JP2006168317A - Multi-layered heat shrinkable polyester-based film and label - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat shrinkable polyester-based film which causes little wrinkles due to shrinking, little spots and little distortion, and hardly generates a problem such as a fold or the like during shrinking of a label even with time after printing. <P>SOLUTION: The multi-layered heat shrinkable polyester-based film comprising at least two layers is characterized in that the shrinkage in the direction perpendicular to the major shrinkage direction is -3% or more in a case that the shrinkage in the major direction is 40%, the shrinkage is 5 to 70% by the treatment at 70°C for 5 s, the shrinkage is 75% or more by the treatment at 85°C for 5 s, the shrinkage in the direction perpendicular to the major shrinkage direction is not more than 10% by the treatment at 85°C for 5 s, and the difference Δ(%) of heat shrinkage is 10 to 20% wherein Δ=X0-X10, X0 is the shrinkage in case that the film shrunk by 10% in the major shrinkage direction is shrunk by the treatment in warm water at 95°C for 5 s, and X10 is the shrinkage in case that the shrunk film in warm water at 95°C for 5 s is further treated in warm water at 25°C for 10 s, and that the film is curled to one surface side during shrinkage. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a heat-shrinkable polyester film, and more particularly to a heat-shrinkable polyester film suitable for label applications. More specifically, the present invention relates to a heat-shrinkable polyester film that is used for full labeling of bottles, particularly for full labeling of PET bottles, and is extremely free of wrinkles, shrinkage spots, and distortions due to heat shrinkage and is less likely to cause shrinkage.

  As a heat-shrinkable film, particularly a heat-shrinkable film for labeling the body of a bottle, a film made of polyvinyl chloride, polystyrene or the like is mainly used. However, with regard to polyvinyl chloride, in recent years, there has been a problem of generation of chlorinated gas when incinerated at the time of disposal, and polyethylene has problems such as difficulty in printing. Furthermore, when collecting and recycling PET bottles, it is necessary to separate labels of resins other than polyethylene terephthalate such as polyvinyl chloride and polyethylene. For this reason, polyester-based heat-shrinkable films that do not have these problems are attracting attention.

  In recent years, colored bottles are unsuitable for recycling because of the recycling of PET bottles, and alternatives have been studied. Among them, there is a method of using a non-colored bottle and shrinking the printed label to the whole bottle. There is also a method of shrinking the label from the top to the bottom of the bottle to increase the returnable resistance of the glass bottle.

However, when used as a full label for a bottle, the bottle shape is complicated and there are many types, so the conventional heat shrinkable film may cause a problem in shrinkage finish. Especially in the case of a full bottle label, such as a beverage bottle, where the mouth portion is narrow and the diameter difference from the body is large, the conventional heat-shrinkable film causes insufficient shrinkage at the top (head and neck) of the bottle (for example, , See Patent Document 1).
JP 2000-135737 A

The heat-shrinkable film used for the full label of such a bottle needs heat-shrink characteristics such as a high shrinkage rate.
In addition, there is a problem in that a label that has elapsed from the printing process is liable to have a problem such as a part of the label being folded when contracted. Although the cause of this is not clear, it is considered that the organic solvent remaining in the printing ink has some influence.

  Recently, labels used for various containers such as PET bottles are also expected to reinforce these containers. However, a label obtained from a conventional heat-shrinkable polyester film cannot satisfy both such a reinforcing action and prevention of folding after printing.

  The present invention solves the above-mentioned problems, and the object of the present invention is a heat-shrinkable polyester film for full labeling of bottles, particularly for full labeling of PET bottles and glass bottles. Especially, there is very little generation of wrinkles, shrinkage spots, and distortion due to shrinkage, and heat that has the function of not causing problems such as label folding even after printing and capable of reinforcing the shrink-coated container. It is to provide a shrinkable polyester film.

    A multilayer heat-shrinkable polyester film comprising at least two layers, wherein the heat-shrinkage rate of the polyester-based film is minus in the direction perpendicular to the main shrinkage direction when the shrinkage rate in the main shrinkage direction is 40%. 3% or more, treatment temperature 70 ° C., treatment time 5 to 70% at 5 seconds, 85 ° C. · 5 seconds at 75% or more, and 85 ° C. · 5 seconds in the direction perpendicular to the main shrinkage direction. The shrinkage rate in the main shrinkage direction when the film which is 10% or less and heat-shrinked in the main shrinkage direction by 10% is further treated in warm water at 95 ° C. for 5 seconds is X0 (%) and X10 (%), respectively. The heat shrinkage difference Δ (%) shown by the following formula is 10 to 20%, and is a multilayer heat-shrinkable polyester film characterized by curling to one side when shrinking. The problem can be solved.

The present invention is a multilayer film composed of an A layer and a B layer, and achieves multiple functions by imparting different characteristics to the A layer and the B layer, respectively.
For example, the polyester elastomer content in the A layer is 15% by mass or more and 20% by mass or less. For example, the polyester elastomer content in the B layer is 10% by mass or more and less than 15% by mass. This makes it difficult to cause problems such as label folding failure.

  In this case, the polyester elastomer is, for example, a polyester block copolymer composed of a high melting crystalline polyester segment (Tm 200 ° C. or higher) and a low melting point soft polymer segment (Tm 80 ° C. or lower) having a molecular weight of 400 or more, preferably 400 to 800. A polyester elastomer using a polylactone such as poly-ε-caprolactone in the low melting point soft polymer segment is particularly preferable.

  In this case, when the total of one or more monomer components that can be amorphous components in 100 mol% of the polyhydric alcohol component in all the polyester resins is 16 mol% or more, secondary processing such as solvent adhesion is performed. It becomes easy to satisfy the characteristics, and it is particularly preferably 18 mol% or more.

  In this case, it is preferable that the monomer that can be an amorphous component in the total polyester resin component of the film is neopentyl glycol and / or 1,4-cyclohexanedimethanol.

  In this case, the thickness distribution is preferably 6% or less.

  Furthermore, in this case, a label made using the film is suitable for a bottle.

  Furthermore, in this case, a label produced using the film so that the A layer side is the inner surface and the B layer side is the outer surface is a suitable application for the bottle.

  When the heat-shrinkable polyester film of the present invention is used as a full label for a bottle, it can produce a good finish with very little wrinkles, shrinkage spots, distortion and insufficient shrinkage due to heat shrinkage. Useful.

Embodiments of the present invention will be specifically described below.
The heat-shrinkable polyester film can be obtained as follows. A polyester composed of a dicarboxylic acid component and a polyvalent glycol component is melt-extruded from an extruder and cooled with a conductive cooling roll (such as a casting roll) to form a film (unstretched film).

In the extrusion, the copolyester is extruded alone, or a plurality of polyesters (copolyester, homopolyester, etc.) are mixed and extruded. That is, the film contains a second alcohol component that is different from a base unit (such as a crystalline unit such as polyethylene terephthalate) and a polyvalent glycol component (such as an ethylene glycol component) that constitutes the base unit.
In addition, the content rate of the acid component of this invention and a diol component is a content rate with respect to the acid component of the whole polyester, and a diol component, when mixing and using 2 or more types of polyester. It does not matter whether transesterification has taken place after mixing.

  Any of the above polyesters can be produced by polymerization according to a conventional method. For example, the polyester can be obtained by using a direct esterification method in which a dicarboxylic acid and a diol are directly reacted, or a transesterification method in which a dicarboxylic acid dimethyl ester is reacted with a diol. The polymerization may be performed by either a batch method or a continuous method.

  When a polyester film containing the second alcohol component is stretched, a heat-shrinkable polyester film can be obtained.

  As the second alcohol component, a diol component and a trivalent or higher alcohol component can be used. The diol component includes ethylene glycol, propylene glycol, 1,4-butanediol, 2,2-diethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, -Alkylene glycols such as methyl-1,5-pentanediol, 1,9-nonanediol, 1,10-decanediol; cyclic alcohols such as 1,4-cyclohexanedimethanol; diethylene glycol, collected ethylene glycol, polypropylene glycol, poly Ether glycols such as oxytetramethylene glycol, alkylene oxide adducts of bisphenol compounds or derivatives thereof; and dimer diols. Trivalent or higher alcohols include trimethylolpropane, glycerin, pentaerythritol and the like.

The total of at least one monomer component that can be an amorphous component in 100 mol% of the polyhydric alcohol component in all the polyester resins is preferably 16 mol% or more, and more preferably 18 mol% or more. preferable.
Here, examples of the monomer that can be an amorphous component include neopentyl glycol and 1,4-cyclohexanediol.

  Further, in addition to a heat-shrinkable polyester film having particularly excellent shrinkage finish, in order to improve the shrink finish while having a high heat shrinkage rate, in 100 mol% of the polyhydric alcohol component in the total polyester resin, It is preferable that the neopentyl glycol component is 5 mol% or more and / or the 1,4-cyclohexanedimethanol component is 5 mol% or more. Further, the amount of either neopentyl glycol and 1,4-cyclohexanedimethanol or the combined amount of both monomers is preferably 16 mol% or more, and particularly preferably 18 mol% or more.

  The heat-shrinkable film of the present invention is characterized by curling to one side at the time of heat-shrinking. In order to control the curl within an appropriate range, the difference in the degree of plane orientation of each layer is 0. It is preferably within the range of 05 to 0.03, and more preferably within the range of 0.01 to 0.28. When the difference in the degree of plane orientation is 0.005 or less, curling does not occur, and when it exceeds 0.03, the adhesive strength at the interface between the layers is lowered and peeling at the time of contraction occurs. In order to set the difference in the degree of plane orientation of each layer within the above range, it is preferable to adopt the raw material prescription, production method and conditions described later.

The polyester elastomer content in the A layer is preferably 15% by mass or more and 20% by mass or less, and the polyester elastomer content in the B layer is preferably 10% by mass or more and less than 15% by mass. Here, the polyester elastomer is a polyester block copolymer comprising, for example, a high melting crystalline polyester segment (Tm 200 ° C. or higher) and a low melting point soft polymer segment (Tm 80 ° C. or lower) having a molecular weight of 400 or more, preferably 400 to 800. And polyester elastomers using polylactones such as poly-ε-caprolactone in the low melting point soft polymer segment.
In other words, a multi-layer film composed of an A layer and a B layer is used, and multi-functionalization is achieved by imparting different characteristics to the A layer and the B layer, respectively.
With the above configuration, the resulting film can be controlled to curl to one side during heat shrinkage. For example, the non-curled surface can be printed on the inner surface side of the label to fold after time. It is possible to avoid defects.
The curl amount of the film is preferably 5% to 100%, more preferably 10% to 100% by the evaluation method described later. In the present invention, the curling of the film or label to one side when contracted means that the curl amount is 1% or more in the evaluation method described later.
Moreover, it is possible to make the shrinkage rate of the direction orthogonal to the main shrinkage | contraction direction appropriate by making a polyester elastomer into the said range and combining with the preferable manufacturing method and conditions mentioned later.

  As common to the A layer and the B layer, an aliphatic linear diol having 8 or more carbon atoms (for example, octanediol) or a trihydric or higher polyhydric alcohol (for example, trimethylolpropane, trimethylolethane, glycerin, Diglycerin and the like) are preferably not contained. In the heat-shrinkable polyester film obtained by using polyester containing these diols or polyhydric alcohols, it is difficult to achieve a necessary high shrinkage rate.

  Moreover, it is preferable not to contain diethylene glycol, triethylene glycol, and polyethylene glycol as much as possible. In particular, diethylene glycol is likely to be present because it is a by-product component during polyester polymerization. However, in the polyester used in the present invention, the content of diethylene glycol is preferably less than 4 mol%.

  Furthermore, in order to improve the slipperiness of the heat-shrinkable film, for example, an inorganic lubricant such as titanium dioxide, fine-particle silica, kaolin, calcium carbonate, or an organic lubricant such as a long-chain fatty acid ester may be included. preferable. Moreover, you may contain additives, such as a stabilizer, a coloring agent, antioxidant, an antifoamer, an antistatic agent, and an ultraviolet absorber, as needed.

[Intrinsic viscosity]
The heat-shrinkable polyester film of the present invention preferably has an intrinsic viscosity of 0.60 dl / g or more. If the intrinsic viscosity of the heat-shrinkable film is too small, the molecular weight of the polyester that composes the film will be low, which will reduce the durability of the shrinkage stress during heat shrinkage, resulting in defects such as shrinkage whitening and shrinkage spots. It becomes easy, and it becomes inferior to shrink finish and appearance. Moreover, if the molecular weight of polyester falls, the mechanical strength and tear resistance of a film will be reduced.

    The intrinsic viscosity is preferably 0.60 dl / g or more, more preferably 0.63 dl / g or more.

  As a method for increasing the intrinsic viscosity of the film, for example, (1) a method in which a high molecular weight polyester is used as the polyester that is the raw material of the film (for example, the intrinsic viscosity is 0.63 dl / g or more, preferably 0.68 dl / g More preferably, a method of using a polyester of 0.70 dl / g or more), (2) a method of suppressing thermal decomposition and hydrolysis when forming a film by extruding the polyester (for example, preliminarily using a polyester raw material) (3) A method of using a hydrolysis-resistant polyester as the polyester (for example, having an acid value of 25 eq / ton or less) (Method of using polyester), (4) Antioxidant to polyester (for example, 0.01 to 1 quality) Such as% of content) is a method to the like.

  As the polymerization catalyst, various conventional catalysts can be used. For example, titanium-based catalyst, antimony-based catalyst, germanium-based catalyst, tin-based catalyst, cobalt-based catalyst, manganese-based catalyst, etc., preferably titanium-based catalyst (titanium tetrabutoxide) Etc.), antimony catalysts (such as antimony trioxide), germanium catalysts (such as germanium dioxide), cobalt catalysts (such as cobalt acetate), and the like.

[Heat shrinkage]
The heat-shrinkable polyester film of the present invention is treated with no load in warm water and the length before and after shrinkage is calculated as follows: thermal shrinkage rate = ((length before shrinkage−length after shrinkage) / before shrinkage The heat shrinkage rate of the film calculated by the formula of (length) × 100 (%) is 5 to 60%, preferably 10 to 30% at a treatment temperature of 70 ° C. and a treatment time of 5 seconds in the main shrinkage direction. , 85% at 5 ° C. for 5 seconds, preferably 75 to 95%. Further, in the direction orthogonal to the main shrinkage direction, it is 10% or less at 85 ° C. for 5 seconds, preferably 6% or less.

  When the heat shrinkage rate in the main shrinkage direction is less than 5% at 70 ° C. for 5 seconds, the low-temperature shrinkability is insufficient, and for example, it is necessary to increase the shrinkage temperature. On the other hand, if it exceeds 60%, for example, jumping of the label due to heat shrinkage is likely to occur, which is not preferable.

  The thermal shrinkage rate at 85 ° C. for 5 seconds is preferably 75 to 95%, and when it is less than 75%, for example, the shrinkage of the head of the bottle is not preferable. On the other hand, if it exceeds 95%, the force for further shrinkage remains even after heat shrinkage, and thus, for example, a problem such as the label being likely to jump up is likely to occur, which is not preferable.

  In addition, the heat-shrinkable polyester film of the present invention is the main shrinkage direction when the film before heat shrinkage is further heat-shrinked 10% in the main shrinkage direction and further treated in warm water at 95 ° C. for 5 seconds. When the shrinkage ratios are X0 (%) and X10 (%), respectively, it is preferable that the thermal shrinkage difference Δ (%) represented by the following formula is 10 to 20%. If the heat-shrinkable polyester film has a heat shrinkage difference Δ within the above range, a heat-shrinkable polyester film having a reinforcing effect on the coated container can be obtained.

  In the heat-shrinkable label obtained from the heat-shrinkable polyester film having the heat shrinkage ratio difference Δ below the above range, the reinforcing effect of the covering container becomes insufficient. In the heat-shrinkable polyester film of the present invention, the preferred heat shrinkage difference Δ is 17% or less. In addition, since the said X10 is a value measured using the film which carried out 10% heat shrink, the lower limit of thermal contraction rate difference (DELTA) does not fall below 10%.

  Incidentally, in a normal heat-shrinkable polyester film, the final heat shrinkage rate (first heat shrinkage rate of 10% and the second heat shrinkage rate when the heat shrinkage is once made after 10% heat shrinkage again) And the heat shrinkage rate when the film before heat shrinkage is completely shrunk under the same heat shrink condition. (That is, the thermal contraction rate difference Δ exceeds the above range). In the present invention, as will be described later, the composition of the polyester used in the film is within a suitable range, and the stretching condition of the film is controlled to ensure the heat shrinkage difference Δ in the above range.

  Next, although a specific example is demonstrated about the manufacturing method of the heat-shrinkable polyester film of this invention, it is not limited to this manufacturing method.

  The polyester raw material used in the present invention is dried using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer, melted at a temperature of 200 to 300 ° C., and extruded into a film. In extruding, any existing method such as a T-die method or a tubular method may be employed. After extrusion, it is cooled rapidly to obtain an unstretched film.

  The extrusion temperature is preferably in the range of 250 ° C to 290 ° C. When the extrusion temperature is lower than 250 ° C., for example, a load is excessively applied and normal extrusion becomes difficult. When the extrusion temperature exceeds 290 ° C, for example, the polyester resin is likely to be thermally deteriorated in the extruder, resulting in problems such as a decrease in mechanical strength of the resulting film and excessive shrinkage in the longitudinal shrinkage resulting in a decrease in shrink finish. Arise.

  The stretching ratio (stretching ratio in the main direction) of the film can be appropriately selected according to the type and ratio of the second alcohol component, for example, 4.0 times or more, preferably 4.5 times or more, particularly 5 It is preferable to stretch the film more than twice. Moreover, although there is no restriction | limiting in particular regarding the upper limit of a draw ratio, 7 times or less are preferable from film forming property, and 6 times or less are more preferable.

  Moreover, what is necessary is just to perform extending | stretching in 2 steps | paragraphs, in order to make a heat shrinkage rate and a heat shrinkage rate difference into the said range. Hereinafter, a case where stretching is performed in two stages will be described as an example.

  First, the first stage of stretching is performed. The stretching ratio is 4.4 times or more and 6 times or less, preferably 4.8 times or more and 5.5 times or less with respect to the unstretched film. The stretching temperature in the first stage is a predetermined temperature within the range of Tg-5 ° C to Tg + 15 ° C of the film.

  Next, it is preferable to perform heat setting in a state where the film is tensioned in the stretching direction. It is recommended that the tension rate at that time is 1% or more and 6% or less, preferably 2% or more and 5% or less with respect to the film after the first stage of stretching. Also, the heat setting temperature is the same as the first stage stretching temperature or within the above temperature range, it is about 1-5 ° C. lower than the first stage stretching temperature, and the heat setting time is 0.5 seconds. It is preferably 5 seconds or longer and preferably 1 second or longer and 3 seconds or shorter.

  Next, the second stage of stretching is performed. The draw ratio is 1.1 times or more and 1.5 times or less (preferably 1.3 times or less) with respect to the film after heat setting (after the first stage if heat setting is not performed). The second stage stretching temperature is preferably about 1 to 5 ° C. lower than the heat setting temperature.

  Thereafter, the film is cooled to obtain a heat-shrinkable polyester film, preferably with slight tension applied to the film. The tension rate during cooling is preferably 0.1 to 3% with respect to the stretched film in the second stage.

  In addition, when making the process of extending | stretching into 3 steps | paragraphs, it is desirable to put the said heat setting between extending | stretching of the 2nd step and extending | stretching of the 3rd step. What is necessary is just to determine the conditions of a heat setting process according to said heat setting conditions. Further, the stretching conditions at the third stage may be determined according to the stretching conditions at the second stage.

  From the viewpoint of controlling the heat shrinkage rate of the film, it is preferable that the number of stretching steps is large. However, if the number of steps is too large, it is difficult to design stretching equipment in industrial production. It is preferable to have four or less stages.

[Melting resistivity]
The heat-shrinkable polyester film used in the present invention has a melting specific resistance value of 0.70 × 10 ⁸ Ω · cm or less at a temperature of 275 ° C. When such a film is used, as will be described in detail below, the uniformity of the film thickness can be improved, and the printability on the film and the workability when processing the film into a form that can be mounted on a container. (Stable workability) can be improved.

  In order to control the melting specific resistance value within the above range, it is preferable to contain an alkaline earth metal compound and a phosphorus-containing compound in the film. The melting specific resistance value can be lowered only with the alkaline earth compound, but the melting specific resistance value can be remarkably lowered when the phosphorus-containing compound coexists. Although it is not clear why the specific melt resistance value can be remarkably lowered by combining the alkaline earth metal compound and the phosphorus-containing compound, the amount of foreign matter can be reduced by containing the phosphorus-containing compound, and the charge carrier It is estimated that the amount can be increased.

  There is no particular limitation on the timing of addition of the above-mentioned compounds for reducing the specific resistance value (alkali metal compounds, alkaline earth metal compounds, phosphorus-containing compounds, etc.), and polymerization is performed before esterification, during esterification, and after completion of esterification. It may be at any stage during polymerization, during polymerization, or after polymerization. It is preferably at any stage after the esterification step, more preferably from the end of esterification to the start of the polymerization step. When an alkaline earth metal compound and a phosphorus-containing compound (and an alkali metal compound if necessary) are added after the esterification step, the amount of foreign matter generated can be reduced as compared with the case where it is added before that.

[Thickness distribution value in the maximum shrinkage direction]
Even if the melt specific resistance value is lowered and the film thickness uniformity is increased as described above, it is not sufficient. That is, when forming a film roll, since the said film is elongate (for example, about 300-6000m), there exists a prisoner whose thickness uniformity falls depending on a measurement location.

  The uniformity of the thickness can be determined based on the thickness distribution value represented by the following formula.

Thickness distribution value = (maximum thickness−minimum thickness) / average thickness × 100
The maximum thickness, the minimum thickness, and the average thickness are obtained by cutting a test piece from a roll so that the length in the main shrinkage direction is 20 cm and the width is 5 cm, and the thickness is displaced with respect to the main shrinkage direction using a contact-type thickness meter. Can be determined by measuring.

  The heat-shrinkable polyester film of the present invention preferably has a film thickness distribution value calculated by the above formula of 6% or less. More preferably, it is 5% or less.

A film having a thickness distribution of 6% or less is easy to superimpose colors by, for example, three-color printing performed at the time of shrinkage finish evaluation, whereas a film exceeding 6% is preferable in terms of color superposition. Absent.

  In order for the sample at each location to have the predetermined thickness distribution value, it is not sufficient that the film forming process and the stretching process reach a steady state, and when the molten polyester is extruded and cooled with a cooling roll, It is necessary to stabilize the electrostatic adhesion of the film from the beginning to the end of film production. As the electrode used for the cooling, it is preferable to use an electrode provided with an electrode contaminated surface retracting means and an electrode contaminated surface supplying means. That is, when electricity is applied from an electrode during film formation of molten polyester and the film is electrostatically adhered, the polyester contains a plurality of types of polymers (homopolymers, copolymerized polymers, etc.) and monomers. Since it often contains molecular components, the low molecular components volatilize during melt extrusion and gradually contaminate the electrode. Therefore, if production of the film is continued, the contamination of the electrode gradually becomes severe, and it becomes impossible to apply sufficient electricity to the film, and there is a captive that the electrostatic adhesion of the film is lowered. Therefore, by using the specific electrode, electrode contamination can be saved, and a non-contaminated surface can be supplied instead, and the electrode surface can be maintained in a state with little contamination. Therefore, even if production of the film is continued, there is no prisoner that the electrostatic adhesion decreases, and the samples at each location have the predetermined thickness distribution.

  In order for the sample at each location to have the predetermined thickness distribution, (A) a method of homogenizing a polyester raw material during film production, together with the method of stabilizing electrostatic adhesion from the beginning to the end of film production It is desirable to employ (B) a method for stabilizing the production process and / or (C) a method for stabilizing the film stretching process.

(A) Method of homogenizing polyester raw material during film production Fine powder (fine powder polyester chip) generated by scraping raw material chips used promotes the occurrence of raw material segregation. Reduction in raw material segregation can also be achieved.

  The ratio of the fine powder in the polyester chip is preferably controlled within 1% by mass and more preferably within 0.5% by mass throughout the entire process until the raw material chip enters the extruder.

  As a method for reducing the fine powder, for example, a method of removing fine powder generated in the process (classification removal, etc.) can be adopted. For example, a method of passing a sieve at the time of chip formation by a strand cutter, a method of passing a cyclonic air filter when the raw material chips are fed by air, and the like can be adopted.

  Moreover, a method of using a funnel-shaped hopper as the final hopper and bringing its hypotenuse (side wall) closer to the vertical can be mentioned. If the hypotenuse (side wall) is brought closer to the vertical, a large chip can be easily dropped like a small chip, and the upper end of the content descends while maintaining a horizontal plane, which is effective in reducing raw material segregation. is there.

  The inclination angle of the hypotenuse (side wall) is, for example, 65 ° or more, preferably 70 ° or more. The inclination angle of the hypotenuse (side wall) is an angle between the funnel-like hypotenuse (side wall) and a horizontal line segment.

(B) Method for Stabilizing Film Formation Methods for stabilizing the film formation process include a method for suppressing fluctuations in the discharge amount from the extruder, a method for suppressing fluctuations in the rotation speed of the cooling roll (casting roll), and the like. It is done.

  In order to suppress the discharge amount fluctuation from the extruder, for example, it is preferable to stabilize the discharge amount within a range of ± 2% of the average discharge amount. In order to suppress the discharge amount fluctuation, for example, it is preferable to use a gear pump as the discharge means.

  In order to suppress the rotational speed fluctuation of the cooling roll (casting roll), for example, it is preferable to stabilize the rotational speed within a range of ± 2% of the average rotational speed. In order to suppress the rotational speed fluctuation, it is preferable to use, for example, a means for controlling the rotational accuracy of the roll drive system, for example, an inverter for controlling the rotational speed.

(C) Method of Stabilizing Film Stretching Process In order to impart heat shrinkability to the film, it is necessary to stretch the unstretched film. When stabilizing the stretching process of the film, various devices for stabilization are applied to a general stretching method.

  When controlling the stretching temperature, the stretching temperature is controlled so as not to become too high. If the stretching temperature is too high, the film thickness distribution value may become too large. If the stretching temperature is too high, the heat shrinkage rate of the film may be insufficient, and further, the strength of the film will be insufficient when the obtained heat-shrinkable film is mounted on a container (such as a bottle) at high speed. In some cases.

  The stretching temperature is preferably controlled to, for example, glass transition temperature (Tg) + 40 ° C. or lower (preferably + 15 ° C. or lower).

  Although the relationship with the thickness distribution value is small, the stretching temperature is preferably a glass transition temperature (Tg) of −20 ° C. or higher (preferably −5 ° C. or higher). If the stretching temperature is too low, the transparency of the film may decrease.

  When the internal heat generation of the film accompanying stretching is suppressed, the temperature unevenness of the film in the stretching direction (such as the width direction) can be reduced, and the uniformity of the thickness of the stretched film (heat-shrinkable film) can be enhanced.

  In order to control the internal heat generation, it is preferable to appropriately control the heating conditions (for example, to increase the supply speed of hot air) so that the film is easily heated. When there is an insufficiently heated portion, internal heat generation due to stretching orientation occurs. On the other hand, when the film is sufficiently heated, the molecular chain easily slips during stretching, so that internal heat generation hardly occurs.

When the heating condition is represented by a heat transfer condition, for example, the heat transfer coefficient is 0.0038 J / cm ² · sec · ° C. (0.0009 calories / cm ² · sec · ° C.) or more, preferably 0.0046 to 0.00. It is about 0071 J / cm ² · sec · ° C. (0.0011 to 0.0017 calories / cm ² · sec · ° C.).

(3) Control of preliminary preheating conditions When controlling the preliminary preheating conditions, it is preferable to control so that the film is gradually heated. When the film is gradually heated in the preliminary preheating step, the temperature distribution of the film can be made substantially uniform, so that the uniformity of the thickness of the stretched film (heat-shrinkable film) can be enhanced.

When the preheating condition is represented by a heat transfer condition, for example, the heat transfer coefficient is about 0.00054 J / cm ² · sec · ° C. (0.0013 calories / cm ² · sec · ° C.) or less. In the preheating, the film surface temperature is preferably heated until it reaches a temperature within the range of Tg + 0 ° C. to Tg + 60 ° C., and the temperature of the hot air is preferably about Tg + 10 ° C. to Tg 90 ° C.

  Examples of the method for achieving the heat transfer coefficient include a method of slowing the hot air supply rate.

(4) Soaking the surface temperature of the film during stretching When stretching the film, if the fluctuation of the surface temperature of the film is reduced (soaking), stretching or heat treatment is performed at the same temperature over the entire length of the film. The thickness distribution value and heat shrinkage behavior can be made uniform.

  As for the fluctuation range of the surface temperature, the temperature at each point when the surface temperature of the film is measured at an arbitrary point is preferably, for example, within the average temperature of the film ± 1 ° C., and the average temperature ± 0.5 ° C. More preferably, it is within.

  When stretching the film, some of these steps are used to stretch the film through various steps such as a preheating step before stretching, a stretching step, a heat treatment step after stretching, a relaxation treatment step, and a re-stretching step. In all, it is preferable to use equipment that can reduce the fluctuation range of the surface temperature of the film (equalize). In particular, in order to make the thickness distribution value uniform over the entire length of the film, in the preheating step and the stretching step (and in the heat treatment step after stretching if necessary), the equipment that can reduce the surface temperature fluctuation range of the film Is preferably used. In order to make the heat shrinkage behavior uniform, it is preferable to use equipment that can reduce the fluctuation range of the surface temperature of the film in the stretching step.

Examples of equipment that can reduce the fluctuation range of the film temperature include, for example, equipment equipped with a wind speed control means (such as an inverter) for controlling the supply speed of hot air for heating the film, and stably heating the air. Examples include equipment provided with heating means for adjusting the hot air [heating means using low pressure steam of 500 kPa or less (5 kgf / cm ² or less) as a heat source].

  The thickness of the heat-shrinkable polyester film is not particularly limited. For example, when used for labeling, it is about 10 to 200 μm, preferably about 20 to 100 μm.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples, unless the summary is exceeded.

  The evaluation method of the film of the present invention is as follows.

(1) Heat shrinkage rate The film was cut into a 10 cm × 10 cm square, heat-shrinked in warm water at a predetermined temperature ± 0.5 ° C. under no load for 5 seconds, and then longitudinal and transverse directions of the film. Were measured, and the thermal shrinkage rate was determined according to the following formula. The direction in which the heat shrinkage rate is large was taken as the main shrinkage direction.

Thermal shrinkage rate = ((length before shrinkage−length after shrinkage) / length before shrinkage) × 100 (%)

(2) A mold having two chucks facing each other is prepared so that only a pair of opposing ends of a film having a difference in thermal contraction rate can be gripped. The heat-shrinkable polyester film is cut into a square or a rectangle parallel to the main shrinkage direction. The cut film is fixed with the above mold. For fixing, grip both ends of the film perpendicular to the main shrinkage direction with a chuck, and loosen the film so that the ratio of the film length between chucks and the distance between chucks of the mold is 1: 0.9. Do it. Thereafter, the film fixed on the mold was immersed in warm water at 95 ° C. ± 0.5 ° C. for 5 seconds in a no-load state and thermally contracted. Soak for a second and pull up. The film is removed from the mold and the adhering water is removed to obtain a film thermally contracted by 10% in the main shrinkage direction. Thereafter, this film is placed in an airless state in an environment of 25 ° C. or lower and subjected to the next step in as short a time as possible.
This film is cut into a 10 cm × 10 cm square, immersed in warm water at 95 ° C. ± 0.5 ° C. for 5 seconds under no load, and then immersed in warm water at 25 ° C. ± 0.5 ° C. for 10 seconds. Then, the length in the vertical and horizontal directions of the sample is drawn out from the water, and the heat shrinkage rate X10 in the main shrinkage direction is obtained according to the above heat shrinkage rate calculation formula. Further, the thermal shrinkage rate in the main shrinkage direction measured at 95 ° C. in the above (1) is X0. From these values, the heat shrinkage ratio difference Δ is calculated according to the following equation.

Δ = X0−X10

(3) Shrinkage Finishing Properties Three colors were printed in advance on a heat-shrinkable film with grass, gold, and white ink from Toyo Ink Manufacturing Co., Ltd. The printing surface was the A layer side of the film. A label was produced from the printed film with a folding diameter of 108.5 mm and a height of 195 mm. The label was printed on the inside.
Using a steam tunnel (model: SH-1500-L) manufactured by Fuji Astec Inc, with a transit time of 10 seconds and a zone temperature of 90 ° C., a 334 ml glass bottle (height 190 cm, central diameter 6.9 cm) (Asahi Breweries) (Both used for Steiny Super Dry) (number of measurements = 20).
Evaluation was made visually and the criteria were as follows.
○: No wrinkles, jumping up, or insufficient contraction occurred ×: Wrinkles, jumping up, or insufficient contraction occurred

(4) Label folding after lapse of printing After the printed label is aged at 20 ° C. for 2 months, a steam tunnel (model: SH-1500-L) manufactured by Fuji Astec Inc. is used, and the passing time is 5 seconds. The test was conducted at a temperature of 90 ° C. using a 334 ml glass bottle (height 190 cm, central diameter 6.9 cm) (bottle used for Asahi Breweries' Steiny Super Dry) (measurement number = 20).
Evaluation was made visually and the criteria were as follows.
○: No folding at the top of the label ×: Folding at the top of the label

(5) Tg (glass transition point)
Using DSC (model: DSC220) manufactured by Seiko Denshi Kogyo Co., Ltd., 10 mg of an unstretched film was heated from −40 ° C. to 120 ° C. at a heating rate of 20 ° C./min. From the obtained endothermic curve Asked. A tangent line was drawn before and after the inflection point of the endothermic curve, and the intersection was defined as Tg (glass transition point).

(6) Thickness distribution Using a contact thickness meter (model: KG60 / A) manufactured by Anritsu Co., Ltd., the thickness of the sample of 5 cm in the vertical direction and 50 cm in the horizontal direction was measured (measurement number = 20). The thickness distribution (thickness variation) was determined by the following formula. Moreover, the average value (n = 50) of the thickness distribution was evaluated according to the following criteria.
Thickness distribution = ((maximum thickness−minimum thickness) / average thickness) × 100 (%)
○: 6% or less △: Greater than 6% and less than 10% ×: 10% or more

(7) Intrinsic Viscosity 0.1 g of a sample (film or chip) was precisely weighed and dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane = 3/2 (mass ratio), and then 30 ± 0.1 with an Ostwald viscometer. Measured at ° C. The intrinsic viscosity [η] is determined by the following formula (Huggins formula).

η _sp / c = [η] + k [η] ² c
k is a so-called Huggins constant and is a measure of hydrodynamic interaction between solute molecules.
[Η] is obtained by plotting η _{sp /} c against _c from viscosity measurements of several solutions having different concentrations and extrapolating the obtained straight line from c → 0.
η _sp is the specific viscosity when the concentration is c.

(8) Composition ratio of film-copolymerized polyester Approximately 5 mg of polymer piece sample of the measurement target layer cut out from each side of the laminated film was dissolved in 0.7 ml of a mixed solution of deuterated chloroform and trifluoroacetic acid (volume ratio 9/1). 1H-NMR (manufactured by varian, UNITY 50) was used.

(9) Hot water curl rate After cutting the film into a 10cm x 10cm square and making a 1cm length x 1cm width cut in a direction perpendicular to the main shrinkage direction, in hot water at 70 ± 0.5 ° C, It heat-processed by processing for 3 second in the load state. The curl rate was calculated from the following formula for the cut portion of the film.

Curling rate (%) = (L1 / L2) × 100

L1: Length (mm) connecting the corners of the cutting tip with straight lines
L2: Length of cut root part (mm)

○: Curled on one side (curl amount of 5% or more)
X: No curling (curl amount less than 5%)

(10) Difference in degree of plane orientation between front and back surfaces of film Using Atsube refractometer 1T manufactured by ATAGO, the refractive index was measured from each face, and the degree of plane orientation was determined from the following formula to determine the difference.

AO = (Nx + Ny) / 2−Nz

AO: degree of plane orientation Nx: refractive index in the main shrinkage direction Ny: refractive index in a direction orthogonal to the main shrinkage direction Nz: refractive index in the film thickness direction

(11) Container reinforcement effect 1,3-Dioxolane was applied with a width of 3 mm ± 1 mm slightly inside from one end of one side of the film using a tube-shaped forming device (amount applied: 3.0 g ± 0. 3 / mm @ 2) Immediately roll up the film and overlap the ends to form a tube, which is wound in a flattened state. This tube is cut into a cylindrical label having a height of 14 cm and a diameter of 6.7 cm. Mass: 20.5 g of a 500 ml round PET bottle [height 21 cm, center (body) 6.5 cm] is filled with 500 ml of water and sealed, and the above cylindrical label is attached to it, and then Fuji The label is shrunk by passing the entire amount of label through a steam tunnel (SH-1500-L) manufactured by Astech Co. under the conditions of a tunnel passage time of 2.5 seconds and a zone temperature of 85 ° C.

The diameter (W1) of the center of the bottle when a load of 15 kg is applied in the compression mode to the center of the side surface of the label-coated bottle thus obtained using “Strograph V10-C” manufactured by Toyo Seiki Co., Ltd. The bottle diameter change rate (%) is obtained according to the following formula.
Bottle diameter change rate (%) = 100 × (W1-W2) / W2
Here, W2 is the diameter of the central portion of the bottle before the load is applied.

The polyester used in the examples is as follows.
Polyester A: Polyethylene terephthalate (Intrinsic viscosity (IV): 0.75 dl / g)
Polyester B: Polyester composed of 30 mol% neopentyl glycol 70 mol% ethylene glycol and terephthalic acid (IV: 0.75 dl / g)
Polyester C: Polyester composed of 30 mol% of 1.4-cyclohexanedimethanol, 30 mol% of ethylene glycol and terephthalic acid (IV: 0.75 dl / g)
Polyester D: Polybutylene terephthalate (IV: 1.24 dl / g)
Polyester elastomer: Polyester comprising 70% by mass of polybutylene terephthalate and 30% by mass of ε-caprolactone (reduced viscosity (ηsp / c) 1.30)

Example 1
Polyester A 6% by mass, polyester B 38.5% by mass, polyester C 38% by mass, and polyester elastomer 17.5% by mass were mixed as the A layer, and the polyester A 6% by mass, polyester B 41% by mass, polyester C40.5 as the B layer. 1% by mass of polyester and 12.5% by mass of polyester elastomer were melted at 260 ° C., co-extruded from a T-die so that the layer thickness ratio was A layer / B layer = 50/50, and rapidly cooled with a chill roll. An unstretched multilayer film having a thickness of 260 μm was obtained. The unstretched multilayer film had a Tg of 62 ° C.

  The unstretched film was preheated at 80 ° C. for 3 seconds and then stretched in the transverse direction with a tenter. For stretching, first stretched 4.75 times at 72 ° C. (first stage), then tensioned 3% of the film width at the end of the first stage at 72 ° C. for 5 seconds (heat setting), then 70 ° C. The film was stretched (second stage) to 1.1 times the film width at the end of heat setting. Next, the film was cooled while applying a tension of 1% with respect to the film width at the end of the second stage of drawing to obtain a film having a thickness of 50 μm.

(Example 2)
Polyester mixed with 15% by mass of polyester A, 34.5% by mass of polyester B, 34% by mass of polyester C, and 16.5% by mass of polyester elastomer as the A layer, and 6% by mass of polyester A, 5% by mass of polyester B40, and 5% by mass of polyester C40. 1% by mass of polyester and 13.5% by mass of polyester elastomer were melted at 270 ° C., co-extruded from a T-die so that the layer thickness ratio was A layer / B layer = 50/50, and rapidly cooled with a chill roll. An unstretched multilayer film having a thickness of 260 μm was obtained. The unstretched multilayer film had a Tg of 61 ° C.
A 50 μm thick film was obtained from the unstretched film in the same manner as in Example 1.

(Example 3)
Polyester A 6% by mass, polyester B 39% by mass, polyester C 39% by mass, and polyester elastomer 16% by mass were mixed as the A layer, and polyester A 6% by mass, polyester B 40% by mass, polyester C 40% by mass, polyester elastomer 14 as the B layer. Each of the polyesters mixed with mass% is melted at 260 ° C., co-extruded from a T die so that the layer thickness ratio is A layer / B layer = 40/60, and quenched with a chill roll to form an unstretched multilayer film having a thickness of 260 μm. Obtained. The unstretched multilayer film had a Tg of 61 ° C.
A 50 μm thick film was obtained from the unstretched film in the same manner as in Example 1.
Example 4
Polyester mixed with 10% by weight of polyester A, 81% by weight of polyester B and 9% by weight of polyester elastomer as the A layer, and 270 ° C. for polyester with 10% by weight of polyester A, 85% by weight of polyester B and 5% by weight of polyester elastomer as the B layer. And was coextruded from a T die so that the layer thickness ratio was A layer / B layer = 50/50, and quenched with a chill roll to obtain an unstretched multilayer film having a thickness of 260 μm. The unstretched multilayer film had a Tg of 64 ° C.
A film having a thickness of 50 μm was obtained in the same manner as in Example 1 except that the unstretched film had a preheating temperature of 88 ° C., a first stage stretching temperature of 74 ° C., a heat setting temperature of 74 ° C., and a second stage stretching temperature of 70 ° C. .

(Comparative Example 1)
A polyester in which 15% by mass of polyester A, 75% by mass of polyester B and 10% by mass of polyester D were mixed was melted at 280 ° C., extruded from a T-die, and quenched with a chill roll to obtain an unstretched film having a thickness of 260 μm. The unstretched film had a Tg of 67 ° C.
A 50 μm thick film was obtained from the unstretched film in the same manner as in Example 1.

(Comparative Example 2)
A polyester in which 6% by mass of polyester A, 79% by mass of polyester C and 15% by mass of polyester elastomer were mixed was melted at 280 ° C., extruded from a T-die, and quenched with a chill roll to obtain an unstretched film having a thickness of 260 μm. The unstretched film had a Tg of 61 ° C.
A film having a thickness of 50 μm was obtained from the unstretched film in the same manner as in Example 1.

(Comparative Example 3)
Polyester A 6% by mass, polyester B 38.5% by mass, polyester C 38% by mass, polyester elastomer 17.5% by mass mixed as an outer layer, polyester A 6% by mass, polyester B 41% by mass, polyester C 40.5% by mass Polyester mixed with 12.5% by mass of polyester elastomer was melted at 280 ° C., co-extruded from T-die so that the layer thickness ratio was outer layer / center layer / outer layer = 25/50/25, and quenched with chill roll. Thus, an unstretched multilayer film having a thickness of 260 μm was obtained. The unstretched multilayer film had a Tg of 62 ° C.
A 50 μm thick film was obtained from the unstretched film in the same manner as in Example 1.

(Comparative Example 4)
Polyester A 6% by mass, polyester B 38.5% by mass, polyester C 38% by mass, and polyester elastomer 17.5% by mass were mixed as the A layer, and the polyester A 6% by mass, polyester B 41% by mass, polyester C40.5 as the B layer. 1% by mass of polyester and 12.5% by mass of polyester elastomer were melted at 300 ° C., co-extruded from a T-die so that the layer thickness ratio was A layer / B layer = 50/50, and rapidly cooled with a chill roll. An unstretched multilayer film having a thickness of 260 μm was obtained. The unstretched multilayer film had a Tg of 62 ° C.
The unstretched film was preheated until the film temperature reached 95 ° C., and then stretched 5 times at 80 ° C. in the transverse direction by a tenter to obtain a film having a thickness of 50 μm.

  Table 1 shows the evaluation results of the films obtained in Examples 1 to 3 and Comparative Examples 1 to 4. As is clear from Table 1, the films obtained in Examples 1 to 3 all had good shrinkage finish. The thickness distribution was also good. Moreover, there was no label folding at the time of shrinkage after printing. The heat-shrinkable polyester film of the present invention has high quality and high practicality, and is particularly suitable for shrinkage labels.

  On the other hand, the heat-shrinkable films obtained in Comparative Examples 1 to 4 are folded when the label is shrunk after printing, and all have poor shrinkage finish. Thus, all the heat-shrinkable polyester films obtained in the comparative examples were inferior in quality and low in practicality.

  When the heat-shrinkable polyester film of the present invention is used as a full label for a bottle, it can produce a good finish with very little wrinkles, shrinkage spots, distortion and insufficient shrinkage due to heat shrinkage. Useful.

Claims (8)

A multilayer heat-shrinkable polyester film comprising at least two layers, wherein the heat-shrinkage rate of the polyester-based film is minus in the direction perpendicular to the main shrinkage direction when the shrinkage rate in the main shrinkage direction is 40%. 3% or more, treatment temperature 70 ° C., treatment time 5 to 70% at 5 seconds, 85 ° C. · 5 seconds at 75% or more, and 85 ° C. · 5 seconds in the direction perpendicular to the main shrinkage direction. The shrinkage rate in the main shrinkage direction when the film which is 10% or less and heat-shrinked in the main shrinkage direction by 10% is further treated in warm water at 95 ° C. for 5 seconds is X0 (%) and X10 (%), respectively. The multilayer heat-shrinkable polyester film is characterized in that the heat shrinkage ratio difference Δ (%) represented by the following formula is 10 to 20% and curls to one side when shrinking.
Δ = X0−X10   2. The multilayer heat-shrinkable polyester film according to claim 1, wherein the maximum value of the heat shrinkage stress in hot air at 90 ° C. is 7 MPa or more in the direction of the film after heat shrinkage of 10% in the main shrinkage direction. A multilayer heat-shrinkable polyester film characterized by   The multilayer heat-shrinkable polyester film according to claim 1 or 2, wherein the polyester film has a heat shrinkage rate in the main shrinkage direction. When the rate is 40%, the shrinkage rate in the direction orthogonal to the main shrinkage direction is minus 3% or more, the treatment temperature is 70 ° C., the treatment time is 5 seconds to 5 to 70%, and the 85 ° C. for 5 seconds is 75% Above, in the direction orthogonal to the main shrinkage direction, it is 10% or less at 85 ° C. for 5 seconds, and the refractive index of the surface opposite to the surface is calculated by measuring the refractive index of the surface of one side of the film. A multilayer heat-shrinkable polyester film, wherein the difference in the degree of plane orientation calculated in the above is 0.005 or more.   The heat-shrinkable polyester film according to any one of claims 1, 2, and 3, wherein the polyester elastomer has a high melting point crystalline polyester segment having a melting point of 200 ° C or higher and a molecular weight of 400 or higher and a melting point of 80 ° C or lower. A multilayer heat-shrinkable polyester film, which is a polyester block copolymer composed of a low melting point soft polymer segment.   The heat-shrinkable polyester film according to any one of claims 1, 2, 3, and 4, wherein the monomer that can be an amorphous component in all the polyester resin components is neopentyl glycol and / or 1,4-cyclohexane di A heat-shrinkable polyester film, which is methanol.   The heat-shrinkable polyester film according to any one of claims 1, 2, 3, 4 or 5, wherein the thickness distribution is 6% or less.   The label produced using the heat-shrinkable polyester-type film in any one of Claim 1, 2, 3, 4, 5 or 6.   A label produced by using the heat-shrinkable polyester film according to any one of claims 1, 2, 3, 4, 5, 6 or 7 so as to curl to the outer surface side of the label when shrinking.