JP4578177B2 - Coating agent, plastic label and labeled container with excellent heat resistance and slipperiness - Google Patents

Description

  The present invention relates to a coating agent, a plastic label and a labeled container excellent in heat resistance and slipperiness.

  As a container for beverages such as soft drinks and coffee beverages, a plastic label such as a film (shrink label) having heat shrinkability printed on the side surface of a plastic container body such as a polyethylene terephthalate bottle (PET bottle). The attached container is used.

  However, containers such as PET bottles equipped with conventional labels are filled with heated contents or hot vendors (heating vending machines) for the purpose of heating beverages such as coffee and tea. ) And hot warmers (heating devices in stores), etc., for example, about 60 to 70 ° C., causing fusion (blocking) between containers due to the adhesive label There was a problem that it was easy. In particular, when such a container is housed in a hot vendor, the container is clogged in the vendor, causing troubles such as being unable to take out the product.

  As a label for preventing such pseudo thermal adhesion, a shrink label having a thermal adhesion preventing layer composed of a coating agent in which an acrylic resin having a specific glass transition temperature, polyethylene wax having a specific melting point, and silica is mixed is proposed. (For example, refer to Patent Document 1). According to this shrink label, it is possible to prevent thermal adhesion by being attached to a container, but there are problems such as inferior sliding property between containers.

  On the other hand, a plastic label in which a coating agent layer containing a fluororesin powder is applied on the non-contact surface side with respect to a container has been proposed (for example, see Patent Document 2). According to this plastic label, a certain level of slipperiness can be imparted when it is mounted on a container, but there is a risk that the fluororesin powder will cause dusting on the production line and the appearance will deteriorate. In particular, when printing was performed at a high speed in order to improve productivity, the problem due to dusting was significant. In order to avoid the above problems, it is conceivable to use a coating agent to which a liquid lubricant such as silicone oil is added in order to maintain good slipping while reducing the amount of fluororesin powder used. When a liquid lubricant is added to the coating agent disclosed in Document 2, the base resin swells, causing problems such as a decrease in coating film strength and a decrease in blocking resistance.

JP 2003-261172 A JP 2002-327149 A

An object of the present invention is to provide a plastic label which is excellent in blocking resistance during heating and has good slipping property.
Another object of the present invention is to provide a labeled container in which the container surface is slippery even during warming and is not easily clogged in a hot bender.

  As a result of intensive studies to achieve the above object, the present inventors have a specific friction coefficient, and according to a plastic label having a coating layer on its outer surface having a specific range of peel strength within a specific range, It has been found that the slipperiness is good and the blocking resistance at the time of heating is excellent, so that it is possible to avoid defective discharge of the container when the container with the label is accommodated in a hot bender, and the present invention has been completed.

That is , the present invention is a plastic label in which a coating layer is formed on at least the surface of the substrate that does not contact the adherend, and the coating layer comprises an acrylic resin having a glass transition temperature of 60 ° C. or higher. And a silicone oil having a functional group containing a hetero atom, and the ratio of the silicone oil is 0.1 to 5% by weight with respect to the total solid content (nonvolatile content) of the coating agent. Provide plastic labels. The coating agent may further contain a lubricant having a melting point of 90 ° C. or more in an amount of 0.1 to 10% by weight with respect to the total solid content (nonvolatile content) of the coating agent. As the lubricant at 90 ° C. or higher, fluorine-modified wax is preferably used.

Furthermore, the present invention provides a plastic label coating layer on the side of the surface not in contact with at least the adherend substrate are formed, the coating layer is, glass transition temperature is above 75 ° C. acrylic thermally A fluorine-modified wax containing a plastic resin in a proportion of 60% by weight or more based on the total solid content of the coating agent and having a melting point of 90 ° C. or higher is 0.1 to 30% by weight based on the total solid content of the coating agent. that provides plastic labels being formed by a coating agent containing.

Further, the present invention is selected from acrylic thermoplastic resins having a glass transition temperature of 60 ° C. or higher, amino-modified silicone oil, amide-modified silicone oil, carboxyl-modified silicone oil, alcohol-modified silicone oil, and fluorine-modified silicone oil. A coating agent comprising 0.1 to 5% by weight of silicone oil based on the total solid content of the coating agent is provided.

The present invention also provides a glass transition temperature of 75 ° C. or more thermoplastic acrylic resin comprises a ratio of more than 60 wt% with respect to the total solid content of the coating agent, and a melting point above 90 ° C. The fluorine-modified wax , that provides a coating agent containing 0.1 to 30 wt% with respect to the total solid content of the coating agent.

The present invention also provides a labeled container equipped with the plastic label of the present invention. At this time, the plastic label is preferably a label in which a coating layer is not formed on a portion that has been heat shrunk by 30% or more.

In the present specification, “solid content of the coating agent” means a non-volatile content remaining after the coating agent is dried. Specifically, the residue after the coating agent is dried at 105 ° C. for 1 hour. Is shown. In addition to the above invention, the present specification includes a plastic label in which a coating layer is formed on at least the surface of the substrate that does not contact the adherend, and the coating layer has a glass transition temperature. 71% or higher acrylic resin is contained in a proportion of 60% by weight or more based on the total solid content of the coating agent, and a lubricant having a melting point of 90 ° C. or higher is 0.1 to 0.1% of the total solid content of the coating agent. A plastic label formed of a coating agent containing 30% by weight, the plastic label in which a lubricant of 90 ° C. or higher is a fluorine-modified wax, an acrylic resin having a glass transition temperature of 60 ° C. or higher, and a functional group containing a hetero atom A coating agent containing 0.1 to 5% by weight of the silicone oil having a total glass content of 71 ° C. or more based on the total solid content of the coating agent. Contains 0.1% to 30% by weight of the lyl-based resin in a ratio of 60% by weight or more based on the total solid content of the coating agent and a melting point of 90 ° C. or higher based on the total solid content of the coating agent. The coating agent to be used, the coating agent in which the lubricant at 90 ° C. or higher is a fluorine-modified wax, and the labeled container to which the plastic label is attached are also described.

  Since the plastic label of the present invention is excellent in both blocking resistance and slipperiness during heating, when the container equipped with the label is accommodated in a hot bender or hot warmer, the containers due to thermal bonding of the labels Since the container surface is easy to slip, the container can be prevented from clogging in the vendor.

  Embodiments of the present invention will be described below with reference to the drawings as necessary. FIG. 1 is a schematic sectional view showing an example of the plastic label of the present invention. The plastic label 1 includes a printing layer (not shown), a base material 2 and a coating layer 3. In the plastic label of the present invention, it is only necessary that the coating layer 3 is formed on the surface of the substrate 2 that does not come into contact with the adherend (outer surface side), the interlayer between the substrate 2 and the coating layer 3, And / or other layers may be provided on the surface of the substrate 2 where the coating layer 3 is not formed.

  The plastic label 1 of the present invention only needs to be a plastic film as the substrate 2, and is a stretch label, a shrink label, a stretch shrink label, an in-mold label, a tack label, a roll label (a wrap-type glued label), a heat-sensitive adhesive label. Any of these may be used.

  One of the characteristics of the plastic label 1 of the present invention is that the coefficient of friction of the outer surface of the label on the coating layer 3 side is 0.3 or less (for example, 0.1 to 0) with respect to the outer surface of the similar plastic label on the coating layer side. .3). That is, the coefficient of friction between the outer surfaces of the plastic labels of the present invention is 0.3 or less. In particular, when the plastic label 1 is a shrink label, it is preferably about 0.15 to 0.25. If the coefficient of friction exceeds 0.3, the slipperiness of the container equipped with the plastic label is lowered, so that it is difficult to pass or fall through a predetermined passage when the container with the label is loaded into or removed from the vendor. Adjacent containers do not slip and may clog in the vendor. The coefficient of friction is preferably 0.3 or less even when heated (65 ° C.).

  For the same reason as described above, the plastic label 1 has a coefficient of friction on the outer surface on the coating layer 3 side of, for example, 0.45 or less (for example, 0.2 to 0.45) with respect to the stainless steel plate. In particular, when the plastic label 1 is a shrink label, it is preferably about 0.25 to 0.40. The coefficient of friction is preferably 0.45 or less even when heated (65 ° C.).

  In the present invention, a dynamic friction coefficient and a static friction coefficient can be employed as the friction coefficient on the coating layer surface of the plastic label. That is, it is preferable that both the static friction coefficient and the dynamic friction coefficient with respect to the outer surface similar to the plastic label are 0.3 or less. Moreover, it is preferable that both the static friction coefficient and the dynamic friction coefficient with respect to a stainless steel plate are 0.45 or less.

  In addition, the static friction coefficient and dynamic friction coefficient in this invention can be measured based on JISK7125. The coefficient of friction can be adjusted by appropriately selecting the type and amount of components (resin, lubricant, etc.) of the coating agent that forms the coating layer.

  Another feature of the plastic label 1 of the present invention is that the outer surfaces of the label on the coating layer 3 side are overlapped, and the peel strength after pressing at a temperature of 70 ° C. for 180 seconds under a pressure of 0.38 MPa is 0.1 N / It is in the point which is 15 mm or less. When the peel strength is 0.1 N / 15 mm or more, the outer surfaces of the labels may be blocked when heated (inferior in blocking resistance). Therefore, when the container equipped with the label is stored in the hot bender, At a temperature of (for example, about 70 ° C.), the containers are fused with each other, causing the containers to become clogged in the bender. The peel strength can be adjusted by appropriately selecting the type and amount of the components (resin, lubricant, etc.) of the coating agent that forms the coating layer.

  The peel strength can be measured by a T-type peel test (peel rate of 200 mm / min) according to JIS K 6854-3.

  The coating layer 3 can be formed of a coating agent that can impart the characteristics of the plastic label of the present invention. The coating agent contains a resin and a lubricant. The resin is not particularly limited as long as it can be dissolved or dispersed in a solvent. For example, a thermoplastic resin such as polyester, polyvinyl chloride, polyvinyl acetate, cellulose resin, acrylic resin, or urethane resin is used alone. Or a mixture of two or more. Among them, an acrylic resin is preferable from the viewpoint of effectively exhibiting the above characteristics, and particularly an acrylic resin having a glass transition temperature of 60 ° C. or higher (for example, 60 to 180 ° C.) from the viewpoint of heat resistance and slipperiness. Examples of the acrylic resin having a glass transition temperature (Tg) of 60 ° C. or higher include trade names “Dianar GR 5491” (Tg 65 ° C.), “Dianar GR 5539” (Tg 150 ° C.) manufactured by Mitsubishi Rayon Co., Ltd.

  The amount of the resin can be appropriately selected within a range not impairing the characteristics of the present invention, and is, for example, 50% by weight or more (50 to 100% by weight), preferably 60% by weight or more (60%) with respect to the total solid content of the coating agent. ~ 100 wt%).

  The coating agent may contain a silicone oil having a functional group containing a hetero atom as a lubricant. In the present invention, the hetero atom means an atom excluding a carbon atom and a hydrogen atom, and examples thereof include a halogen atom such as a nitrogen atom, an oxygen atom, a sulfur atom, and a fluorine atom. As the functional group containing a hetero atom, for example, an amino group, an amide group, an epoxy group, a carboxyl group, a hydroxyl group, a fluorine atom, or the like is preferably used. As the silicone oil having a functional group containing a hetero atom, for example, amino-modified silicone oil, amide-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, alcohol-modified silicone oil, fluorine-modified silicone oil and the like are preferably used. . In particular, amino-modified silicone oil, fluorine-modified silicone oil and the like are preferable. When silicone oils having functional groups containing these heteroatoms are used, good orientation and compatibility with the resin contained in the coating agent are exhibited by the action of the functional groups in the molecule, and the resin does not swell. Therefore, it is possible to impart excellent blocking resistance and slipperiness without causing a decrease in coating film strength and the like.

  Silicone oil having a functional group containing a hetero atom is not an essential component and can be used in an appropriate amount within a range not impairing the characteristics of the present invention. For example, 0.1 to 5% by weight relative to the total solid content of the coating agent %, Preferably about 0.1 to 3% by weight. If it is less than 0.1% by weight, the effect of adding silicone oil is insufficient, and if it exceeds 5% by weight, the orientation and compatibility are lowered, and the adhesion to the film constituting the substrate 2 is lowered.

  In the present invention, a coating agent containing 0.1 to 5% by weight of an acrylic resin having a glass transition temperature of 60 ° C. or more and a silicone oil having a functional group containing a hetero atom with respect to the total solid content of the coating agent can be used. . According to this coating agent, the acrylic resin having a glass transition temperature of 60 ° C. or higher gives heat resistance, in particular, blocking resistance even under heating conditions, and also has excellent slipperiness due to the action of the functional group of the silicone oil. A coating layer imparted with blocking resistance can be formed.

  In the present invention, an acrylic resin having a glass transition temperature of 71 ° C. or higher is contained in a proportion of 60% by weight or more with respect to the total solid content of the coating agent, and a lubricant having a melting point of 90 ° C. or higher is used. A coating agent containing 0.1 to 30% by weight with respect to the total solid content can also be used. According to this coating agent, it is possible to form a coating layer which is imparted with heat resistance and further blocking resistance under heating conditions, and excellent in slipperiness.

  The coating agent may contain a lubricant other than silicone oil having a functional group containing a hetero atom. Such a lubricant is not particularly limited, and may be either an organic lubricant or an inorganic lubricant, and examples thereof include particulate solid substances such as inorganic particles and organic particles, wax, and liquid components. Specific examples of the lubricant are shown below, but from the viewpoint of heat resistance imparted to the coating layer, a lubricant having a melting point of 90 ° C. or higher is preferable, and organic particles, waxes, particularly fluororesins and fluorine-modified waxes are particularly preferable. used.

  When a label having a coating layer containing a lubricant on the outer surface comes into contact with the metal, soft lubricants (fluorine resin, etc.) are easily crushed due to wear with the metal, and the effect of improving slipperiness may be impaired. Has excellent wear resistance against metals. Further, the compatibility with the resin constituting the coating agent is that the fluorine-modified wax is better than the fluororesin, and powdering is less likely to occur on the production line. For example, when printing is performed at high speed to improve productivity, the volatilization of the solvent contained in the coating agent cannot catch up, and in particular, a lubricant with low compatibility with the resin (binder, etc.) constituting the coating agent is applied. It easily detaches from the subsequent coating agent and easily causes dusting. From the above viewpoint, fluorine-modified wax is more preferably used.

  Particulate solid materials include silica, talc, mica, kaolin, bentonite, clay, graphite, fluorinated graphite, carbon black, titanium oxide, zinc oxide, magnesium oxide, boron nitride, molybdenum disulfide, tungsten disulfide, calcium carbonate Inorganic particles such as calcium sulfate, calcium titanate, calcium phosphate, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, glass powder, alumina, metal powder; higher alcohols such as stearyl alcohol, higher fatty acids such as stearic acid, stearic acid Higher fatty acid esters such as butyl, fatty acid and polyhydric alcohol partial esters such as glycerin fatty acid esters, higher fatty acid amides such as stearic acid amide and ethylenebisstearyl amide, barium stearate, calcium stearate, Salts of higher fatty acids such as zinc phosphate, aluminum stearate, magnesium stearate (metal soap), fluororesin, polyacetal, poly (meth) acrylic acid metal salt, polyacrylonitrile, polyacrylamide, melamine resin, phenolic Organic particles such as resin, starch powder, and cellulose powder are included.

  The fluororesin may be a resin containing at least a fluorine atom-containing monomer as a monomer component. For example, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF) ), Polyvinyl fluoride (PVF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether (Co) polymer comprising one or more fluorine atom-containing monomers such as copolymer (EPE); tetrafluoroethylene-ethylene copolymer (ETFE), chlorotrifluoroethylene-ethylene Such as Ren copolymer (ECTFE) 1 or more kinds of fluorine-containing monomer and other copolymerizable monomers, and a copolymer of, and the like.

  The wax includes mineral wax such as microcrystalline wax, oxidized microcrystalline wax, paraffin, oxidized paraffin, and montan wax; polyethylene wax, polypropylene wax, oxidized polyethylene wax, oxidized polypropylene wax, fluorine-modified wax, chlorinated polyethylene wax Synthetic waxes such as chlorinated polypropylene wax, ethylene-acrylic acid copolymer wax, ethylene-vinyl acetate copolymer wax, polycarbonate wax; Natural waxes such as wax, cane wax, candelilla wax, shellac wax, rice wax and sugar wax are included. The lubricants can be used alone or in admixture of two or more.

  Examples of the fluorine-modified wax include those formed by a method such as a method of subjecting the above exemplified wax to a fluorine gas treatment, and commercially available products can be used. Specific examples include fluorine-modified polyolefin waxes such as fluorine-modified polyethylene wax and fluorine-modified polypropylene wax; fluorine-modified synthetic waxes such as fluorine-modified oxidized polyolefin waxes such as fluorine-modified polyethylene oxide wax and fluorine-modified oxidized polypropylene wax. Of these, fluorine-modified polyolefin waxes such as fluorine-modified polyethylene wax and fluorine-modified polypropylene wax are preferable.

  When a coating agent using a particulate solid substance such as a fluororesin or a wax such as a fluorine-modified wax is applied as a lubricant by gravure printing, the average particle diameter of the lubricant is 30 μm or less (for example, 1 to 25 μm, preferably 1 ˜20 μm, more preferably about 2-15 μm). When a fluorine-modified wax is used as a lubricant, a spherical particle shape is suitable, and those having a uniform particle shape and size (particle size) are more preferably used.

  The amount of the lubricant can be appropriately selected within a range not impairing the above characteristics, and is, for example, about 0.1 to 30% by weight, preferably about 0.1 to 20% by weight, based on the total solid content of the coating agent. Moreover, when using the silicone oil which has the functional group containing the said hetero atom as a lubricant, the lubricant other than this silicone oil is not used, or the usage-amount of a lubricant is 10 weight% or less (0.1-10). Even when it is reduced to about weight%), slipperiness is not impaired and powdering can be prevented. Further, when the melting point of the lubricant is 90 ° C. or higher, excellent blocking resistance and slipperiness are exhibited even under heating conditions.

  In addition to the above, the coating agent includes an anti-settling agent (such as an amide anti-settling agent), a dispersion stabilizer (such as a surfactant), a matting agent, an extender pigment, various colorants, a filler, an antioxidant, an ultraviolet ray Additives such as an absorbent and an antistatic agent may be included.

  The coating agent is prepared by dissolving or dispersing the above components (resin, lubricant, additive, etc.) in a solvent. As the solvent, for example, an organic solvent having low toxicity, for example, acetates such as ethyl acetate and n-propyl acetate, and alcohols such as methanol, ethanol and isopropyl alcohol can be preferably used.

  The thickness of the coating layer 3 can be appropriately selected within a range in which the above characteristics can be exhibited, and is, for example, 0.5 to 5 μm, preferably 1 to 3 μm. The coating layer 3 is preferably transparent.

  Examples of the base material 2 include polyester films made of polyethylene terephthalate, styrene resin films made of styrene-butadiene block copolymers, olefin resin films such as polypropylene, and plastic films such as vinyl chloride resin films. . The substrate can be formed of one or more materials, and may be a single layer or a multilayer, and may be an unstretched film, a uniaxially stretched film or a biaxially stretched film. When the plastic label is a shrink label, as a preferred substrate, a heat-shrinkable single-layer or multi-layer styrene resin film having a shrinkage ratio of 50% or more in one direction, a polyester film, a cyclic polyolefin film, and the above A film in which a nonwoven fabric is laminated on a polyester film is used.

  The surface of the substrate 2 on the printed layer side may be subjected to conventional surface treatment such as corona discharge treatment or plasma treatment in order to improve printability. Moreover, you may add various additives, such as a filler, a heat stabilizer, antioxidant, a ultraviolet absorber, an antistatic agent, a flame retardant, and a coloring agent, to the base material 2 as needed. The thickness of the base material 2 can be selected within a range that does not impair the handleability, workability, and the like when used as a label, and is, for example, about 20 to 80 μm, preferably about 30 to 60 μm.

  A printing layer (not shown) can be provided on at least one surface of the substrate 2 by a conventional printing method such as gravure printing.

  As the plastic label 1 of the present invention, the coating layer 3 includes an acrylic resin having a glass transition temperature of 60 ° C. or more and a silicone oil having a functional group containing a hetero atom, and the ratio of the silicone oil is a coating agent. The plastic label formed with the coating agent that is 0.1 to 5% by weight with respect to the total solid content of the coating material, or the coating layer 3 is an acrylic resin having a glass transition temperature of 71 ° C. or more, and the solid content of the coating agent. A plastic label which is formed of a coating agent containing a lubricant having a melting point of 90 ° C. or higher and a melting point of 90 ° C. or higher with respect to the total amount of 0.1 to 30% by weight with respect to the total solid content of the coating agent. Can be used.

  Since these plastic labels have the above-described configuration, the friction coefficient of the outer surface on the coating layer 3 side is 0.3 or less with respect to the same surface, and has good slipperiness, and two plastic labels. Is peeled off after pressurizing at a temperature of 70 ° C for 180 seconds under conditions of 0.38MPa pressure and 0.1N / 15mm or less, and is excellent in blocking resistance. Is preferable.

  The plastic label 1 of the present invention can be produced, for example, by applying a coating agent to the surface of a plastic film (base material 2) that has been subjected to stretching treatment as necessary, by a method such as printing such as gravure printing.

  The plastic label 1 obtained by the above method is processed into a desired shape and used according to the purpose. For example, when the plastic label 1 is a shrink label, the coating layer 3 is on the outer side, and the base 2 is rounded into a cylindrical shape so that the main stretching direction (usually the width direction) is the circumferential direction, and both ends are It is possible to obtain a cylindrical shrink label by bonding with a solvent or the like to form a continuous tubular shrink label continuous body and cutting into each label. In addition, in order to obtain favorable adhesiveness, it is preferable that a coating agent is not applied to the bonded portion.

  In the labeled container of the present invention, for example, the plastic label 1 is mounted on the container 4 as shown in FIG. The material of the container 4 is not particularly limited, and may be any of a plastic container made of polyester such as polyethylene terephthalate, a glass container, and a metal container. The shape of the container 4 may be any of a polygonal shape having a substantially rectangular cross section, a cylindrical shape having a circular cross section, and the like.

  The container with a label of the present invention supplies, for example, a cylindrical plastic label (shrink label) 1 having an outer surface on the coating layer 3 side to an automatic label mounting device, cuts it to a required length, It can be manufactured by being externally fitted to the filled container 4 and passing through a hot air tunnel or a steam tunnel at a predetermined temperature, or by heat shrinkage by heating with radiant heat such as infrared rays. At this time, since the label fitted to the container 4 is thermally contracted, the label fits closely to the shape of the shoulder portion of the container 4, but the coating is applied when the label is highly contracted according to the shape of the container 4. The layer 3 may whiten the highly contracted portion of the label and impair the appearance. On the other hand, by using a plastic label in which a coating layer is not formed on a part where the label is highly shrunk, for example, a part that is thermally shrunk by 30% or more, a part where the containers come into contact with each other (for example, the body of a bottle-shaped container) This is preferable because the whitening of the label due to the presence of the coating layer does not occur while maintaining the slipperiness of the film.

  FIG. 3 is a schematic view showing another example of the labeled container of the present invention. In FIG. 3, a plastic label 1 ′ (shrink label) covering the outer periphery of the bottle-shaped container body 4 has a layer structure corresponding to the area covered by the label. Specifically, in the plastic label 1 ′, the part a covering the container body 4 a is composed of the base material 2 and the coating layer 3, and the part b covering the shoulder part 4 b is composed of only the base material 2. . For this reason, the label portion b which is highly shrunk in the container shoulder 4b is not whitened, can maintain a good appearance, and has a container body 4a (within the vendor) provided with a coating layer. The portion in contact with the other container) can exhibit good slipperiness and blocking resistance.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
Mixed solution of acrylic resin in ethyl acetate / isopropyl alcohol [trade name “Dyanal GR5491”, manufactured by Mitsubishi Rayon Co., Ltd .: glass transition temperature 65 ° C., molecular weight 90000, solid content 35.7 wt%, acid value 0 mgKOH / g ( solid)] 54 parts by weight, amino-modified silicone oil (trade name “KF-859”, manufactured by Shin-Etsu Silicone Co., Ltd.) 0.5 part by weight, fluororesin powder (melting point 325 ° C., average particle size 9 μm): trade name “Aflon L150J ", manufactured by Asahi Glass Fluoropolymers Co., Ltd.), 0.5 parts by weight, 35 parts by weight of ethyl acetate and 10 parts by weight of propyl acetate were mixed to form a coating agent (95% by weight of acrylic resin relative to the total solid content, silicone Containing 2.5% by weight of oil).
This coating agent is applied to one surface of a heat-shrinkable polyester film [thickness 50 μm: product name “S7561” manufactured by Toyobo Co., Ltd.] by gravure printing so that the thickness is 0.5 to 2 μm. Thus, a shrink label having a coating layer was obtained.
The obtained shrink label was rounded into a cylindrical shape so that the width direction of the base film would be the circumferential direction, and both ends were welded by heat to obtain a long tubular shrink label continuous body. The shrink label continuum is supplied to an automatic label mounting device, cut into each label, and then externally fitted into a 500 ml PET bottle with a cross section of a square shape filled with coffee (temperature 85 ° C.). The container with a label shown in FIG. 2 was manufactured by passing through (temperature 90 ° C.) and causing heat shrinkage.

Example 2
In Example 1, an acrylic resin ethyl acetate / isopropyl alcohol mixed solution [trade name “Dyanal GR5539”, manufactured by Mitsubishi Rayon Co., Ltd .: Glass instead of the acrylic resin solution “Dianar GR5491” as a coating agent. The same components as in Example 1 were mixed except that the transition temperature was 150 ° C., the molecular weight was 50000, the solid content was 41.3 wt%, and the acid value was 20 mg KOH / g (solid)]. 95.5% by weight of acrylic resin and 2.2% by weight of silicone oil were prepared with respect to the total amount).
Using this coating agent, a shrink label was obtained in the same manner as in Example 1.
A labeled container was produced by the same operation as in Example 1 using the obtained label.

Comparative Example 1
In Example 1, instead of the acrylic resin solution “Dianar GR5491”, a mixed solution of acrylic resin in ethyl acetate / isopropyl alcohol [trade name “Dyanal GR5492”, manufactured by Mitsubishi Rayon Co., Ltd .: Glass Transition The same components as in Example 1 were mixed except that the temperature was 55 ° C., the molecular weight was 90,000, the solid content was 35.8% by weight, and the acid value was 0 mg KOH / g (solid)]. 95.0% by weight of acrylic resin and 2.5% by weight of silicone oil).
Using this coating agent, a shrink label was obtained in the same manner as in Example 1.
A labeled container was produced by the same operation as in Example 1 using the obtained label.

Comparative Example 2
In Example 1, the same components as in Example 1 were mixed except that 35.5 parts by weight of ethyl acetate was used as the coating agent without using silicone oil. Containing 97.4% by weight of an acrylic resin).
Using this coating agent, a shrink label was obtained in the same manner as in Example 1.
A labeled container was produced by the same operation as in Example 1 using the obtained label.

Example 3
In Example 1, instead of amino-modified silicone oil (trade name “KF-859”, manufactured by Shin-Etsu Silicone Co., Ltd.) as a coating agent, amino-modified silicone oil (trade name “TSF4702”, GE Toshiba Silicone Co., Ltd.) The same components as in Example 1 were mixed except that 0.5 part by weight of the product was used, and the coating agent (acrylic resin was 95.0% by weight and silicone oil was 2.5% with respect to the total solid content). Containing% by weight).
Using this coating agent, a shrink label was obtained in the same manner as in Example 1.
A labeled container was produced by the same operation as in Example 1 using the obtained label.

Example 4
In Example 1, instead of amino-modified silicone oil, 0.5 parts by weight of epoxy-modified silicone oil (trade name “XC96-A4463”, manufactured by GE Toshiba Silicone Co., Ltd.) was used as a coating agent. The same components as in Example 1 were mixed to prepare a coating agent (containing 95.0 wt% acrylic resin and 2.5 wt% silicone oil based on the total solid content).
Using this coating agent, a shrink label was obtained in the same manner as in Example 1.
A labeled container was produced by the same operation as in Example 1 using the obtained label.

Example 5
In Example 1, except that 0.5 parts by weight of carboxyl-modified silicone oil (trade name “TSF4770”, manufactured by GE Toshiba Silicone Co., Ltd.) was used as a coating agent instead of amino-modified silicone oil. The same component as 1 was mixed to prepare a coating agent (containing 95.0 wt% acrylic resin and 2.5 wt% silicone oil based on the total solid content).
Using this coating agent, a shrink label was obtained in the same manner as in Example 1.
A labeled container was produced by the same operation as in Example 1 using the obtained label.

Example 6
In Example 1, except that 0.5 parts by weight of alcohol-modified silicone oil (trade name “TSF4750”, manufactured by GE Toshiba Silicones Co., Ltd.) was used as a coating agent instead of amino-modified silicone oil. The same component as 1 was mixed to prepare a coating agent (containing 95.0 wt% acrylic resin and 2.5 wt% silicone oil based on the total solid content).
Using this coating agent, a shrink label was obtained in the same manner as in Example 1.
Using the resulting shrink label, a labeled container was produced by the same operation as in Example 1.

Example 7
In Example 1, except that 0.5 parts by weight of fluorine-modified silicone oil (trade name “FQF501”, manufactured by GE Toshiba Silicones Co., Ltd.) was used instead of amino-modified silicone oil as a coating agent. The same component as 1 was mixed to prepare a coating agent (containing 95.0 wt% acrylic resin and 2.5 wt% silicone oil based on the total solid content).
Using this coating agent, a shrink label was obtained in the same manner as in Example 1.
Using the resulting shrink label, a labeled container was produced by the same operation as in Example 1.

Comparative Example 3
In Example 1, except that 0.5 parts by weight of alkyl-modified silicone oil (trade name “TSF4422”, manufactured by GE Toshiba Silicone Co., Ltd.) was used instead of amino-modified silicone oil as the coating agent. The same component as 1 was mixed to prepare a coating agent (containing 95.0 wt% acrylic resin and 2.5 wt% silicone oil based on the total solid content).
Using this coating agent, a shrink label was obtained in the same manner as in Example 1.
Using the resulting shrink label, a labeled container was produced by the same operation as in Example 1.

Example 8 (referred to as a reference example)
Mixed solution of acrylic resin in ethyl acetate / isopropyl alcohol [trade name “Dyanal GR5511,” manufactured by Mitsubishi Rayon Co., Ltd .: glass transition temperature 75 ° C., molecular weight 50000, solid content 35.6 wt%, acid value 0 mgKOH / g ( solid)], 54 parts by weight, modified polyethylene wax (melting point 135-150 ° C .: trade name “EFKA 6903”, manufactured by Wilber Ellis Co., Ltd.) 1.5 parts by weight, ethyl acetate 34.5 parts by weight and propyl acetate 10 parts by weight Parts were mixed to prepare a coating agent (containing 92.8% by weight of acrylic resin and 7.2% by weight of modified polyethylene wax with respect to the total solid content).
Using this coating agent, a shrink label was obtained in the same manner as in Example 1.
Using the resulting shrink label, a labeled container was produced by the same operation as in Example 1.

Examples 9-15
In Examples 1-7, it is the same as that of Examples 1-7 except that 0.5 weight part of fluorine-modified polyethylene wax (trade name “LUNCO-WAX TF1778”, manufactured by LUBRIZOL) was used instead of the fluororesin powder. A coating agent was prepared by the above procedure, and a shrink label and a labeled container were produced using the coating agent. In addition, each content of acrylic resin and silicone oil with respect to the solid content whole quantity which comprises the coating agent in Examples 8-16 was the same as that of corresponding Examples 1-7.

Example 16
In Example 8, a coating agent was prepared in the same manner as in Example 8 except that 1.5 parts by weight of fluorine-modified polyethylene wax (trade name “LUNCO-WAX TF1778”, manufactured by LUBRIZOL) was used instead of the modified polyethylene wax. Prepare 92.8% by weight acrylic resin and 7.2% by weight fluorine-modified polyethylene wax based on the total solid content, and manufacture shrink labels and labeled containers using this coating agent did.

Comparative Examples 4-6
Comparative Examples 1 to 3 were the same as Comparative Examples 1 to 3 except that 0.5 parts by weight of fluorine-modified polyethylene wax (trade name “LUNCO-WAX TF1778”, manufactured by LUBRIZOL) was used instead of the fluororesin powder. A coating agent was prepared by the above procedure, and a shrink label and a labeled container were produced using the coating agent. In addition, each content of the acrylic resin and silicone oil with respect to the solid content whole quantity which comprises the coating agent in Comparative Examples 4-6 was the same as that of the corresponding Comparative Examples 1-3.

(Evaluation test)
The results of the evaluation tests by the following methods are shown in Table 1 for Examples 1 to 8 and Comparative Examples 1 to 3, and in Table 2 for Examples 9 to 16 and Comparative Examples 4 to 5, respectively.
Sliding property About the shrink labels obtained in Examples and Comparative Examples, the outer surfaces of the shrink labels were overlapped with each other in accordance with JIS K 7125, and the static friction coefficient and the dynamic friction coefficient were measured. The case where any friction coefficient was 0.30 or less was indicated by “◯”, and the case where any one friction coefficient exceeded 0.30 was indicated by “x”, and the slipperiness was evaluated.

Blocking resistance The outer surfaces of the shrink labels obtained in Examples and Comparative Examples were overlapped and pressed at a temperature of 70 ° C. for 180 seconds under a pressure of 0.38 MPa, and a T-type peel test according to JIS K 6854-3. The peel strength was measured by (peel rate 200 mm / min). A peel strength of 0.1 N / 15 mm or less was indicated by “◯”, and a peeling strength of 0.1 N / 15 mm or more was indicated by “x”, and blocking resistance was evaluated.

Hot Bender Mounting Evaluation The labeled containers (products) obtained in the examples and comparative examples are loaded into a vending machine (vendor temperature 65 ° C.) manufactured by Sanyo Electric Co., Ltd. It was investigated whether (100 pieces) would come out to the product take-out port (mounting evaluation). All 100 labeled containers in the example came out to the product take-out port. Sometimes it did not come out to the outlet.

It is a schematic sectional drawing which shows an example of the plastic label of this invention. It is a perspective view which shows an example of the labeled container of this invention. It is a perspective view which shows the other example of the labeled container of this invention.

Explanation of symbols

1,1 'plastic label
2 Base material
3 Coating layer
4 containers
4a Container body
4b Container shoulder
a Label part covering the container body
b Label part covering the container shoulder

Claims (8)

  A plastic label in which a coating layer is formed on at least a surface of a substrate that does not come into contact with an adherend, wherein the coating layer has a functional group containing an acrylic resin having a glass transition temperature of 60 ° C. or higher and a hetero atom. And a silicone oil having a group, and the ratio of the silicone oil is 0.1 to 5% by weight based on the total solid content of the coating agent. Coating agent, plastic label of claim 1, wherein the melting point of the 90 ° C. or more lubricants, containing 0.1 to 10% by weight relative to the total solid content of the coating agent. The plastic label according to claim 2 , wherein the lubricant having a melting point of 90 ° C or higher is a fluorine-modified wax. A plastic label in which a coating layer is formed on at least a surface of a substrate that does not come into contact with an adherend, and the coating layer comprises an acrylic thermoplastic resin having a glass transition temperature of 75 ° C. or more, It is formed of a coating agent containing 0.1 to 30% by weight of a fluorine-modified wax containing 60% by weight or more with respect to the total solid content and having a melting point of 90 ° C. or more with respect to the total solid content of the coating agent. Plastic labels. An acrylic thermoplastic resin having a glass transition temperature of 60 ° C. or higher and a silicone oil selected from amino-modified silicone oil, amide-modified silicone oil, carboxyl-modified silicone oil, alcohol-modified silicone oil, and fluorine-modified silicone oil are used as a coating agent. A coating agent containing 0.1 to 5% by weight based on the total solid content. A fluorine-modified wax having an acrylic thermoplastic resin having a glass transition temperature of 75 ° C. or higher in a proportion of 60% by weight or more with respect to the total solid content of the coating agent and a melting point of 90 ° C. or higher is included in the solid content of the coating agent. Coating agent containing 0.1 to 30% by weight based on the total amount. A labeled container to which the plastic label according to any one of claims 1 to 4 is mounted. The labeled container according to claim 7 , wherein the plastic label is a label in which a coating layer is not formed on a portion that has been heat shrunk by 30% or more.

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