JP7283175B2 - film protractor - Google Patents

Description

TECHNICAL FIELD The present invention relates to a film-like protractor using a polyester film, and more particularly to a film-like protractor having excellent folding retention performance after being stored in an environment of 20° C. for 24 hours.

Conventionally, the protractor has generally been made of a plate-shaped plastic material having a thickness of about 1 to 1.5 mm, such as a hard vinyl chloride resin plate or an acrylic resin plate, and printed with the necessary pattern for the protractor.

Patent Literature 1 discloses an underlay with a ruler and a protractor in which dimensional scales and angle scales are plotted and printed on the surface of an opaque sheet, and have the effect of being able to measure both length and angle. The thickness of the underlay is generally about 1 to 1.5 mm, like the protractor.

The above prior art protractors are used to measure angles in planes and are almost inflexible, so they cannot measure angles in curved surfaces such as the sides of cylinders. Also, when drawing a design such as a figure that includes two or more lines with a predetermined angle, first draw a straight line using a ruler, then use a protractor to draw a straight line at a predetermined angle. A complicated operation was required.

Utility Model Registration No. 3168928

The present invention has been made to solve the above problems, and its object is to provide a film-like protractor capable of measuring the angle on a curved surface and having excellent retention of the folded shape (folding retention performance). To provide a film-like protractor capable of easily drawing a straight line with a predetermined angle.

In order to solve the above problems, the present inventors conducted various studies and found that the intended purpose can be achieved by using a film having a predetermined folding retention performance, and completed the present invention.
The present invention, which has solved the above problems, has the following configuration.
1. A film having a polyester film and a printed part including a protractor pattern, and having a folding retention angle of 80 degrees or less and a thickness of 200 μm or less after being stored in an environment of 20° C. for 24 hours. protractor.
2. Having a print containing a protractor pattern between two polyester films1. The film-like protractor according to .
3. The polyester film has 50 mol% or more of ethylene terephthalate units in 100 mol% of all ester units,
It is composed of a polyester resin in which the sum of the ratio of the amorphous alcohol component in 100 mol% of the total alcohol component and the ratio of the amorphous acid component in 100 mol% of the total acid component is 12 mol% or more and 30 mol% or less. 1. or 2. The film-like protractor according to any one of 1.
4. 1. The polyester film is a stretched polyester film; ~3. The film-like protractor according to any one of 1.

ADVANTAGE OF THE INVENTION According to the present invention, there is provided a film-like protractor that can measure angles on a curved surface, has excellent retention of a folded shape (folding retention performance), and can easily draw a straight line at a predetermined angle. can do.

It is a figure which shows the measuring method of the folding holding angle of the film-like protractor based on this invention. It is a photograph showing an example of a film-like protractor according to the present invention. It is a photograph which shows an example which folded the film-shaped protractor based on this invention at an angle of 60 degrees.

The film-like protractor of the present invention will be described in detail below.

The film-like protractor of the present invention has a polyester film and a printed part including a protractor handle, and has a folding retention angle of 80 degrees or less after being stored in an environment of 20° C. for 24 hours, and a thickness of 200 μm or less. characterized by being

As described above, the film-shaped protractor of the present invention satisfies a folding holding angle of 80 degrees or less after being stored in an environment of 20° C. for 24 hours, so that it can be easily folded by hand and folded. It can maintain its shape. It has been found that if the folding retention angle after storage is controlled to 80 degrees or less, it is possible to achieve both easy foldability and shape retention after folding, especially when folding. The film-shaped protractor of the present invention can be firmly folded once folded, so that it can be folded at a predetermined angle (60 degrees) and held at that angle, as shown in FIG. 3, for example. Yes, it can be used like a ruler to easily draw two straight lines at a given angle along the edges of the folded film.
The folding holding angle is preferably 70 degrees or less, more preferably 60 degrees or less, and particularly preferably 55 degrees or less. Although the lower limit of the folding holding angle is not particularly limited, the practically achievable value is about 20 degrees or more.

In addition, since the film-like protractor of the present invention has a polyester film and a printed part including a protractor handle, and has a thickness of 200 μm or less, it is flexible and can be used on a curved surface such as the side surface of a cylindrical object. Angles can be measured. As described above, the conventional protractor is made of a material such as a rigid vinyl chloride resin plate or an acrylic resin plate, and has a thickness of about 1 to 1.5 mm. The protractor is used to measure angles on a plane, and is almost unbendable. If it is forced to bend, it will break. .
The thickness is preferably 150 μm or less, more preferably 100 μm or less, even more preferably 80 μm or less, and particularly preferably 60 μm or less. On the other hand, when the thickness is less than 5 μm, the film stiffness required for handling cannot be obtained, and the handleability in folding may deteriorate. The lower limit of the thickness is preferably 5 µm or more, more preferably 7 µm or more, and even more preferably 10 µm or more.

In addition, the film-shaped protractor of the present invention has a thickness of 200 μm or less as described above, which is about one-fifth or less of the thickness of a conventional protractor, and thus reduces the environmental load at the time of disposal. be able to.

The film-like protractor of the present invention preferably has a printed portion containing the protractor handle between two plastic films. With the above configuration, the printed part is protected and can be used for a long period of time, and it is possible to prevent the problem that the protractor pattern cannot be read due to the occurrence of defective parts or missing parts in the printed part. In particular, when folding, defects are likely to occur in the printed portion of the folded portion, but the above-described configuration makes it possible to suppress these defects. The printed portion may be a single layer, or may be two or more layers.

The printed portion can be formed by printing a printing ink on the plastic film constituting the film protractor of the present invention. The printing ink preferably contains a pigment or dye for coloring, an organic resin binder, and an organic solvent. As the printing ink, for example, Fine Wrap (registered trademark) of Dainippon Ink Kogyo Co., Ltd., Shrink Pack (registered trademark) of Sakata Inx, or the like can be used. The thickness of the printed portion is preferably 2 to 8 μm, more preferably 3 to 6 μm.

The printed portion includes a protractor handle. A protractor handle includes at least a plurality of concentric circles and an angular scale. By including the plurality of concentric circles and angular scale, angles from 0 to 360 degrees can be measured. Further, it is preferable to include numerical values indicating angles at intervals of 10 degrees or 20 degrees in the vicinity of the angle scale. The angle scale may be provided along one circle, or may be provided along a plurality of circles. It is preferable because it becomes easier. Moreover, it is preferable to colorize a specific angle range, because it makes it easier to measure the angle. In the example of FIG. 2, colors are applied at angles of 10 to 20 degrees, 30 to 40 degrees, 50 to 60 degrees, etc., and transparent portions and colored portions are alternately provided every 10 degrees.
It is preferable that the portion other than the printed portion includes a transparent portion.

The polyester film constituting the film protractor of the present invention is preferably a transparent film. That is, it is preferable that the portion other than the printed portion includes a transparent portion. In the present invention, a transparent film is defined as a polyester film having a haze value of 25% or less in a portion not including a printed portion. The haze value is measured according to JIS-K-7105, and the values are measured at three different points, and the average value is taken as the haze value.

The composition of the polyester film that constitutes the film-like protractor of the present invention is not particularly limited as long as the film-like protractor is kept at an angle of 80 degrees or less after being stored in an environment of 20° C. for 24 hours. For example, polyester films containing ethylene terephthalate units are preferred.

The above polyester film preferably has 50 mol % or more, more preferably 60 mol % or more of ethylene terephthalate units in 100 mol % of all ester units. Ethylene terephthalate units contain ethylene glycol and terephthalic acid as major constituents. By using ethylene terephthalate as a main component in this manner, excellent heat resistance and transparency can be obtained. The upper limit of the ethylene terephthalate unit is preferably less than 100 mol%, more preferably 95 mol% or less, even more preferably 90 mol% or less, most preferably 88 mol% or less.

Examples of dicarboxylic acid components other than terephthalic acid constituting the polyester film include aromatic dicarboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid and orthophthalic acid, and aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid. dicarboxylic acids, alicyclic dicarboxylic acids, and the like.

The polyester film preferably does not contain trivalent or higher polyvalent carboxylic acids (eg, trimellitic acid, pyromellitic acid, anhydrides thereof, etc.). This is because a film obtained using a polyester containing these polyvalent carboxylic acids may have a poor appearance due to the generation of foreign matter during the film formation by melt extrusion.

Diol components other than ethylene glycol constituting the polyester film include aliphatic diols such as 1,3-propanediol, 1,4-butanediol, neopentyl glycol and hexanediol; 1,4-cyclohexanedimethanol; Aromatic diols such as bisphenol A and the like can be mentioned.

Among these, cyclic diols such as 1,4-cyclohexanedimethanol; It is useful as a Tg component, and by adding one or more of these components, the glass transition point (Tg) can be adjusted to 60 to 70°C.

The polyester film preferably contains an amorphous component (an amorphous alcohol component and an amorphous acid component), and the proportion of the amorphous alcohol component in 100 mol% of the total alcohol component and 100 mol% of the total acid component A preferable total ratio of the amorphous acid component in the mixture is 12 mol % or more and 30 mol % or less. By containing ethylene terephthalate as a main component and containing 12 mol % or more of a monomer component that can be an amorphous component, the folding retention angle of the film can be easily adjusted to a lower retention angle. It is more preferably 15 mol % or more, still more preferably 17 mol % or more, and even more preferably 18 mol % or more. On the other hand, if the total amount of monomer components that can be amorphous components exceeds 30 mol %, tear resistance and heat resistance tend to be insufficient.

Monomers for the amorphous acid component (carboxylic acid component) include, for example, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid.

Monomers for the amorphous alcohol component (diol component) include, for example, neopentyl glycol, 1,4-cyclohexanedimethanol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl -1,3-propanediol, 2,2-isopropyl-1,3-propanediol, 2,2-di-n-butyl-1,3-propanediol, hexanediol and the like.

Among these monomer components, neopentyl glycol, 1,4-cyclohexanedimethanol or isophthalic acid are preferred, and neopentyl glycol is particularly preferred.

The polyester film does not contain a diol having 8 or more carbon atoms (e.g., octanediol, etc.) or a trihydric or higher polyhydric alcohol (e.g., trimethylolpropane, trimethylolethane, glycerin, diglycerin, etc.). is preferred. If a diol having 8 or more carbon atoms is contained, the mechanical strength of the film may be impaired. In addition, when a polyhydric alcohol having a valence of 3 or more is contained, there is a possibility that foreign matter may be generated during melt extrusion to form a film, resulting in poor appearance.

Moreover, it is preferable that the said polyester film uses a polyester-type elastomer together. As a result, the degree of amorphousness is increased, and the folding retention property is improved. A preferred polyester elastomer used in the present invention is a polyester block copolymer composed of a high melting point crystalline polyester segment (hard segment) and a low melting point soft polymer segment (soft segment) having a number average molecular weight of 400 or more.

Here, the high-melting-point crystalline polyester segment means a segment having a melting point of 200° C. or higher when a polymer is formed only from its constituent components.
Examples of the high melting point crystalline polyester segment include residues of aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid, pentamethylene glycol, 2,2 - polyesters consisting of residues of aliphatic, aromatic or cycloaliphatic diols such as dimethyltrimethylene glycol, hexamethylene glycol, decamethylene glycol, p-xylene glycol, cyclohexanedimethanol; p-(β-hydroxyethoxy ) polyesters consisting of oxyacid residues such as benzoic acid and p-oxybenzoic acid pivalolactone; fragrances such as 1,2-bis(4,4'-dicarboxymethylphenoxy)ethane and di(4-carboxyphenoxy)ethane polyether esters consisting of residues of a group ether dicarboxylic acid and residues of the above aliphatic, aromatic, or cycloaliphatic diols; Examples thereof include polyamide esters composed of residues and residues of the above aliphatic, aromatic, or alicyclic diols. Further, a copolymer polyester or the like using two or more kinds of the dicarboxylic acid residue and/or the diol residue can also be used.

On the other hand, the low-melting-point soft polymer segment exhibits a substantially amorphous state in the polyester-based elastomer. means a segment that The number average molecular weight of the low melting point soft polymer segment is preferably 400-8000, more preferably 700-5000.

Examples of the soft polymer segment having a low melting point include polyethylene oxide glycol, polypropylene oxide glycol, polytetramethylene oxide glycol, glycols of copolymers of ethylene oxide and propylene oxide, and glycols of copolymers of ethylene oxide and tetrahydrofuran. polyethers; aliphatic polyesters such as polyneopentyl azelate, polyneopentyl adipate and polyneopentyl sebacate; and polylactones such as poly-ε-caprolactone. Considering the compatibility with the polyester constituting the polyester film, a polyester-based elastomer using a polylactone such as poly-ε-caprolactone in the soft segment is preferable.
The proportion of the low melting point soft polymer segment in the polyester elastomer is preferably 1 to 90% by mass, more preferably 5 to 80% by mass.

As the polyester-based elastomer, in the present invention, an ε-caprolactone-based polyester elastomer comprising a copolymer polyester of terephthalic acid, butanediol, and ε-caprolactone is preferably used (see polyester raw material E in Table 1 below). As a result, the degree of amorphousness is increased, and the folding retention performance is exhibited even better. In order to fully exhibit such an effect, the content of the ε-caprolactone polyester elastomer in 100 mol% of the polyester resin constituting the polyester film is preferably 1 to 30 mol%, preferably 3 to 25 mol%. is more preferred, and 5 to 20 mol % is even more preferred. When the content of the ε-caprolactone-based polyester elastomer is less than 1 mol %, the effect of adding the ε-caprolactone-based polyester elastomer is not sufficiently exhibited. On the other hand, if the content of the ε-caprolactone-based polyester elastomer exceeds 30 mol %, the physical strength such as tear resistance, strength and heat resistance of the film may not be sufficiently obtained.

Various additives can be added to the polyester raw material used in the present invention, if necessary. The additives are not particularly limited, and known additives such as waxes, antioxidants, antistatic agents, crystal nucleating agents, viscosity reducing agents, heat stabilizers, coloring pigments, coloring inhibitors, and ultraviolet absorbers. is mentioned.

In order to improve the workability (slipperiness) of the film, it is preferable to add fine particles acting as a lubricant to the polyester raw material. As the fine particles, any fine particles can be selected regardless of the type of inorganic fine particles or organic fine particles. Examples of inorganic fine particles include silica, alumina, titanium dioxide, calcium carbonate, kaolin, and barium sulfate. Examples of organic fine particles include acrylic resin particles, melamine resin particles, silicone resin particles, crosslinked polystyrene particles, and the like. The average particle diameter of the fine particles is preferably in the range of about 0.05 to 3.0 μm when measured with a Coulter Counter. The lower limit of the fine particle content in the polyester film is preferably 0.01% by weight, more preferably 0.015% by weight, still more preferably 0.02% by weight. If it is less than 0.01% by weight, the lubricity may deteriorate. The upper limit is preferably 1% by weight, more preferably 0.2% by weight, and still more preferably 0.1% by weight. If it exceeds 1% by weight, the transparency may be lowered, which is not very preferable.

The method of blending the fine particles in the polyester raw material is not particularly limited, and for example, it can be added at any stage in the production of the polyester resin. It is preferable to add as a slurry dispersed in ethylene glycol or the like in the previous stage to proceed with the polycondensation reaction. In addition, a method of blending a slurry of particles dispersed in ethylene glycol or water or the like with a polyester resin raw material using a kneading extruder with a vent, or a method of blending fine particles and a polyester resin raw material dried using a kneading extruder. and a method of blending.

Furthermore, the above polyester film can be subjected to corona treatment, coating treatment, flame treatment, etc. in order to improve the adhesiveness of the film surface.

The film-like protractor of the present invention may be a single-layer film or a laminated film of two or more layers. In the case of a single-layer film, a printed portion including a protractor pattern can be formed by surface printing using a scratch-resistant ink or the like. In the case of a laminated film, it can further contain an adhesive layer. Thereby, it is possible to obtain a laminated film composed of a plurality of layers laminated via adhesive layers. Specifically, for example, a polyester film in which the printed part side of the polyester film and the adhesive layer side of the polyester film are laminated like the laminated film in Table 3 below / printed part / adhesive / polyester film (in Table 3 No. 1 to 10), and a laminated structure such as polyester film/printed part/adhesive/printed part/polyester film (No. 11 in Table 3) in which the printed part sides of the film are laminated via an adhesive. be done.

The adhesive used in the present invention is preferably a polyurethane adhesive, for example, from the viewpoint of exhibiting good design properties such as patterns applied to the printed portion while having folding retention performance. Examples of polyurethane adhesives include Takelac (registered trademark) manufactured by Mitsui Chemicals, Takenate (registered trademark) manufactured by Mitsui Chemicals, and dry lamination adhesives such as TM-250HV, TM-556S, and TM-265L manufactured by Toyo Ink Co., Ltd. is mentioned.
The thickness of the adhesive layer is preferably 1-6 μm, more preferably 2-5 μm.

However, the laminated film does not necessarily have to be produced through the adhesive layer, and it is possible to produce the laminated film without the adhesive layer by, for example, a co-extrusion method.

At least one of the types of films constituting the laminated film may be a film that satisfies the requirements of the present invention. Preferably, all films satisfy the requirements of the present invention like the laminated films shown in Table 3 below. It's a film.

The film-like protractor of the present invention preferably has an area that can be handled manually, thereby making it easier to achieve the effects of the present invention. The area of the film protractor according to the present invention is preferably 800 cm ² or less, more preferably 600 cm ² or less, even more preferably 400 cm ^{2 or} less. The area is the area of the entire film-like protractor, including the margin other than the handle of the protractor.

The overall shape of the film-shaped protractor according to the present invention is not particularly limited, and it is possible to employ shapes such as triangle, quadrangle, pentagon, hexagon, heptagon, octagon, circle, and ellipse. A square is preferred, and a square is more preferred.

Next, a method for producing a polyester film according to the present invention will be described. Although a polyester film containing a copolyester is used in the following description, it is not limited to this.

The above polyester film can be produced by melt-extruding the polyester raw material described above with an extruder to form an unstretched film, and then uniaxially or biaxially stretching the unstretched film by a predetermined method shown below. . The polyester can be obtained by polycondensing the above-described suitable dicarboxylic acid component and diol component by a known method. Two or more kinds of chip-shaped polyesters are usually mixed and used as a raw material for the film.

First, the raw material resin is melt extruded. At that time, it is preferable to dry the polyester raw material using a dryer such as a hopper dryer, a paddle dryer, or a vacuum dryer.
After the polyester raw material is dried in this way, it is melted at a temperature of 200 to 300° C. and extruded into a film using an extruder. Any existing method such as a T-die method, a tubular method, or the like can be employed for the extrusion.

Then, an unstretched film can be obtained by rapidly cooling the extruded sheet-shaped molten resin. As a method for rapidly cooling the molten resin, a method of obtaining a substantially non-oriented resin sheet by casting the molten resin from a die onto a rotating drum and rapidly cooling and solidifying the resin can be suitably employed.

Next, the unstretched film is stretched. The stretching direction of the film may be either the vertical (longitudinal) direction or the horizontal (width) direction of the film. In the following, the biaxial stretching method by lateral stretching - longitudinal stretching, in which lateral stretching is performed first and then longitudinal stretching, will be described, but even if the order is reversed, the main orientation direction will change. It doesn't matter if it's just Alternatively, although it is preferable to carry out biaxial stretching as described above, uniaxial stretching, either lateral stretching or longitudinal stretching, may be used.

First, stretching in the horizontal direction is performed. The stretching in the transverse direction is preferably carried out at 65 to 85° C. by a factor of about 3.5 to 5 in a tenter (first tenter) in which both ends in the width direction of the film are held by clips. Preheating is preferably performed before stretching in the transverse direction, and the preheating is preferably performed until the film surface temperature reaches 70 to 100°C.

After transverse stretching, the film is preferably passed through an intermediate zone in which no active heating operation is performed. If there is a temperature difference between the transverse stretching zone and the intermediate heat treatment zone of the first tenter, the heat of the intermediate heat treatment zone (hot air itself or radiant heat) flows into the transverse stretching process, and the temperature of the transverse stretching zone becomes unstable. Since the film quality may not be stable, it is preferable to carry out the intermediate heat treatment after passing the film after the transverse stretching and before the intermediate heat treatment through the intermediate zone over a predetermined period of time. In this intermediate zone, when a strip of paper is hung without passing through the film, the accompanying flow accompanying the running of the film, the transverse stretching zone, and the intermediate heat treatment are applied so that the strip of paper hangs almost completely in the vertical direction. A film of stable quality can be obtained by shutting off the hot air from. About 1 to 5 seconds is sufficient for passing through the intermediate zone. If it is shorter than 1 second, the length of the intermediate zone will be insufficient and the heat shielding effect will be insufficient. It is preferable that the intermediate zone is long, but if it is too long, the equipment becomes large, so about 5 seconds is sufficient.

After passing through the intermediate zone, the intermediate heat treatment before longitudinal stretching may or may not be carried out. When the intermediate heat treatment is carried out after the lateral stretching, if the temperature of the intermediate heat treatment is increased, the molecular orientation that contributes to the foldability is relaxed and the crystallization proceeds, so that the foldability is slightly deteriorated. In addition, unevenness in thickness similarly worsens. From this point of view, the intermediate heat treatment is preferably performed at 140° C. or lower. Here, the passing time through the intermediate heat treatment zone is preferably 20 seconds or less. A longer intermediate heat treatment zone is preferable, but about 20 seconds is sufficient. A laterally uniaxially stretched polyester film is thus obtained.

Next, longitudinal stretching is performed. As described above, the longitudinal stretching after the lateral stretching is not necessarily required, but longitudinal stretching is preferable because it improves the tensile breaking strength of the film. Specifically, for example, a laterally uniaxially stretched polyester film may be introduced into a longitudinal stretching machine in which a plurality of roll groups are continuously arranged. In longitudinal stretching, it is preferable to preheat the film with preheating rolls until the film temperature reaches 65 to 110°C. If the film temperature is lower than 65° C., it becomes difficult to stretch the film in the longitudinal direction (that is, the film tends to break), which is not preferable. On the other hand, if the temperature is higher than 110° C., the film tends to stick to the roll, and the roll tends to become dirty during continuous production, which is not preferable.

When the film temperature reaches the above range, it is longitudinally stretched. The longitudinal draw ratio differs depending on whether the main orientation direction is the longitudinal direction or the transverse direction. When the main orientation direction is the longitudinal direction, the longitudinal draw ratio is preferably 2 to 5 times. On the other hand, when the main orientation direction is the horizontal direction, the longitudinal draw ratio is preferably 1.2 to 1.8 times.

After the longitudinal stretching, the film is preferably cooled once, and preferably cooled with cooling rolls having a surface temperature of 20 to 40° C. before the final heat treatment. Quenching after longitudinal stretching is preferable because the molecular orientation of the film is stabilized and the natural shrinkage of the film after the product is reduced.

Next, the longitudinally stretched and cooled film is introduced into a second tenter for heat treatment (relaxation treatment), and heat treatment (relaxation treatment) is performed. The relaxation process is a process of loosening the film by 0 to 30% while gripping both ends of the film in the width direction with clips. The rate of contraction in the lateral direction can be changed by the rate of relaxation. The lower limit of the relaxation rate is 0%, and the upper limit is 99%. However, if the relaxation rate is too high, the width of the film product will be shortened, which is undesirable. Therefore, the upper limit of the relaxation rate is preferably about 30%.

The temperature of the heat treatment (relax treatment) is preferably 65 to 140°C. If the heat treatment temperature is lower than 65°C, the effect of the heat treatment will not be effectively exhibited. On the other hand, if the heat treatment temperature is higher than 140° C., the film is crystallized and the film tends to have poor retention of the folding angle, which is not preferable. The lower limit of the heat treatment temperature is more preferably 70° C. or higher, more preferably 75° C. or higher. On the other hand, the upper limit of the heat treatment temperature is more preferably 130° C. or lower, more preferably 120° C. or lower.

Finally, a polyester film roll is obtained by winding the film while cutting and removing both ends of the film.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples, and it is of course possible to implement it by making changes within the scope that can conform to the gist of the above and later descriptions. and all of them are included in the technical scope of the present invention. In the following description, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

In this example, single layer films 1 to 8 in Table 2 and laminated film No. 3 in Table 3 using the above single layer films were used. 1 to 10 (invention examples with map information) were produced and evaluated by the following methods. Furthermore, using the laminated film 1, a tubular film having perforations was produced.

[Folding holding angle]
(for single layer film)
Each film was left for 24 hours in a constant temperature room at 20° C. and 50% RH. Immediately thereafter, each film was cut into 10 cm×10 cm squares under an environment of 20° C. and 65% RH and folded into four (2.5 cm×2.5 cm squares overlapped). After that, a weight of 5 kg with a bottom size of 3 cm×3 cm was put on the film folded in four for 20 seconds. Then, after removing the weight, as shown in FIG. 1, the four corners of the sample 1 are in contact with the glass plate 2 or located near the glass plate 2 [the apex of the fold (the central part of the sample 1 before folding in four) Place the sample 1 folded in four on the glass plate 2 so that it is positioned away from the glass plate 2], and after 1 minute, the folded monolayer film opens at an angle 3 (completely folded state 0 degree) was measured to determine the folded holding angle. The fold retention angles in both the longitudinal and transverse directions of the film were similarly measured, and the larger value was taken as the fold retention angle of the film. In the measurement of the folding holding angle, in the case of a film sample in which the longitudinal direction and the lateral direction of the film are unclear, one direction is tentatively defined as the longitudinal direction, and the direction perpendicular to the tentative longitudinal direction is the tentative lateral direction. determined. In the table, the example in which the folding retention angle is x means that the folded state could not be retained after 1 second even though it was folded as described above.

(For laminated film)
For the laminated film, the folding retention angle was measured in the same manner as for the single layer film except for the following points.
Before folding in four (2.5 cm×2.5 cm squares overlapped), it was first folded in two. At that time, the folding holding angle when one side (front surface) of the laminated film is folded in two so that it is a mountain fold surface, and the other surface (back surface) of the laminated film is folded in two so that it is a mountain fold surface. The folding retention angle was measured in each case, and the smaller value was taken as the folding retention angle.

[Amorphous component content]
The content of the amorphous component was determined by dissolving about 5 mg of the sampled film in 0.7 mL of a mixed solution of deuterated chloroform and trifluoroacetic acid (volume ratio: 9/1), followed by ¹ H-NMR (UNITY50, manufactured by Varian). Asked for using. Specifically, the proton NMR spectrum of the sample solution was measured under the conditions of a temperature of 23° C. and an integration number of 64 times.

In this example, the contents of neopentyl glycol (NPG) and 1,4-cyclohexanedimethanol (CHDM) were determined as amorphous components. Specifically, the content of each amorphous component was calculated as follows.
Based on the frequency of the proton peak in the measurement chart of the NMR spectrum, the monomer type of the structural unit of the polyhydric alcohol component constituting the polyester in the sample solution was identified. Then, based on the value of the predetermined proton peak intensity corresponding to each monomer type, the amount of neopentyl glycol or the amount of 1,4-cyclohexanedimethanol in 100 mol% of the polyhydric alcohol component constituting the polyester in the sample solution is calculated. It was calculated as the content (mol%) of the amorphous component.

<Synthesis of polyester raw material>
[Synthesis of polyester raw material A]
A stainless steel autoclave equipped with a stirrer, thermometer and partial reflux condenser was charged with 100 mol % dimethyl terephthalate (DMT) as the dicarboxylic acid component and 100 mol % ethylene glycol (EG) as the polyhydric alcohol component. , Ethylene glycol was charged so that the molar ratio was 2.2 times that of dimethyl terephthalate, zinc acetate was used as a transesterification catalyst at 0.05 mol% (relative to the acid component), and the resulting methanol was distilled out of the system. The transesterification reaction was carried out while removing Then, 0.225 mol % (relative to the acid component) of antimony trioxide is added as a polycondensation catalyst, and the polycondensation reaction is carried out under reduced pressure conditions of 26.7 Pa at 280° C., resulting in an intrinsic viscosity of 0.75 dl/g. A polyester raw material A was obtained. This polyester raw material A is polyethylene terephthalate. Table 1 shows the composition of the monomer components of the polyester raw material A.

In Table 1, TPA is terephthalic acid, BD is 1,4-butanediol, NPG is neopentyl glycol, CHDM is 1,4-cyclohexanedimethanol, DEG is diethylene glycol, and ε-CL is ε-caprolactone. In Table 1, the "acid component" column indicates the content of the monomer component (TPA in Table 1) in 100 mol% of the total acid component, and the "polyhydric alcohol component" and "ester component" columns indicate the content of all polyhydric alcohol components. The content of each monomer component in 100 mol % of the total of the hydric alcohol component and all the ester components is shown.

[Synthesis of Polyester Raw Materials B to F]
Polyester raw materials B to F having different monomer components were obtained based on the same procedure as for the polyester raw material A. The polyester raw material F was produced by adding SiO ₂ (Sylysia 266 manufactured by Fuji Silysia Co., Ltd.) as a lubricant at a rate of 7,000 ppm to the polyester. Each polyester was appropriately chipped. Table 1 shows the composition of these monomer components. The intrinsic viscosity of each polyester raw material is B: 0.72 dl/g, C: 0.80 dl/g, D: 1.20 dl/g, E: 0.77 dl/g, and F: 0.75 dl/g. there were.

<Production of single layer film>
(Production of film 1)
The polyester raw material A, the polyester raw material B, the polyester raw material D, and the polyester raw material F were mixed at a mass ratio of 5:60:30:5 and fed into an extruder. Thereafter, the mixed resin was melted at 280° C., extruded through a T-die, wound around a rotating metal roll cooled to a surface temperature of 30° C., and quenched to obtain an unstretched film having a thickness of 240 μm. At this time, the take-up speed of the unstretched film (rotational speed of the metal roll) was about 20 m/min. Next, the unstretched film was led to a tenter (first tenter) in which a lateral stretching zone, an intermediate zone, and an intermediate heat treatment zone were continuously provided. In the intermediate zone, the hot air from the stretching zone and the hot air from the heat treatment zone are cut off so that when a strip of paper hangs down without the film passing through it, the paper hangs down almost completely in the vertical direction. controlled to be

Then, the unstretched film guided to the first tenter is preheated until the film temperature reaches 80 ° C., then stretched 4 times in the lateral direction at 70 ° C. in the lateral stretching zone, and passed through the intermediate zone. (Passing time = about 1.2 seconds), introduced to an intermediate heat treatment zone, and heat treated at a temperature of 80°C for 8 seconds to obtain a transversely uniaxially stretched film with a thickness of 60 µm.

Further, the transversely uniaxially stretched film was guided to a longitudinal stretching machine in which a plurality of roll groups were continuously arranged, preheated on preheating rolls until the film temperature reached 70° C., and then stretched 3 times. After that, the longitudinally stretched film was forcibly cooled by cooling rolls whose surface temperature was set to 25°C.

Then, the film after cooling is guided to a tenter (second tenter), heat-treated in the second tenter in an atmosphere of 100 ° C. for 10 seconds while relaxing in the width direction by 1%, and then cooled. By cutting and removing the edges, a biaxially stretched film having a thickness of 20 μm was continuously formed over a predetermined length to obtain a film roll composed of film 1 .

(Production of film 2)
A film roll composed of film 2 having a thickness of 20 μm was obtained in the same manner as film 1 except that polyester raw material B was changed to polyester raw material C in film 1 above.

(Production of film 3)
A film roll of film 3 having a thickness of 20 μm was obtained in the same manner as in film 1 except that polyester raw material D was changed to polyester raw material E in film 1 above.

(Production of film 4)
In the film 1, the thickness of the unstretched film was changed to 80 μm, the intermediate heat treatment temperature after the transverse stretching was changed to 82° C., and the thickness was 20 μm by stretching only in the transverse direction without performing longitudinal stretching and final heat treatment. A film roll consisting of film 4 was obtained.

(Production of film 5)
In the film 1, the weight ratio of the polyester raw material B was changed from 60 to 80, and the weight ratio of the polyester raw material D was changed from 30 to 10. A film roll was obtained.

(Production of film 6)
In the film 1, the weight ratio of the polyester raw material A was changed from 5 to 35, and the weight ratio of the polyester raw material B was changed from 60 to 50. A film roll was obtained.

(Production of film 7)
A film roll of film 7 having a thickness of 40 μm was obtained in the same manner as in film 1 except that the film thickness was changed from 20 μm to 40 μm.

(Production of film 8)
A film roll composed of film 8 having a thickness of 12 μm was obtained in the same manner as in film 1 except that the film thickness was changed from 20 μm to 12 μm.

(Production of film 9)
Film 9 is a biaxially stretched polyethylene terephthalate film (E5100 manufactured by Toyobo Co., Ltd., thickness 12 μm).

(Production of film 10)
The film 10 is a biaxially oriented polypropylene film (P2161 manufactured by Toyobo Co., Ltd., thickness 20 μm).

The properties of Films 1 to 10 (single layer films) thus obtained were evaluated by the methods described above, and are also shown in Table 2.

From Table 2, all films 1 to 8 have a folding retention angle of 80 degrees or less and have good properties. Among these, Film 5, in particular, had the highest content of amorphous components, and thus had the highest folding retention angle of 24 degrees. On the other hand, film 9 is a polyethylene terephthalate film containing no amorphous component, and has a folding holding angle of 100 degrees, which is inferior to films 1 to 8 in folding holding performance.
Also, the film 10 was also a polypropylene film containing no amorphous component, and even though it was folded, the folded state could not be maintained.

<Production of laminated film>
Using the films 1 to 10 described above, laminated film No. 1 was printed with a protractor pattern in the following manner. 1-11 were produced.

(Manufacture of No. 1)
The protractor pattern shown in FIG. 2 was printed on the film 1 by gravure printing using "Shrink Pack" (registered trademark) manufactured by Sakata Inx Co., Ltd. as printing ink.
Separately from the above, the film 1 was coated with a urethane-based two-component curing adhesive ["Takelac (registered trademark) A525S" and "Takenate (registered trademark) A50" manufactured by Mitsui Chemicals, Inc.] and ethyl acetate (Nacalai Tesque Co., Ltd. ) was applied at a mass ratio of 13.5:1:8.8 using a wire bar #5 to a thickness of 3 μm, and then allowed to stand in an oven at 60 ° C. for 30 seconds to evaporate the solvent. bottom.
Thereafter, the printed portion side of the film 1 subjected to the above printing and the adhesive layer side of the film 1 having the adhesive applied thereto are laminated by a dry lamination method. Cut into a square of 150 mm (225 cm ² ) and obtain a No. No. 1 laminated film (film-like protractor) was produced. The printed protractor pattern is a circular pattern with a diameter of 134 mm.

(Production of Nos. 2 to 10)
No. above. 1 except that films 2 to 10 were used instead of film 1. No. 1 in the same procedure as 1. 2 to 10 laminated films were produced.

From Table 3, no. Laminated films (film-like protractors) Nos. 1 to 8 all have a folding retention angle of 80 degrees or less, are easy to fold, and are excellent in shape retention after folding. Moreover, no defect in appearance was observed in the printed portion of the folded portion.
No. above. 1 to 8 laminated films (film-like protractor) were used and folded at an angle of 60 degrees as shown in FIG. 3, and they were easily folded. In addition, both of them are excellent in shape retention after folding, and after folding, they can be used like a ruler to draw two straight lines with a 60-degree angle on paper using a pencil. I was able to

Furthermore, using the laminated film (film-like protractor), the angle of the canned coffee pattern on the side surface (curved surface) of a commercially available canned coffee (52 mm in diameter and 103 mm in height) was measured. It could be easily measured using 1-8 laminated films (film protractor).

On the other hand, No. 1 using comparative films 9 and 10 which do not satisfy the requirements of the present invention. Laminated films Nos. 9 and 10 have the following problems.
No. No. 9 has a folding holding angle of 120 degrees. Compared to 1-8, the folding holding angle is large. Therefore, the above-mentioned film is difficult to be folded, has poor folding workability, and is inferior in shape retention after being folded.
No. above. When the laminated film No. 9 (film-like protractor) was used and folded at an angle of 60 degrees as shown in FIG. In addition, the shape retention after folding was also poor, and after folding, it was used like a ruler to draw two straight lines with a 60-degree angle on paper using a pencil. However, the angle was about 75 degrees, and a clean straight line could not be drawn.

No. The fold retention angle of No. 10 was evaluated as x, similarly to the single layer film of film 10, and the folded state could not be retained. In addition, the shape retention after folding was also poor, and after folding, it was used like a ruler to draw two straight lines with a 60-degree angle on paper using a pencil. However, it was impossible because the shape could not be maintained.

In addition, using a commercially available semicircular protractor (thickness 1.0 mm, made of acrylic resin), the angle of the canned coffee pattern on the side (curved surface) of a commercially available canned coffee (52 mm in diameter, 103 mm in height) When I tried to measure , I could not bend the protractor along the curved surface and could not measure it.

ADVANTAGE OF THE INVENTION According to the present invention, there is provided a film-like protractor that can measure angles on a curved surface, has excellent retention of a folded shape (folding retention performance), and can easily draw a straight line at a predetermined angle. can do. Since the environmental load at the time of disposal can be reduced as compared with the conventional protractor, it has a wide industrial utility value.

1 sample 2 glass plate 3 angle

Claims (4)

It has a polyester film and a printed part including a protractor pattern, and the protractor pattern has graduation lines for all angles at intervals of at least 10 degrees in an angle ranging from 0 degrees to 360 degrees, under an environment of 20 ° C. A film-like protractor characterized by having a folding retention angle of 80 degrees or less and a thickness of 200 μm or less after being stored at room temperature for 24 hours. 2. A film protractor according to claim 1, having a printed portion containing the protractor pattern between two polyester films. The polyester film has 50 mol% or more of ethylene terephthalate units in 100 mol% of all ester units,
It is composed of a polyester resin in which the sum of the ratio of the amorphous alcohol component in 100 mol% of the total alcohol component and the ratio of the amorphous acid component in 100 mol% of the total acid component is 12 mol% or more and 30 mol% or less. 3. The film protractor according to claim 1 or 2. The film protractor according to any one of claims 1 to 3, wherein said polyester film is a stretched polyester film.

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