TWI682017B - Heat-shrinkable polyester label, packaging body, and method for manufacturing heat-shrinkable polyester label - Google Patents

Abstract

The present invention provides a heat-shrinkable polyester label that has a thin thickness and does not cause solvent penetration, and can also obtain a stable and high-peel strength solvent bonding portion in a high-speed tube forming step; and provides a packaging body .

The first aspect of the present invention is a heat-shrinkable polyester label, which is a tube-shaped heat-shrinkable polyester label formed by overlapping both ends of a heat-shrinkable polyester film and then using a solvent; The solvent includes: 1,3-dioxolane, or a mixed solvent of 1,3-dioxolane and an organic solvent compatible with 1,3-dioxolane; the solvent of the aforementioned heat-shrinkable polyester label The concentration of 1,3-dioxolane remaining in the following part is 4000 ppm or more and 16000 ppm or less; of the residual solvent remaining in the solvent following part, 100% by mass, isopropyl alcohol, ethyl acetate, butyl acetate, propyl acetate and The total amount of one or more types of non-cyclic compounds selected from the group consisting of butanone is 1% by mass or more and 10% by mass or less; the peel strength of the solvent bonding portion is 3N/15 mm or more.

Description

Heat-shrinkable polyester label, packaging body, and method for manufacturing heat-shrinkable polyester label

The present invention relates to a heat-shrinkable polyester-based label formed by rolling a heat-shrinkable polyester-based film into a tubular shape, and joining the two ends of the aforementioned film to each other with a solvent. The thickness of the film forming the label is thin, and the heat-shrinkable polyester label that is less likely to cause excessive penetration of the solvent in the solvent bonding portion is also unlikely. In addition, it relates to a heat-shrinkable polyester label having a high peeling strength of a solvent adhesion part even when a large amount of highly crystalline polyethylene terephthalate recovered raw material is used as a film raw material.

In recent years, it has been widely used in applications such as protecting glass bottles or plastic bottles, and label packaging, capping films, integrated packaging, etc. that represent products, which are made of polyester with high heat resistance, easy to burn, and excellent solvent resistance. The amount of heat-shrinkable polyester labels obtained from heat-shrinkable films tends to increase with the increase in PET (polyethylene terephthalate) bottle containers and the like.

However, heat-shrinkable labels will become garbage after use. Recently, from the environmental perspective, it is necessary to reduce the amount of garbage. Labels (thin heat shrinkable labels).

Further, in response to the environment, there is a heat-shrinkable polyester film with a high ratio of recycled raw materials in PET bottles.

In addition, to form a tubular label from a heat-shrinkable film, it is necessary to overlap and fix one end in the width direction of the film to the other end. As the aforementioned fixing method, a solvent bonding method (Patent Documents 1 and 2) or a method using an adhesive (Patent Document 3) and the like are conventionally used. Among these, the solvent bonding method can be processed into tubular labels at high speed, so it is widely used.

In the step of processing the surfaces of the heat-shrinkable polyester film into a tubular label by the aforementioned solvent bonding method (tube forming step), it is required to increase the production efficiency and reduce the cost, so the speed is increased. In order to obtain a solvent adhesion part with high peel strength (adhesion strength) stably in a high-speed tube forming step, it is sufficient to increase the coating amount of 1,3-dioxolane which is generally used as an adhesion solvent, but if 1,3- The coating amount of dioxolane increases a lot, and in the case of a thin heat-shrinkable polyester film, the solvent will penetrate from the coated surface side to the film inner surface side (solvent penetration), so that the solvent adheres to the inner surface. Next, when the tubular label after the solvent is rolled into a roll shape, the tubular label will be flattened, but when the solvent penetration portion has a solvent penetration, the label in contact with the inside of the solvent adhesion portion will then lose its function as a tube , And it becomes sticky and becomes unable to open the roller.

On the other hand, if 1,3-dioxic is reduced in a way that does not cause solvent penetration The coating amount of pentane tends to cause unevenness in the coating amount of 1,3-dioxolane in the tube forming step at high speed, and when the coating amount is small, there is a problem that sufficient peel strength cannot be obtained.

On the other hand, in a heat-shrinkable polyester film that uses a large amount of PET bottle recovered raw materials, it is difficult to perform solvent bonding due to the high crystallinity of the PET bottle recovered raw materials. Oxypentane has a problem that the peel strength of the adhesive part is insufficient.

[Prior Technical Literature] [Patent Document]

Patent Document 1: Japanese Patent No. 3075019.

Patent Document 2: Japanese Patent No. 3452021

Patent Document 3: Japanese Patent Laid-Open No. 2014-43520.

An object of the present invention is to provide a heat-shrinkable polyester label having a solvent adhesion portion that does not cause solvent penetration even if the film thickness is thin; and to provide a packaging body. In particular, it provides a heat-shrinkable polyester label, which has a solvent adhesion which can obtain a stable and high peel strength even if the heat-shrinkable polyester film recovers raw materials even when the tube forming step at high speed is used, or even when a large amount of PET bottles are used to recover raw materials Department; and provide a packaging body.

The present invention is a tubular heat-shrinkable polyester label formed by overlapping two ends of a heat-shrinkable polyester-based film and then using a solvent; the solvent includes: 1,3-dioxolane, or 1 ,3-Dioxolane and a mixed solvent of organic solvents compatible with 1,3-dioxolane; the concentration of 1,3-dioxolane remaining in the solvent adhesive portion of the aforementioned heat-shrinkable polyester label It is 4000 ppm or more and 16000 ppm or less; among 100% by mass of the residual solvent remaining in the solvent connection part, one or more non-selected non-isopropyl alcohol, ethyl acetate, butyl acetate, propyl acetate, and methyl ethyl ketone The total amount of the cyclic compound is 1% by mass or more and 10% by mass or less; and the peel strength of the solvent adhesive portion is 3N/15 mm (hereinafter referred to as the first aspect).

In the first aspect, the thickness of the heat-shrinkable polyester film is preferably 12 μm or more and 30 μm or less.

In the first aspect, the heat-shrinkable polyester label can be adhered by using a solvent, and the aforementioned solvent includes: 1,3-dioxolane, or 1,3-dioxolane and 1, A mixed solvent of 3-dioxolane compatible organic solvents; and the aforementioned acyclic compounds.

The first aspect of the present invention also includes a packaging body having a heat-shrinkable polyester label of the first aspect on at least a part of the outer periphery of the object to be packaged.

In addition, the first aspect of the present invention also includes a method for producing a heat-shrinkable polyester-based label, which is pre-coated on a part or the entire surface of the solvent-adhesive surface of the heat-shrinkable polyester-based film and contains one or more types of non-rings The solvent of the compound, the aforementioned non-cyclic compound is one or more selected from the group consisting of isopropyl alcohol, ethyl acetate, butyl acetate, propyl acetate and butanone, followed by 1,3-dioxolane , Or a mixed solvent of 1,3-dioxolane and an organic solvent compatible with 1,3-dioxolane, overlapping and adhering the two ends of the aforementioned film; and the manufacture of a heat-shrinkable polyester label The method is to apply a bonding solvent to the end of the solvent bonding portion of the heat-shrinkable polyester film, and then overlap the two ends of the film, the bonding solvent includes: 1,3-dioxolane, Or a mixed solvent of 1,3-dioxolane and an organic solvent compatible with 1,3-dioxolane; and composed of isopropyl alcohol, ethyl acetate, butyl acetate, propyl acetate and butanone One or more non-cyclic compounds selected by the group.

In the case of using a large amount of heat-shrinkable polyester film for recycling raw materials in PET bottles, it is preferable to form the heat-shrinkable polyester label by overlapping both ends of the heat-shrinkable polyester film and then using an organic solvent. The organic solvent contains a cyclic compound having a dielectric constant of 6.2 or more and 9.8 or less and an aromatic ring structure; the concentration of the cyclic compound remaining in the solvent adhesive portion of the heat-shrinkable polyester label is 4000 ppm or more and 25000 ppm or less; The peel strength of the solvent adhesive part is 3 N/15 mm or more (hereinafter referred to as the second aspect). The aforementioned cyclic compound is preferably one or more selected from the group consisting of o-chlorophenol, p-chlorophenol and phenol.

In the second aspect, it is preferable that the residual solvent in the solvent adjoining part of the label contains one selected from the group consisting of isopropyl alcohol, ethyl acetate, butyl acetate, propyl acetate, butanone, and acetone. The above non-cyclic compounds. At this time, in 100% by mass of the residual solvent in the solvent adhering part of the label, the content rate of the acyclic compound is preferably 1% by mass or more and 20% by mass or less. The heat-shrinkable polyester film having a thickness of 12 μm or more and 50 μm or less is a second preferred embodiment of the present invention.

In addition, the second aspect of the present invention includes a packaging body having a heat-shrinkable polyester label of the second aspect on at least a part of the outer periphery of the object to be packaged.

In addition, the second aspect of the present invention includes a method for producing a heat-shrinkable polyester-based label in which a part or the entire surface of the solvent-bonded surface of the heat-shrinkable polyester-based film is pre-coated with alcohols, esters, and ketones. The solvent of one or more non-cyclic compounds selected by the group is then dried, and the solvent containing the above-mentioned non-cyclic compound is dried, and a dielectric constant of 6.2 or more and 9.8 or less is coated on the inner side of one end in the film width direction And an organic solvent of a cyclic compound having an aromatic ring structure, the two ends of the film are overlapped and bonded; and a method for manufacturing a heat-shrinkable polyester label is used as a solvent-bonding portion of the heat-shrinkable polyester film After coating the end with a solvent, the two ends of the film are overlapped and bonded. The solvent for the adhesion includes a cyclic compound having a dielectric constant of 6.2 or more and 9.8 or less and an aromatic ring structure, and alcohols, esters and More than one type of acyclic group selected by ketones Compound.

In the second aspect, the alcohol is isopropyl alcohol, the ester is one or more selected from the group consisting of ethyl acetate, butyl acetate, and propyl acetate, and the ketone is butanone and/or Acetone is a preferred embodiment of the production method of the present invention in the second aspect.

In the present invention, a heat-shrinkable polyester label can be provided, in which a poor solvent for polyester is coated on the solvent-adhesive side of the heat-shrinkable polyester film before the solvent bonding step, or an appropriate amount is used to mix the aforementioned It is a solvent for poor solvent adhesion, which has a thin film thickness and does not cause solvent penetration. It also provides a stable and high peel strength solvent adhesion portion in the high-speed tube forming step, and provides a packaging body. In addition, a heat-shrinkable polyester label can be provided, which uses a cyclic compound with a specific dielectric constant as a solvent for adhesion, and has a thin film thickness that does not cause solvent penetration and can obtain a high peel strength solvent Next section; and provide a packaging body.

The heat-shrinkable polyester label of the present invention is a tubular heat-shrinkable polyester label formed by overlapping both ends of a heat-shrinkable polyester film and using an organic solvent. Here, the end refers to the width direction (along the long direction Direction).

In addition, the heat-shrinkable polyester film of the present invention includes a film composed of only one layer of polyester, and also includes a laminate film composed of a laminate of resin/polyester other than polyester/polyester and The outer layer is a laminated film of polyester film.

In the first aspect, the main component of the subsequent solvent is 1,3-dioxolane. 1,3-Dioxolane is a good solvent for polyester, which can quickly dissolve the polyester film, so the resulting solvent adhesion system exhibits high peel strength. In addition, as the solvent, a mixed solvent of an organic solvent compatible with 1,3-dioxolane and 1,3-dioxolane can be used. The organic solvent compatible with 1,3-dioxolane is preferably a good solvent for polyester, and examples include 1,4-dioxane, tetrahydrofuran, 1,2,2,2-tetrachloroethane, Benzene, toluene, xylene, etc. The organic solvents that are compatible with 1,3-dioxolane are preferably 0-50 mass parts relative to 100-mass parts of 1,3-dioxolane.

In the second aspect, the solvent system is then used to contain a cyclic compound having a dielectric constant of 6.2 or more and 9.8 or less and having an aromatic ring structure. Examples of the aforementioned cyclic compound include o-chlorophenol (dielectric constant 6.3), p-chlorophenol (dielectric constant 9.5), phenol (dielectric constant 9.8), etc. These can be used alone or in combination of two or more. Polyester generally has a benzene ring containing an aromatic dicarboxylic acid, so a cyclic compound having the same aromatic ring structure is a good solvent for polyester, and sufficient peel strength can be obtained by being used in a solvent. Here, when dissolving a polymer compound in a solvent, the closer the dielectric constants of the two are, the polymer compound The tendency of substances to be more soluble in solvents. If the organic solvent (adhesive solvent) used next is a cyclic compound having an aromatic ring structure with a dielectric constant of 6.2 or more and 9.8 or less, the difference in dielectric constant from the polyester resin is small and it is a good solvent. On the other hand, even a cyclic compound with an aromatic ring structure, if the dielectric constant is less than 6.2 or greater than 9.8, the difference between the dielectric constant of the polyester resin is large and the solubility of the polyester resin is low, so it cannot be a good solvent .

In the second aspect, 1,3-dioxolane was not used as the main and subsequent solvent. The reason is as follows. Although 1,3-dioxolane is known as a good solvent for polyester, polyester with high crystallinity for PET bottles is difficult to dissolve in 1,3-dioxolane, and the raw materials are recovered in PET bottles In a polyester film having a content of more than 25% by mass, it is difficult to obtain sufficient peel strength even if 1,3-dioxolane is used for solvent bonding. However, if it is about several mass%, 1,3-dioxolane can be used together with other solvents as a subsequent solvent.

In addition, in the present invention, in order to prevent the penetration of the solvent, a poor solvent for the polyester is used before or during the solvent adhering step. The aforementioned poor solvent system uses one or more non-cyclic compounds selected from the group consisting of isopropyl alcohol, ethyl acetate, butyl acetate, propyl acetate, and butanone. Polyesters generally have benzene rings containing aromatic dicarboxylic acids, so cyclic solvents with the same ring structure are generally good solvents for polyesters, but the aforementioned acyclic compounds hardly dissolve polyesters. In the second aspect, the non-cyclic compound also includes acetone. Hereinafter, the non-cyclic compound in the second aspect includes acetone, and unless otherwise specified, it is common to the first aspect and the second aspect Bright.

These non-cyclic compounds are coated in advance on a part or the whole of the side of the solvent adhesive surface of the heat-shrinkable polyester film, thereby reducing the amount of the polyester film dissolved by the subsequent solvent and suppressing the penetration of the solvent. The coating part is located slightly closer to the inside of the film (from the end of the film to the inside of about 2 to 6 mm) than the solvent adhesive part (the side of the central part), which can certainly prevent the penetration of the solvent, so it is better, but if the film is coated all over The coating step can be simplified, so it is better. When coating, the non-cyclic compound can be mixed with water and coated. The coating amount at this time is preferably about 50 to 500 mg/m ² in terms of the adhesion amount. The method for applying the non-cyclic compound is not particularly limited, and a known method can be used.

In addition, the aforementioned non-cyclic compound (poor solvent) can be mixed and used in a solvent for subsequent use. Preferably, the solvent for bonding is prepared in the following manner. The total amount of the non-cyclic compounds is 1 mass% of the total amount of the non-cyclic compounds, and the total amount of non-cyclic compounds in the residual solvent remaining in the solvent bonding portion when forming the label is 100 mass %. More than 10% by mass or less. In order to make the total amount of the acyclic compound in the residual solvent 100% by mass be 1% by mass or more and 10% by mass or less, it is sufficient to use the acyclic compound in the range of 1 to 10% by mass in the subsequent solvent 100% by mass . If the amount of the non-cyclic compound (poor solvent) is small, the effect of suppressing the penetration of the solvent cannot be exhibited, and if it is too large, it is difficult to obtain a high adhesive strength stably in the tube forming step at a higher speed. When using a solvent mixed with a poor solvent, it does not need to be applied to the entire surface of the film, as long as it is applied to the inside of about 2 to 6 mm from the end of the film. Also, in the second aspect, when the label is formed Of 100% by mass of the residual solvent remaining in the solvent bonding section, the upper limit of the total amount of non-cyclic compounds is allowed to 20% by mass.

In the tube forming step, it is preferred that the heat-shrinkable polyester-based film be used at a concentration of 50 to 550 mg/m ² (second aspect) with a solvent (including a non-cyclic compound and a non-cyclic compound). Medium is about 50~700mg/m ² ), using a known center sealer or the like. If the subsequent solvent is applied at a coating speed of 1 to 7 g/min, the amount in the aforementioned range can be applied. When the coating amount of the poor solvent in advance to a film coating, preferably a coating amount of poor solvent -50mg / m ² ~ coating amount of the poor solvent + 300mg / m (a second aspect of the poor solvent for ² -250mg / m ² ~ Coating amount of poor solvent + 500 mg/m ² ) The solvent for subsequent application is applied in the range of around. Next, when the solvent is lower than the coating amount of the poor solvent-50 mg/m ² (the second aspect is the coating amount of the poor solvent-250 mg/m ² ), there is a possibility that the peel strength of the solvent bonding portion cannot become 3 N/15 mm or more If the coating amount of the subsequent solvent exceeds the coating amount of the poor solvent + 300 mg/m ² (the coating amount of the poor solvent in the second aspect + 500 mg/m ² ), there is a possibility of solvent penetration.

The speed of the tube forming step is not particularly limited, but it is preferably 300 to 500 m/min in view of high speed (200 to 500 m/min in the second aspect). After the tube forming step, the tubular label is generally flattened and rolled into a roll, and then the label is pulled out and cut to a specific length to form the final product, but it can also be cut after the tube forming step without being rolled into a roller .

In the heat-shrinkable polyester label having a solvent adhesion part, the 1,3-dioxolane (the aforementioned cyclic compound in the second aspect) contained in the solvent adhesion part (including the label) is 4000 ppm (mass basis, The same applies hereinafter) to 16000 ppm or more (25000 ppm in the second aspect) or less. In addition, the total amount of the non-cyclic compound in 100% by mass of the residual solvent remaining in the solvent bonding part is 1 to 10% by mass (1 to 20% by mass in the second aspect). Cut out the sample (each label) from the solvent connection part, heat and desorb GC/MC (Gas Chromatography/Mass Chromatogram; gas chromatograph/mass spectrometer) and perform qualitative and quantitative analysis of volatile components, by which The amount of 1,3-dioxolane in the solvent adhering part (the second cyclic compound in the second aspect) and the amount and composition of the residual solvent remaining in the solvent adhering part are grasped.

In the heat-shrinkable polyester label of the present invention, the peel strength of the solvent adhesive portion is 3 N/15 mm or more. If the peel strength is 3 N/15 mm or more, defects such as peeling can be prevented during use. The method for measuring the peel strength is described in the examples.

The thickness of the heat-shrinkable polyester label of the present invention is preferably 12 μm or more and 30 μm or less (in the second aspect, it is 12 μm or more and 50 μm or less). If it is in the aforementioned range, it can respond to the demand for thinner thickness. More preferably, it is 25 μm or less.

In the heat-shrinkable polyester label of the present invention, the heat shrinkage rate in 90°C hot water is preferably 50% or more in the main shrinkage direction (40% in the second aspect) the above). If the heat shrinkage ratio is 50% or more (40% or more in the second aspect), beautiful shrinkage finish can be obtained. If it is less than 50% (40% in the second aspect), the heat shrinkage force is insufficient, and when the coating shrinks to the container, etc., it cannot adhere to the container, and the appearance is poor, which is not good. In the direction perpendicular to the main shrinkage direction, the heat shrinkage rate in 90° C. hot water is preferably 12% or less. If it exceeds 12%, the label shrinks in the longitudinal direction, and it is easy to produce a phenomenon called longitudinal stretching, which is not good. In addition, the heat shrinkage rate in the main shrinkage direction refers to the heat shrinkage rate in the maximum shrinkage direction of the sample, and the main shrinkage direction is determined by the length of the vertical or horizontal direction of the square sample. In addition, the details of the measurement method of the heat shrinkage rate (%) are described in Examples.

The polyester used for the heat-shrinkable polyester label of the present invention preferably has ethylene terephthalate units as the main constituent component. This system is excellent in strength and heat resistance. In 100 mol% of the constituent units of polyester, the ethylene terephthalate unit is preferably 50 mol% or more, and more preferably 60 mol% or more.

In the second aspect, the ethylene terephthalate unit system may contain units derived from PET bottle recycled raw materials. PET bottle recycling raw materials refer to those who process PET bottles for beverages into flakes or ingots. When forming a polyester film, among 100% by mass of the polyester raw material, it is preferable that the raw material recovered using the aforementioned PET bottle is 90% by mass or less. If the raw material recovered from the PET bottle exceeds 90% by mass, the polyethylene terephthalate constituting the PET bottle has high crystallinity, so there is a possibility that the solvent adhesion and heat shrinkage characteristics of the resulting film may be reduced. In order to promote recycling, compare Jiawei uses PET bottles to recover 20% or more of the raw materials in 100% of the raw materials of polyester.

Examples of other dicarboxylic acid components constituting the polyester of the present invention include aromatic dicarboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid, and phthalic acid; adipic acid, azelaic acid, sebacic acid, and decane Aliphatic dicarboxylic acids such as alkane dicarboxylic acids; and alicyclic dicarboxylic acids.

When the aliphatic dicarboxylic acid (eg, adipic acid, sebacic acid, decane dicarboxylic acid, etc.) is contained in the polyester, the content rate is preferably less than 3 mol% (in 100 mol% of the dicarboxylic acid component) ). The heat-shrinkable polyester label obtained by using polyester containing 3 mol% or more of these aliphatic dicarboxylic acids tends to have insufficient film rigidity during high-speed packaging.

In addition, it is preferable that the polyester does not contain a polyvalent carboxylic acid having a trivalence or higher (for example, trimellitic acid, pyromellitic acid, and anhydrides thereof). It is difficult to achieve the necessary high shrinkage rate of the heat-shrinkable polyester label obtained by using the polyester containing these polycarboxylic acids.

The diol components constituting the polyester include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and hexanediol; 1,4 -Alicyclic diols such as cyclohexanedimethanol; aromatic diols such as bisphenol A;

The polyester used in the present invention is preferably a cyclic diol containing 1,4-cyclohexanedimethanol or the like, or a diol having 3 to 6 carbon atoms (for example, 1,3-propanediol, 1, 4-butanediol, neopentyl glycol, hexanediol, etc.), and the glass transition point (Tg) is adjusted to 60-80℃ polyester.

In addition, in the polyester, the total amount of one or more monomer components that can be an amorphous component in the polyol component in 100 mole% of the all-polyester resin or the polycarboxylic acid component in 100 mole% is 15 mole. Ear% or more, preferably 16 mole% or more, more preferably 17 mole% or more, and particularly preferably 18 mole% or more. In addition, the total upper limit of the monomer components that can be an amorphous component is not particularly limited, but it is preferably 30 mol%.

Examples of monomers that can become amorphous components include neopentyl glycol, 1,4-cyclohexane dimethanol, isophthalic acid, 1,4-cyclohexane dicarboxylic acid, and 2,6-naphthalene dicarboxylic acid. Acid, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-isopropyl-1,3-propane Glycol, 2,2-di-n-butyl-1,3-propanediol, hexanediol. Among these, neopentyl glycol, 1,4-cyclohexanedimethanol or isophthalic acid is preferably used.

The polyester preferably does not contain a diol having 8 or more carbons (for example, octanediol, etc.), or a polyvalent alcohol having more than 3 valences (for example, trimethylolpropane, trimethylolethane, glycerin, Diglycerin, etc.). In heat-shrinkable polyester labels obtained by using polyesters containing these diols or polyols, it is difficult to achieve the necessary high shrinkage. Moreover, it is preferable that polyester does not contain diethylenedioxide as much as possible Alcohol, triethylene glycol, polyethylene glycol.

In the heat shrinkable polyester film forming resin used in the label of the present invention, various additives such as waxes, antioxidants, antistatic agents, crystal nucleating agents, viscosity reducing agents, heat stabilizers can be added as needed , Coloring pigments, coloring inhibitors, ultraviolet absorbers, etc.

In the resin forming the heat-shrinkable polyester film, it is preferable to add fine particles as a slip agent that improves the workability (slidability) of the film. The fine particles can be arbitrarily selected, but examples thereof include inorganic fine particles of silica, alumina, titanium dioxide, calcium carbonate, kaolin, barium sulfate, etc.; organic fine particles of acrylic resin particles, melamine resin particles, polysiloxane resin particles , Cross-linked polystyrene particles, etc. The average particle diameter of the microparticles can be appropriately selected in the range of 0.05 to 3.0 μm (when measured with a Coulter counter) as needed.

The method of blending the aforementioned particles into the resin forming the heat-shrinkable polyester film can be added at any stage of the production of the polyester resin, but it is preferably condensation polymerization in the esterification stage or after the transesterification reaction is completed In the stage before the start of the reaction, a slurry dispersed in ethylene glycol or the like is added, and then the condensation polymerization reaction is performed. Furthermore, it is preferable to use a kneading extruder with a vent to mix a particle slurry dispersed in ethylene glycol, water, etc. and a polyester resin raw material, or a kneading extruder to mix and dry the particles and the polyester system. Resin raw material method and so on.

In the aforementioned heat-shrinkable polyester film, in order to improve the adhesion of the film surface, corona treatment, coating treatment, flame treatment, etc. may be performed.

The specific film and label manufacturing method is to dry the raw material sheet using a dryer such as a hopper dryer, paddle dryer, or vacuum dryer, and extrude it into a film form at a temperature of 200 to 300°C. Or, in a vented extruder, the undried polyester raw material is extruded into a film shape while removing moisture. Any existing methods such as T die method and film blowing method can be used for extrusion. After extrusion, it is cooled rapidly to obtain an unstretched film. In addition, the above-mentioned "unstretched film" also includes a film to which the necessary tension required for feeding the film is applied.

The unstretched film is stretched. The stretching treatment may be continuously performed after cooling by a casting roll or the like, or may be temporarily rolled into a roll shape after cooling.

The maximum shrinkage direction is the film transverse (width) direction, which is more practical in terms of production efficiency. The following shows an example of the stretching method when the maximum shrinkage direction is the transverse direction. In addition, when the maximum shrinkage direction is the longitudinal (long) direction of the film, the stretching direction in the method described later may be changed by 90° or the like, and may be stretched according to a general operation.

In addition, if the focus is to make the thickness distribution of the heat-shrinkable polyester film uniform, and the tenter is used to extend in the horizontal direction, it is preferable Before the step, a preliminary heating step is performed. In the aforementioned preliminary heating step, it is preferable to perform heating to a temperature in the range of Tg+0°C to Tg+60°C.

The extension in the lateral direction is preferably 2.3 to 7.3 times the specific temperature in the range of Tg-20°C to Tg+40°C, preferably 2.5 to 6.0 times. After that, at a specific temperature in the range of 60°C to 110°C, a final heat treatment is carried out while performing 0 to 15% stretching or 0 to 15% relaxation as necessary to obtain a heat-shrinkable polyester film.

The stretching method is not only a horizontal uniaxial stretching with a tenter, but also a longitudinal stretching of 1.0 times to 4.0 times, preferably 1.1 times to 2.0 times. When biaxial stretching is performed as described above, it may be sequential biaxial stretching or simultaneous biaxial stretching, and may be re-extended as necessary. Moreover, in the sequential biaxial stretching, the order of stretching may be any of vertical, horizontal, vertical, horizontal, vertical, and horizontal.

After that, the aforementioned tube forming step is performed and cut to a specific length to form a heat-shrinkable polyester label.

The present invention also includes a package having at least a part of the outer periphery of the object to be packaged having the heat-shrinkable polyester label of the present invention. That is, the heat-shrinkable polyester label is applied to the packaged body and heat-shrinked, thereby obtaining the package.

This case claims priority based on Japanese Patent Application No. 2014-183426 filed on September 9, 2014 and Japanese Patent Application No. 2014-231491 filed on November 14, 2014. As a reference, the entire contents of the Japanese Patent Application No. 2014-183426 filed on September 9, 2014 and the Japanese Patent Application No. 2014-231491 filed on November 14, 2014 are incorporated into this case.

(Example)

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to the examples described below, and it is also included in the present invention without changing the scope of the scope of the present invention. In addition, the measurement methods of the physical properties of the films obtained in Examples and Comparative Examples are as follows.

[Heat Shrinkage Rate (Hot Water Heat Shrinkage Rate)]

Cut the film into a 10cm×10cm square along the long direction and its orthogonal direction (width direction), immerse it in hot water at 90℃±0.5℃ for 10 seconds without load and shrink it, then immerse it at 25℃ 10 seconds in water at ±0.5°C, then pull out from the water and measure the length of the sample in the vertical and horizontal directions, which is the value obtained from the following formula.

Heat shrinkage (%) = {(length before shrinkage-length after shrinkage)/length before shrinkage}

In this embodiment, the direction with the largest film shrinkage (the main shrinkage direction) is the width direction.

[Solvent adhesion method]

After applying the poor solvent to the entire surface of the solvent adhering surface of the film and drying it with a dryer, a film roll with a length of 1000 m in the longitudinal direction was manufactured while cutting the film to a width of 380 mm. The film is pulled out from the film roll, and on the inside of one end in the width direction of the film, the coating width is 4±2 mm (in the second aspect, j is 4±1 mm), and the coating is continuously applied in the long direction and then used. For the solvent, the solvent coating portion is moved to the other end of the film in the width direction, the film is folded so that the overlapping portion becomes the center, and the solvent is adhered.

The solvent subsequent processing speed was 200 m/min in Example 6 and Example 17, 100 m/min in Comparative Example 8, and 400 m/min. The solvent-followed film roll was wrapped in a paper tube at a rate of 200 m/min. The roller of the obtained tubular label was aged for 24 hours in an environment of 23°C.

[Evaluation of solvent penetration]

The aging tube label with a length of 1000 m after solvent aging was pulled out 500 m from the surface of the roller by hand. If there was a sticking phenomenon, it was judged that the solvent penetrated and was evaluated in the following manner.

Non-sticking: Evaluation of solvent penetration ○ (no penetration)

Bonding: Evaluation of solvent penetration × (with penetration)

[Measurement method of peeling strength of solvent adhesive part]

The surface layer portion of the tubular label roll with a length of 500 m after pulling out 500 m from the surface layer of the roller during the evaluation of the penetration of the solvent described above, with the solvent bonding portion at the center In this way, a sample with a width of 15 mm (equivalent to the length in the long direction) is cut along the circumferential direction (the length should be about 100 mm). The number of samples n is 10. It was installed in a universal tensile testing machine "STM-50" manufactured by BALDWIN, and a 180° peel test was carried out at a tensile speed of 200 mm/min. The average value of 10 samples was used as the peeling strength (N/15mm) of the solvent adhesion part.

[Measurement method of residual solvent]

After peeling off the solvent adhering portion of the tubular label, 1 mg of the solvent coating portion of each label was sampled, and the sample was heated at 120°C for 30 minutes by heating and desorption GC/MS ("Automass 15" manufactured by JEOL Ltd.). The generated gas is cooled and captured by the capturing part, the capturing part is heated again, and the captured gas components are introduced into the heating desorption GC/MS, qualitative and quantitative analysis is performed, and the amount of residual solvent in the toluene-converted label is calculated.

[Glass Transfer Point (Tg)]

A differential scanning calorimeter (model: DSC220) manufactured by SEIKO Electronics Industry Co., Ltd. was used, and it was determined in accordance with JIS K7121. 10 mg of the unstretched film was heated from 25°C to 120°C at a temperature increase rate of 10°C/min to obtain a temperature increase curve. The temperature at the intersection of the extension line of the base line below the glass transition temperature and the line showing the maximum inclination in the transition part was taken as the glass transition temperature.

[Dielectric constant of solvent]

Refer to "Chemical Handbook 5th Edition Basic Edition" (Editor of the Japanese Chemical Society, issued by Maruzen Co., Ltd.), and Matsushima Machinery Research Institute Co., Ltd. (now Matsushima Measure Tech)'s electrical conductivity meter.

Synthesis example (synthesis of polyester)

In a stainless steel autoclave equipped with a blender, thermometer and partial reflux cooler, mix 100 mol% of dimethyl terephthalate (DMT) as a dicarboxylic acid component and ethylene glycol (EG) as a diol component ) 100 mol%, so that the molar ratio of diol is 2.2 times that of dimethyl terephthalate, add 0.05 mol% of zinc acetate as a transesterification catalyst (relative to the acid component) The methanol produced is distilled out of the system and the transesterification reaction proceeds. After that, 0.025 mol% (relative to the acid component) of antimony triacid as a condensation polymerization catalyst was added, and condensation polymerization was carried out under a reduced pressure condition of 280°C and 26.6 Pa (0.2 torr) to obtain an intrinsic viscosity. 0.70dl/g of polyester A. The aforementioned polyester is polyethylene terephthalate. In addition, when manufacturing the polyester A, 8000 ppm of SiO ₂ (SYLYSIA 266 manufactured by FUJI SILYSIA) as a slip agent was added to the polyester. In the same manner as described above, polyesters (B, C, D) shown in Table 1 and polyesters E, F, and G shown in Table 2 were synthesized. In addition, as the raw material for recycling PET bottles, "clean tablets" (manufactured by Yono Bottle Recycling Co.; intrinsic viscosity 0.63dl/g) was used as the sheet H.

In the table, CHDM is 1,4-cyclohexanedimethanol, NPG is neopentyl glycol, IPA is isophthalic acid, and BD is 1,4-butanediol. Intrinsic viscosity of polyester in Table 1 and Table 2, polyester A is 0.70dl/g, polyester B is 0.70dl/g, Polyester C is 0.73dl/g, polyester D is 0.73dl/g, polyester E is 0.70dl/g, polyester F is 0.73dl/g, polyester G is 0.73dl/g, polyester H is 0.63 dl/g. In addition, each polyester system is formed into a suitable sheet shape.

<Manufacturing method of film I>

Each of the flakes obtained in the above synthesis example was preliminarily dried. As shown in Table 3, 5 mass% of flake A, 15 mass% of flake B, and 80 mass% of flake C were mixed and put into an extruder. The aforementioned mixed resin was melted at 280°C and extruded from a T-die, and a rotating metal roll cooled to 30°C in contact surface temperature was rapidly cooled, thereby obtaining an unstretched film having a thickness of 90 μm. Amorphous components in the film The amount and Tg are shown in Table 3. At this time, the drawing speed (rotation speed of the metal roller) of the unstretched film was about 20 m/min.

The aforementioned unstretched film was led to a tenter, heated to 100°C in a preheating zone, and stretched 5 times in the width direction at a stretched zone with a set temperature of 78°C. Next, it was heat-treated at 82°C for 5 seconds and then cooled. The two edge portions were cut and removed, and rolled into a roll shape with a width of 500 mm, thereby continuously manufacturing a transverse uniaxially stretched film with a thickness of 1100 m and a thickness of 18 μm. The resulting film is a heat-shrinkable polyester film that shrinks only in the width direction. The thermal shrinkage rate of hot water measured at 90°C is shown in Table 3.

<Manufacturing method of film II>

Except that the sheet D was used instead of the sheet C, a transverse uniaxially stretched film with a length of 2000 m and a thickness of 18 μm was continuously produced in the same manner as the film I. The resulting film is a heat-shrinkable polyester film that shrinks only in the width direction. The thermal shrinkage rate of hot water measured at 90°C is shown in Table 3.

<Manufacturing method of film A>

Each sheet obtained in the foregoing synthesis example was individually prepared for drying, and as shown in Table 4, 5% by mass of sheet E, 70% by mass of sheet F, and 25% by mass of sheet H were mixed and put into an extruder. The aforementioned mixed resin was melted at 280°C and extruded from a T-die, and a rotating metal roll cooled to 30°C in contact surface temperature was rapidly cooled, thereby obtaining an unstretched film having a thickness of 90 μm. Table 4 shows the amounts of amorphous components and Tg in the film. At this time, the drawing speed of the unstretched film (rotation speed of the metal roller) was about 20 m/min.

The aforementioned unstretched film was led to a tenter, heated to 100°C in a preheating zone, and stretched 5 times in the width direction at a stretched zone with a set temperature of 78°C. Next, it was heat-treated at 82°C for 5 seconds and then cooled. Both edges were cut and removed, and a roll of 500 mm in width was rolled into a roll shape, thereby continuously manufacturing a uniaxially stretched film with a thickness of 1100 m and a thickness of 18 μm. The obtained film A was a heat-shrinkable polyester film that was heat-shrinkable only in the width direction. The thermal shrinkage rate of hot water measured at 90°C is shown in Table 4.

<Manufacturing method of film B>

Except for using 5 mass% flake E, 15 mass% flake G, and 80 mass% flake H, a lateral uniaxially stretched film with a length of 1000 m and a thickness of 18 μm was continuously produced in the same manner as the film A. The resulting film B is a heat-shrinkable polyester film that shrinks only in the width direction. The thermal shrinkage rate of hot water measured at 90°C is shown in Table 4.

<Manufacturing method of film C>

Except that the thickness of the unstretched film was changed from 90 μm to 225 μm, a lateral uniaxially stretched film with a length of 1000 m and a thickness of 45 μm was continuously produced in the same manner as the film A. The obtained film C is a heat-shrinkable polyester film that heat-shrinks only in the width direction. The thermal shrinkage rate of hot water measured at 90°C is shown in Table 4.

<Manufacturing method of film D>

Using 5% by mass of sheet E, 25% by mass of sheet F, and 70% by mass of sheet H, the thickness of the unstretched film was changed to 72 μm, and the widthwise The stretch magnification was changed from 5 times to 4 times, and the final heat treatment temperature was changed from 82°C to 79°C. Except for the same method as the film A, a uniaxially stretched film with a length of 1000 m and a thickness of 18 μm was continuously produced. The shrinkage rate of the obtained film D is reduced, but it is a heat-shrinkable polyester film that heat-shrinks only in the width direction. The thermal shrinkage rate of hot water measured at 90°C is shown in Table 4.

Example 1

On one side of the film I, a poor solvent of 200 mg/m ² mixed with 40/40/10/10 (mass ratio) of water/isopropyl alcohol/propyl acetate/ethyl acetate was applied. It dried in the oven of a hot air dryer of 80 degreeC for 10 seconds. On the film coated with poor solvent, 1,3-dioxolane was coated in a width of 4 mm and 250 mg/m ² , and the solvent was adhered at a processing speed of 400 m/min to obtain a tubular label roll. Table 5 shows the solvent adhesion conditions. In addition, the presence or absence of solvent penetration, the peel strength of the solvent adhering part, and the amount of residual solvent in the solvent adhering part were measured by the aforementioned method. There is no solvent penetration and the peel strength of the solvent adhesive part is large, which is a good label.

Example 2

Except that the film II was used instead of the film I, the poor solvent was applied and the solvent was adhered in the same manner as in Example 1 to obtain a tubular label roll. The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. There is no solvent penetration and the peel strength of the solvent adhesive part is large, which is a good label.

Example 3

A tubular label roll was obtained in the same manner as in Example 1, except that a solvent mixed with 40/40/10/10 (mass ratio) of water/isopropanol/butanone/butyl acetate was used as a poor solvent. The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. Although the peel strength of the solvent adhesive portion was slightly lower than that of Example 1, it was practically no problem and it was a good label.

Example 4

In addition to using a solvent with 10/70/10/10 (mass ratio) mixed water/isopropanol/propyl acetate/ethyl acetate as a poor solvent, 1,3 is coated with a width of 4 mm and 150 mg/m ² when the solvent is adhered -A tubular label roll was obtained in the same manner as in Example 1 except for dioxolane. The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. Although the peel strength of the solvent adhesive portion was slightly lower than that of Example 1, it was practically no problem and it was a good label.

Example 5

A tubular label roll was obtained in the same manner as in Example 1, except that 1,3-dioxolane was applied at a width of 4 mm and 150 mg/m ² when the solvent was adhered. The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. Although the peeling strength of the solvent adhesive portion is lower than that of Example 1, it has no practical problem and is a good label.

Example 6

In addition to changing the processing speed of the solvent from 400m/min to 200m/min, coating with a width of 4mm and 500mg/m ² (the processing speed is half, so the coating amount is 2 times) 1,3-dioxolane, and The tubular label roll was obtained in the same manner as in Example 1. The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. The peel strength of the solvent adhesive part was higher than that of Example 1, and it was a good label.

Example 7

A tubular label roll was obtained in the same manner as in Example 1, except that 50/50 (mass ratio) of 1,3-dioxolane/tetrahydrofuran was used as the subsequent solvent. The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. Although the peel strength of the solvent adhesive portion was slightly lower than that of Example 1, it was practically no problem and it was a good label.

Example 8

Except mixing 60/20/20 (mass ratio) with isopropyl alcohol/propyl acetate/ethyl acetate as poor solvent and coating 400mg/m ² , coating 1,3-dioxolane with a width of 4mm and 450mg/m ² Except for this, a tubular label roll was obtained in the same manner as in Example 1. The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. The peel strength of the solvent adhesive part was higher than that of Example 1, and it was a good label.

Example 9

A tubular label roll was obtained in the same manner as in Example 1, except that the coating amount of the poor solvent was 100 mg/m ² . The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. The peel strength of the solvent adhesive part was higher than that of Example 1, and it was a good label.

Example 10

On the film I which is not coated with poor solvent, 1,3-dioxolane/isopropanol is mixed at 90/10 (mass ratio) and then coated with a solvent, coated with a width of 4 mm and 250 mg/m ² at a processing speed 400m/min for solvent adhering to obtain a tubular label roll. The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. There is no solvent penetration and the peel strength of the solvent adhesive part is large, which is a good label.

Comparative example 1

A tubular label roll was obtained in the same manner as in Example 9, except that 1,3-dioxolane was coated with a width of 4 mm and 500 mg/m ² . The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. Although the peeling strength of the solvent adhesive part is large, but the solvent penetrates, it is not good as a label.

Comparative example 2

A tubular label roll was obtained in the same manner as in Example 1, except that the poor solvent was not coated on one side of the film and 1,3-dioxolane was applied at a width of 4 mm and 450 mg/m ² . The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. Although the peeling strength of the solvent adhesive part is large, but the solvent penetrates, it is not good as a label.

Comparative Example 3

It was obtained in the same manner as in Example 1, except that a solvent in which isopropanol/propyl acetate/ethyl acetate was mixed at 60/20/20 (mass ratio) was used as the poor solvent, and the aforementioned coating amount was 400 mg/m ² . Tubular label roll. The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. Although there is no solvent penetration, the peel strength of the solvent adhesive part is small, which is not good as a label.

Comparative Example 4

In addition to using a solvent mixed with 60/20/20 (mass ratio) of isopropanol/propyl acetate/ethyl acetate as a poor solvent, 1,3-dioxolane is applied at a width of 4 mm and 100 g/m ² to: A tubular label roll was obtained in the same manner as in Example 1. The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. Although there is no solvent penetration, the peel strength of the solvent adhesive part is small, which is not good as a label.

Comparative example 5

On the film I that is not coated with a poor solvent, a mixed solvent of 1,3-dioxolane/isopropanol=50/50 (mass ratio) is coated with a width of 4 mm and 250 mg/m ² at a processing speed of 400 m/min After the solvent is adhered, a tubular label roll is obtained. The solvent adhesion conditions are shown in Table 5, and the evaluation results are shown in Table 6. Although there is no solvent penetration, the peel strength of the solvent adhesive part is small, which is not good as a label.

[Table 6]

Example 11

On one side of the film A, apply a poor solvent of 35/10/10/10/35 (mass ratio) mixed with isopropyl alcohol/propyl acetate/ethyl acetate/acetone/water and apply 200 mg/m ^{2 to} pass Dry in the oven of a hot air dryer at 80°C for 10 seconds. Next, a solution of 2 g of o-chlorophenol dissolved in 150 ml of water at 30° C. was prepared, and the aqueous solution of o-chlorophenol was applied so that the coating amount of o-chlorophenol was 150 mg/m ² at the processing speed of 400 m on the film coated with the poor solvent. /Min for solvent bonding to obtain a tubular label roll. The solvent adhesion conditions are shown in Table 7. In addition, the presence or absence of solvent penetration, the peel strength of the solvent adhering portion, and the amount of residual solvent in the solvent adhering portion were measured by the aforementioned method. There is no solvent penetration and the peel strength of the solvent adhesive part is large, which is a good label.

Example 12

The poor solvent was applied in the same manner as in Example 11 except that o-chlorophenol was changed to p-chlorophenol and it was directly applied without being dissolved in hot water. And the solvent is followed by a tubular label roll. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. There is no solvent penetration and the peel strength of the solvent adhesive part is large, which is a good label.

Example 13

A tubular label roll was obtained in the same manner as in Example 11, except that o-chlorophenol was changed to phenol and applied directly without dissolving in hot water. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. There is no solvent penetration and the peel strength of the solvent adhesive part is large, which is a good label.

Example 14

A tubular label roll was obtained in the same manner as in Example 13 except that the film A was changed to the film B. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. There is no solvent penetration and the peel strength of the solvent adhesive part is large, which is a good label.

Example 15

A tubular label roll was obtained in the same manner as in Example 14 except that the film B was changed to the film C and the coating amount of phenol was 350 mg/m ² . The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. There is no solvent penetration and the peel strength of the solvent adhesive part is large, which is a good label.

Example 16

The same as Example 15 except that the film C was changed to the film D The way to get a tubular label roll. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. There was no solvent penetration, and although the peel strength of the solvent adhesive portion was slightly lower than that of Example 11, there was no problem in practical use, and it was a good label.

Example 17

A tubular label roll was obtained in the same manner as in Example 16, except that the coating amount of phenol was changed to 700 mg/m ² and the solvent subsequent processing speed was changed to 200 m/minute. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. Although the peel strength of the solvent adhesive portion was slightly lower than that of Example 11, there was no practical problem, and it was a good label.

Example 18

In addition to using a solvent of 49/17/17/17 (mass ratio) mixed with isopropyl alcohol/propyl acetate/ethyl acetate/acetone as a poor solvent, 350 mg/m ^{2 is} applied, and p-chlorophenol as a subsequent solvent is applied A tubular label roll was obtained in the same manner as in Example 12, except for 140 mg/m ² coating. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. Although the peel strength of the solvent adhesive portion was slightly lower than that of Example 11, there was no practical problem, and it was a good label.

Example 19

A tube was obtained in the same manner as in Example 16, except that a solvent in which isopropyl alcohol/propyl acetate/ethyl acetate/acetone/water was mixed at 15/5/5/5/70 (mass ratio) was used as a poor solvent. Label roll. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. Peel strength is slightly less than Example 11 but practical There is no problem on it, it is a good label.

Example 20

Prepare a solution of 2 g of o-chlorophenol dissolved in 150 ml of water/isopropanol = 80/20 (mass ratio) at 30° C. On the film A that is not coated with poor solvent, the coating amount of o-chlorophenol is 150 mg/m ² The coating method is adopted, and the solvent is adhered at a processing speed of 400 m/min to obtain a tubular label roll. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. There is no solvent penetration and the peel strength of the solvent adhesive part is large, which is a good label.

Reference Example 1

A tubular label roll was obtained in the same manner as in Example 11 except that the o-chlorophenol for the subsequent solvent was changed to 1,3-dioxolane and the aforementioned coating amount was changed to 250 mg/m ² . The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. The peel strength was slightly lower than that of Example 11, but there was no problem in practical use, and it was a good label.

Comparative Example 6

A tubular label roll was obtained in the same manner as in Reference Example 1 except that the film A was changed to the film D. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. The peel strength of the solvent adhesive part is small, which is not good as a label.

Comparative Example 7

A tubular label roll was obtained in the same manner as in Comparative Example 6, except that 600 mg/m ² of 1,3-dioxolane as a subsequent solvent was applied. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. The peel strength of the solvent adhesive part is small, which is not good as a label.

Comparative Example 8

A tubular label roll was obtained in the same manner as in Example 13 except that 800 mg/m ² of phenol as a solvent for adhesion was applied and the solvent subsequent processing speed was changed to 100 m/min. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. Although the peeling strength of the solvent adhesive part is large, but the solvent penetrates, it is not good as a label.

Comparative Example 9

A tubular label roll was obtained in the same manner as in Example 16, except that the solvent for the adhesive was changed from phenol to m-dichlorobenzene. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. Although there is no solvent penetration, the peel strength of the solvent adhesive part is small, which is not good as a label.

Comparative Example 10

A tubular label roll was obtained in the same manner as in Example 16, except that the solvent for the adhesive was changed from phenol to o-dichlorobenzene. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. Although there is no solvent penetration, the peel strength of the solvent adhesive part is small, which is not good as a label.

Comparative Example 11

A tubular label roll was obtained in the same manner as in Example 16, except that the solvent for the adhesive was changed from phenol to cyclohexanone. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. Although there is no solvent penetration, the peel strength of the solvent adhesive part is small, which is not good as a label.

Comparative Example 12

A tubular label roll was obtained in the same manner as in Example 11, except that only 800 mg/m ² of ethyl acetate as a poor solvent was applied and 30 mg/m ² of o-chlorophenol as a subsequent solvent was applied. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. Although there is no solvent penetration, the peel strength of the solvent adhesive part is small, which is not good as a label.

Comparative Example 13

Prepare a solution of 2g of o-chlorophenol dissolved in a 150ml solution of water/isopropanol=10/90 (mass ratio) mixed at 30°C. On the film A not coated with poor solvent, the amount of o-chlorophenol applied is 150mg /m ² coating method, at a processing speed of 400m/min for solvent bonding to obtain a tubular label roll. The solvent adhesion conditions are shown in Table 7, and the evaluation results are shown in Table 8. Although there is no solvent penetration, the peel strength of the solvent adhesive part is small, which is not good as a label.

[Table 7]

(Industry availability)

The heat-shrinkable polyester label of the present invention can meet the requirements of thinner thickness, and it is difficult to cause defects such as solvent penetration, so it is used as a label for beverage bottles Department is useful. In addition, even if a large amount of PET bottles with high crystallinity are used to recover the raw materials, the peel strength of the solvent bonding portion is also high. From this point of view, it is useful as a label for beverage bottles.

Claims (15)

A heat-shrinkable polyester label, which is a tubular heat-shrinkable polyester label formed by overlapping two ends of a heat-shrinkable polyester film and then using a solvent; the solvent includes: 1,3-bis Oxypentane, or a mixed solvent of 1,3-dioxolane and an organic solvent compatible with 1,3-dioxolane; 1,3 remaining in the solvent adhesive portion of the aforementioned heat-shrinkable polyester label -The concentration of dioxolane is 4000 ppm or more and 16000 ppm or less; 100% by mass of the residual solvent remaining in the aforementioned solvent connection part is composed of isopropyl alcohol, ethyl acetate, butyl acetate, propyl acetate, and methyl ethyl ketone The total amount of the selected one or more types of non-cyclic compounds is 1% by mass or more and 10% by mass or less; the peel strength of the solvent bonding portion is 3N/15 mm or more. The heat-shrinkable polyester label according to claim 1, wherein the thickness of the heat-shrinkable polyester film is 12 μm or more and 30 μm or less. The heat-shrinkable polyester label as described in claim 1 or 2 is adhered by a solvent, and the aforementioned solvent includes: 1,3-dioxolane or 1,3-dioxolane And mixed solvents of organic solvents compatible with 1,3-dioxolane; and the aforementioned acyclic compounds. A packaging body having a heat-shrinkable polyester label as described in claim 1 or 2 on at least a part of the outer periphery of a packaging object. A method for manufacturing a heat-shrinkable polyester label, which is to manufacture the heat-shrinkable polyester label as described in any one of claims 1 to 3, a part of the solvent-bonded surface of the heat-shrinkable polyester film or Fully pre-applied A solvent containing more than one acyclic compound, the acyclic compound is one or more selected from the group consisting of isopropyl alcohol, ethyl acetate, butyl acetate, propyl acetate, and methyl ethyl ketone; 1,3-dioxolane, or a mixed solvent of 1,3-dioxolane and an organic solvent compatible with 1,3-dioxolane, the two ends of the film are overlapped and bonded. A method for manufacturing a heat-shrinkable polyester label, which manufactures the heat-shrinkable polyester label as described in any one of claims 1 to 3 at the end of the solvent-bonding portion of the heat-shrinkable polyester film After the application of the solvent is applied, the two ends of the film are overlapped; the solvent for the adhesion includes: 1,3-dioxolane, or 1,3-dioxolane and 1,3-dioxolane A mixed solvent of alkane-compatible organic solvents; and one or more non-cyclic compounds selected from the group consisting of isopropyl alcohol, ethyl acetate, butyl acetate, propyl acetate, and butanone. The method for producing a heat-shrinkable polyester label according to claim 5 or 6, wherein the acyclic compound is added in the range of 1% by mass to 10% by mass in 100% by mass of the subsequent solvent. A heat-shrinkable polyester label, which is a heat-shrinkable polyester label formed by overlapping two ends of a heat-shrinkable polyester film and then using an organic solvent; the organic solvent contains a dielectric constant of 6.2 or more and 9.8 or less and a cyclic compound having an aromatic ring structure; the concentration of the cyclic compound remaining in the solvent adhesive part of the heat-shrinkable polyester label is 4000 ppm or more and 25000 ppm or less; The peel strength of the solvent bonding portion is 3 N/15 mm or more. The heat-shrinkable polyester label according to claim 8, wherein the cyclic compound is one or more selected from the group consisting of o-chlorophenol, p-chlorophenol and phenol. The heat-shrinkable polyester label as described in claim 8 or 9, wherein the residual solvent in the solvent adjoining part of the label includes isopropyl alcohol, ethyl acetate, butyl acetate, propyl acetate, butanone And one or more non-cyclic compounds selected from the group consisting of acetone. The heat-shrinkable polyester label according to claim 10, wherein the content of the non-cyclic compound is 100% by mass or less and 20% by mass or less in 100% by mass of the residual solvent in the solvent adhesive portion of the label. The heat-shrinkable polyester label according to claim 8 or 9, wherein the thickness of the heat-shrinkable polyester film is 12 μm or more and 50 μm or less. A packaging body having a heat-shrinkable polyester label as described in claim 8 or 9 on at least a part of the outer periphery of a packaging object. A method for manufacturing a heat-shrinkable polyester label, which manufactures the heat-shrinkable polyester label as described in any one of claims 8 to 12; a part of the solvent-bonded surface of the heat-shrinkable polyester film or A solvent containing an acyclic compound is pre-coated on all sides, and the acyclic compound is one or more selected from the group consisting of isopropyl alcohol, ethyl acetate, butyl acetate, propyl acetate, and methyl ethyl ketone; and then dried The solvent containing the aforementioned non-cyclic compound is coated with an organic solvent containing a cyclic compound on the inside of one end in the width direction of the film Agent, the two ends of the film are overlapped and bonded, and the cyclic compound has a dielectric constant of 6.2 or more and 9.8 or less and has an aromatic ring structure. A method for manufacturing a heat-shrinkable polyester label, which manufactures the heat-shrinkable polyester label as described in any one of claims 8 to 12; at the end of the solvent-bonding portion of the heat-shrinkable polyester film After applying the adhesive for the part, the two ends of the film are overlapped; the solvent for the adhesive contains a cyclic compound having a dielectric constant of 6.2 or more and 9.8 or less and an aromatic ring structure, and isopropyl alcohol and ethyl acetate , Butyl acetate, propyl acetate, and methyl ethyl ketone selected from the group of more than one type of acyclic compound.