JPH09300565A - Manufacture of orientation-laminated polyester support - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an orientation-laminated polyester support which is capable of substantially solving the problem of curling inevitably generated in the intermediate and the surface layer part of a rolled support by rolling the support. SOLUTION: This orientation-laminated polyester support consists of polyethylene terephthalate or polyethylene-2,6-naphthalate as a main constituent, and is of at least two layers of polyethylene terephthalate or polyethylene-2,6- naphthalate whose layers have mutually different copolymerization component ratios. The difference in the polymerization component ratios of the layers, constituting the outermost layer of the support is 2-15mol.%. The laminated polyester support is stretched and thermally fixed, and is rolled in such a manner that the support face with a smaller ratio of the copolymerization component of the laminated polyester support is faced inwardly.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to polyethylene terephthalate (hereinafter referred to as "PET") or polyethylene-2,6-naphthalate (hereinafter referred to as "PEN-2,"
6 ”) as a main constituent component, and PET or PEN-2,6 having different ratios of copolymerization components from each other, at least two or more layers are laminated. More specifically, it unwinds the support rolled and stored in a roll shape, surface treatment such as corona treatment, coating of undercoat layer, backcoat layer, emulsion layer, magnetic layer, etc., punching, perforation, slitting, etc. The present invention relates to a method for producing an oriented laminated polyester support having good flatness by suppressing curling due to curl during processing. As a field where this technology (oriented laminated polyester support) is required, a field in which a support is secondarily processed into a product,
Examples include photographic film, roentgen film, magnetic tape, magneto-optical disk, surface treatment process (corona treatment, etc.) for drawing, coating process (coating of undercoat layer, emulsion layer, magnetic layer, etc.). No, slit,
It can be applied to the ones in which the dimensional accuracy is changed in the punching process or the flatness is deteriorated due to curling.

[0002]

BACKGROUND OF THE INVENTION Polyester supports are thermal, mechanical,
It has excellent physical, chemical and optical properties. Therefore, the polyester support is used for photographic light-sensitive materials (color, X-
Suitable for magnetic recording applications (audio, video, floppy, etc.), electrical applications (capacitors, electrical insulating materials, etc.), vapor deposition applications, packaging applications, etc.

Conventionally, a thermoplastic support is generally subjected to a secondary processing process such as coating (coating of an undercoat layer, an emulsion layer, a magnetic layer, etc.), slitting and punching, in the longitudinal direction (traveling direction) of the support. It was required to be a flat support without curl.

However, since the support is generally supplied in a roll state, the curl generated in the longitudinal direction of the support impairs the flatness in the secondary processing process.
Often reduces yield. In particular, the curl around the core of the support roll is tight, and the curl strongly curls in the longitudinal direction of the support, sometimes resulting in a non-product.

Among them, especially PET or PEN-
Thick polyester supports such as 2, 6 and the like have the drawback that they tend to have curl and are difficult to remove.

Therefore, conventionally, from the viewpoint of preventing curling curl, (1) the support is wound into a roll, or the core diameter of the winding core is increased, or (2) the support is wound into a roll. Measures have been taken to avoid the effect of curling curls that have occurred by taking measures such as winding an extra support on the core in advance to allow for loss.

[0007]

However, these methods are difficult to cope with when only a small-diameter core can be used due to the process, or when the loss of the winding core of the support increases. The scope of its application was limited. Then, by winding the support in a roll shape, curling curl is unavoidable in the middle layer and the surface layer portion of the rolled support, and the appearance of a support that is essentially hard to curl has been desired.

Therefore, an object of the present invention is to (1) to provide a winding core for winding a support in a roll shape without increasing the core diameter of a winding core for winding a support in a roll shape. ,
It is not necessary to take measures to avoid the effect of curling curls that have occurred by taking measures such as winding an extra support in anticipation of loss in advance, (3)
By winding the support in a roll shape, it is possible to essentially eliminate the inevitable curl curl that is inevitably generated in the middle layer and the surface layer of the rolled support. An object of the present invention is to provide a method for producing a difficult oriented laminated polyester support.

[0009]

The above objects of the present invention have been attained by the following constitutions.

(1). A laminated support in which at least two layers of polyethylene terephthalate or polyethylene-2,6-naphthalate, which contains polyethylene terephthalate or polyethylene-2,6-naphthalate as a main constituent component and has different copolymerization component ratios, are laminated. And a difference in the ratio of the copolymerization components of the layers forming the outermost layer of the support is 2 mol% or more and 15 mol% or less, stretching,
A method for producing an oriented laminated polyester support, comprising: a heat-fixed laminated polyester support, which is wound with the surface of the laminated polyester support having a small proportion of copolymerization components inside.

(2). The method for producing an oriented laminated polyester support according to (1), wherein the difference in the ratio of the copolymerization components of the layers forming the outermost layer of the support is 4 mol% or more.

(3). The method for producing an oriented laminated polyester support according to (1) or (2), wherein the copolymerization component is adipic acid, cyclohexanedicarboxylic acid, diethylene glycol, or neopentyl glycol.

Hereinafter, the present invention will be described in detail.

The present invention is a laminated support in which at least two layers of PET or PEN-2,6 having PET or PEN-2,6 as a main constituent and having different ratios of copolymerization components are laminated. And a stretched and heat-fixed laminated polyester support, wherein the difference in the ratio of the copolymerization components of the layers constituting the outermost layer of the support is 2 mol% or more and 15 mol% or less. By winding the support surface with a small proportion of the copolymerization component of the inside, it is found that when the support is pulled out from the roll, that is, during processing, a flat support without curling can be obtained,
The present invention has been reached.

That is, two of the same kind having different copolymerization ratios are used.
PE in which two or more polyester polymer layers of the same kind are laminated, and the two or more polyester polymer layers of the same kind have different ratios of the copolymerization component to the reaction product.
PET having T or PEN-2,6 as a main constituent and having different ratios of copolymerization components, or PEN-.
An oriented laminated polyester support in which at least two layers of 2 and 6 are laminated, wherein the oriented laminated polyester support is wound with the side of the support having a small proportion of the copolymerization component inside. Is the way.

The copolymerization component may preferably contain adipic acid, cyclohexanedicarboxylic acid, diethylene glycol or neopentyl glycol monomer in an amount of 15 mol% or less, preferably 10 mol% or less. When the content of the copolymerization component exceeds 15 mol%, the mechanical properties originally possessed by the polyester support are impaired, which is not preferable. Adipic acid as a copolymerization component is added as dimethyl adipic acid. In addition, a support composed of a copolyester-based polymer single layer containing up to 15 mol% of these copolymerization components has a higher draw ratio, heat setting temperature, etc. than a support composed of a polyester homopolymer single layer. If the film conditions are almost the same, the orientation is slightly different depending on the kind and ratio of the copolymerization components, but almost the same orientation can be obtained. Therefore, it means that a mechanical strength equivalent to that of a support composed of a polyester homopolymer single layer can be obtained.

By the way, a copolymerized PET or a copolymerized PEN-2,6 containing a copolymerization component such as dimethylisophthalate, dimethylbiphenylcarboxylate, dimethylnaphthalenecarboxylate or dimethanolhexane.
The low-temperature heat shrinkage rate of the support composed of a single layer of a polymer-based polymer, that is, the heat shrinkage rate at a low temperature (room temperature to around 55 ° C.) below the glass transition temperature is determined by using adipic acid, cyclohexanedicarboxylic acid, diethylene glycol and neopentyl glycol. Copolymer PET or PEN-2,6 containing
Compared to a support composed of a single layer of polymer based polymer, the difference in the copolymerization ratio of the copolyester based polymer constituting the outermost layer is 15 mol% at maximum when used as a laminated support.
In this case, however, the curl characteristic of curling on the side of the copolymerized polyester polymer having a large copolymerization ratio due to the difference in shrinkage ratio is not sufficiently expressed. Therefore, it is not possible to obtain a flat support member that cancels out the curl curl that is generated by curling the curl curl generated by winding the core around the roll.

In order to solve these problems, as a result of diligent studies, especially when a copolymerized PET or a copolymerized PEN-2,6 containing adipic acid, cyclohexanedicarboxylic acid, diethylene glycol or neopentyl glycol is used, It has been found that the shrinkage rate is extremely large, these problems can be easily solved, and a support having the same mechanical strength as the polyester homopolymer simple support can be obtained, and the present invention has been achieved. is there.

Needless to say, these polyesters containing copolymerization components may be used in combination with different types of copolymerization components.

That is, the degree of curling of the laminated polyester polymer support varies depending on the type of the copolymerization component, the ratio of the copolymerization component to the reaction product, the thickness of the composition, and the number of layers laminated, but the curling occurs on one side of the support. It is intended to obtain a flat support in which the desired curl curl is eliminated by canceling the curl curl in the opposite direction generated by winding the core around in a roll shape. .

Therefore, in the case of a combination of the same type of polyester polymers having different kinds of copolymerization components, curling may not always occur on the side having a large proportion of copolymerization components, but most of them have a large proportion of copolymerization components. Curl to the side. Therefore, the present invention is more strictly described as "PET or
It is limited to PETs having PEN-2, 6 as a main constituent and having different ratios of copolymerization components, or a laminated support in which at least two layers of PEN-2, 6 are laminated.

The support of the present invention in which two or more different polyester polymer layers are laminated may be laminated in any number, but two or three layers are preferable from the viewpoint of ease of production.

Since the description will be simplified below, an explanation will be given using two-layer and three-layer examples.

In the case of a two-layer laminated polyester-based polymer support, if the laminated thickness is the same, in the case of the same copolymerization component, the layer having a large ratio of the copolymerization component to the reaction product is inwardly curled. In this case, the curl shows the maximum when the laminated thickness on the curling side occupies 1/2 of the total thickness.

In the two-layer laminated polyester-based polymer support, the thickness (m ₂ ) of the inner side of the copolyester-based polymer layer to be curled and the outer side of the curl of the copolyester-based polymer layer ( m ₁ )
, That is, a combination of the thickness composition ratios of m ₂ / m ₁ (generally, the same copolymerization component and the copolymerization component ratio of m ₂ are m ₁
If it is larger, the above-mentioned curl phenomenon occurs with m ₂ inside. ) May be a combination of (0 to 100%) / (100 to 0%), but from the viewpoint of the cost of the laminated polyester-based polymer support, the cost of the polyester having a small copolymerization ratio is low, and the thickness of m ₂ is It is preferable that the composition ratio is small. The thickness composition ratio of m ₂ / m ₁ is preferably (2
0-50)% / (80-50)%, more preferably,
A combination of (30 to 50)% / (70 to 50)% is preferable.

In the case of a two-layer laminated polyester polymer support composed of the same copolymer component, the difference in the ratio of the copolymer components of the copolymer polyester polymer supports constituting both layers is preferably 2 to 15 mol%. Is preferably 4 mol% or more and 15 mol% or less. This extreme combination is
It is a combination of a copolyester polymer and a polyester homopolymer. If this range is satisfied, the curling force of the two-layer laminated polyester polymer support acts as an anti-curling force against curling curl in the opposite direction generated by winding the core around the core.

In the case of a combination of different types of copolymerization components, the direction and degree of curl differ depending on the combination.
Although it may not be specified in some cases, generally, the laminated polyester support may be wound into a roll with the surface of the support having a small proportion of the copolymerization component inside.

In the case of a three-layer laminated polyester-based support, a copolyester-based polymer layer is laminated on both surfaces of the central polyester-based support. The polyester support layer of the central layer may be the same as or different from the copolyester layers on both sides, but a polyester homopolymer is preferable from the viewpoint of ensuring mechanical strength. If the two layers constituting the copolyester-based polymer layer on both sides have the same laminated thickness and the same kind of copolymerization component, the side having a large ratio of the copolymerization component to the reaction product is placed inside. Curl. In this case, the curling behavior is maximized if the laminated thickness on the inside curl side is the same as the laminated thickness on the opposite side. Also, in the case of a combination of different types of copolymerization components, the curling direction differs depending on the combination and may not be specified in some cases, but since it generally curls to the side where the ratio of the copolymerization components of the laminated polyester support is high. It may be wound into a roll with the surface of the support having a small proportion of the copolymerization component inside.

In the case of a three-layer laminated polyester-based polymer support, when the outermost layer is composed of the same copolymerization component, the difference between the copolymerization components of the two layers is 2 regardless of the polyester-based polymer support of the central layer. ~ 15 mol%, preferably 4
It is good to be more than mol%.

By utilizing the curling characteristic of the support described above and winding and storing the support in a direction opposite to the curling direction, the curling curl that occurs is canceled and a flat support is obtained. It is about trying to get a body.

The present invention will be described in more detail below.

First, the polyester polymer support of the present invention will be described.

In the present invention, a support having polyethylene terephthalate (PET) or polyethylene-2,6-naphthalate (PEN-2,6) as a main constituent means a terephthalic acid, naphthalene-2,6 as an acid component.
A dicarboxylic acid is a polyester mainly using ethylene glycol as a glycol component, and a difunctional acid such as adipic acid or cyclohexyl adipic acid is used as an acid component for copolymerization, or 15 mol% or less of two or more of them. The copolymer or polymer mixture used may be used, and as the glycol component, one of diol compounds of diethylene glycol and neopentyl glycol,
Alternatively, it may be a copolymer or polymer mixture containing two or more kinds of 15 mol% or less.

The polyester-based polymer support may contain stabilizers such as phosphoric acid, phosphorous acid and their esters.

The difference in the ratio of the copolymerization component between the two layers constituting the outermost layer of the laminated polyester polymer support to the reaction product varies depending on the type of the copolymerization component, the constitutional thickness and the number of layers, but is 2 mol% or more. It is 15 mol% or less, preferably 4 mol% or more and 15 mol% or less. The greater the difference in the ratio of the copolymerization component between the two layers constituting the outermost layer to the reaction product, the greater the degree of curling. On the other hand, the core used for winding the support in a roll shape has a diameter of 3 to 10 inches in many cases, and if the support surface having a small ratio of the copolymerization component is inwardly wound up into a roll,
If the curl curl generated in this range of diameter and the curl generated due to the support cancel each other out and fall within the range of the laminated film having the above-mentioned structure, a flat support can be obtained.

The polyester polymer used in the present invention is melt-polymerized by a conventionally known method.

The support may contain inorganic fine particles, antioxidants, UV absorbers, antistatic agents, dyes, pigments, dyes, etc., in order to impart functionality, within a range not impeding the object of the present invention. Is possible.

The polymer used for forming the polyester polymer film has an intrinsic viscosity of 0.45 in the case of PET.
0.75, PEN-2,6 has an intrinsic viscosity of 0.35
.About.0.65 (measured at 35.degree. C. of o-chlorophenol. The unit is 100 cc / g). PE
In the case of T, those of 0.50 to 0.70 are preferably used, and if the intrinsic viscosity is less than 0.45, it is not possible to obtain a support having excellent film-forming properties and strength characteristics. On the other hand, PEN-
In the case of 2 and 6, the intrinsic viscosity is preferably 0.40 to 0.
The one of 60 is used. If the intrinsic viscosity is less than 0.35, it is impossible to obtain a support having excellent film-forming properties and strength characteristics. When the intrinsic viscosity exceeds 0.45-0.50, PEN
Since the melt viscosity of -2 and 6 during polymerization becomes extremely high and the polymerization becomes difficult, the melt polymerization is completed at an intrinsic viscosity of 0.45 to 0.50, and thereafter, it is vacuum or inert such as nitrogen. PEN-2,6 having an intrinsic viscosity of 0.65 can be obtained by solid-phase polymerization while heating in a gas atmosphere.

Regarding the upper limit of the intrinsic viscosity, in the case of PET, about 0.75 is PEN-2, from the viewpoints of film-forming property (breakage due to increase in drawing tension) and increase in melt viscosity (filter pressure). In the case of 6, the limit is about 0.65.

Further, the polyester-based polymer support of the present invention comprises polyester-based polymer pellets of 120 to 18
Crystallize and dry at 0 ° C. for 1-24 hours under vacuum or atmospheric pressure under an inert gas atmosphere such as air or nitrogen.
The moisture content of the target pellets is not particularly limited, but it is preferable to dry it to 0.05% or less, preferably 0.01% or less, from the viewpoint of preventing the mechanical strength and the like of the support from being lowered by hydrolysis. However, these methods are not particularly limited as long as the purpose is achieved.

The laminated polyester-based polymer support comprises two polyester-based polymer pellets having different copolymerization components.
After laminating in a molten state at 60 to 350 ° C.,
An unstretched support is prepared by pressing from a T die and cooling and solidifying while applying static electricity on a casting roll, or a polyester-based unstretched support or a polyester-based uniaxially stretched support that has been cooled and solidified has different copolymerization components. Alternatively, a polyester-based molten polymer having the same copolymerization component but a different copolymerization ratio is extrusion-laminated, and then stretched in both the longitudinal and transverse directions or in the direction orthogonal to the uniaxial stretching direction, and heat-set.

The stretching method is a known method, for example,
In addition to the sequential biaxial stretching method in which longitudinal stretching and transverse stretching are performed in order,
Sequential biaxial stretching method of stretching / longitudinal stretching, horizontal / longitudinal / longitudinal stretching method, longitudinal
・ Horizontal / longitudinal stretching method, vertical / longitudinal / horizontal stretching method, or simultaneous biaxial stretching
It is possible to adopt the stretching method and the required mechanical and thermal
It can be appropriately selected according to various characteristics, but (Tg ₁
-25) ° C ~ (Tg_TwoVertical temperature range of +60) ° C
And transversely stretched 2.5 to 5.0 times, 200 to 25
The manufacturing method of heat treatment at 0 ° C. is aimed at supporting the oriented laminated layer.
It is the preferred method of making the body. PET homopolymer
Tg of 70-75 ° C, of PEN-2,6 homopolymer
It has a Tg of 120 to 125 ° C.
Copolymer PET and CoPEN containing up to 15 mol%
Tg of -2,6 is about 20 ℃, and about 30 ℃
Decreased to 56 ° C and 91 ° C, respectively.

Here, Tg ₁ and Tg ₂ represent the highest and lowest glass transition temperatures of the polymers constituting the laminated support, respectively.

Generally, a sequential biaxial stretching method is preferred in which stretching is carried out first in the longitudinal direction and then in the width direction. In the case of a laminated polyester-based support, the glass transition temperature (Tg) of each laminated layer varies depending on the copolymerization ratio and the stretching temperature is not uniquely determined, but it is preferable to stretch at 50 to 150 ° C. The stretching temperature in the width direction is preferably slightly higher than that in the longitudinal direction.

Next, the stretched support is heat-treated. As the heat treatment temperature, a temperature of 200 to 250 ° C. is adopted for magnetic recording, electrical insulation, vapor deposition, packaging, photography, printing sensitive material, and medical applications that require dimensional stability. The heat treatment time is not particularly limited, but is usually 3 seconds to 1
About 00 seconds is adopted.

Here, the film forming conditions of PET and PEN-2, 6 are dealt with collectively, but in comparison with PET, P
The stretching and heat setting temperatures of EN-2 and 6 are set higher. Further, it goes without saying that vertical heat relaxation, horizontal heat relaxation treatment, etc. may be carried out if necessary.

In addition to the above, surface treatment (giving a gas barrier property by coating with vinylidene chloride, imparting slipperiness, adhering property by in-line coating, etc.) may be carried out. The above-mentioned film forming method can be appropriately changed according to its use and purpose.
The present invention is not limited to these methods for any reason.

The thickness of the oriented laminated polyester support thus obtained is 5 to 75 μm for magnetic recording, 60 to 122 μm for photographic light-sensitive material, color sensitive material, medical and printing sensitive material. 100 μm, 175 μm for X ray,
For electrical insulation, with a wide range of thicknesses from 6 to 250 μm,
It is usefully used for those having a thickness of 5 to 250 μm.

In particular, when the thickness of the support becomes thick, curling curl is strongly generated. Therefore, the support of the present invention has a thickness of 5 mm.
It is usefully used for those of 0 to 250 μm.

[0050]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

An example of producing an oriented laminated polyester support will be described.

The laminated support was manufactured as follows.

(1) Polymerization of Polyester Homopolymer and Copolymerized Polyester In the usual polymerization of polyester homopolymer, the copolymerization monomers shown in Tables 1 to 4 are added to the polyester basic skeleton to prepare a polyester-based polymer. A copolymerized polymer was obtained.

(2) Preparation of Oriented Laminated Polyester Support The obtained polymer pellets of polyester homopolymer and copolymerized polyester were dried at 160 ° C. for 3 hours in a nitrogen atmosphere and crystallized to obtain PET homopolymer and copolymerized PET. The polymer is PEN at 260-320 ° C.
-2,6 homopolymer and copolymerized PEN-2,6 polymer are melted at 270 to 330 ° C, the polymers are extruded from separate extruders, and the polymers are laminated in a molten state in a laminating die to form a support. 30 by melt extrusion and electrostatic application
It was rapidly cooled and solidified on a cooling drum at a temperature of ℃ to obtain an unstretched support having a thickness composition ratio of each layer of the laminated unstretched support of 990 μm, which is the content described in Tables 1 to 5.

In Examples 1 to 23 and Comparative Examples 1 to 11, the unstretched support was stretched 3.1 times in the machine direction at 75 to 110 ° C, and then stretched at 85 to 120 ° C in the transverse direction at 3. The film was stretched 2 times, heat-set at 215 ° C. for 30 seconds, and the biaxially oriented laminated polyethylene terephthalate polymer support having a thickness of 100 μm was wound up to obtain a roll-shaped support.

In Examples 24 to 28 and Comparative Examples 12 and 13,
After stretching 3.1 times in the machine direction at 85 to 120 ° C., 95
Stretched 3.2 times in the transverse direction at ~ 130 ° C and 30 at 230 ° C
After heat setting for 2 seconds, a biaxially oriented laminated polyethylene-2,6-naphthalate polymer support having a thickness of 100 μm was wound up to obtain a roll-shaped support.

The samples obtained as described above were evaluated as follows.

<< Evaluation Method >> (1) Curling curl The curling curl of the oriented laminated polyester support has an outer diameter of 3
61 cm width (horizontal direction during manufacturing) x 60 in inch core
A sample of m (longitudinal direction at the time of production) was wound with the support surface (curled convex portion of the laminated polyester support) of the laminated polyester support having a small proportion of copolymerization components inside, and 23 ° C., 55% After conditioning the humidity for 1 day under RH conditions, heat treatment was performed for 4 hours in an atmosphere of 55 ° C. and 20% RH. The curl curl at this time indicates the curl in the lengthwise direction of the first surface layer. The curl curl test conditions almost correspond to the state after storage for 2 years.

Then, after allowing to cool in an atmosphere of 23 ° C. and 55% RH for 30 minutes, it was released from the core, and after 1 minute, the side surface of this support piece was erected on a horizontal plane, and the lamination was performed. + (Plus) curl curl that occurs with the surface of the polyester support, which has a high proportion of copolymerization components, facing inward
Expressed as Therefore, the curl degree of curl is 1 / when the curl with the surface of the support having a small proportion of the copolymerization component of the laminated polyester support as the inside is- (minus).
It is represented by R (m ^-1 ).

This R represents the radius of curvature of the curled support, and its unit is m (meter). Curling curl is maximum when it is equal to a core with an outer diameter of 3 inches (7.62 cm) (that is, a radius of curvature of 0.0381 m), 2
6.25 (m ^-1 ), which is the worst and when the support is flat, the radius of curvature becomes infinite and the degree of curl is 0.
(M ^-1 ). Therefore, the smaller the value of the degree of curl, the better.

(2) Workability (flatness) Evaluation was made according to the following criteria.

◎: The support is extremely flat, and the dimensional accuracy is not affected by the coating process (undercoating layer coating, emulsion layer coating, magnetic layer coating, etc.), slitting and punching process. ○: In the same process I am a little worried about the support curl,
It can be used without problems by raising the support take-up tension in the process without any problem. X: The curl of the support was too tight, and the problem could not be used because of the same process.

The results of << Examples 1 to 14 and Comparative Examples 1 to 4 >> are shown in Tables 1 and 2.

[0064]

[Table 1]

[0065]

[Table 2]

As is clear from Tables 1 and 2, the results of Examples 1 to 11 and Comparative Examples 1 and 2 shown in Table 1, and Examples 12 to 14 and Comparative Examples 3 and 4 shown in Table 2. From this, it is understood that the oriented laminated polyethylene terephthalate polymer support obtained by the present invention has a small curling curl and is extremely excellent in workability. At this time, if the thickness composition ratio of the layers forming both outermost layers of the laminated support is 1: 1 and the difference in the copolymerization component is 2 mol% or more, preferably 4 mol% or more, the support is wound. It is understood that the curl is small and the workability is extremely excellent.

Table 3 shows the results of Examples 15 to 23 and Comparative Examples 5 to 7.

[0068]

[Table 3]

As is clear from Table 3, Examples 15-2
3. From the results of Comparative Examples 5 to 7, two layers of copolymerized PET and PET homopolymer in which the copolymerization component is * 2 (cyclohexanedicarboxylic acid), * 3 (diethylene glycol), * 4 (neopentyl glycol) When the thickness composition ratio of the layers constituting both outer layers of the laminated support is 1: 1, the curl degree is small and the workability is low when the difference in the copolymerization components is 7 mol% or more, preferably 11 mol% or more. Is understood to be excellent.

Table 4 shows the results of << Comparative Examples 8 to 11 >>.

[0071]

[Table 4]

As is clear from Table 4, Comparative Examples 8-11
From the results, it is understood that the copolymerized PET / PET homopolymer laminate support containing these copolymerization components as constituents has a large curl curl degree, is poor in workability, and cannot be used.

<< Examples 24-28, Comparative Examples 12-13 >>
The results are shown in Table 5.

Biaxially oriented laminated polyethylene-2,6-naphthalate polymer support

[0075]

[Table 5]

As is clear from Table 5, Examples 24-2
8. From the results of Comparative Examples 12 to 13, it is understood that the oriented laminated polyethylene-2,6-naphthalate polymer support obtained has a small curling curl and is extremely excellent in workability. Further, at this time, the thickness constituting ratio of the layers forming both outermost layers of the laminated support is 1: 1 and the difference in the copolymerization component is 2: 1.
It is understood that when it is at least mol%, preferably at least 4 mol%, curling curl of the support is small and workability is extremely excellent.

As is clear from the above, the laminated P of the present invention is
By using the ET-based polymer support, it is possible to more efficiently obtain a support that is hard to curl and has excellent dimensional stability.

[0078]

EFFECTS OF THE INVENTION According to the present invention, (1) it is not necessary to increase the core diameter of the winding core for winding the support in a roll shape,
(2) Measures to avoid the influence of curling curls that have occurred by taking measures such as winding an extra support on the core that winds the support into a roll in advance, taking into account loss. (3) an intermediate layer of the rolled support by winding the support in a roll,
It has been possible to provide a method for producing an oriented laminated polyester support which is essentially hard to curl, which can essentially eliminate the occurrence of inevitable curl curl which inevitably occurs in the surface layer portion.

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Claims (3)

[Claims] 1. Polyethylene terephthalate or polyethylene-2,6-naphthalate as a main constituent and polyethylene terephthalate or polyethylene-2,6-naphthalate having different ratios of copolymerization components are laminated in at least two or more layers. A laminated support,
A stretched and heat-fixed laminated polyester support in which the difference in the ratio of the copolymerization components of the layers constituting the outermost layer of the support is 2 mol% or more and 15 mol% or less. A method for producing an oriented laminated polyester support, characterized in that the support surface having a small proportion of components is wound up with the support surface inside. 2. The method for producing an oriented laminated polyester support according to claim 1, wherein the difference in the ratio of the copolymerization components of the layers forming the outermost layer of the support is 4 mol% or more. 3. The copolymerization component is adipic acid, cyclohexanedicarboxylic acid, diethylene glycol or neopentyl glycol, according to claim 1 or 2.
The method for producing an oriented laminated polyester support according to item 1.