JPH08230124A - Laminated film roll - Google Patents

Abstract

PURPOSE: To provide an aromatic polyamide film roll which has no longitudinal and lateral wrinkles and no aging wrinkle. CONSTITUTION: A roll is made of a film of a biaxially oriented film formed by providing a layer (layer A) made of aromatic polyamide resin or aromatic polyamide resin A containing inert particles at least on one surface of a layer (layer B) made of aromatic polyamide resin or aromatic polyimide resin B and having the ratio t/d of the thickness (t) of the layer A to the mean particle size (d) of the particle contained in the layer A of 0.1 to 10, the lateral thickness spot of the layer S of 50% or less, the moisture absorption rate of a laminate of 3.5% or less, the longitudinal and lateral Young's moduluses of the laminate of 800kg/mm<2> or more. A laminated film roll has the winding hardness of the roll of a range of 85 to 100.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a laminated film roll.

[0002]

2. Description of the Related Art Film roll technology is
Regarding a thermoplastic resin, a thermoplastic resin film roll (for example, Japanese Patent Laid-Open No. 57-193322) in which the relationship between the center line average roughness of the film and the winding hardness is in a specific range, and the particle diameter, the laminated thickness, and the winding hardness are in specific ranges. There is a thermoplastic resin film roll (JP-A-2-194924).

[0003]

However, the above-mentioned conventional film rolls are limited to thermoplastic resins, and in recent years, due to their high mechanical properties (especially Young's modulus) and heat resistance, thin film magnetic recording medium base films and Until now, no technique has been presented for aromatic polyamide-based films and aromatic polyimide-based films, which are rapidly increasing in use as flexible printed circuit boards. Since the aromatic polyamide-based film and the aromatic polyimide-based film are used in the field of miniaturization and thinning to take advantage of the excellent characteristics as described above, the winding shape of the film roll (longitudinal direction, width direction Wrinkles, and wrinkles over time) affect productivity and quality of the resulting product. In addition, since aromatic polyamide and aromatic polyimide generally have higher hygroscopicity than thermoplastic resins such as polyethylene terephthalate, deterioration of the winding shape due to moisture absorption is observed. An object of the present invention is to solve the above problems and to provide a film roll having an excellent winding shape in which wrinkles in the longitudinal and width directions and wrinkles with time do not occur.

[0004]

In order to solve the above-mentioned problems, the present invention provides a layer (A) made of an aromatic polyamide resin or aromatic polyimide resin A containing inert particles.
Is a biaxially oriented film which is formed on at least one side of a layer (B layer) made of an aromatic polyamide resin or an aromatic polyimide resin B and has a thickness t of the A layer.
And the ratio of the average particle diameter d of the inert particles contained in the A layer, t
/ D is 0.1 to 10, the thickness variation of the A layer in the width direction is 50% or less, the moisture absorption rate of the laminate is 3.5% or less, and the Young's modulus in the longitudinal direction and the width direction of the laminate is both A laminated film roll, which is a roll made of a film having a weight of 800 kg / mm ² or more, characterized in that the winding hardness of the film roll is in the range of 85 to 100 is its gist.

The aromatic polyamide resins A and B constituting the present invention are represented by the following general formula (I) and / or general formula (I
It means that the repeating unit represented by I) contains 50 mol% or more, and more preferably 70 mol% or more.

Formula (I)

Embedded image General formula (II)

Embedded image Here, Ar ₁ , Ar ₂ and Ar ₃ are, for example,

Embedded image And the like, X and Y are —O—, —CH ₂ —, —CO—, —SO ₂ —, —S—,
-C (CH ₃ ) _2- , but not limited thereto. Further, some of the hydrogen atoms on these aromatic rings are halogen groups (especially chlorine), nitro groups, C ₁ -C ₃ alkyl groups, C
It also includes those substituted with a substituent such as a _{1 to} C ₃ alkoxy group, and also those in which hydrogen in the amide bond constituting the polymer is substituted with another substituent.

From the characteristic point of view, the above-mentioned aromatic ring bonded in the para-position, which is composed of 50 mol% or more of the constituent units, has a high Young's modulus, so that the generation of wrinkles during winding is small, Further, it is preferable because the generation of wrinkles over time is suppressed, and more preferably 60 mol% or more, and further preferably 70 mol% or more.

Further, a polymer having 30% or more of the aromatic ring in which a part of hydrogen on the aromatic ring is replaced with an electron-withdrawing group reduces the hygroscopicity, so that the dimensional change due to humidity change is small. This is preferable because wrinkles are less likely to occur over time. The electron-withdrawing group is, for example, a halogen group such as chlorine or fluorine, or a nitro group, and among them, chlorine is more preferable as a substituent for lowering hygroscopicity, and the ratio of the aromatic ring to be substituted is more preferable. Is 30 mol% or more, and more preferably 50 mol% or more.

Aromatic polyamide resins A and B of the present invention
Represents a repeating unit represented by the general formula (I) and / or the general formula (II) in an amount of 50 mol% or more,
If it is less than 50 mol%, other repeating units may be copolymerized or blended, and conductive particles may be added to such an extent that the physical properties of the film are not impaired.

The aromatic polyamide resin A of the present invention,
The B's may be the same as or different from each other as long as they are the polymers shown above, but it is advantageous from the viewpoint of productivity that they are the same.

The aromatic polyimide resins A and B constituting the present invention contain at least one aromatic ring and at least one imide ring in the repeating unit of the polymer, and have the general formula (III) and / or
Alternatively, those containing 50 mol% or more of the repeating unit represented by the general formula (IV) are preferable, and more preferably 70 mol%
That is all.

General formula (III)

[Chemical 4] General formula (IV)

Embedded image Here, Ar ₄ and Ar ₆ include at least one aromatic ring, and two carbonyl groups forming an imide ring are bonded to adjacent carbon atoms on the aromatic ring. This Ar ₄ is derived from an aromatic tetracarboxylic acid or its anhydride.
The following are typical examples.

[0013]

[Chemical 6] Wherein Z is _{-O -, - CH 2 -,} - CO -, - SO 2 -, - S-,
-C (CH _{3) 2} - is chosen from such, but is not limited thereto.

Ar ₆ is derived from carboxylic acid anhydride or its halide. Ar ₅ and Ar ₇ are, for example,

[Chemical 7] And the like, X and Y are —O—, —CH ₂ —, —CO—, —SO ₂ —, —S—,
-C (CH _{3) 2} - is chosen from such, but is not limited thereto. Further, a part of hydrogen atoms on these aromatic rings is a substituent such as a halogen group (especially chlorine), a nitro group, a C ₁ -C ₃ alkyl group (especially a methyl group), a C ₁ -C ₃ alkoxy group and the like. And those in which hydrogen in the amide bond constituting the polymer is replaced by another substituent.

Aromatic polyimide resins A and B of the present invention
Contains 50 mol% or more of the repeating unit represented by the general formula (III) and / or the general formula (IV), and less than 50 mol% is copolymerized or blended with another repeating unit. It does not matter if you

The type of the inert particles in the layer A of the present invention is not particularly limited, but substantially spherical silica particles derived from colloidal silica, particles of a crosslinked polymer (for example, crosslinked polystyrene), etc. are more wound. It is particularly preferable because it becomes good. However, other particles, alumina silicate, silica in which primary particles are aggregated, internally precipitated particles,
Even with particles of calcium carbonate, titanium dioxide, alumina or the like, a sufficiently good winding shape can be obtained by appropriately controlling the ratio between the thickness t of the A layer and the average particle diameter d.

The average particle diameter of the inactive particles in the layer A of the present invention is not particularly limited, but is 0.007 to 2.5 μm, and particularly preferably 0.
When it is in the range of 02 to 1 μm, the winding shape is further improved, which is desirable.

It is preferable that the content of the inert particles in the layer A of the present invention is 0.1 to 40 wt%, preferably 0.2 to 30 wt%, because the winding shape is further improved.

The ratio of the thickness t of the layer A of the present invention to the average particle diameter d of the inert particles contained in the layer A, t / d is 0.1 to 10,
Preferably 0.3-10, more preferably 0.3-8.
Must be in the range 0. When it is less than 0.1, the inactive particles fall off, and when it is more than 10, blocking occurs, and as a result, wrinkles occur in the longitudinal and width directions.

The moisture absorption of the layer A and layer B laminate of the present invention must be 3.5% or less, preferably 3.0% or less, and more preferably 2.5% or less. This is because if the moisture absorption rate is higher than 3.5%, the dimensional change due to moisture absorption is large, and as a result wrinkles occur over time.

The Young's modulus of the laminate of the layers A and B of the present invention is 800 kg / mm ² or more, preferably 900 kg / mm ² or more, more preferably 1000 kg / mm ² or more in both the longitudinal and width directions. And need to. This is because the high Young's modulus makes it possible to counter high tension and fluctuations in tension during winding, and since Young's modulus serves as a guide for molecular chain orientation, it has a high tensile strength against tension fluctuations that occur due to some cause during storage. This is because it is possible to suppress the generation of wrinkles over time.

It is not necessary that the layer B of the present invention contains inert particles, but the average particle size is 0.007 to 1 μm.
m, especially 0.02 to 0.45 μm of inert particles is 0.0
It is preferable that the content is 05 to 5%, especially 0.01 to 3%, because the wound form is further improved. The types and sizes of the particles contained in the A layer and the B layer may be the same or different.

The thickness variation in the widthwise direction of the layer A of the film constituting the present invention must be 50% or less, preferably 25% or less, more preferably 20% or less. If the thickness unevenness in the width direction is larger than the above range, wrinkles easily occur in the width direction, which is not preferable.

The thickness of the layer A of the film constituting the present invention is 0.005 to 3 μm, preferably 0.01 to 2.5 μm.
m, more preferably in the range of 0.01 to 2.0 μm, the winding shape is further improved, which is preferable.

In the present invention, the above-mentioned laminated film is wound around a core or the like and wound to a required length to complete the film roll of the present invention. The material of the core is not particularly limited, paper,
Known materials such as plastic can be used. The outer diameter is 1
Those having 10 to 10 inches, particularly 2 to 8 inches are preferably used. The core length is 150 to 2000 mm, especially 500 to
It is preferably 1500 mm.

The winding hardness of the roll of the present invention is 85 to 10
0, preferably 87-100, more preferably 90-1
It must be in the range of 00. If the winding hardness is smaller than the above range, widthwise winding wrinkles are likely to occur, and if the winding hardness is large, longitudinal winding wrinkles are likely to occur, which is not preferable.

Next, the method for producing the film roll of the present invention will be described, but the method is not limited to this.

First, regarding the method for producing an aromatic polyamide, when it is obtained from acid chloride and diamine, N-methylpyrrolidone (NMP) and dimethylacetamide (DM) are used.
It is synthesized by solution polymerization in an aprotic organic polar solvent such as Ac) or dimethylformamide (DMF) or by interfacial polymerization using an aqueous medium. When acid chloride and diamine are used as monomers in the polymer solution, hydrogen chloride is by-produced.When neutralizing this, inorganic neutralizing agents such as calcium hydroxide, calcium carbonate and lithium carbonate, and ethylene Oxide, propylene oxide,
Organic neutralizing agents such as ammonia, triethylamine, triethanolamine, diethanolamine are used. The reaction between isocyanate and carboxylic acid is carried out in the presence of a catalyst in an aprotic organic polar solvent.

These polymer solutions may be used directly as a film-forming stock solution, or the polymer may be isolated once and then redissolved in the above organic solvent or an inorganic solvent such as sulfuric acid to prepare a film-forming stock solution. Good.

In order to obtain the aromatic polyamide film of the present invention, the intrinsic viscosity of the polymer (value measured at 30 ° C. in a solution of 0.5 g of polymer in 100 ml of sulfuric acid) is 0.
It is preferably 5 or more.

Inorganic salts such as calcium chloride, magnesium chloride, lithium chloride and lithium nitrate may be added as a dissolution aid to the stock solution for film formation. The polymer concentration in the stock solution for film formation is preferably about 2 to 40 wt%.

On the other hand, a solution of aromatic polyimide or polyamic acid is obtained as follows. That is, polyamic acid is N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DM).
It can be prepared by reacting a tetracarboxylic acid dihydrate with an aromatic diamine in an aprotic organic polar solvent such as F). The aromatic polyimide can be prepared by heating a solution containing the above polyamic acid or adding an imidizing agent such as pyridine to obtain a polyimide powder, which is dissolved again in a solvent. Polymer concentration in the film forming solution is 5
About 40 wt% is preferable.

As a method of incorporating the inert particles into the polymer thus obtained, the particles are sufficiently slurried in a solvent in advance and then used as a solvent for polymerization or a solvent for dilution, or a stock solution for film formation is used. A method of directly adding after preparation can be adopted.

The stock solution for film formation prepared as described above is formed into a film by a so-called solution film forming method. The solution film-forming method includes a dry-wet method, a dry method, a wet method and the like, and film formation may be performed by any method.

The dry method is a method in which a polymer solution cast on a support such as a drum or an endless belt is heated by hot air or the like to evaporate the solvent. After drying on the support, the film is peeled and heat-treated. Get the final film.
However, when the polymer solution contains an inorganic salt, the mechanical properties of the film are likely to deteriorate.

When a film is formed by a dry-wet method, the stock solution is extruded from a spinneret onto a support such as a drum or an endless belt to form a thin film, and then introduced into a dry process. Then, the solvent is scattered from the thin film layer and concentrated, and the thin film is dried until it has self-supporting property. At this time, it is necessary to adjust so that the solvent does not suddenly scatter from the film surface.
It is dried at 0 ° C. to 200 ° C., preferably 70 ° C. to 150 ° C. for several tens of seconds to several tens of minutes. When the temperature is 50 ° C or lower, the drying time is prolonged, and when the temperature is 200 ° C or higher, voids are generated due to rapid heating,
This is because the surface is roughened and a practical film as an industrial material or magnetic material cannot be obtained. The film that has undergone the dry process is peeled from the support and introduced into the wet process. Here, the ionic inorganic compound contained in the film is removed. This bath is generally composed of an aqueous medium, and may contain an organic solvent, an inorganic salt or the like in addition to water. However, generally, the water content is 30% or more, preferably 50% or more, and the bath temperature is usually 0 to 100 ° C.

In this wet process the peeled film is immersed in such a bath under tension and the inorganic compounds in the film are extracted to less than 0.1, preferably 0.05% or less. The amount of inorganic salt as a solubilizing agent is at most the same as the neutralized salt produced by neutralization, or the amount of the inorganic salt is small and the extraction rate is fast because the amount of inorganic salt is small, and the amount of inorganic salt or organic salt in the bath is high. Solvent recovery is also easy.

The film after the dry process is stretched in the range of 1.05 to 2.5 times in the longitudinal direction (MD) of the film before being introduced into the wet process, in the wet bath, or after the completion of the wet process. Done. If it is 1.05 times or less, the mechanical properties in the stretching direction are not improved, and if it is 2.5 times or more, fibrillation occurs in the stretching direction, and an extremely brittle film is likely to be formed. The film thus obtained is then 200
C. to 500.degree. C., preferably 250.degree. C. to 350.degree. C., is heat-treated under tension for 10 seconds to 60 minutes to give a final film.
A biaxially stretched film can also be obtained by stretching in the range of 05 to 2.5 times.

When a film is formed by a wet method, a method is adopted in which the stock solution is extruded directly from a die into a film forming bath, or once extruded onto a support such as a drum and the whole support is introduced into the wet bath. It The ionic inorganic compound and the organic solvent contained in the film are extracted in the wet bath. The wet bath has the same composition as that of the dry-wet film forming bath, and the addition of an organic solvent, an inorganic salt or the like in order to adjust the desalting and desolvation rates is also the same as described above. Further, in the wet bath or after the completion of the wet process, MD stretching can be performed in the range of 1.05 to 2.5 times as in the dry-wet method. Further, similarly to the dry-wet method, the film after the wet process is finished at 200 ° C to 500 ° C, preferably 250 ° C to 35 ° C.
The final film is heat-treated under tension at 0 ° C for 10 seconds to 60 minutes, but before or during heat treatment.
It is also possible to obtain a biaxially stretched film by stretching in the range of 1.05 to 2.5 times in the D direction.

In order to form a laminated film to be the film roll of the present invention, two types of known methods, for example, a stock solution for film formation corresponding to the A layer side and a stock solution for film formation corresponding to the B layer side, are known, for example, Japanese Patent Application Laid-Open It can be formed by stacking with a confluent pipe as in Japanese Patent Laid-Open No. 56-162617 or by stacking in a die. It is also possible to form a film from any one of the film-forming stock solutions, cast another film-forming stock solution thereon, and remove the solvent to obtain a laminated film. In particular, when laminating in a confluent pipe or a die, it is preferable to adjust the viscosity of the stock solution to 100 to 10000 poise. If it is less than this range, the liquids are easily mixed with each other before the stock liquid comes out of the die, which is not preferable. On the contrary, if it is larger than this range, melt fracture occurs and the surface is apt to be roughened.

Although it is preferable that the viscosity of each layer is the same,
There may be some difference in viscosity, and the difference in viscosity may be targeted within 50%.

When the dry method or the dry-wet method is adopted,
The liquids may mix during the drying process. The undiluted solution cast on the support once decreases in viscosity when heated and then increases as the solvent evaporates.
If it is lower than the poise, it will be easier for each liquid to mix, so 10
Poises It is necessary to adjust the drying conditions sufficiently so that the viscosity does not drop below 50 poises. For example, it is possible to adopt a method of drying at a temperature not exceeding 240 ° C. or raising the drying temperature in at least two stages.

The mill roll of the laminated film thus obtained is set in a slitter of a system using both center wind and surface wind, and wound up to a predetermined length to complete the laminated film roll of the present invention. To adjust the winding hardness, it is effective to control the film tension and the surface pressure of the contact roll in contact with the film roll in a slitter when winding the product roll from the mill roll.

[0044]

[Measurement method of physical properties and evaluation method of effect]

(1) Average particle size of particles The cross section of the film is photographed with a transmission electron microscope (TEM) to detect particles. This photograph is numerically processed with an image analyzer for 100 or more particles, and the number average diameter D is taken as the average particle diameter. However, when the particles are aggregated, the aggregate is treated.

D = di / N (where di is the equivalent circle diameter of the particle (= (maximum diameter + shortest diameter) / 2), N is the number of particles) (2) Center line average height (Ra), center Line depth (Rp) Using a thin film step measuring device (ET-10) manufactured by Kosaka Laboratory,
Palpation tip radius 0.5 μm, cut-off value 0.008 m
10 points were measured under the conditions of m and a measurement length of 0.5 mm, and Ra and Rp were represented by the average value.

(3) Young's modulus At 25 ° C. and 65 ° C. using an Instron type tensile tester according to the method specified in JIS-Z-1702.
It was measured by% RH.

(4) Moisture absorption rate The weight of the film after drying at 200 ° C. for 1 hour in an absolutely dried state is W0, and the weight of the film after moisture absorption in 75% RH for 48 hours is W1 (W1-W0) / The moisture absorption rate was expressed by a value obtained by multiplying W0 by 100.

(5) Lamination Thickness of A Layer Using a secondary ion mass spectrometer (SIMS), the concentration ratio of the element resulting from the highest concentration of particles in the film and the carbon element of the aromatic polyamide ( With M ⁺ / C ⁺ ) as the particle concentration, analysis is performed in the depth (thickness) direction from the surface of the A layer. In the surface layer, the particle concentration is low due to the interface called the surface, and the particle concentration increases as the distance from the surface increases. In the case of the film of the present invention, the particle concentration once reaching the maximum value at the depth (I) starts to decrease again. Based on this concentration distribution curve, the depth (II) (where II
> I) was the laminate thickness.

When the most abundant particles in the film are organic polymer particles, it is difficult to measure by SIMS. Therefore, while etching from the surface, XPS (X-ray photoelectron spectroscopy), IR (infrared spectroscopy) or The depth profile of the particle concentration may be measured with a confocal microscope or the like, and the laminated thickness may be determined by the same method as above. (6) Thickness unevenness in width direction of layer A The laminated thickness of the film was measured in the width direction of the roll, and the difference a between the maximum value and the minimum value was divided by the average value b to obtain a / b of 10
The value (%) multiplied by 0 was defined as the thickness unevenness in the width direction. However, the entire width excluding 10 mm at both ends of the film roll was divided into 20 equal parts, and the central part of each equal part was measured.

(7) Rolling hardness of film roll The hardness was measured by pressing a hard nester (Type C) manufactured by Kobunshi Keiki Co., Ltd. from the outside of the film roll. Five measuring points were measured in the width direction of the roll and three measuring points were arranged at 120 ° intervals in the circumferential direction for a total of 15 points, and the arithmetic average value of these was taken as the winding hardness of the film roll. However, the entire width excluding 10 mm at both ends of the film roll was divided into 5 equal parts, and the central part of each equal part was measured.

(8) Winding appearance After leaving the film roll for 30 days in an atmosphere of a temperature of 40 ° C. and a humidity of 80% RH, visually observing the roll, there is no wrinkle (longitudinal and width direction). The product with wrinkles was evaluated as x.

[0052]

EXAMPLES The present invention will be described below based on examples.
However, the present invention is not limited to these examples.

Example 1 First, a slurry of colloidal silica dispersed in N-methyl-2-pyrrolidone (NMP) with an average particle size of 0.05 μm is prepared.

A polymerization tank was charged with NMP and the above colloidal silica slurry, in which 80 mol% of 2-chloroparaphenylenediamine and 20 mol% of 4,4'-diaminodiphenyl ether diamine component and 100 mol of 2-chloroterephthalic acid chloride were added. % Of acid chloride was added for polymerization, and further neutralized with calcium carbonate to obtain a polymer for layer A. The content of colloidal silica is 5 wt% with respect to the aromatic polyamide. By the same method, a polymer for layer B containing 0.2 wt% of colloidal silica having an average particle diameter of 0.04 μm was prepared. Each polymer solution was adjusted to a polymer concentration of 11% and the solution viscosity was adjusted to 3500 poise at 30 ° C. to prepare a stock solution for film formation.

These stock solutions were supplied to the die by two extruders, laminated in the die and cast on a metal belt. Adjust the extrusion amount to make the thickness of layer A of the final film 0.0.
The thickness of the layer B was 5 μm, and the thickness of the layer B was 5 μm. This cast film is dried at 180 ° C. until it has self-supporting property, then peeled off from the belt and introduced into a water tank for desolvation and desalting, followed by drying, heat treatment and cooling in a tenter. It was In the meantime, the film was stretched 1.25 times in the longitudinal direction in the water tank and 1.
It was stretched 35 times to obtain a biaxially oriented film. The heat treatment is 3
Cooling was carried out at 00 ° C. for 3 minutes, and cooling was performed at room temperature at 50 ° C./minute.

The mill roll of this film was set in a slitter of the system using both center wind and surface wind, slitted to a width of 600 mm, and wound on a plastic core having an outer diameter of 6 inches at a length of 6000 m and a winding hardness of 97.

The Young's modulus of this laminated film is
It was an isotropic film having a width direction of 1200 kg / mm ² and a moisture absorption rate of 1.7%, which was excellent in humidity characteristics.

Further, the film was excellent in the winding shape in which wrinkles did not occur in the longitudinal direction and the width direction and wrinkles did not occur with time.

Example 2 An aromatic polyamide roll was prepared in the same manner as in Example 1 except that the layer A had a thickness of 0.1 μm and a winding hardness of 87. The winding shape of this roll was excellent as in Example 1.

Example 3 The average particle size of the colloidal silica containing the layer A was 0.3 μm,
Content 10%, thickness 1.0 μm, thickness of layer B 4 μm
m, and the winding hardness was adjusted to 95, and an aromatic polyamide roll was prepared in the same manner as in Example 1. The winding shape of this roll was excellent as in Example 1.

Example 4 A film-forming stock solution was prepared in the same manner as in Example 1 except that a slurry in which silica particles having a primary particle diameter of 0.02 μm were dispersed in NMP was used for the layer A. The content of the inert particles at this time was 2 wt% with respect to the aromatic polyamide.

Using the same stock solution for B layer as in Example 1, A
An aromatic polyamide roll was prepared in the same manner as in Example 1 by adjusting the layer thickness to 1.0 μm, the B layer thickness to 2.5 μm, and the winding hardness to 98. The average particle size of the inert particles in the layer A at this time was 0.2 μm.

The winding shape of this roll was excellent as in Example 1.

Comparative Examples 1 to 4 As shown in Table 1, aromatic polyamide rolls were prepared by changing the average particle size, thickness and winding hardness of the layer A, but none of them satisfied the winding shape.

Comparative Example 5 The polymer concentration of the stock solution for forming layer A in Example 1 was 11
%, And prepared so as to be 1200 poise at 30 ° C., and an aromatic polyamide roll was prepared in the same manner as in Example 1. The thickness unevenness of the layer A of this laminated film was as large as 70%, and wrinkles had already occurred in the longitudinal direction and the width direction during roll formation.

Comparative Example 6 100 mol% of m-phenylenediamine having a polymer composition of diamine and 100 mole% of terephthalic acid chloride as an acid component.
An aromatic polyamide roll was prepared in the same manner as in Example 1 in terms of mol%. Young's modulus of this laminated film is 750 kg
It was as low as / mm ² and the winding shape was poor.

Comparative Example 7 An aromatic polyamide roll was prepared in the same manner as in Example 1 except that the polymer composition was diamine, p-phenylenediamine was 100 mol%, the acid components were terephthalic acid chloride 75 mol% and isophthalic acid chloride 25 mol%. . The Young's modulus of this laminated film was as high as 1400 kg / mm ² , but the moisture absorption rate was as high as 3.8%, and the wound form was poor.

Example 5 The film-forming stock solution of Example 1 was used to prepare a three-layer film of A / B / A using a rectangular three-layer lamination feed block, and a film roll was prepared in the same manner. The winding shape of this film roll was excellent.

Example 6 A stock solution for film formation was obtained by using the stock solution for film formation used in Example 4 for the layer A and a slurry in which silica particles having a primary particle diameter of 0.02 μm were dispersed in NMP for the layer B. It was A three-layer film of A / B / A was produced from this stock solution for film formation in the same manner as in Example 5.

At this time, the average particle diameter of the particles containing the layer A was 0.
2 μm, content 2%, thickness 1.3 μm, average particle diameter of B layer-containing particles is 0.3 μm, content 2%, thickness 2.
It was 4 μm. This film was adjusted to a winding hardness of 98 to prepare a film roll. The winding shape of this film roll was excellent.

[0071]

[Table 1]

[0072]

EFFECT OF THE INVENTION The laminated film roll of the present invention is a film roll having an excellent winding shape in which wrinkles in the longitudinal and width directions and wrinkles do not occur over time. Therefore, wrinkling causes productivity (yield) to increase. It is extremely useful as a base film for magnetic recording media, which greatly decreases, and a film roll for flexible printed circuits.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area B29K 79:00 105: 16 B29L 9:00

Claims (4)

[Claims] 1. A layer (A) made of an aromatic polyamide resin or an aromatic polyimide resin A containing inert particles.
Is a biaxially oriented laminated film having at least one side of a layer (B layer) made of an aromatic polyamide resin or an aromatic polyimide resin B. The ratio of the average particle diameter d of the inert particles contained in the layer, t / d is 0.1 to 10, and the thickness unevenness in the width direction of the A layer is 5
0% or less, the moisture absorption rate of the laminated film is 3.5% or less, and the Young's modulus of the laminated film in both the longitudinal direction and the width direction is 8
A roll made of a laminated film having a weight of 00 kg / mm ² or more, wherein the winding hardness of the film roll is in the range of 85 to 100. 2. The laminated film roll according to claim 1, wherein both of the aromatic polyamide resins A and B are composed of 50% by mole or more of constituent units of para-bonded aromatic polyamide. 3. The aromatic polyamide-based resins A and B both comprise an aromatic polyamide containing 30% or more of aromatic rings in which at least one of hydrogens on the aromatic rings is substituted with an electron-withdrawing group. Alternatively, the laminated film roll described in 2. 4. The laminated film roll according to claim 1, wherein the thickness of the A layer is in the range of 0.005 to 3 μm.