VI) is formed.

上記の反応は常温で進行し、ガスバリア性組成物は、調製中に粘度が増加する。このガスバリア性組成物を、生分解性フィルム上の無機酸化物の蒸着膜の上に塗布し、加熱して溶媒および重縮合反応により生成したアルコールを除去すると重縮合反応が完結し、生分解性フィルム上の無機酸化物の蒸着膜の上に透明な塗布膜が形成される。なお、上記の塗布膜を複数層積層する場合には、層間の塗布膜中の複合ポリマー同士も縮合し、層と層との間が強固に結合する。

The above reaction proceeds at room temperature, and the viscosity of the gas barrier composition increases during preparation. When this gas barrier composition is applied on a vapor-deposited film of an inorganic oxide on a biodegradable film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed and biodegradable. A transparent coating film is formed on the inorganic oxide vapor deposition film on the film. In addition, when laminating | stacking two or more said coating films, the composite polymer in the coating film of an interlayer is also condensed, and a layer couple | bonds firmly between layers.

  Furthermore, the organic reactive group of the silane coupling agent and the hydroxyl group generated by hydrolysis are bonded to the hydroxyl group on the surface of the biodegradable film or the deposited film of the inorganic oxide on the biodegradable film, The adhesion between the biodegradable film or the surface of the inorganic oxide vapor-deposited film and the coating film is also good. Thus, in the present invention, the inorganic oxide vapor-deposited film and the gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by hydrolysis / co-condensation reaction. Adhesion between the oxide vapor deposition film and the gas barrier coating film is improved, and a better gas barrier effect can be exhibited by the synergistic effect of the two layers.

In the present invention, when the amount of water added is adjusted to 0.8 to 2 mol, preferably 1.0 to 1.7 mol, relative to 1 mol of alkoxides, the above linear polymer is used. Is formed. Such a linear polymer has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part. Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the molecular aggregation energy is high. Since the rigidity is also high, it is particularly excellent in gas barrier properties (blocking and blocking permeation of O ₂ , N ₂ , H ₂ O, CO ₂ , etc.).

  Examples of the method for applying the gas barrier composition of the present invention include, for example, once by a roll coater such as a gravure roll coater, spray coat, spin coat, dipping, brush, bar code, applicator or the like. A coating film having a dry film thickness of 0.01 to 30 μm, preferably about 0.1 to 10 μm, can be formed by applying a plurality of times. Further, under a normal environment, 50 to 300 ° C., preferably The gas barrier coating film of the present invention is formed by performing condensation at a temperature of 70 to 200 ° C. by heating and drying for 0.005 to 60 minutes, preferably 0.01 to 10 minutes. Can do.

(Ii-3) Plasma treatment In the present invention, the gas barrier coating film is preferably subjected to a plasma treatment in the surface treatment, thereby improving printability.

In the plasma treatment for the gas barrier coating film, an inorganic gas such as oxygen gas, nitrogen gas, argon gas, and helium gas can be used as the plasma gas. In particular, oxygen gas or oxygen gas and argon gas can be used. It is preferable to perform plasma treatment using an inorganic gas containing oxygen gas as a plasma gas, such as a mixed gas. Further, it is possible to perform plasma treatment at a lower voltage, whereby there is no discoloration of the surface of the gas barrier coating film, and the surface of the gas barrier coating film has an OH group, for example, by a chemical reaction or the like. Etc., and Si—C bonds existing in the gas barrier coating film can be converted to SiO ₂ . Furthermore, by the above plasma treatment, the crosslink density of the gas barrier coating film by the gas barrier composition is increased, the humidity dependency thereof is improved, the gas barrier property against oxygen gas, as well as the barrier property against water vapor, Relatively, it is possible to stably maintain a high gas barrier property against oxygen gas, water vapor, etc., and furthermore, a plasma gas composed of an inorganic gas containing oxygen gas is applied to the surface of the gas barrier coating film in a vacuum. By using the plasma treatment to form a plasma treatment layer, a substrate such as an alkali-soluble heat-sensitive adhesive layer, an anchor coat layer, a heat sealable resin layer, or the like is laminated on the plasma treatment layer. In such a case, it is possible to improve the tight adhesion and the like and remarkably increase the lamination strength and the like.

Specifically, it is desirable to use a mixed gas of oxygen gas and argon gas, and the gas pressure of the mixed gas of oxygen gas and argon gas is about 1 × 10 ^{−1 to} 10 −10 Torr, More preferably, the 1 × 10 ⁻² to 1 × 10 ⁻⁸ Torr position is desirable, and the ratio of oxygen gas to argon gas is oxygen gas: argon gas = 100: 0 to 30:70 in terms of partial pressure ratio. More preferably, the 90:10 to 70:30 position is desirable, and the plasma output is preferably about 100 to 2500 W, more preferably about 500 to 1500 W, and the processing speed is 100 ˜600 m / min, more preferably 200 to 500 m / min. When the partial pressure ratio between the oxygen gas and the argon gas is increased, if the argon gas partial pressure is increased, oxygen molecules activated by the plasma are reduced, the argon gas acts as a reducing gas, and the introduction of hydroxyl groups is inhibited. Is not preferable. In addition, when the plasma output is less than 100 W, more preferably less than 500 W, the activation of oxygen gas is lowered, and it is difficult to produce highly active oxygen atoms. Furthermore, if it exceeds 2500 W, the plasma output is too high, which is not preferable because it causes a problem that the physical properties of the coating itself deteriorate due to the deterioration of the gas barrier coating film or the like.

  Further, when the above processing speed is less than 100 m / min, further less than 250 m / min, the amount of oxygen plasma is small, and when it exceeds 600 m / min, and further exceeds 500 m / min, a gas barrier is obtained. Oxidation of the conductive coating film proceeds rapidly and the transparency becomes high, but the barrier property is lowered, which is not preferable.

  In the present invention, in plasma processing, plasma is generated by using three types of devices such as direct current glow discharge, radio frequency (AF) discharge, and microwave discharge. Can do. In the present invention, a high frequency (AF) discharge device of 3.56 MHz can be used.

(3) Alkali-soluble heat-sensitive adhesive layer As the alkali-soluble heat-sensitive adhesive layer constituting the body-wound label, one that is solid at room temperature (alkali-soluble hot melt adhesive) and one that is liquid (alkali-soluble delayed tack adhesive) There is. The alkali-soluble hot melt adhesive needs to be melted at a high temperature during application, and has a high viscosity. On the other hand, the alkali-soluble delayed tack adhesive does not need to be heated at the time of application, and has a low viscosity.

  In the present invention, the body-wrapped label has an alkali-soluble heat-sensitive adhesive layer, but if the heat-sensitive adhesive is alkali-soluble, the container and the label can be easily treated by treating the container after use with alkali. This is because they can be separated. The alkali-soluble heat-sensitive adhesive is one that can be dissolved by alkali and is dissolved in an aqueous solution having an alkali concentration of 1.5 w / w% at 85 ° C. to 90 ° C. for 15 minutes. If dissolved under these conditions, the label can be easily peeled off by alkali treatment regardless of whether it is attached to any container, and the label can be peeled off quickly in accordance with the spirit of the recycling method. In the present invention, “dissolution” means that the heat-sensitive adhesive is dissolved in an aqueous solution of sodium hydroxide having a temperature of 85 to 90 ° C. and a concentration of 1.5 w / w% for 15 minutes. This includes a state in which the adhesion to the adherend is reduced and the container can be peeled off.

(I) Alkali-soluble hot melt adhesive The alkali-soluble hot melt adhesive that can be used in the present invention comprises a base polymer composed of a thermoplastic resin component, a tackifier, and additives such as waxes. Can be illustrated.

  The role of the thermoplastic resin used in the hot melt adhesive of the present invention is to improve the flexibility of the hot melt adhesive and to impart cohesive force. A hot-melt adhesive that does not contain a thermoplastic resin has high rigidity, and is hard and brittle. The thermoplastic resin is a polymer having an acid value of 90 mgKOH / g or more, preferably 95 mgKOH / g or more, more preferably 98 mgKOH / g or more. Typical polymers having an acid value of 90 mgKOH / g or more include ethylene- (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, α-olefin-maleic anhydride copolymer. There are styrene- (meth) acrylic acid copolymers and the like, and ethylene- (meth) acrylic acid copolymers are preferred in consideration of tackifier and wax compatibility and hot melt flexibility. In addition, when a polymer having an acid value of less than 90 mgKOH / g is used, the peelability with an alkaline aqueous solution may be inferior.

  The hot-melt adhesive that can be used in the present invention may contain a wax. The wax can reduce the melt viscosity of the hot melt adhesive to improve workability, and can prevent blocking, adjust open time, and improve heat resistance. If wax is not used in the hot melt adhesive, the viscosity is high and workability is poor, and it is considered that stringing occurs during coating. Typical waxes include carnauba wax, candelilla wax, montan wax, fatty acid, fatty acid glyceride, polyethylene wax, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polypropylene wax, oxidized wax, and ethylene-acrylic acid co-polymer. Examples thereof include a polymer wax and an ethylene-methacrylic acid copolymer wax. In consideration of alkali peelability, montan wax and ethylene-acrylic acid copolymer wax are preferable.

  The hot melt adhesive may include a tack fire. The tackifier can improve the adhesion and improve the wetness and workability of the hot melt adhesive. Typical tackifiers include rosin, rosin derivatives (hydrogenated rosin, disproportionated rosin, polymerized rosin, acrylic acid modified rosin, fumaric acid modified rosin, maleic acid modified rosin, rosin esters thereof (alcohol, glycerin, pentaerythritol). Esterified rosin)), terpene resin (α-pinene, β-pinene), terpene phenol resin, aromatic modified terpene resin, hydrogenated terpene resin, aliphatic petroleum resin, aromatic petroleum resin, copolymerization Base petroleum resin, alicyclic petroleum resin, coumarone-indene resin, styrene resin, phenol resin and the like. In consideration of alkali dispersibility, the acid value of the tackifier is preferably 150 mgKOH / g or more, and such tackifier is rosin or a rosin derivative, for example, raw rosin, (meth) acrylic acid-modified rosin, (anhydrous) maleic acid Examples include modified rosin, fumaric acid-modified rosin, hydrogenated rosin, and polymerized rosin. In consideration of the blocking property of the heat sensitive label, the softening point of the tackifier is 75 ° C. or higher, preferably 85 ° C. or higher, more preferably 100 ° C. or higher.

  The viscosity of the hot melt adhesive is 10 cps to 1,000,000 cps at 140 ° C., preferably 50 cps to 500,000 cps. If it is less than 10 cps or exceeds 1,000,000 cps, coating may be difficult.

  In order to prevent thermal degradation and thermal decomposition in the present invention, high molecular weight hindered polyphenols, triazine derivatives, high molecular weight hindered phenols, dialkyl phenol sulfides, 2,2′-methylene-bis- (4-methyl-6- Tert-butylphenol, 4,4'-methylene-bis- (2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,4-trimethyl-1, 2-dihydroquinoline polymer, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, nickel dibutyl dithiocarbamate, 1-oxy- - methyl-4-isopropylbenzene, 4,4'-butylidenebis - (3-methyl-6-tert - butylphenol, no problem even with the addition of antioxidants such as 2-mercaptobenzimidazole.

  The acid value of the hot melt adhesive used for the body-wrapped label is 100 mgKOH / g or more, preferably 150 mgKOH / g or more. When the acid value is less than 100 mgKOH / g, the label and the glass do not adhere to each other, or even if they are adhered, there is no water resistance, or the aqueous alkali solution is not dispersed or dissolved. Moreover, when the softening point of the hot-melt adhesive used for the body-wound label is less than 50 ° C., the blocking property is poor, and when the body-wound label is stacked or stored in a roll shape, it cannot be used due to blocking. When it exceeds 120 ° C, it does not adhere to glass bottles etc. when it is attached to a container using a high-speed thermal labeler (a machine that develops adhesiveness by heating the adhesive layer of the thermal label and applies it to various objects) It peels off immediately or easily by hand.

  The alkali-soluble hot melt adhesive used in the present invention may use one or more of the above-mentioned thermoplastic resins, tackifiers, and waxes. In addition to polymer, tackifier, and wax, silicone or the like may be added to prevent blocking. However, when silicone is used, adhesion and water resistance may deteriorate.

  The hot melt adhesive according to the present invention has a composition ratio of 10 to 70 parts by weight of thermoplastic resin, 10 to 70 parts by weight of tackifier, and 1 to 70 parts by weight of wax.

  The hot melt adhesive can be applied to the label base material by roll coater method using direct roll, gravure roll, extrusion coater method, slit orifice coater method, etc. Of course, after dissolving and coating in a solvent, the solvent may be removed by heating and drying.

The coating amount of the hot melt adhesive is 7 to 15 g / m ² . When the amount applied to the label substrate is less than 7 g / m ^2, it does not adhere to a glass bottle, a plastic bottle or the like, or even when adhered, it does not have water resistance or condensation resistance. On the other hand, if it exceeds 15 g / m ² , it is not economical.

  Such an alkali-soluble hot melt adhesive may be a commercially available product, for example, KIC KRONES “Colfix HM4433 / 1”, manufactured by Toyo Petrolite Co., Ltd., and trade name “label melt”.

(Ii) Alkali-soluble delayed tack adhesive On the other hand, the alkali-soluble delayed tack adhesive that can be used in the present invention includes a base polymer composed of a thermoplastic resin component, a tackifier, and a crystalline solid plasticizer. What is formed is preferably used.

  The thermoplastic resin of the alkali-soluble delayed tack adhesive is also an alkali-soluble resin, which can be easily removed by an alkali treatment when the label is peeled off.

  For example, ethylene-vinyl acetate copolymer resin, methyl acrylate, ethyl acrylate, acrylic acid-isopropylene, isobutyl acrylate, n-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, etc. Examples thereof include acrylic acid ester copolymers such as acrylic resins and methacrylic acid esters, and copolymer resins made of unsaturated carboxylic acids such as acrylic acid and maleic acid, styrene-acrylic acid esters, and styrene-butadiene. Further, the self-crosslinking acrylic acid ester copolymer has a property of improving water resistance when heated, and is suitable.

  Among these, the ethylene-vinyl acetate copolymer resin has such an adhesive strength that the label does not peel off when circulating through the labeled container, and can easily be peeled off from the container by hand after use. It is preferable at the point which has peelability. In particular, the ethylene-vinyl acetate copolymer resin contains a vinyl acetate component in a range of 25 mol% to 35 mol%, and more preferably in a range of a melt index of 5 to 200. Within the above range, the adhesive strength between the container and the label and the adhesive strength between the labels can be maintained in the range of 0.5 to 12 N / 15 mm or less, and the label can be easily removed from the container after use. It is possible to ensure easy peelability to such an extent that it can be peeled off.

  As the solid plasticizer of the alkali-soluble heat-sensitive adhesive, the resin is not plasticized below the melting point and is in a crystalline state, and melts by heating and is compatible with the resin to swell or soften the resin. It becomes a non-adhesive anti-blocking agent and has a function of becoming adhesive when heated. For example, sucrose benzoate, ethylene glycol dibenzoate, trimethylol ethane tribenzoate, glyceride tribenzoate, pentaerythritol tetrabenzoate, diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, dihydroabiethyl phthalate, isophthalate Examples include dimethyl acid, sucrose octaacetate, tricyclohexyl citrate, N-cyclohexyl-p-toluenesulfonamide, and the like. Among these, those having a melting point of about 50 to 100 ° C. can be preferably used. If the melting point is 50 ° C. or lower, the adhesive may be activated during storage of the label, and storage and transportation before use become severe, which is not preferable. When the melting point is 100 ° C. or higher, the efficiency for activating the adhesive layer of the label deteriorates, which is not preferable.

  The tackifier for the alkali-soluble heat-sensitive adhesive has an effect of improving the pressure-sensitive adhesive performance of the pressure-sensitive adhesive. For example, terpene resin, aliphatic petroleum resin, aromatic petroleum resin, coumarone-indene resin, styrene resin, phenol resin, terpene-phenol resin, rosin derivative (rosin, polymerized rosin, hydrogenated rosin, and glycerin thereof. And esters with pentaerythritol, resin acid dimers, etc.).

  The solid plasticizer, thermoplastic resin and tackifier are an emulsion in which thermoplastic resin particles (solid particles or droplets) are emulsified and dispersed in water, or the thermoplastic resin is dissolved or dispersed in an organic solvent. These can be used alone or in a mixture of two or more. Moreover, a dispersing agent, an antifoamer, a thickener etc. can also be used as needed.

  The alkali-soluble delayed tack adhesive formed by dispersing a base polymer comprising a thermoplastic resin component as described above, a tackifier, and a solid plasticizer in a solvent is a gravure coating method or a roll coating method in an emulsion state. , Using a means for applying a normal heat-sensitive adhesive such as reverse roll coating method, lip coating method, knife coating method, etc., or on the entire surface of the surface on which the printed layer of the base film is formed, or By partially applying it to form an alkali-soluble heat-sensitive adhesive layer, for example, by drying at a temperature of 40 to 60 ° C., a body-wrapped label is obtained.

The coating amount of the alkali-soluble delayed tack adhesive is preferably about 1.5~15g / m ^2, about 3 to 8 g / m ² is more preferable. A coating amount of 1.5 g / m ² or less is not preferable because sufficient adhesive strength cannot be obtained. In addition, when the coating amount is 15 g / m ² or more, sufficient adhesive strength can be obtained, but since the drying speed is slow, productivity is poor, and it is difficult to peel off the label when separating the label from the container. This is not preferred because it tends to cause adhesive residue in the container. In addition, the adhesive may be applied repeatedly, which is not preferable because productivity decreases.

  The alkali-soluble delayed tack type adhesive layer can be applied to the entire surface of the biodegradable label while the adhesive layer is sticky, or partially (only at one location, or in the form of dots, lines, or grids). May be formed).

  In the case of partial coating, in order to obtain the necessary adhesive strength, the coating width of the first adhesive portion and the second adhesive portion is preferably 3 mm to 25 mm.

  A commercially available product can be used as the alkali-soluble delayed tack type adhesive, for example, a delayed tack agent mainly composed of ethylene-vinyl acetate copolymer resin (product name “KP011” manufactured by Daicel Chemical Industries, Ltd.), etc. Can be preferably used.

  As described above, the alkali-soluble thermosensitive adhesive used in the present invention preferably has a label-to-label adhesive strength of 0.5 to 12 N / 15 mm between the container and the label. This is to ensure adhesive strength in the distribution process.

  In the present invention, the labeled container with the label attached is immersed in water for one day, then removed from the water, the adhesive strength of the label from the container, and the ends of the label in which both ends of the label are superimposed Is preferably 0.5 to 12 N / 15 mm. If the adhesive strength is in the above range, it does not cause wrinkles, label displacement or label dropout even when immersed in water, and can be easily removed by hand when removing the label from the container. is there. If the adhesive strength after immersion is 0.5N / 15mm or less, when stored in a refrigerator, or when cooled in water at a stall or cooler box, it will wrinkle, the label will shift, May occur. On the other hand, when the adhesive strength after immersion is 15 N / 15 mm or more, when the label is peeled off from the container, it cannot be easily peeled off by hand, and the separation and recovery may be inferior.

(4) Anchor coat layer In the present invention, it is preferable to provide an anchor coat layer in order to improve the adhesion between the base film of the body-wrapped label and the alkali-soluble heat-sensitive adhesive layer. Examples of such an anchor coat layer include non-cured or curable anchor coat agents such as polyolefin-based, organic titanate-based, polyethyleneimine-based, polybutadiene-based, isocyanate-based, polyester-based, and acrylic-based layers.

  The anchor coating agent is coated by roll coating, gravure coating, knife coating, dip coating, spray coating, other coating methods, etc., and the coating film is dried to remove the solvent and diluent, and if necessary An anchor coat layer can be formed by performing an aging treatment or the like.

(5) Design printing layer The body-wrapped label of the present invention may have a printing layer laminated inside the label of the base film. The print layer may be formed over the entire length of the body-wrapped label, and the design print layer may not be provided in the alkali-soluble heat-sensitive adhesive layer. Moreover, the design printing layer may be printed on the outer side of the base film. The thickness of the design print layer is, for example, about 1 to 8 μm, preferably about 2 to 5 μm. In addition, when forming the design print layer on the outside of the substrate film, in order to protect the formed design print layer, it is necessary to provide an overcoat layer formed by a transparent varnish or the like as described later. desirable.

  There is no limitation in the printing method, for example, a printing layer can be formed by gravure printing. As the printing layer, one or more ordinary ink vehicles are prepared from a resin and a solvent, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, and a curing agent. 1 to 2 or more kinds of auxiliaries such as additives, crosslinking agents, lubricants, antistatic agents, fillers, etc. are optionally added, and further colorants such as dyes and pigments are added, and solvents, diluents, etc. The ink composition obtained by sufficiently kneading and adjusting the ink composition can be used.

  As such an ink vehicle, a commonly used ink having adhesiveness with a base film and having necessary resistance can be used, and among them, it is preferable that the ink vehicle is made of an ink having high heat resistance. For example, it is desirable to use an ink made of a urethane resin-based ink composition, an acrylic resin-based ink composition, or a chlorinated polypropylene-based ink composition. In addition, when the binder for ink is made of a modified resin made from a natural product such as a modified corn starch, an aliphatic polyester resin, etc., the entire label with printing ink can be decomposed naturally even if discarded after use. preferable. The ink vehicle serves to carry the colorant from the plate to the printing material and fix it as a coating.

  Further, the drying property of the ink varies depending on the solvent. The main solvents used in printing inks are toluene, MEK, ethyl acetate, and IPA. Solvents with a low boiling point are used for quick drying. However, if the drying is too fast, the printed matter may be faded or printing may not be successful. Yes, a solvent having a high boiling point can be appropriately mixed. This makes it possible to print fine characters neatly. Colorants include dyes that are soluble in solvents and pigments that are insoluble in solvents, and gravure inks use pigments. Pigments are classified into inorganic pigments and organic pigments. Examples of inorganic pigments include titanium oxide (white), carbon black (black), and aluminum powder (gold and silver), and organic pigments are preferably azo. be able to.

  Although the above was demonstrated by gravure printing, printing systems, such as letterpress printing, screen printing, transfer printing, flexographic printing, etc., may be sufficient. The printing may be back printing or front printing.

(6) Primer layer In the present invention, a primer layer is preferably formed in advance on the surface of the base film constituting the body-wrapped label according to the present invention at least on the surface on the start end side of the label.

  By forming a primer layer in advance on the surface of the label on the starting end side, there is an advantage that the adhesive strength of the overlapping portion between the label and the label can be improved. Specifically, a primer layer can be formed in advance on the label surface.

  As the primer layer, for example, chlorinated polypropylene, ethyl-vinyl acetate, styrene-maleic acid, isocyanate, polyolefin, organic titanate, polyethyleneimine, polybutadiene, polyester, acrylic, etc. Examples thereof include a mold or a curable primer coating agent.

  The primer composition is coated by roll coating, gravure coating, knife coating, dip coating, spray coating, other coating methods, etc., the coating film is dried to remove the solvent and diluent, and if necessary An aging process etc. can be performed and it can be set as a primer layer.

(7) Outer layer The body-wrapped label of the present invention may be further provided with an outer layer on the surface side of the base film. As such an outer layer, it can be appropriately selected depending on the use and design properties of the body-wound label, and when giving the label surface slipperiness, OP varnish, when giving the tactile feeling when touching the label In the case of using a suede ink, it is preferable to use a matte OP or the like when giving a matte feeling. The outer layer may be a printed layer, or the outer layer may be a laminate composed of two or more layers such as a printed layer and another layer. In addition, if polylactic acid is used as such an outer layer, biodegradability is further improved.

  The thickness of the outer layer varies depending on the outer layer forming method and the like. For example, when an outer layer film is applied, the thickness is 6 to 100 μm, preferably 9 to 50 μm.

(8) Inner layer The body-wrapped label of the present invention may be provided with an inner layer on the base film. By disposing the inner layer, for example, a protective layer for a deposited film can be obtained. For such an inner layer, polylactic acid can be used, thereby improving biodegradability.

  The thickness of the inner layer varies depending on the inner layer forming method and the like. For example, when an inner layer film is applied, the thickness is 6 to 100 μm, preferably 9 to 50 μm.

(9) Body-wound label The body-wound label of the present invention includes a base film made of a gas barrier film in which a gas barrier layer is provided on a biodegradable film, and an alkali-soluble thermosensitive adhesive layer provided on both ends of the label of the base film. Consists of. Since the label can be directly attached to the container by the alkali-soluble heat-sensitive adhesive layers provided at both ends of the label, it is not necessary to form a cylinder in advance when attaching the label to the container. In addition, since a highly functional gas barrier performance can be secured by forming a specific gas barrier layer, the thickness of the biodegradable film relative to the thickness of the base film can be reduced, thus ensuring excellent biodegradability. can do. For this reason, it is a biodegradable body-wound label attached directly to the container.

  Moreover, although a base film is a biodegradable film, when this biodegradable film has heat shrinkability, the body-wound label of this invention can be used as a shrink label. As described above, when the biodegradable film is stretched, for example, in the case of a longitudinal uniaxially stretched film, the shrinkage direction is the film flow direction. In the case of a laterally uniaxially stretched film, the film shrinks in the film width direction, so that the thermal shrinkage rate in the film width direction is 5 to 85%. In the case of a biaxially stretched film, for example, the heat shrinkage rate can be adjusted to 5 to 85% in the vertical direction and the heat shrinkage rate to 5 to 85% in the horizontal direction. Even when an inorganic oxide vapor deposition layer is formed on this base film and the gas barrier coating film is laminated, these are thin layers with respect to the biodegradable film thickness. The shrink property corresponding to the heat shrinkage rate of the degradable film can be exhibited. Therefore, the body-wound label of the present invention can be a body-wound shrink label or a biodegradable body-wound shrink label.

  In addition, the alkali-soluble heat-sensitive adhesive layer is soluble in an aqueous solution having an alkali concentration of 1.5 w / w% at 85 ° C. to 90 ° C. for 15 minutes. According to the Recycling Law “Independent Design Guidelines for Type 2 Designated PET Bottles”, labels are peeled off when immersed in a cleaning solution of 1.5 w / w% alkali concentration at 85 ° C. to 90 ° C. for 15 minutes, and the adhesive is bottled. However, the remaining adhesive varies depending on the surface condition of the attached container. In the present invention, the alkali-soluble heat-sensitive adhesive used is used in any container by specifying that it is soluble in an aqueous solution with an alkali concentration of 1.5 w / w% at 85 ° C. to 90 ° C. for 15 minutes. In some cases, it can be peeled off. For this reason, it can be said that it is an alkali peelable body-wound label.

  And when the said alkali-soluble thermosensitive adhesive has the said water resistance with respect to tap water, it can be used conveniently for the container for liquids which require refrigeration. In this respect, it can be a refrigerated body-wound label.

(10) Method for producing body-wound label When the body-wound label of the present invention has a design printing layer inside the label of the base film as shown in FIG. 2, the design printing layer is formed in advance on the base film, Next, it is convenient to form an alkali-soluble heat-sensitive adhesive layer on the attached part. In the case where the body-wrapped label has an outer layer, it can be formed by forming a design printing layer on the base film and then inverting it and performing printing with, for example, OP varnish.

  In the body-wrapped label of the present invention, there are a roll coater method, an extrusion coater method, a slit orifice coater method using a direct roll, a gravure roll, etc. to form an alkali-soluble heat-sensitive adhesive layer. Any coating method may be used, and the solvent may be removed after dissolving and coating in a solvent. For example, a method in which an alkali-soluble heat-sensitive adhesive is applied to a laminated film in which a design print layer or an outer layer is previously formed on a base film using an adhesive coater or an adhesive applicator can be employed. In the present invention, the alkali-soluble heat-sensitive adhesive layer is formed by cutting the roll-wrapped label roll without the alkali-soluble heat-sensitive adhesive into a predetermined size when attaching the roll-wrap label to a container, A soluble heat-sensitive adhesive layer may be formed and then attached to the container. According to this, it is possible to prepare a body-wrapped label having an activated alkali-soluble heat-sensitive adhesive layer without providing a hot-air heating device for activating the alkali-soluble heat-sensitive adhesive layer, and immediately prepare the container If it attaches to, a container with a trunk winding label can be manufactured efficiently.

  In the body-wrapped label of the present invention, an opening perforation may be engraved from the upper end to the lower end. Furthermore, two vertical perforations may be provided starting from the label opening tab (separation start portion), and the label can be easily broken by the perforations. The perforation is not limited to two, but it is possible to provide one or more than three. The perforation is, for example, a disk-shaped cutting tool in which a cutting portion and a non-cutting portion are repeatedly formed around a method in which a laser beam is used to cut and form a predetermined depth in the thickness direction of the packaging material. It can give by the method of forming by pressing. The perforation can be applied at an appropriate stage in the process of producing the label. When the label attached to the container is peeled off by hand after use, the label is easily peeled off by the opening perforation. can do.

(11) Container There is no particular limitation on the container to which the body-wrapped label of the present invention can be attached, and any resin that can be bonded by the alkali-soluble heat-sensitive adhesive may be used. Accordingly, the adherend to which the body-wound label of the present invention is applied includes synthetic resin containers such as PET; inorganic containers such as ceramic containers; metal containers such as aluminum, iron, and SUS; glass, synthetic resin, ceramic, There are containers made of composite materials including metal, paper and the like. On the other hand, when the container has biodegradability, it can be decomposed in the soil after use, which makes it possible to eliminate the need for incineration, which is preferable. Moreover, although such a biodegradable container is inferior in gas barrier property, gas barrier property can be provided to a container by coat | covering the trunk-wrap label which is excellent in gas barrier property of this invention.

  Examples of such biodegradable containers include polyε-caprolactone, polybutylene succinate / polyethylene succinate, and poly-L-lactide (poly-L-lactic acid) described in the section of the biodegradable film. Microbial production polymers such as aliphatic polyester, cellulose, chitosan, lignin, starch, moisture, grafted starch and other natural products, 3-hydroxybutyrate-3-hydroxyvalerate copolymer, pullulan, bacterial cellulose, etc. A container made of such as a raw material can be suitably used.

  The polylactic acid can be produced by polymerizing lactic acid obtained by fermenting starch or saccharides made from corn or the like. Polylactic acid includes glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxy-n-butyric acid, 2-hydroxy-3,3-dimethylbutyric acid, and 2 without departing from the spirit of the present invention. -Copolymerization component of other hydroxycarboxylic acid units such as bifunctional aliphatic hydroxycarboxylic acids such as hydroxy-3-methylbutyric acid, 2-methyllactic acid and 2-hydroxycaproic acid, and lactones such as caprolactone, butyrolactone and valerolactone May be included. Furthermore, a chain extender residue and, if necessary, a heat stabilizer, a light stabilizer, a light absorber, a lubricant, a plasticizer, an inorganic filler, a colorant, a pigment, and the like may be added. As a polymerization method of lactic acid and other copolymerization components, for example, polymerization can be performed by a method such as a dehydration condensation polymerization method or a ring-opening polymerization method.

  On the other hand, the container used in the present invention is not limited to a biodegradable plastic. When the container is a synthetic resin container, if a polyester resin such as PET is used, it is lightweight and excellent in mechanical strength, heat resistance, gas barrier properties, chemical resistance, aroma retention, hygiene, etc. Therefore, it is preferable. When the container used in the present invention is made of a resin, it can be produced by injection molding, vacuum forming, pressure forming or the like of such a resin.

  In the present invention, the cap body attached to the mouth portion needs to have heat resistance, pressure resistance, water resistance, and light shielding properties. Specifically, the cap body is, for example, polyethylene resin, polypropylene resin, polystyrene resin, polycarbonate resin, polyester resin, polyamide resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile- Resins rich in heat resistance such as styrene-butadiene copolymer (ABS resin), polyacetal resin, and the like can be used. In addition, when the cap body is biodegradable, it is preferable to use a cap made of polylactic acid or the like as in the case of the container. The cap can be manufactured by using the above resin using an injection molding method or the like.

  In the above, a cap or the like provided with an annular body having a pilfer loop function may be used. Also in this case, it can be manufactured by using an injection molding method or the like using a resin as described above, using a molding die or the like matching the shape.

  Further, the cap is made of a metal such as aluminum or a plastic having a structure in which an oxygen gas barrier resin layer is provided on the inner surface side of the resin layer rich in heat resistance to give oxygen gas barrier properties. A cap can be used. The specification of the plastic cap may be a one-piece specification in which an oxygen gas-absorbing resin layer is formed on the inner surface of the cap by in-shell molding, or a sheet having the same function, a so-called liner, is bonded to the inner surface. A two-piece specification may be used.

  As the shape of the container, the container cross section of the body-wound label adhering portion of the body portion is not limited to a round shape, and may be a polygonal shape such as a square or an octagon. Further, the container body portion of the body-wound label adhering portion is not limited to the same diameter over the entire length of the body portion, and other than the case where the container body longitudinal section is a square, for example, a gourd type Good.

(12) Manufacturing method of container with a body-wound label The container with a body-wound label of the present invention can be manufactured by attaching the body-wound label to the container. Using a generally used labeling machine, the body-wound label of the present invention is heated, the alkali-soluble heat-sensitive adhesive provided on the label is activated, and then the entire container is heated with hot air or the like The said label is pressed and a body-wound label is attached to a container.

  Specifically, the roll label original roll is mounted on the original roll supply section of the labeling machine. The body-wrapped label pulled out from the original fabric roll is transferred to the cutting device through the drawing device while maintaining the tension constant by the tension roller. In the cutting device, the body-wrapped label is cut into a predetermined size and transferred to the sticking drum via a transfer drum in the vicinity of the cutting device. The alkali-soluble heat-sensitive adhesive of the body-wound label is heated by a heating device facing the sticking drum, and this label is transferred toward the sticking point of the container by the rotation of the sticking drum. Contacting the container supplied by the transport device, the label is glued, wound and secured to the container. Adhesion between the container and the label is performed by adhering the label at the start end of the label and the container, and then winding the remainder of the label around the outer periphery of the container, and then the label surface of the start end affixing part and the label innermost layer of the end affixing part It can be performed by adhering via an adhesive at the terminal sticking part. In addition, when attaching a label to a container, you may press the label attached to the container with a hot plate.

  The body-wrapped label may be heated a plurality of times at any appropriate stage before the label is attached to the container, and the alkali-soluble heat-sensitive adhesive of the label is reheated to, for example, about 90 to 100 ° C. with hot air from a heater. Then, the labeled container may be manufactured by bringing the label into close contact with the activated container. When attaching the label, press the label and attach it to the container while heating it by applying radiant heat such as steam, high-frequency seal, or infrared rays that heats the whole container with hot air, steam, or steam condensing steam. May be.

(13) Container with body-wound label The container with body-wound label of the present invention is excellent in gas barrier properties. Even if the container is inferior in gas barrier property, the contents can be protected from oxidation or the like by the gas barrier property of the body-wound label of the present invention. Such a container with a body-wound label may be filled with the contents after the label is attached to the container, or the label may be attached after the container is filled with the contents and sterilized as necessary. In particular, the method of attaching a label after filling the contents eliminates the need for an empty container transport process, can produce the required amount when necessary, facilitates inventory management, and eliminates the need for a large storage space. Thus, for example, a non-heated product can be manufactured by preparing a container from a preform as needed, filling and sealing the contents sterilized by an aseptic filling device, and then attaching the wound label of the present invention to the container. . The product has excellent contents quality, excellent gas barrier properties of the container after labeling, so it has excellent quality retention function, easy label management after filling the contents, and no steps such as transferring empty containers are required. After use, it decomposes without incineration due to biodegradability and is suitable for environmental protection.

  Furthermore, the container with a body-wound label according to the present invention is excellent in water resistance, so that the labeled container with the label attached is immersed in water for one day and then taken out of the water, and the adhesive strength of the label from the container and both ends of the label are determined. Since the adhesive strength between the end portions of the superimposed labels is 0.5 to 12 N / 15 mm, wrinkles do not occur, label position shifts and label dropouts do not occur even when immersed in water. For this reason, it can be used by cooling it in water at a stall or cooler box, and can also be stored in a refrigerator. In addition, since adhesive strength is the said range, it can peel easily from a container after use and can be peeled off, and it is excellent in a fraction collection property.

  The container with a body-wound label of the present invention can be used for various applications. Its contents include beer, wine, vitamin drinks, milk and milk drinks, juice, carbonated drinks, water, tea and other drinking water, oils and fats, seasonings, pharmaceuticals, cosmetics, detergents, and other various liquid foods. There is.

  EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all.

Example 1
(1) A biaxially stretched polylactic acid film having a thickness of 15 μm (product name “Ecologe SA101” manufactured by Mitsubishi Plastics Co., Ltd.) was used and mounted on a delivery roll of a plasma chemical vapor deposition apparatus. Under the conditions, a deposited film of an organic silicon oxide film having a thickness of 100 mm was formed on the corona-treated surface of the biaxially stretched polylactic acid film.

(Deposition conditions)
Deposition surface; corona-treated surface,
Introduced gas amount; hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 1.0 (unit: slm),
Degree of vacuum in the vacuum chamber; 2-6 × 10 ⁻⁶ mBar,
Degree of vacuum in the deposition chamber; 2-5 × 10 ⁻³ mBar,
Cooling and electrode drum supply power: 10 kW,
Line speed: 100 m / min,
Next, immediately after forming a silicon oxide vapor deposition film having a thickness of 100 mm as described above, a glow discharge plasma generator is used on the vapor deposition film surface of the organic silicon oxide film, and the power is 10 kw, oxygen gas (O ₂ ): Using a mixed gas composed of argon gas (Ar) = 8.0: 2.0 (unit: slm), oxygen / argon mixed gas plasma treatment was performed at a mixed gas pressure of 7 × 10 ⁻⁵ mBar and a processing speed of 100 m / min. As a result, a plasma-treated surface was formed in which the surface tension of the deposited surface of the organic silicon oxide film was improved by 54 dyne / cm or more.
A primer layer was formed by cloth.

  (2) Next, urethane-based ink (manufactured by Dainichi Seika Kogyo Co., Ltd., product name “Hilamic Abrasion White 100 / NB Hardener 5” on the plasma-treated surface of the biaxially stretched polylactic acid film on which the organic silicon oxide film is formed. ), And a gravure printing method was used to print a print pattern composed of characters, symbols, patterns, graphics, etc., to form a desired print pattern layer.

(3) Next, a delayed tack agent (manufactured by Daicel Chemical Industries, Ltd., product name “KP011”) containing ethylene-vinyl acetate copolymer resin as a main component is used as an alkali-soluble heat-sensitive adhesive layer on the printed pattern layer. Then, dilute with a solvent so as to have a non-volatile component of 61%, and apply by a gravure coating method at a coating amount of 6.5 g / m ² and a width of 10 mm to the portion that will be the beginning and end of the label. Then, a primer (manufactured by Dainichi Seika Kogyo Co., Ltd., product name “SECADINE”) is applied on the surface of the base film side with a gravure plate at a coating amount of 3 g / m ² and a width of 10 mm, and used for a wound label. A laminated film was obtained.

  (4) The obtained laminated film was cut into a height of 100 mm and a width of 240 mm to obtain a single-waist body-wound label according to the present invention.

(Example 2)
(1) A biaxially stretched polylactic acid film with a thickness of 15 μm (Mitsubishi Resin Co., Ltd., product name “Ecologe SA101”) is used, and this is attached to the feed roll of a wind-up type vacuum evaporation apparatus. Under the conditions shown below, by using vacuum as the electron beam (EB) heating method while supplying oxygen gas to the corona-treated surface of the above-mentioned biaxially stretched polylactic acid film as the vapor deposition source, A vapor-deposited film of aluminum oxide having a thickness of 200 mm was formed.

(Deposition conditions)
Deposition surface: Corona-treated surface,
Deposition source: Aluminum,
Degree of vacuum in the deposition chamber (before oxygen introduction): 2 to 10 × 10 ⁻⁵ mbar,
Degree of vacuum in the deposition chamber (after oxygen introduction): 1 to 10 × 10 ⁻⁴ mbar,
Line speed: 600 m / min,
Next, immediately after the above-described aluminum oxide vapor deposition film having a thickness of 200 mm was formed, a plasma-treated surface was formed on the aluminum oxide vapor deposition film surface in the same manner as in Example 1 above.

  (2) Next, urethane-based ink (manufactured by Dainichi Seika Kogyo Co., Ltd., product name “Hilamic Abrasion White 100 / NB Hardener 5” is formed on the plasma-treated surface of the biaxially stretched polylactic acid film on which the aluminum oxide vapor deposition film is formed. )) Was used to print a printing pattern composed of characters, symbols, patterns, figures, etc. by a gravure printing method to form a desired printing pattern layer.

(3) Next, a delayed tack agent (manufactured by Daicel Chemical Industries, Ltd., product name “KP011”) containing ethylene-vinyl acetate copolymer resin as a main component is used as an alkali-soluble heat-sensitive adhesive layer on the printed pattern layer. Then, dilute with a solvent so as to have a non-volatile component of 61%, and apply by a gravure coating method at a coating amount of 6.5 g / m ² and a width of 10 mm to the portion that will be the beginning and end of the label. Then, a primer (manufactured by Dainichi Seika Kogyo Co., Ltd., product name “SECADINE”) is applied on the surface of the base film side with a gravure plate at a coating amount of 3 g / m ² and a width of 10 mm, and used for a wound label. A laminated film was obtained.

  (4) The obtained laminated film was cut into a height of 100 mm and a width of 240 mm to obtain a single-waist body-wound label according to the present invention.

(Example 3)
(1) A biaxially stretched polylactic acid film having a thickness of 15 μm (product name “Ecologe SA101” manufactured by Mitsubishi Plastics Co., Ltd.) was used and mounted on a delivery roll of a plasma chemical vapor deposition apparatus. Under conditions, a vapor-deposited film of an organic silicon oxide film having a thickness of 100 mm was formed on the corona-treated surface of the biaxially stretched polylactic acid film.

(Deposition conditions)
Deposition surface; corona-treated surface,
Introduced gas amount; hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 1.0 (unit: slm),
Degree of vacuum in the vacuum chamber; 2-6 × 10 ⁻⁶ mBar,
Degree of vacuum in the deposition chamber; 2-5 × 10 ⁻³ mBar,
Cooling and electrode drum supply power: 10 kW,
Line speed: 100 m / min,
Next, immediately after forming a silicon oxide vapor deposition film having a thickness of 100 mm as described above, a glow discharge plasma generator is used on the vapor deposition film surface of the organic silicon oxide film, and the power is 10 kw, oxygen gas (O ₂ ): Using a mixed gas composed of argon gas (Ar) = 8.0: 2.0 (unit: slm), oxygen / argon mixed gas plasma treatment was performed at a mixed gas pressure of 7 × 10 ⁻⁵ mBar and a processing speed of 100 m / min. As a result, a plasma-treated surface was formed in which the surface tension of the deposited surface of the organic silicon oxide film was improved by 54 dyne / cm or more.

  On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixture of polyvinyl alcohol aqueous solution, silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.

次に、上記の（１）で形成したプラズマ処理面に、上記で製造したガスバリア性組成物を使用し、これをグラビアロールコート法によりコーティングして、次いで、１００℃で３０秒間、加熱処理して、厚さ０．４ｇ／ｍ²（乾操状態）のガスバリア性塗布膜を形成した。

Next, the plasma-treated surface formed in the above (1) is coated with the gas barrier composition produced above by the gravure roll coating method, and then heat-treated at 100 ° C. for 30 seconds. Thus, a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) was formed.

  (2) Next, a urethane-based ink (manufactured by Dainichi Seika Kogyo Co., Ltd., product name “HIRAMIC Abrasion White 100 / NB Hardener 5”) is used for the gas barrier coating film of the barrier film, and the gravure printing method is used. Then, a print pattern composed of characters, symbols, designs, figures, etc. was printed to form a desired print pattern layer.

(3) Next, a delayed tack agent (manufactured by Daicel Chemical Industries, Ltd., product name “KP011”) containing ethylene-vinyl acetate copolymer resin as a main component is used as an alkali-soluble heat-sensitive adhesive layer on the printed pattern layer. Then, dilute with a solvent so as to have a non-volatile component of 61%, and apply by a gravure coating method at a coating amount of 6.5 g / m ² and a width of 10 mm to the portion that will be the beginning and end of the label. Then, a primer (manufactured by Dainichi Seika Kogyo Co., Ltd., product name “SECADINE”) is applied on the surface of the base film side with a gravure plate at a coating amount of 3 g / m ² and a width of 10 mm, and used for a wound label. A laminated film was obtained.

  (4) The obtained laminated film was cut into a height of 100 mm and a width of 240 mm to obtain a single-waist body-wound label according to the present invention.

Example 4
(1) A biaxially stretched polylactic acid film with a thickness of 15 μm (Mitsubishi Resin Co., Ltd., product name “Ecologe SA101”) is used, and this is attached to the feed roll of a wind-up type vacuum evaporation apparatus. Under the conditions shown below, by using vacuum as the electron beam (EB) heating method while supplying oxygen gas to the corona-treated surface of the above-mentioned biaxially stretched polylactic acid film as the vapor deposition source, A vapor-deposited film of aluminum oxide having a thickness of 200 mm was formed.

(Deposition conditions)
Deposition surface: Corona-treated surface,
Deposition source: Aluminum,
Degree of vacuum in the deposition chamber (before oxygen introduction): 2 to 10 × 10 ⁻⁵ mbar,
Degree of vacuum in the deposition chamber (after oxygen introduction): 1 to 10 × 10 ⁻⁴ mbar,
Line speed: 600 m / min,
Next, immediately after the above-described aluminum oxide vapor deposition film having a thickness of 200 mm was formed, a plasma-treated surface was formed on the aluminum oxide vapor deposition film surface in the same manner as in Example 1 above.

  On the other hand, according to the composition shown in Table 2 below, composition a. EVOH (ethylene copolymerization ratio 29%) A composition prepared in advance in an EVOH solution dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzate composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, followed by stirring, and a composition prepared in advance c. A mixed liquid composed of an aqueous polyvinyl alcohol solution, acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating liquid.

次に、上記の（１）で形成したプラズマ処理面に、上記で製造したガスバリア性組成物を使用し、これをグラビアロールコート法によりコーティングして、次いで、１００℃で３０秒間、加熱処理して、厚さ０．４ｇ／ｍ²（乾操状態）のガスバリア性塗布膜を形成した。

Next, the plasma-treated surface formed in the above (1) is coated with the gas barrier composition produced above by the gravure roll coating method, and then heat-treated at 100 ° C. for 30 seconds. Thus, a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) was formed.

  (2) Next, a urethane-based ink (manufactured by Dainichi Seika Kogyo Co., Ltd., product name “HIRAMIC Abrasion White 100 / NB Hardener 5”) is used for the gas barrier coating film of the barrier film, and the gravure printing method is used. Then, a print pattern composed of characters, symbols, designs, figures, etc. was printed to form a desired print pattern layer.

(3) Next, a delayed tack agent (manufactured by Daicel Chemical Industries, Ltd., product name “KP011”) containing ethylene-vinyl acetate copolymer resin as a main component is used as an alkali-soluble heat-sensitive adhesive layer on the printed pattern layer. Then, dilute with a solvent so as to have a non-volatile component of 61%, and apply by a gravure coating method at a coating amount of 6.5 g / m ² and a width of 10 mm to the portion that will be the beginning and end of the label. Then, a primer (manufactured by Dainichi Seika Kogyo Co., Ltd., product name “SECADINE”) is applied on the surface of the base film side with a gravure plate at a coating amount of 3 g / m ² and a width of 10 mm, and used for a wound label. A laminated film was obtained.

  (4) The obtained laminated film was cut into a height of 100 mm and a width of 240 mm to obtain a single-waist body-wound label according to the present invention.

(Comparative Example 1)
(1) A plasma treatment is performed on a biaxially stretched polylactic acid film (product name “Ecologe SA101” manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 15 μm in the same manner as in (1) of Example 1, Using urethane-based ink (manufactured by Dainichi Seika Kogyo Co., Ltd., product name “HIRAMIC Abrasion-resistant White 100 / NB Hardener 5”), print a printing pattern consisting of letters, symbols, patterns, figures, etc. by gravure printing. Thus, a desired printed pattern layer was formed.

(2) Next, a delayed tack agent (manufactured by Daicel Chemical Industries, Ltd., product name “KP011”) containing ethylene-vinyl acetate copolymer resin as a main component is used as an alkali-soluble heat-sensitive adhesive layer on the printed pattern layer. Then, it was diluted with a solvent so as to have a non-volatile component of 61%, and applied by a gravure coating method at a coating amount of 6.5 g / m ² and a width of 10 mm to the portion that would be the beginning and end of the label. .

(3) Thereafter, a primer layer (product name “SECADINE”, manufactured by Dainichi Seika Kogyo Co., Ltd.) is applied to the surface of the base film on the starting end side with a gravure plate at a coating amount of 3 g / m ² and a width of 10 mm. A laminated film for labels was obtained.

  (4) The obtained laminated film was cut to a height of 100 mm and a width of 240 mm to obtain a body-wrapped label.

(Comparative Example 2)
Instead of the biaxially stretched polylactic acid film used in Comparative Example 1, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and the same operation as in Comparative Example 1 was performed to obtain a body-wrapped label.

(Experiment)
The body-wrapped labels (height 100 mm, width 240 mm) obtained in Examples 1 to 4 and Comparative Examples 1 and 2 are configured with the same diameter over a height of 100 mm on the outer periphery of a PET bottle having a height of 230 mm and an outer periphery of 230 mm. Wrapped around the surface of the cylindrical part with a labeling machine, heated at 100 ° C to 110 ° C for 1 second to adhere to the adhesive part between the bottle / label and heated to give adhesiveness The label / label was adhered by the label / label adhesive portion to obtain a container with a body-wrapped label.

  Gas barrier properties and biodegradability of the wound label obtained in Examples 1 to 4 and Comparative Examples 1 and 2, and adhesive strength between the wound label and the container in the container attached with the wound label, peelability, appropriate alkali treatment, water resistance Sex was evaluated. Each characteristic was evaluated according to the following. The results are shown in Table 3.

(1) Gas barrier properties (i) Measurement of oxygen permeability:
The measurement was performed with a measuring instrument (model name, OX-TRAN 2/20) manufactured by MOCON, USA under the conditions of a temperature of 23 ° C. and a humidity of 90% RH.

(Ii) Measurement of water vapor permeability:
The measurement was performed with a measuring instrument (model name, Permatran 3/31) manufactured by MOCON, USA, under conditions of a temperature of 40 ° C. and a humidity of 90% RH. The results are shown in Table 2. In Table 2, the unit of oxygen permeability is [cc / m ² / day · 23 ° C./90% RH], and the unit of water vapor permeability is [g / m ² / day · 40 ° C. · 90 % RH].

(2) adhesive strength;
The labels of Examples 1 to 4 and Comparative Examples 1 and 2 were affixed to the flat surface of a PET bottle and aged at room temperature for 1 week.

  Next, the test piece was cut out to a length of 10 mm and a width of 15 mm, and this was measured at a tensile speed of 300 mm / min by 180-degree peeling according to JIS K6848 using a tensile tester (Orientec). Evaluation based on the criteria. In Table 3, the adhesive strength per 15 mm (unit: N / 15 mm) is shown.

  ○: The adhesive strength is 0.5 to 12 N / 15 mm, and the label and the PET bottle are sufficiently adhered, but can be easily peeled by hand.

  X: Adhesive strength is less than 0.5 N / 15 mm, and when it comes into contact with another labeled container, the label is easily displaced.

(3) Peelability;
The label was peeled from the PET bottle by hand from the corner of the label, and the remaining amount of glue (or label) was visually evaluated on the surface of the PET bottle.

  ○: No glue (or label) left.

  X: The adhesive (or label) remainder has adhered to the container.

(4) Alkali treatment suitability;
The labeled PET bottles of Examples 1 to 4, Comparative Example 1 and Comparative Example 2 were cut into 8 mm lengths and 8 mm widths to obtain test pieces. This was immersed in an aqueous sodium hydroxide solution at 85 ° C. to 90 ° C. and 1.5 w / w% concentration for 15 minutes, stirred, and the label was separated from the container without peeling the label by hand. Thereafter, the remaining state of the glue (or label) was visually evaluated on the peeling surface of the PET bottle. The evaluation results are shown in Table 3.

  ○: No glue (or label) left.

  X: The glue (or label) remainder has adhered to the bottle.

(5) water resistance;
The container with the label is immersed in tap water at a water temperature of 5 ° C. for 1 day and then taken out of the water. The container with the label is cut out to a length of 10 mm and a width of 15 mm to form a test piece. Using a machine (Orientec Co., Ltd.), in accordance with JIS K6848, it was measured at a tensile rate of 300 mm / min by 180-degree peeling and evaluated according to the following criteria.

  ○: Adhesive strength is 1 N / 15 mm or more, and the adhesive label and the PET bottle are sufficiently adhered, but can be easily peeled by hand.

  X: Adhesive strength is less than 1 N / 15 mm, and natural peeling is easy.

  Or if it is 15 N / 15 mm or more, a strong force is required for peeling, and the label is broken and remains in the PET bottle.

(6) biodegradability;
The labels of Examples 1 to 4 and Comparative Examples 1 and 2 were cut into a size of 100 mm × 100 mm to obtain sample pieces. This was buried in soil with a depth of 10 cm, left for 3 months, then excavated, and biodegradability was evaluated according to the following criteria.

  ○: The weight of the sample after being left for 3 months is decomposed to less than half of the weight of the sample before being left.

  X: The weight of the sample after being left for 3 months is almost the same as the weight of the sample before being left, and is not decomposed.

  Since the body-wound label according to the present invention has biodegradability and excellent gas barrier properties, it has excellent content retention performance, and uses an alkali-soluble heat-sensitive adhesive. Therefore, the label can be easily removed by alkali treatment after using the container. Can be useful.

FIG. 1 is a cross-sectional view illustrating a body-wound label used in the present invention, and is a cross-sectional view of a label having a base film composed of a biodegradable film and a gas barrier layer. FIG. 2 is a cross-sectional view illustrating a body-wound label used in the present invention, which is a cross-sectional view of a label having a base film composed of a biodegradable film and a gas barrier layer, and further having a printing layer. FIG. 3 is a cross-sectional view illustrating a body-wrapped label used in the present invention, which has a base film composed of a biodegradable film and a gas barrier layer, and further has a primer layer on the label surface. It is. FIG. 4 is a schematic configuration diagram illustrating an example of a low-temperature plasma chemical vapor deposition apparatus. FIG. 5 is a schematic configuration diagram illustrating an example of a take-up vacuum deposition apparatus.

Explanation of symbols

10 ... base film,
11 ... biodegradable film,
15 ... gas barrier layer,
20 ... alkali-soluble heat-sensitive adhesive layer,
30 ... Design printing layer,
40 ... Primer layer,
W: Attached part.

Claims (24)

A body-wound label that is wound around the outer surface of the body of the container,
It consists of a base film and at least an alkali-soluble heat-sensitive adhesive layer provided on both ends of the label,
The base film is a gas barrier film in which a gas barrier layer is provided on a biodegradable film,
The alkali-soluble heat-sensitive adhesive layer is a body-wrapped label that dissolves in an aqueous solution having an alkali concentration of 1.5 w / w% at 85 ° C. to 90 ° C. for 15 minutes.   The said gas-barrier film is a body-wound label of Claim 1 in which the vapor deposition film | membrane of an inorganic oxide was formed in the single side | surface or both surfaces of a biodegradable film. The gas barrier film is provided with an inorganic oxide vapor-deposited film on one surface of a biodegradable film, and the general formula R ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents M A gas barrier obtained by polycondensation by a sol-gel method, which contains at least one alkoxide represented by the formula (1) and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. The body-wrapped label according to claim 1, which is a gas barrier film provided with a gas barrier coating film made of an adhesive composition.   4. The body-wrapped label according to claim 2, wherein the inorganic oxide vapor-deposited film is an inorganic oxide vapor-deposited film formed by chemical vapor deposition or physical vapor deposition.   The body-wrapped label according to any one of claims 2 to 4, wherein the inorganic oxide vapor-deposited film is an organic silicon oxide vapor-deposited film formed by chemical vapor deposition.   The body-wrapped label according to any one of claims 2 to 4, wherein the inorganic oxide vapor-deposited film is an aluminum oxide vapor-deposited film formed by physical vapor deposition. The general formula R ¹ _n M M of (OR ²⁾ in _m, silicon, wrapping label according to any one of claims 3 to 6 zirconium, titanium, or characterized in that it consists of aluminum.   The said alkoxide consists of an alkoxysilane, the hydrolyzate of an alkoxide, or the hydrolysis condensate of an alkoxide, The body-wound label in any one of said Claims 3-7 characterized by the above-mentioned.   The body-wrapped label according to any one of claims 3 to 8, wherein the gas barrier composition contains a silane coupling agent.   The body-wrapped label according to any one of claims 3 to 9, wherein the gas barrier coating film is a composite polymer layer in which one layer or two or more layers are stacked.   The gas barrier coating film is a base film on which a gas barrier composition is applied and provided with a coating film, at a temperature of 20 ° C. to 180 ° C. and a temperature equal to or lower than the melting point of the above base film for 10 seconds to 10 seconds. The body-wrapped label according to any one of claims 3 to 10, wherein the body-wrapped label comprises a cured film that has been heat-treated for a minute.   The wrapping label according to any one of claims 3 to 11, wherein the sol-gel catalyst is a tertiary amine that is substantially insoluble in water and soluble in an organic solvent.   The body-wrapped label according to claim 12, wherein the tertiary amine is N, N-dimethylbenzylamine.   The body-wound label according to any one of claims 3 to 13, wherein water is used at a ratio of 0.1 to 100 moles with respect to 1 mole of alkoxide.   The said biodegradable film is a body-wound label in any one of Claims 1-15 which is a film which extended | stretched the biodegradable plastic to the uniaxial or the biaxial.   The biodegradable film is a multilayer laminated film in which a biodegradable plastic or a biodegradable nonwoven fabric is laminated on a film obtained by uniaxially or biaxially stretching a biodegradable plastic. The trunk-wrap label in any one.   The body-wrapped label according to claim 1, wherein the biodegradable film is a polylactic acid film.   18. The body-wound label according to claim 1, wherein the alkali-soluble heat-sensitive adhesive layer is an alkali-soluble delayed tack adhesive and is formed on the base film by a gravure printing method.   The body-wrapped label according to any one of claims 1 to 17, wherein the alkali-soluble heat-sensitive adhesive layer is an alkali-soluble hot melt adhesive.   The body-wrapped label according to any one of claims 1 to 19, wherein the base film has a primer layer on at least a surface on a start end side of the label.   The body-wrapped label according to any one of claims 1 to 20, wherein a design print layer is formed inside the base film.   The design print layer is mainly composed of an aliphatic polyester resin ink composition, a urethane resin ink composition, an acrylic resin ink composition, or a chlorinated polypropylene ink composition, and one side of the base film, The body-wrapped label according to claim 21, wherein the body-wrapped label is formed on both sides.   The alkali-soluble heat-sensitive adhesive layer has an adhesive strength between a container and a label of 0.5 to 12 N / 15 mm and / or an adhesive strength between labels of 0.5 to 12 N / 15. The body winding label in any one of -22.   A container with a body-wound label, characterized in that the body-wound label according to any one of claims 1 to 23 is mounted on the outer peripheral surface of the body portion of the container with the application surface of the alkali-soluble heat-sensitive adhesive layer inside. .

Images