KR102361868B1 - The manufacturing method of a cyclic olefin resin film, a cyclic olefin resin film, a composite film - Google Patents

Abstract

An extruder having a supply section, a compression section and a metering section to which a raw resin containing a cyclic olefin resin and an elastomer having a specific melt flow rate are supplied is used, and the resin transport efficiency of the feed section satisfies 0.75 ≤ the resin transport efficiency of the feed section ≤ 1.0 The manufacturing method of a cyclic olefin resin film which has a process of supplying and melting the said raw material resin and melt-extruding from die|dye into a film form, supplying and melting|fusing the said raw material resin, a cyclic olefin resin film, and the said cyclic olefin resin film A composite film having

Description

The manufacturing method of a cyclic olefin resin film, a cyclic olefin resin film, a composite film

This indication relates to the manufacturing method of a cyclic olefin resin film, a cyclic olefin resin film, and a composite film.

In recent years, a cyclic olefin resin film attracts attention as a film with a small optical characteristic change with respect to environmental temperature-humidity change.

DESCRIPTION OF RELATED ART Cyclic olefin resin film is used by various uses, such as an optical film used for a liquid crystal display device etc. as a polarizing plate, a film for liquid crystal displays, etc., and the film for solar cell back surface protection.

A cyclic olefin resin film is formed into a film by fusing|melting cyclic olefin resin with an extruder, extruding into die|dye, for example, discharging this molten resin in sheet form from die|dye, and cooling and solidifying.

Moreover, improving a physical property is also attempted by making a cyclic olefin resin film contain an elastomer.

As such a cyclic olefin resin film or its manufacturing method, what was described in Unexamined-Japanese-Patent No. 5646793, Unexamined-Japanese-Patent No. 2008-137328, or International Publication No. 2017/126572 is known.

Japanese Patent Publication No. 5646793 contains a cyclic olefin resin having a refractive index of n1 and a glass transition point (Tg) of 170°C or higher, and a styrene-based elastomer having a refractive index of n2 and Δn=│n2-n1│ of 0.012 or less, JIS K7136 Based on the above, the internal haze value measured in the polyethylene glycol solution is 1.0% or less for a test piece having a thickness of 100 µm, and the melt index (MI) at 270°C and a load of 2.16 kg of the cyclic olefin resin is higher than the MI A transparent film containing at least the small said styrene-based elastomer is disclosed.

Japanese Patent Laid-Open No. 2008-137328 discloses a method for producing an optical film characterized by performing melt extrusion molding of resin pellets using an extruder having an opening in an inert gas atmosphere with an oxygen concentration of 10 ppm or less.

In International Publication No. 2017/126572, a cylinder having a supply port through which the raw material resin is supplied and an extrusion port through which the molten resin in which the raw material resin is melted is extruded, and a screw shaft and a flight arranged spirally around the screw shaft, , using an extruder having a screw rotating in the cylinder, in the cylinder, from the side of the supply port along the screw shaft, in order, a supply part, a compression part, and a metering part, and the supply part resin transport efficiency calculated by the following formula A thermoplastic resin film having a step of supplying and melting the raw resin under the conditions satisfying this 0.75 ≤ supply part resin transport efficiency ≤ 1.0, and melt-extruding the molten resin extruded from the extrusion port into a film form from a die A method of preparation is described.

[Equation 1]

W: Spacing of screw flights in the supply section (mm)

Hf: Groove depth at the feed (mm)

D: inner diameter of cylinder (mm)

Ψ: screw flight angle at the supply (°)

Q: Extrusion amount of molten resin (kg/h)

ρ: specific gravity of the raw resin (g/cm ³ )

N: number of screw revolutions per minute (rpm)

Compression ratio: volume per pitch of screw flights in the feed section/volume per pitch of screw flights in the metering section

Among the cyclic olefin resin films, the cyclic olefin resin to which heat resistance is imparted has a small quality change in a display manufacturing process that becomes high temperature, and has durability that can be used in harsh environments such as in automobiles in summer. Widespread development as a film is expected.

Although the highly heat-resistant cyclic olefin resin has the outstanding characteristic as an optical film, improvement of physical properties may be calculated|required.

As one problem requiring improvement, there is coexistence of the plane shape of a film and impact strength. When the glass transition point (Tg) of a cyclic olefin resin is raised in order to provide heat resistance, a film becomes brittle, the crack at the time of a bending|flexion, and dust generation at the time of a cutting|disconnection become a problem, and the manufacturing process aptitude of a display may fall.

Japanese Patent Publication No. 5646793 discloses a method of mixing a styrene-based elastomer with a cyclic olefin resin in order to improve the brittleness of the cyclic olefin resin film.

However, the present inventors discovered that generation|occurrence|production of the foreign material in a film may become a problem in the cyclic olefin resin film with which the elastomer of Unexamined-Japanese-Patent No. 5646793 was mixed.

When manufacturing a cyclic olefin resin film by the melt-extrusion method, the foreign material (Hereinafter, it may simply call a "foreign material") by thermal oxidation deterioration of resin etc. may generate|occur|produce. In particular, in the case of an optical film, a foreign material contained in the film becomes a point defect, and the flatness of the film tends to decrease when a foreign material occurs, such as a decrease in light transmittance due to the point defect, an increase in unevenness, and a decrease in surface smoothness.

Especially, since high heat-resistant cyclic olefin resin has a high glass transition temperature (Tg), there exists a tendency for a processing temperature to become high, and there exists a characteristic that such a foreign material is easy to generate|occur|produce.

In addition, as described in Japanese Patent Application Laid-Open No. 5646793, when an elastomer is mixed to improve brittleness, it is considered that the generation of foreign substances becomes more remarkable due to an increase in the heat history during mixing or poor dispersion of the elastomer. That is, when mixing an elastomer for the purpose of improving brittleness, it is thought that generation|occurrence|production of a foreign material and the fall of surface smoothness accompanying it become a more serious subject.

As a countermeasure for suppressing the generation of foreign substances, for example, in Japanese Patent Application Laid-Open No. 2008-137328, by setting the oxygen concentration of the opening of an extruder used for melt film forming in an inert gas atmosphere of 10 ppm or less, thermal oxidation deterioration of the resin It has been disclosed to inhibit.

However, when the present inventors manufactured the cyclic olefin resin film with which the elastomer was mixed by the method of Unexamined-Japanese-Patent No. 2008-137328, it discovered that generation|occurrence|production of the foreign material in a film may become a problem.

Although the method described in Unexamined-Japanese-Patent No. 2008-137328 is an effective method from the point of suppressing the thermal oxidation deterioration at the time of melt film forming of a cyclic olefin resin, when mixing an elastomer for brittleness improvement, at the time of mixing It is thought that this is because the effect cannot be said to be sufficient about the generation|occurrence|production of a foreign material and the fall of the surface smoothness by the increase of a heat history or the dispersion|distribution defect of an elastomer.

The method described in International Publication No. 2017/126572 is an effective method in that it suppresses thermal oxidation deterioration at the time of melt film forming of cyclic olefin resin. However, in the case of mixing an elastomer for brittleness improvement, it is not considered about the method of suppressing the generation|occurrence|production of a foreign material.

The problem which one Embodiment of this indication intends to solve is providing the manufacturing method of the cyclic olefin resin film from which generation|occurrence|production of a foreign material is suppressed and the cyclic olefin resin film excellent in impact strength is obtained.

The subject which other embodiment of this indication intends to solve is providing the composite film which has the cyclic olefin resin film which is excellent in surface smoothness and is excellent in impact strength, and the said cyclic olefin resin film.

The following aspects are contained in the means for solving the said subject.

<1> a cylinder having a supply port to which a raw resin containing a cyclic olefin resin and an elastomer is supplied and an extrusion port through which a molten resin in which the raw resin is melted is extruded;

having a screw shaft and a flight spirally arranged around the screw shaft,

and a screw rotating in the cylinder;

In the cylinder, an extruder having a supply part, a compression part, and a metering part in order from the side of the supply port along the screw shaft is used,

Supplying and melting of the raw material resin is performed under the condition that the supply part resin transport efficiency calculated by the following formula satisfies 0.75 ≤ supply part resin transport efficiency ≤ 1.0,

having a process of melt-extruding the molten resin extruded from the extrusion port into a film form from a die,

When the glass transition temperature of the cyclic olefin resin film obtained is Tg degreeC, the melt flow rate of the said elastomer in Tg+50 degreeC and load 49N is 0.3 ^cm3 /10min or more ^and less than 9.0 cm3/10min, Cyclic olefin resin A method of making a film.

[Equation 2]

W: Spacing of screw flights in the supply section (mm)

Hf: Groove depth at the feed (mm)

D: inner diameter of cylinder (mm)

Ψ: screw flight angle at the supply (°)

Q: Extrusion amount of molten resin (kg/h)

ρ: specific gravity of the raw resin (g/cm ³ )

N: number of screw revolutions per minute (rpm)

Compression ratio: volume per pitch of screw flights in the feed section/volume per pitch of screw flights in the metering section

<2> The manufacturing method of the cyclic olefin resin film as described in said <1> whose density|concentration of the said elastomer contained in the cyclic olefin resin film obtained is 1 mass % or more and less than 20 mass % with respect to the total mass of the cyclic olefin resin film obtained.

<3> The manufacturing method of the cyclic olefin resin film as described in said <1> or <2> whose said elastomer is a styrene-type thermoplastic elastomer.

The ratio of the melt flow rate of the cyclic olefin resin film obtained in the said Tg+50 degreeC and load 49N with respect to the melt flow rate of the said elastomer in <4> said Tg+50 degreeC and load 49N is 80 % or more The manufacturing method of the cyclic olefin resin film in any one of said <1>-<3> which is 120 % or less.

<5> The above <1> to further comprising the step of introducing the molten resin obtained by the step of melt-extruding into a film, into a clamping portion formed in a gap between a pair of smooth rolls, and clamping the molten resin The manufacturing method of the cyclic olefin resin film in any one of <4>.

<6> A cyclic olefin resin film, comprising:

a cyclic olefin resin and an elastomer;

Per 100 µm in thickness of the cyclic olefin resin film, the number of foreign substances having a longest diameter of 30 µm or more is 0.3 pieces/cm ² or less, and the number of foreign substances having a longest diameter of 5 µm or more and less than 30 µm is 100 pieces/cm ² or less,

When the glass transition temperature of the cyclic olefin resin film is Tg°C, the melt flow rate of the elastomer under Tg+50°C and a load of 49N is 0.3 cm ³ /10 min or more and less than 9.0 cm ³ /10 min, cyclic olefin resin film.

The cyclic olefin resin film as described in said <6> whose content of the <7> said elastomer is 1 mass % or more and less than 20 mass % with respect to the total mass of a cyclic olefin resin film.

<8> The cyclic olefin resin film according to <6> or <7>, wherein the elastomer is a styrene-based thermoplastic elastomer.

<9> The ratio of the melt flow rate of the cyclic olefin resin film at Tg+50°C and load 49N to the melt flow rate of the elastomer at Tg+50°C and load 49N is 80% or more 120 % or less, the cyclic olefin resin film in any one of said <6>-<8>.

<10> The cyclic olefin resin film in any one of said <6>-<9> whose average particle diameters of the said elastomer are 100 nm or more and less than 1000 nm.

<11> Said Tg degreeC is 130 degreeC or more and less than 170 degreeC, The cyclic olefin resin film in any one of said <6>-<10>.

<12> The composite film which has the cyclic olefin resin film in any one of said <6>-<11>.

According to one Embodiment of this indication, generation|occurrence|production of a foreign material is suppressed and the manufacturing method of the cyclic olefin resin film from which the cyclic olefin resin film excellent in impact strength is obtained can be provided.

According to another embodiment of this indication, it is excellent in surface smoothness, and the composite film which has the cyclic olefin resin film excellent in impact strength, and the said cyclic olefin resin film can be provided.

1 : is schematic which shows an example of the whole structure of the apparatus for implementing the manufacturing method of the cyclic olefin resin film which concerns on this indication.
It is a schematic diagram which shows an example of the structure of the extruder which can be used with the manufacturing method which concerns on this indication.
FIG. 3 : is a schematic diagram which expands and shows the supply part of the extruder shown in FIG.

Hereinafter, the content of the present disclosure will be described in detail. Although description of the structural requirements described below may be made based on typical embodiment of this indication, this indication is not limited to such an embodiment.

In addition, in the present disclosure, "~" indicating a numerical range is used in a sense including the numerical values described before and after that as the lower limit value and the upper limit value.

In the numerical range described in steps in the present disclosure, the upper limit or lower limit described in one numerical range may be substituted with the upper limit or lower limit of the numerical range described in another step. In addition, in the numerical range described in this indication, you may substitute the upper limit or lower limit of the numerical range with the value shown in the Example.

In addition, in the present disclosure, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified, when a plurality of substances corresponding to each component exist in the composition.

In addition, in the description of the group (atomic group) in the present disclosure, the description not describing substitution and unsubstituted includes those having no substituent and those having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present disclosure, "(meth)acryl" is a word used as a concept including both acryl and methacryl, and "(meth)acryloyl" refers to both acryloyl and methacryloyl. A word used as a concept to include.

In the present disclosure, "(co)polymer" means both or one of a homopolymer and a copolymer including specific structural units.

In addition, the term "step" in the present disclosure includes not only an independent step, but also a case where it cannot be clearly distinguished from other steps, if the intended purpose of the step is achieved. In addition, in this disclosure, "mass %" and "weight %" have the same meaning, and "mass part" and "weight part" have the same meaning.

In addition, in this indication, the combination of two or more preferable aspects is a more preferable aspect.

In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure are, unless otherwise specified, a column of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are trade names manufactured by Tosoh Corporation). It is a molecular weight converted using the solvent THF (tetrahydrofuran) and a differential refractometer by a gel permeation chromatography (GPC) analysis apparatus, and using polystyrene as a standard material.

Hereinafter, the present disclosure will be described in detail.

(Method for producing cyclic olefin resin film)

In the manufacturing method of the cyclic olefin resin film which concerns on this indication (henceforth "the manufacturing method which concerns on this indication" may be called), the supply port to which the raw material resin containing a cyclic olefin resin and an elastomer is supplied, and the said raw material resin A cylinder having an extrusion port through which molten molten resin is extruded, and a screw shaft and a flight spirally arranged around the screw shaft, the screw having a screw rotating in the cylinder, wherein the supply is in the cylinder along the screw shaft From the sphere side, using an extruder having a supply part, a compression part, and a metering part in this order, the supply part resin transport efficiency calculated by the following formula satisfies 0.75 ≤ the supply part resin transport efficiency ≤ 1.0, the supply of the raw resin and It melts and has the process of melt-extruding the said molten resin extruded from the said extrusion port from die|dye into film form, When the glass transition temperature of the cyclic olefin resin film obtained is made into Tg degreeC, Tg+50 degreeC, load 49N In the above, the melt flow rate (also referred to as "MFR") of the elastomer is 0.3 cm ³ /10 min or more and less than 9.0 cm ³ /10 min.

[Equation 3]

W: Spacing of screw flights in the supply section (mm)

Hf: Groove depth at the feed (mm)

D: inner diameter of cylinder (mm)

Ψ: screw flight angle at the supply (°)

Q: Extrusion amount of molten resin (kg/h)

ρ: specific gravity of the raw resin (g/cm ³ )

N: number of screw revolutions per minute (rpm)

Compression ratio: volume per pitch of screw flights in the feed section/volume per pitch of screw flights in the metering section

In the present disclosure, "raw material resin" means a resin composition including additives added as necessary in addition to the resin component.

In addition, in this indication, a cyclic olefin resin film may be described as a "film".

The present inventors discovered that, according to the manufacturing method which concerns on this indication, generation|occurrence|production of a foreign material was suppressed and the cyclic olefin resin film excellent in impact strength was obtained, as a result of earnestly examining.

Although the detailed mechanism by which the said effect is acquired is unknown, it is guessed as follows.

The process of melting and mixing cyclic olefin resin and an elastomer WHEREIN: It is thought that an elastomer melts before cyclic olefin resin. This molten elastomer acts like a cushion that maintains the friction acting between the cyclic olefin resins or between the cyclic olefin resin and the processing machine to an appropriate degree, thereby suppressing local heat generation due to friction and suppressing the generation of foreign substances. I think.

On the other hand, when the melt viscosity of the elastomer is too high, the friction becomes too large, and foreign matter may be generated due to local heat generation. In addition, if the melt viscosity of the elastomer is too low, the friction becomes too small, and the melting of the cyclic olefin or the elastomer is not stabilized. It may become

Specifically, when the MFR of the elastomer is 0.3 cm ³ /10 min or more, the melt viscosity of the elastomer is lowered, so that the friction acting between the cyclic olefin resins or between the cyclic olefin resin and the processing machine is sufficiently low, and the local heat generation is reduced. It is thought that generation|occurrence|production of the foreign material by this is suppressed.

When the MFR of the elastomer is less than 9.0 cm ³ /10 min, since the melt viscosity of the elastomer is not too low, friction acting between the cyclic olefin resins or between the cyclic olefin resin and the processing machine increases. As a result, the melting of the cyclic olefin resin and the elastomer is It is stabilized and generation|occurrence|production of the foreign material by local heat_generation|fever is suppressed, or it is hard to generate|occur|produce the cyclic olefin and elastomer which are not melt|melted completely, and it is thought that it is hard to become a foreign material.

If the supply part resin transport efficiency is 0.75 or more, the elastomer is easily mixed sufficiently and contact with oxygen is difficult to be suppressed, so it is thought that the generation of foreign substances is suppressed.

It is thought that friction between cyclic olefin resin becomes small that supply part resin transport efficiency is 1.0 or less, and generation|occurrence|production of a foreign material is suppressed.

As mentioned above, according to the manufacturing method of the cyclic olefin resin film which concerns on this indication, the cyclic olefin resin film by which generation|occurrence|production of the foreign material was suppressed can be obtained.

Moreover, in the manufacturing method of the cyclic olefin resin film which concerns on this indication, the cyclic olefin resin film excellent in impact strength can be obtained by including an elastomer.

Moreover, by the said impact strength being high, the crack at the time of film conveyance, and generation|occurrence|production of the dust at the time of cutting|disconnection are suppressed, favorable conveyance can be acquired, and the yield at the time of manufacture is also easy to improve.

First, the outline of the manufacturing apparatus and manufacturing method used by the manufacturing method of the cyclic olefin resin film which concerns on this indication is demonstrated.

In each figure, the same code|symbol indicates the same or functionally similar element.

1 : has shown schematically an example of the whole structure of the film forming apparatus (cyclic olefin resin film manufacturing apparatus) for implementing the manufacturing method of the cyclic olefin resin film which concerns on this indication.

The film forming apparatus 10 shown in FIG. 1 includes a hopper 12 into which raw resin is injected, an extruder 14 that melts the raw resin supplied from the hopper 12, and the amount of extrusion of molten resin (molten resin). A gear pump 16 for stabilizing the molten resin, a filter 18 for filtering the molten resin, a die 20 for melt-extruding the molten resin into a film, and multi-stage cooling of the high-temperature raw material resin discharged from the die 20 a plurality of cooling rolls (hereinafter, the cooling roll may be referred to as a casting roll) 22 , 24 , 26 , and the raw material resin 100 discharged from the die 20 , A sandwiching contact roll (hereinafter, a contact roll may be referred to as a touch roll) 28 is provided. Moreover, although not shown in figure, the peeling roll which peels a cyclic olefin resin film from the last 3rd cooling roll 26, and the winder which winds up the cooled film are normally provided.

2 : has schematically shown an example of the structure of the extruder which can be used for the manufacturing method which concerns on this indication.

As shown in FIG. 2, the extruder 14 is equipped with the cylinder 44 and the screw 50 arrange|positioned in the cylinder.

The cylinder 44 has a supply port 52 through which the raw material resin is supplied and an extrusion port 54 through which the molten resin in which the raw material resin is melted is extruded, and the cylinder 44 is supplied along the screw shaft 46 . In order from the sphere 52 side, a supply unit (region indicated by A in Fig. 2) for transporting the raw resin supplied from the supply port 52 while preheating, and a compression unit for kneading and melting the raw resin while compressing it (Fig. It has a region indicated by B in 2) and a metering unit (region indicated by C in Fig. 2) for measuring the molten resin and stabilizing the extrusion amount. 3 : is a figure which enlarges and schematically shows the supply part A of the extruder 14. As shown in FIG.

Moreover, the hopper 12 shown in FIG. 1 is attached to the supply port 52 of the cylinder 44 shown in FIG.

The screw 50 has a screw shaft 46 and a flight (hereinafter, sometimes referred to as a screw flight) 48 arranged spirally around the screw shaft 46, and a cylinder ( 44) is configured to rotate within.

Moreover, although not shown in figure, in order to control the temperature of the resin in the cylinder 44, temperature control means (heater etc.) arranged around the cylinder 44 by dividing it into 3-20 division|segmentation, for example in the longitudinal direction. ) is desirable to provide.

When equipped with the extruder 14 which has the structure shown in FIG. 2, and manufacturing a cyclic olefin resin film with the manufacturing apparatus 10 of the cyclic olefin resin film which has a structure shown in FIG. 1, raw material resin is the hopper 12 It is injected into the cylinder 44 and is supplied into the cylinder 44 through the supply port 52 of the cylinder 44 . The raw material resin supplied into the cylinder 44 from the supply port 52 is conveyed toward the extrusion port 54, being preheated in the supply part A by rotation of the screw 50.

In addition, in order to prevent oxidation of the molten resin by oxygen remaining in the cylinder 44, it is more preferable to carry out while evacuating the inside of the extruder in an inert air stream such as nitrogen or using an extruder including a vent.

The raw resin preheated in the supply unit (A) is transported to the compression unit (B). In the compression section (B), the diameter of the screw shaft (46) has a configuration that gradually increases toward the extrusion port (54), and the raw material resin is transported in the compression section (B) in the cylinder (44). It is kneaded while being compressed between the inner wall and the screw 50 , and is heated and melted by contacting the temperature-controlled cylinder 44 . The resin melted in the compression section (B) is transported to the metering section (C), and the molten resin is metered in the metering section (C), thereby stabilizing the extrusion amount from the extrusion port (54).

The molten resin melted in the extruder 14 and extruded from the extrusion port 54 is continuously sent toward the die 20 through the gear pump 16 and the filter 18 through the pipe 40 . And molten resin is melt-extruded from the die|dye 20 in film form. The raw material resin 100 extruded into the film form is shown in FIG.

The film-form raw material resin melt-extruded from the die 20 is sandwiched between the contact roll (touch roll) 28 and the first cooling roll 22, and the second cooling roll 24 and the third cooling roll ( 26), it is wound by a winder (not shown).

In the manufacturing method of the cyclic olefin resin film which concerns on this indication, when manufacturing a cyclic olefin resin film through the steps as described above, the supply part resin transport efficiency calculated by the above formula satisfies 0.75 ≤ supply part resin transport efficiency ≤ 1.0 The raw material resin is supplied and melted under the following conditions, and the molten resin is melt-extruded from the die into a film by the extruder.

The reason that generation|occurrence|production of a foreign material is suppressed in the film obtained by the manufacturing method of the cyclic olefin resin film which concerns on this indication is estimated as follows.

In the formula for calculating the supply part resin transport efficiency in the present disclosure, the numerator "Q/N" of the fraction in the first term means the extrusion amount of the molten resin per screw rotation in the melt extrusion process. On the other hand, the denominator means the theoretical transport amount in the supply section in the cylinder, and by dividing the theoretical transport amount by the compression ratio, it means that the transport can be carried out with high efficiency regardless of the compression ratio. Note that (D/90) ^0.5 is a correction coefficient for the cylinder inner diameter.

And, the supply part resin transport efficiency calculated by the formula of the supply part resin transport efficiency in the present disclosure is 0.75 or more, that is, the solid resin transport efficiency before melting in the extruder supply part is increased to a region close to the original resin density By melting after reducing the space|gap of solid resin in an extruder, oxygen in a space|gap and molten resin become difficult to contact. On the other hand, melt extrusion can be performed by making the supply part resin transport efficiency into 1.0 or less.

Therefore, it is thought that the cyclic olefin resin film by which generation|occurrence|production of the foreign material which generate|occur|produces by reaction of resin and oxygen in the obtained film was suppressed can be manufactured, without carrying out large-scale atmospheric substitution.

Next, the manufacturing method of the cyclic olefin resin film which concerns on this indication is demonstrated more concretely.

<Raw material resin>

The raw material resin used by this indication is not specifically limited as long as a cyclic olefin resin and an elastomer are included, What is necessary is just to select according to the use of the film to manufacture.

[Cyclic Olefin Resin]

Cyclic olefin resin is (co)polymer resin which has a cyclic olefin structure, As an example of polymer resin which has cyclic olefin structure, (1) norbornene-type polymer, (2) polymer of monocyclic cyclic olefin, (3) cyclic conjugated die|dye The polymer of ene, (4) vinyl alicyclic hydrocarbon polymer, and the hydride of (1)-(4), etc. are mentioned.

Among them, (1) norbornene-based polymers and (2) monocyclic cyclic olefin polymers and hydrides thereof are preferable.

In addition, the norbornene-type polymer in this indication is used by the meaning containing the homopolymer containing the structural unit which has a norbornene structure, and a copolymer, and the norbornene structure may be ring-opened.

For example, as a polymer resin which has a cyclic olefin structure, the addition (co)polymer cyclic polyolefin containing at least 1 type or more of structural units represented by the following general formula (II), and a structure represented by general formula (I) if necessary The addition copolymer cyclic polyolefin which further contains at least 1 or more types of units is mentioned.

Moreover, as polymer resin which has a cyclic olefin structure, the ring-opened (co)polymer which contains at least 1 type of cyclic structural unit represented by General formula (III) can also be used suitably.

[Formula 1]

[Formula 2]

[Formula 3]

In general formulas (I), (II), and (III), m represents the integer of 0-4. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X ¹ , X ² , X ³ , Y ¹ , Y ² and Y ³ is each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, -(CH ₂ ) _n COOR ¹¹ , -(CH ₂ ) _n OCOR ¹² , -(CH ₂ ) _n NCO, -(CH ₂ ) _n NO ₂ , -(CH ₂ ) _n CN, -(CH ₂ ) _n CONR ¹³ R ¹⁴ , -(CH ₂ ) _n NR ¹³ R ¹⁴ , -(CH ₂ ) _n OZ, -(CH ₂ ) _n W, or (-CO) ₂ O or (-CO) ₂ consisting of X ¹ and Y ¹ , X ² and Y ² , or X ³ and Y ³ NR ¹⁵ is shown. In addition, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, Z represents a hydrocarbon group or a hydrocarbon group substituted with a halogen, W is SiR ¹⁶ _p D Represents _3-p (R ¹⁶ represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, -OCOR ¹⁶ or -OR ¹⁶ , p represents an integer of 0 to 3), n represents an integer from 0 to 10.

X ¹ , X ² , X ³ , Y ¹ , Y ² and Y ³ By introducing a functional group with high polarization into all or part of the substituents, the thickness direction retardation (Rth) of the optical film is increased, and in-plane retardation is achieved. (Re) can be enlarged. A film with large Re expression property can enlarge Re value by extending|stretching in a film forming process.

The highly polarizable functional group means a functional group containing two or more types of atoms having different electronegativity and having a dipole moment. Specific examples of the highly polarizable functional group include, for example, a carboxy group, a carbonyl group, an epoxy group, an ether group, a hydroxy group, an amino group, an imino group, a cyano group, an amide group, an imide group, an ester group, a sulfone group, etc. can be heard

Norbornene-based addition (co)polymers are disclosed in Japanese Patent Application Laid-Open No. 10-007732, Japanese Patent Application Laid-Open No. 2002-504184, US Patent Application Laid-Open No. US2004/0229157A1 or International Publication No. 2004/070463A1. The norbornene-based addition (co)polymer can be obtained, for example, by addition polymerization of norbornene-based polycyclic unsaturated compounds. Moreover, a norbornene-type addition (co)polymer is a norbornene-type polycyclic unsaturated compound as needed, ethylene, propylene, butene; conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as ethylidene norbornene; It can also be obtained by addition polymerization of linear diene compounds, such as acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, acrylic acid ester, methacrylic ester, maleimide, vinyl acetate, and vinyl chloride.

As the norbornene-based addition (co)polymer, a commercially available product may be used. Norbornene-based addition (co)polymers are commercially available under the trade name of Appel (registered trademark) from Mitsui Chemicals Co., Ltd., and have different glass transition temperatures (Tg), for example, APL8008T (Tg: 70° C.), APL6013T ( There are grades such as Tg: 125°C) and APL6015T (Tg: 145°C). Norbornene-based addition (co)polymers such as TOPAS8007, Copper 6013, and Copper 6015 are commercially available as pellets from Polyplastics Co., Ltd. In addition, as a norbornene-based addition (co)polymer from Ferrania, Appear3000 is commercially available.

The hydride of a norbornene-type polymer can be obtained by hydrogenating a polycyclic unsaturated compound after addition polymerization or metathesis ring-opening polymerization. About the hydride of a norbornene-type polymer, Unexamined-Japanese-Patent No. 1-240517, Unexamined-Japanese-Patent No. 7-196736, Unexamined-Japanese-Patent No. 60-026024, Unexamined-Japanese-Patent No. 62-019801, for example. Japanese Patent Application Laid-Open No. 2003-159767 and Japanese Patent Application Laid-Open No. 2004-309979, etc. are disclosed, and these descriptions can be referred to in the present disclosure.

As a norbornene-type polymer used in the manufacturing method which concerns on this indication, the polymer containing the cyclic structural unit represented by the said General formula (III) is preferable, In the cyclic structural unit represented by General formula (III), R ⁵ and R ⁶ is preferably a hydrogen atom or —CH ₃ , X ³ and Y ³ are preferably a hydrogen atom, —Cl or —COOCH ₃ , and other groups are appropriately selected.

Norbornene-based resins are marketed under the trade names Arton (registered trademark) G or Arton F by JSR Corporation, and Zeonor (Zeonor: registered trademark) ZF14, ZF16, and Zeonex ( Zeonex: registered trademark) 250 or Zeonex 280 are marketed under the trade name, and these can be used.

[elastomer]

The elastomer contained in the raw resin is not particularly limited, and examples thereof include styrene-based thermoplastic elastomer, olefin-based elastomer, urethane-based elastomer, polyester-based elastomer, polyamide-based elastomer, acrylic-based elastomer, and silicone-based elastomer. , a styrene-based thermoplastic elastomer, or an olefin-based elastomer is preferable, and a styrene-based thermoplastic elastomer is more preferable.

In the present disclosure, the elastomer refers to a high molecular compound exhibiting rubber elasticity at room temperature (25°C).

-Styrene-based thermoplastic elastomer-

The styrene-based thermoplastic elastomer is not particularly limited as long as it contains a structural unit derived from a styrene compound as a unit of the copolymer, and a conventionally known one can be used.

As the conventionally known styrene-based thermoplastic elastomer, for example, SIBS (styrene-isobutylene-styrene copolymer), SEBS (styrene-ethylene-butylene-styrene copolymer), SEPS (styrene-propylene- styrene copolymer), SEEPS (hydrogenated styrene-isoprene-butadiene-styrene copolymer), MBS (methyl methacrylate-butadiene-styrene copolymer), etc. are mentioned. In addition, these styrene-based thermoplastic elastomers may be hydrogenated to at least a part of the double bonds of the conjugated diene component.

The structure of the styrene-based thermoplastic elastomer is not particularly limited, and may be linear, branched, or crosslinked.

It is preferable that the styrene content rate in a styrene-type thermoplastic elastomer is 20 mol% - 40 mol% from a viewpoint of the haze of the cyclic olefin resin film obtained.

Moreover, it is preferable that weight average molecular weights are 5,000-500,000, as for the molecular weight of a styrene-type thermoplastic elastomer, it is more preferable that it is 10,000-300,000, It is more preferable that it is 50,000-200,000.

In addition, as a styrene-type elastomer, Unexamined-Japanese-Patent No. 5646793, Unexamined-Japanese-Patent No. 2004-156048, Unexamined-Japanese-Patent No. 2016-020412, Unexamined-Japanese-Patent No. 2016-008272, Unexamined-Japanese-Patent No. 2016-183303 The styrene-type elastomer described in etc. is also used suitably.

-Olefin based elastomer-

The olefin-based elastomer is not particularly limited as long as it includes a structural unit derived from an olefin compound as a unit of the copolymer, and a conventionally known elastomer can be used.

For example, a copolymer of α-olefin having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, and 4-methyl-pentene, is preferable, and ethylene-propylene copolymer (EPR), ethylene-propylene -diene copolymer (EPDM) etc. are mentioned, Moreover, alpha- of non-conjugated dienes having 2 to 20 carbon atoms, such as dicyclopentadiene, 1,4-hexadiene, butadiene, and isoprene. An olefin copolymer etc. are mentioned. Moreover, carboxy-modified NBR (acrylonitrile butadiene rubber) obtained by copolymerizing methacrylic acid with a butadiene-acrylonitrile copolymer is mentioned. Specific examples thereof include an ethylene/α-olefin copolymer rubber, an ethylene/α-olefin/non-conjugated diene copolymer rubber, a propylene/α-olefin copolymer rubber, and a butene/α-olefin copolymer rubber.

Moreover, it is preferable that weight average molecular weights are 5,000-500,000, as for the molecular weight of an olefinic thermoplastic elastomer, it is more preferable that it is 10,000-300,000, It is more preferable that it is 50,000-200,000.

-MFR-

When the glass transition temperature of a cyclic olefin resin film is Tg degreeC, MFR of the elastomer in Tg+50 degreeC and load 49N (corresponding to 5 kgf) is 0.3 cm< ³ >/ from a viewpoint of suppressing generation|occurrence|production of a foreign material. 10 min or more and less than 9.0 cm ³ /10 min, and preferably 2.0 cm ³ /10 min or more and 7.5 cm ³ /10 min or less.

The MFR of the elastomer can be measured, for example, by the method described in Examples. Although methyl isobutyl ketone is used in the Example, what is necessary is just to select the solvent to be used according to the kind of cyclic olefin resin and an elastomer.

It is preferable that the ratios of MFR of the cyclic olefin resin film obtained in said Tg+50 degreeC and load 49N with respect to MFR of the said elastomer in said Tg+50 degreeC and load 49N are 80 % or more and 120 % or less.

MFR of the said cyclic olefin resin film can be measured by the method as described in an Example.

It is preferable that they are 130 degreeC or more and less than 170 degreeC, as for the glass transition temperature Tg of the said cyclic olefin resin film, it is more preferable that they are 140 degreeC or more and less than 160 degreeC, It is more preferable that they are 143 degreeC or more and less than 155 degreeC. In addition, in this indication, Tg of a film can be measured by the method in the Example mentioned later. When Tg shall be 130 degreeC or more, it is excellent in heat resistance, and it is easy to acquire sufficient manufacturing process aptitude suitable as an optical film, and it is easy to suppress generation|occurrence|production of the foreign material which generate|occur|produces at the time of melt film forming by setting it as less than 170 degreeC.

It is preferable that the density|concentration of the said elastomer contained in the cyclic olefin resin film obtained is 1 mass % or more and less than 20 mass % with respect to the total mass of the cyclic olefin resin film obtained, It is more preferable that they are 2 mass % or more and 15 mass % or less.

-Method of adding elastomer-

As a method of adding an elastomer to the cyclic olefin resin, at the time of melt film forming, both are put into the extruder as they are, melt-mixed in the extruder, and the cyclic olefin resin and the elastomer are mixed in advance to form a master pellet having an arbitrary elastomer concentration. , You may inject|throw-in cyclic olefin resin and a master pellet to an extruder at the time of melt film forming.

In performing master pelletization, it is preferable to dry cyclic olefin resin beforehand. Moreover, it is preferable to also dry the elastomer beforehand. When drying cyclic olefin resin or an elastomer, a drying method and drying conditions are not specifically limited. Examples of the drying method include a method of heating in a heating furnace at a temperature of 80 ° C. to 110 ° C., preferably around 90 ° C. for a heating time of 8 hours or more, preferably 8 hours to 12 hours, etc. It is not limited here. The heating temperature and heating time at the time of drying resin consider at least any one of the glass transition temperature Tg of cyclic olefin resin or an elastomer, melting|fusing point, etc., and may be selected.

The said drying can also be abbreviate|omitted by using a vent type extruder, for example at the time of master pelletizing of cyclic olefin resin and an elastomer.

The size of the pellets in the master pelletization is, for example, a cross-sectional area of 1 mm ² to 300 mm ² , preferably 1 mm to 30 mm in length, more preferably 2 mm ² to 100 mm ² in cross-sectional area, 1.5 mm to 10 mm in length to be.

In addition, in the production method according to the present disclosure, various additives according to the use of the film to be produced, for example, deterioration inhibitor, ultraviolet inhibitor, retardation (optical anisotropy) regulator, fine particles, peeling accelerator, infrared absorber, etc. can be used. . The additive may be a solid or an oily substance may be sufficient as it.

The said additive may be mixed in the master pellet containing a cyclic olefin resin and/or an elastomer, and when an additive has fluidity|liquidity, such as an oily substance, it injects|throws-in to an extruder as it is, and mixes with a cyclic olefin resin and an elastomer in an extruder. Do it.

As a method of mixing an additive in a master pellet, Paragraph 0043 - 0047 of International Publication No. 2017/126572, etc. can be referred.

In addition, in the formula for calculating the supply part resin transport efficiency in the present disclosure, ρ represents the specific gravity (g/cm ³ ) of the raw resin, and depending on the specific gravity ρ of the resin to be used, other parameters of the supply part resin transport efficiency may be set.

<Supply of raw material resin to the extruder>

The raw resin is put into the hopper 12 , and is supplied into the cylinder 44 from the supply port 52 of the cylinder 44 . The raw material resin injected|thrown-in to the hopper 12 may be the pellet of raw material resin, the pellet containing raw material resin and an additive may be sufficient as it, and flake raw material resin may be sufficient as it.

From the viewpoint of suppressing thermal oxidation of the raw material resin supplied to the cylinder 44, the oxygen concentration in the supply port 52 is preferably low, specifically 0.1% or less by volume. As a method of lowering the oxygen concentration in the supply port 52 , the raw resin is supplied into the cylinder 44 from the supply port 52 through a vacuum hopper, and to the supply port 52 of the cylinder 44 . The method of supplying nitrogen gas, etc. are mentioned. In addition, the oxygen concentration in the supply port 52 can be measured by providing piping (not shown) in the supply port 52, and connecting an oxygen concentration meter (not shown).

In the formula for calculating the supply part resin transport efficiency in the present disclosure, D represents the inner diameter (mm) of the cylinder 44 . The inner diameter D of the cylinder 44 is preferably from 10 mm to 300 mm, more preferably from 20 mm to 250 mm, from the viewpoint of melt-extrusion with the supply part resin transport efficiency of 0.75 or more and 1.0 or less.

The resin supplied into the cylinder 44 is gradually heated by friction caused by rotation of the screw 50 and temperature control means (not shown) disposed around the cylinder 44 . From the viewpoint of supplying the raw resin from the supply port 52 and rapidly melting the raw resin in the cylinder 44, it is preferable that the raw resin is supplied from the supply port in a heated state.

When the glass transition temperature of the raw material resin is Tg (°C), it is preferable that the temperature of the raw material resin supplied from the supply port 52 into the cylinder 44 is Tg-90°C or higher and Tg+10°C or lower, It is more preferable to control to Tg-80 degreeC or more and Tg-10 degreeC or less. As a method of controlling the temperature of the raw material resin supplied from the supply port 52 into the cylinder 44 in the above preferred range, a method of pre-heating the pellets to be put into the hopper, a method of using a hopper equipped with a heating means, A method of providing a heating means in the vicinity of the supply port separately from the hopper is mentioned.

<melting of raw material resin by extruder>

The raw material resin supplied into the cylinder 44 from the supply port 52 is conveyed toward the extrusion port 54, being preheated in the supply part A by rotation of the screw 50.

In the calculation formula of the supply part resin transport efficiency in this indication, W has shown the flight space|interval (mm) of the screw 50 in the supply part in a cylinder. From a viewpoint of melt-extruding by making supply part resin transport efficiency 0.75 or more and 1.0 or less, 10 mm - 300 mm are preferable, and, as for the screw flight space|interval W, 20 mm - 250 mm are more preferable.

In addition, in the calculation formula of the supply part resin transport efficiency in this indication, (psi) has shown the screw flight angle (degree) in the supply part A. The screw flight angle Ψ in the supply portion (A) is preferably 5° to 30°, more preferably 10° to 25°, from the viewpoint of melt-extrusion with the supply portion resin transport efficiency of 0.75 or more and 1.0 or less. .

A full flight, a double flight, etc. can be employ|adopted for the flight in a screw. A double flight screw is preferable from the viewpoint of promoting melt-kneading of the resin in the compression section (B). In addition, a double flight screw is a screw in which two flights are arrange|positioned spirally by the screw shaft in the compression part B.

In the formula for calculating the supply part resin transport efficiency in the present disclosure, Hf is the groove depth (mm) in the supply part A, ie, from the outer peripheral surface of the screw shaft in the supply part A to the outer periphery of the screw flight. The distance in the radial direction of the screw shaft (hereinafter, sometimes referred to as "supply part groove depth") is shown. From a viewpoint of melt-extruding by making supply part resin transport efficiency 0.75 or more and 1.0 or less, 2 mm - 30 mm are preferable and, as for supply part groove|channel depth Hf, 3 mm - 25 mm are more preferable. In addition, the supply part groove|channel depth can be adjusted according to the inner diameter D of the cylinder 44, the outer diameter d1 of the screw shaft in the supply part A, and the height of the screw flight 48.

The resin supplied into the cylinder 44 is gradually heated by friction or the like caused by the rotation of the screw 50 .

In the calculation formula of the supply part resin transport efficiency in this indication, N has shown the screw rotation speed (rpm: rotation/min). In the manufacturing method of the cyclic olefin resin film which concerns on this indication, since a screw is rotated in the state in which raw material resin is dense in a supply part, it is a high torque normally, and a screw is rotated at comparatively low speed. From such a viewpoint, 3 rpm - 150 rpm are preferable and, as for the screw rotation speed (rpm) in the manufacturing method which concerns on this indication, 5 rpm - 100 rpm are more preferable.

It is not necessary that all of the raw resin in the cylinder 44 is melted in the supply section A, but all of the raw resin in the compression section B needs to be melted. On the other hand, in order to smoothly send the raw material resin to the compression part B side by rotation of the screw 50 in the supply part A, in the supply part A and the compression part B, the screw 50 and the cylinder 44 ) and it is preferable that there is a difference in frictional force between the resin.

In general, when the cylinder 44 is high temperature, the friction force of the resin with respect to the cylinder 44 is high, and when the screw 50 is low temperature, the friction force of the resin with respect to the screw 50 is low, a frictional force difference occurs and the resin is compressed into the compression part. (B) It becomes the relationship that it becomes easy to send to the side. When the glass transition temperature of the raw resin is set to Tg (°C), the temperature of the screw 50 is set to a temperature at which the raw resin is softened in the supply part (A) by setting the temperature of the screw 50 higher than Tg, the resin for the screw 50 There is a possibility that the difference between the friction force and the friction force of the resin with respect to the cylinder 44 becomes small, making it difficult to proceed to the compression section B for melting the resin. From such a viewpoint, it is preferable to control the temperature of the screw in the supply part A to Tg-80 degreeC or more and Tg degreeC or less, and it is more preferable to control it to Tg-70 degreeC or more and Tg-10 degrees C or less. For example, by using the screw which has a structure which circulates and supplies a heat medium to the inside of a screw shaft, the temperature of a screw can be controlled with high precision.

The resin heated in the supply unit A is transported to the compression unit B by rotation of the screw, and further heated and melted in the compression unit B. The resin (molten resin) melted in the compression section B is transported to the metering section C again.

In the formula for calculating the resin transport efficiency of the supply part in the present disclosure, the compression ratio represents "volume per pitch of screw flights in the supply part/volume per pitch of screw flights in the metering part". The compression ratio is calculated using the outer diameter d1 of the screw shaft of the supply unit A, the outer diameter d2 of the screw shaft of the metering unit C, the groove depth Hf of the supply unit A, and the groove depth Hm of the metering unit C.

When the compression ratio is too small, the raw material resin is not sufficiently melt-kneaded, an undissolved portion is generated, an undissolved foreign material is likely to remain in the cyclic olefin resin film after production, and bubbles are easily mixed. Thereby, when the intensity|strength of a cyclic olefin resin film falls or when extending|stretching a film, it becomes easy to fracture|rupture, and there exists a possibility that orientation cannot fully be raised. Conversely, when the compression ratio is too large, the shear stress applied to the raw material resin becomes too large and the resin tends to deteriorate due to heat generation, so there is a possibility that yellowish taste appears easily on the cyclic olefin resin film after production. Moreover, when the shear stress applied to raw material resin becomes large too much, in raw resin, molecular cleavage will occur, molecular weight may fall and the mechanical strength of a film may fall.

1.5-4.0 are preferable and, as for a compression ratio, from a viewpoint of melt-extruding the said viewpoint and supply part resin transport efficiency into 0.75 or more and 1.0 or less, 1.5-4.0 are preferable and 2.0-3.5 are more preferable. In addition, the compression ratio can be adjusted by adjusting at least any one of the inner diameter D of the cylinder 44, the outer diameters d1 and d2 of the screw shafts in the supply part and the metering part, the flight interval W of the screw 50, and the flight angle Ψ. .

In the formula for calculating the supply part resin transport efficiency in the present disclosure, L/D is preferably 20 to 70. L/D is the ratio of the cylinder length L to the cylinder bore D.

The extrusion temperature is preferably set to 200°C to 300°C.

The set temperature in the extruder may be the same temperature for the entire region, or may have a different temperature distribution depending on the region. It is preferable to set it as the temperature distribution which differs according to area|region, and it is especially more preferable to make the temperature of the supply part (A) demonstrated above in an extruder higher than the temperature of the compression part (B).

When L/D is too small, it becomes easy to generate|occur|produce insufficient melting or lack of kneading|mixing of the raw material resin in an extruder, and, similarly to the case where a compression ratio is small, the possibility that undissolved foreign material will become easy to generate|occur|produce in the cyclic olefin resin film after manufacture. have. Conversely, when L/D is too large, the residence time of the raw material resin in the extruder becomes too long, and it becomes easy to raise|generate deterioration of resin. Moreover, when residence time becomes long, the molecular weight of a raw material resin may cut|disconnect in raw material resin, or it originates in a molecule|numerator cut|disconnection, the molecular weight of raw material resin falls, and the mechanical strength of a cyclic olefin resin film may fall.

From such a viewpoint, L/D is preferably in the range of 20 to 70, more preferably in the range of 22 to 60, still more preferably in the range of 24 to 50.

The molten resin is extruded from the extrusion port 54 of the cylinder 44 via the metering part C. The metering part C measures molten resin, and the extrusion amount from the extrusion port 54 is stabilized.

Although the molten resin extruded from the extruder 14 is transported toward the die 20 through the pipe 40, it is preferable to perform so-called breaker plate type filtration in which a filter medium is provided at the outlet of the extruder 14. Moreover, it is preferable that the molten resin extruded from the extruder 14 is conveyed to the die 20 via the gear pump 16 and the filter 18. In addition, the molten resin is sometimes called "melt".

[Gear Pump]

In order to improve the thickness precision of a film, it is important to suppress the fluctuation|variation of the discharge amount of the molten resin extruded from the extruder 14 low. It is preferable to provide the gear pump 16 between the extruder 14 and the die 20 from a viewpoint of reducing the fluctuation|variation of discharge amount more, and to supply a fixed amount of molten resin from the gear pump 16.

In the gear pump, a pair of gears composed of a drive gear and a driven gear are accommodated in a meshed state, and by driving the drive gear to rotate both gears in mesh with each other, the molten resin is discharged from a suction port formed in the housing into a cavity. In the same way, a certain amount of resin is discharged from the discharge port formed in the housing. Even if the resin pressure of the front-end|tip part of an extruder has some fluctuation|variation, by using a gear pump, a fluctuation|variation is absorbed, the fluctuation|variation of the resin pressure downstream of a film forming apparatus becomes very small, and thickness fluctuation|variation is improved. By using the gear pump, it is possible to make the fluctuation range of the resin pressure of the die portion within ±1%.

In order to improve the fixed-quantity supply performance by a gear pump, the method of changing the rotation speed of a screw and suppressing the fluctuation|variation of the pressure applied to raw material resin before a gear pump can also be used. In addition, a high-precision gear pump using three or more gears is also effective for suppressing fluctuations in pressure.

〔filter〕

In order to prevent mixing of foreign matter with higher precision, it is preferable to provide the filter 18 after passing through the gear pump 16 . As the filter 18, a filtration device incorporating a so-called leaf disk filter is preferable. Filtration of the raw material resin discharged from the extruder may be filtration performed by providing one filtration unit, or may be multistage filtration performed by providing a plurality of filtration units. It is preferable that the filtration precision of a filter medium is high. However, 15 micrometers - 3 micrometers are preferable, and, as for the filtration precision, 15 micrometers - 3 micrometers are preferable, and, from a viewpoint of considering the internal pressure of a filter medium or suppressing the filtration pressure rise by clogging of a filter medium, 10 micrometers - 3 micrometers are more preferable. In particular, in the case of using a leaf-type disc filter device that finally filters foreign substances, it is preferable to use a filter medium with high filtration accuracy in terms of quality, and the filter medium loaded in the filter unit to ensure suitability for pressure resistance and filter life. With the number of , it is possible to adjust the withstand pressure, the life of the filter, and the like.

As for the kind of filter medium used for a filter, it is preferable to use the filter medium formed from the steel material at the point used under high temperature and high pressure. It is preferable to use especially stainless steel, steel, etc. among the steel materials which form a filter medium, and it is more preferable to use especially stainless steel from a corrosion point.

As the configuration of the filter medium, in addition to the filter medium formed by weaving a wire rod, for example, a sintered filter medium formed by sintering long metal fibers or metal powder can be used, and the sintered filter medium is preferable in terms of filtration accuracy and filter life.

<Melting Extrusion by Die>

The molten resin (melt) continuously sent to the die 20 via the extruder 14 , the gear pump 16 , and the filter 18 is melt-extruded from the die 20 in the form of a film.

As the die 20 , a fish tail die or a hanger coat die other than the generally used T die may be used.

A static mixer for improving the uniformity of the resin temperature may be put just before the die 20 .

The slit spacing (lip clearance) of the die 20 is generally preferably 1.0 to 5.0 times the film thickness, more preferably 1.2 to 3 times, and still more preferably 1.3 to 2 times. If a lip clearance is 1.0 times or more of film thickness, it will be easy to obtain a flat favorable film by film forming. Moreover, the thickness precision of a film can be improved as lip clearance is 5.0 times or less of film thickness.

A die is one of the facilities that influence the thickness precision of a film, and it is preferable that thickness can be controlled with high precision. Usually, the installation space|interval in the width direction of die|dye of the thickness adjustment facility for performing thickness adjustment of the film extruded from die|dye can be selected from the range of 40 mm - 50 mm. The narrower the installation interval of the thickness adjustment facility, the more detailed the thickness control can be, the more preferably the installation interval is 35 mm or less, more preferably 25 mm or less, the thickness of the film thickness adjustment facility can be installed. It is preferable to use a die of an adjustable type.

Moreover, in order to further improve the uniformity of a film, it is preferable to adjust the temperature fluctuation|variation of a die|dye and the conditions which can make as little as possible the flow velocity fluctuation|variation in the width direction. Moreover, it is also effective to reduce the thickness fluctuation|variation in long-term continuous production to use the automatic thickness adjustment die which measures the thickness of a downstream film, calculates thickness deviation, and feeds back the result to thickness adjustment of a die|dye.

For the production of the film, a single-layer film forming apparatus with an inexpensive equipment cost is generally used. However, if necessary, it is also possible to manufacture a film having a structure of two or more layers using a multilayer film forming apparatus in which a functional layer is provided on the outer layer of the cylinder 44 . When forming a multilayer film into a film using a multilayer film forming apparatus, it is generally preferable to laminate|stack as a surface layer the functional layer thinner than the resin film used as a base material on the surface of a cyclic olefin resin film. However, the layer thickness ratio in particular is not limited about the thickness of each layer in a multilayer structure.

In the calculation formula of the supply part resin transport efficiency in this indication, Q has shown the extrusion amount (kg/h) of molten resin. The extrusion amount (kg/h) of the molten resin depends on the feed amount (kg/h) of the raw material resin to the supply port of the extruder, and can also be viewed as the extrusion amount (kg/h) from the extrusion port of the extruder. The extrusion amount Q of the molten resin varies depending on the cylinder capacity of the extruder, the type of die, etc., but from the viewpoint of performing melt extrusion with the supply part resin transport efficiency of 0.75 or more and 1.0 or less, the extrusion amount of the molten resin is 0.5 kg /h - 1800 kg/h are preferable, and 1 kg/h - 900 kg/h are more preferable.

<Cast>

On the said conditions, the molten resin extruded from die|dye into film form is solidified by cooling on a casting roll, and a cyclic olefin resin film is obtained. In addition, by heating the melt-extruded film with a far-infrared heater before the molten resin comes into contact with the casting roll, a leveling effect is expressed on the drum, the surface of the melt-extruded film becomes more uniform, and the film thickness distribution of the obtained film is reduced Thus, the occurrence of die streaks can be suppressed.

With respect to the molten resin melt-extruded on the casting roll, it is preferable to use a method such as an electrostatic application method, an air knife method, an air chamber method, or a vacuum nozzle method to increase the adhesion between the casting roll and the melt-extruded sheet.

It is also preferable that the said adhesive improvement is performed by pinching in the process of pinching mentioned later.

The thickness of the unstretched film produced by the manufacturing method according to the present disclosure may be determined depending on the application, but when used as an optical film, from the viewpoint of mechanical strength and light transmittance, preferably 20 µm to 250 µm, more preferably is 25 μm to 200 μm, more preferably 30 μm to 180 μm.

[the process of cooperating]

In the manufacturing method of the cyclic olefin resin film which concerns on this indication, from a viewpoint of the surface smoothness of the cyclic olefin film obtained, the molten resin obtained by the process of melt-extruding into a film form is applied to the clamping part formed in the clearance gap of one smooth roll. It is preferable to further include the step of introducing and pinching.

The step of pinching can be performed using the above-mentioned casting roll and touch roll as one smooth roll (touch roll method).

The touch roll method is a method of performing cooling and shaping of the film surface, that is, smoothing the film surface, by sandwiching the hot molten resin discharged from the die between the casting roll and the touch roll disposed on the casting roll. The touch roll used in this indication is not a roll with normal high rigidity, but the roll which has elasticity is preferable.

As for the temperature of a touch roll, more than glass transition temperature Tg-10 degreeC of a cyclic olefin resin film, Tg+30 degreeC or less are preferable, More preferably, Tg-7 degreeC or more and Tg+20 degrees C or less, More preferably, Tg-5 ℃ or more and Tg+10℃ or less. When using a some touch roll, it is preferable to adjust any touch roll to the said temperature range. Moreover, it is preferable to also adjust the temperature of a casting roll to the same temperature range as the temperature range of an above-described touch roll.

Specifically, as for a touch roll, the touch roll of Unexamined-Japanese-Patent No. 11-314263 and Unexamined-Japanese-Patent No. 11-235747 is mentioned, for example, The touch roll described here relates to this indication It can be used in a manufacturing method.

Moreover, as for the cooling of the discharged resin, it is more preferable to use a plurality of casting rolls and to perform slow cooling. There is no limitation in particular in the number of the casting rolls used for slow cooling, According to the objective, it selects suitably. For example, although the method of using three casting rolls for slow cooling of resin is mentioned, it is not limited to this.

When a plurality of casting rolls are used for cooling the discharged resin, it is preferable to arrange the touch rolls at a position where they touch the first casting roll on the upstream side (closer to the die).

As for the diameter of a casting roll, 50 mm - 5000 mm are preferable, More preferably, they are 100 mm - 2000 mm, More preferably, they are 150 mm - 1000 mm. When a plurality of casting rolls are used, it is preferable that any casting rolls are within the above diameter range.

When using two or more casting rolls, 0.3 mm - 300 mm are preferable between surfaces, As for the space|interval of adjacent casting rolls, More preferably, they are 1 mm - 100 mm, More preferably, they are 3 mm - 30 mm.

Moreover, it is preferable that the line speed of the upstream side of a casting roll shall be 20 m/min or more and 70 m/min or less.

<winding>

After peeling off the cooled film (unstretched film) from a casting roll, it winds up via a nip roll (not shown).

It is also preferable to trim both ends before winding. Trimming can be performed by a well-known method. The trimming cutter used for trimming may use any type of cutter, such as a rotary cutter, a shear blade, and a knife. About the material of a cutter, carbon steel, stainless steel, etc. are mentioned, You may use the cutter of any material. In general, when a trimming cutter is provided with a cemented carbide blade or a ceramic blade, the life of the blade is long, and generation of cutting chips is suppressed, so it is preferable. The part cut out by trimming may be crushed and used again as a raw material.

It is also preferable to perform a thickness treatment process (knurling process) on one end or both ends of a cyclic olefin resin film. The height of the unevenness|corrugation by a thickness treatment process is preferably 1 micrometer - 200 micrometers, More preferably, they are 10 micrometers - 150 micrometers, More preferably, they are 20 micrometers - 100 micrometers. Thickening processing may be made into the shape used as convex on both surfaces, and even as the shape used as convex on one surface, it is not cared about. As for the width|variety of a thickness treatment process, 1 mm - 50 mm are preferable, More preferably, they are 3 mm - 30 mm, More preferably, they are 5 mm - 20 mm. Thickness treatment processing can be performed at room temperature - 300 degreeC.

When winding up, it is preferable from a viewpoint of flaw prevention to stick a protective film on at least single side|surface. 5 micrometers - 200 micrometers are preferable, as for the thickness of a protective film, 10 micrometers - 150 micrometers are more preferable, and 15 micrometers - 100 micrometers are still more preferable. The material of the protective film is not particularly limited. As a material of a protective film, polyethylene, polyester, polypropylene, etc. are mentioned, for example.

<stretching>

The film formed into a film can be extended|stretched according to the objective.

When extending|stretching, the film formed into a film may perform online extending|stretching to extend|stretch as it is, and after winding up once, it may send out again and may perform offline extending|stretching to extend|stretch.

As an extending|stretching direction, the transverse stretching extended|stretching in the width direction of the film formed into a film may be sufficient, the longitudinal stretching extended|stretching in the film forming direction of the film formed into a film may be sufficient, and both transverse stretching and longitudinal stretching may be implemented.

In addition, in combination with extending|stretching, you may perform the relaxation process mentioned later. These can be implemented, for example by the following combinations.

It is preferable to carry out combining transverse stretching and longitudinal stretching as extending|stretching. When performing lateral stretching and longitudinal stretching, simultaneous biaxial stretching may be performed, and sequential stretching may be performed. Among them, it is more preferable to first perform longitudinal stretching, and then to perform sequential stretching in which transverse stretching is performed.

<Mitigation processing>

By performing a relaxation process after extending|stretching of the obtained resin film, the dimensional stability of a resin film can be improved. The relaxation treatment is preferably a thermal relaxation treatment in which the dimension of at least any one of the longitudinal direction and the transverse direction of the stretched film is relaxed, for example, by about 1% to 8%, and heat setting. Although the temperature in a thermal relaxation process is suitably selected according to the kind of cyclic olefin resin used for a cyclic olefin resin film, Generally, 130 degreeC - 240 degreeC are preferable.

It is preferable to perform thermal relaxation in either or both after longitudinal stretching and after transverse stretching, More preferably, it is after transverse stretching. A relaxation process may be performed online continuously after extending|stretching of a cyclic olefin resin film, and may perform offline with respect to the cyclic olefin resin film wound up after extending|stretching.

According to the manufacturing method which concerns on this indication, generation|occurrence|production of a foreign material is suppressed and the cyclic olefin resin film excellent in impact strength can be manufactured with favorable productivity.

Since generation|occurrence|production of a foreign material is suppressed, an optical characteristic is favorable, and it is excellent in heat resistance and impact strength, you may use the cyclic olefin resin film manufactured by the manufacturing method which concerns on a film independent as an optical film. Moreover, you may use in combination with a polarizing plate, and functional layers, such as a liquid crystal layer, the layer (low reflection layer) which controlled refractive index, and a hard-coat layer, may be provided and used, the application range of the obtained cyclic olefin resin film is wide.

(cyclic olefin resin film)

The cyclic olefin resin film according to the present disclosure contains a cyclic olefin resin and an elastomer, and the number of foreign substances having a longest diameter of 30 µm or more per 100 µm in thickness of the cyclic olefin resin film is 0.3 pieces/cm ² or less, and a longest diameter of 5 µm or more When the number of foreign substances less than 30 µm is 100 pieces/cm ² or less and the glass transition temperature of the cyclic olefin resin film is Tg°C, MFR of the elastomer under Tg+50°C and a load of 49N is 0.3 cm ³ /10 min or more less than 9.0 cm ³ /10 min.

The cyclic olefin resin film which concerns on this indication can be manufactured with the manufacturing method which concerns on this indication, It is preferable that it is what was manufactured with the manufacturing method which concerns on this indication.

Physical properties, such as Tg and MFR of the cyclic olefin resin film which concerns on this indication, are the same meaning as the content described as the physical property of the cyclic olefin resin film obtained by the manufacturing method which concerns on this indication mentioned above, and a preferable aspect is also the same.

The physical properties, such as the kind of cyclic olefin resin and elastomer, MFR, and the relationship between the said physical properties contained in the cyclic olefin resin film which concerns on this indication are the same meaning as the cyclic olefin resin and elastomer in the manufacturing method which concerns on this indication, A preferred aspect is also the same.

-Content of elastomer-

It is preferable that content of the said elastomer in the cyclic olefin resin film which concerns on this indication is 1 mass % or more and less than 20 mass % with respect to the total mass of a cyclic olefin resin film, It is more preferable that they are 2 mass % or more and 15 mass % or less. do.

The said content can be measured by the method in the Example mentioned later.

-Average particle size-

It is preferable that they are 100 nm or more and less than 1,000 nm, and, as for the average particle diameter of the said elastomer in the cyclic olefin resin film which concerns on this indication, it is more preferable that they are 100 nm or more and less than 500 nm.

The said average particle diameter can be measured by the method in the Example mentioned later.

〔alien substance〕

In the cyclic olefin resin film according to the present disclosure, the number of foreign substances having a longest diameter of 30 μm or more is 0.3 pieces/cm ² or less, and the number of foreign substances having a longest diameter of 5 μm or more and less than 30 μm is 100 pieces/cm ² or less per 100 μm in thickness.

The number of foreign substances having the longest diameter of 30 µm or more is preferably 0.2 pieces/cm ² or less, and more preferably 0.1 pieces/cm ² or less.

Moreover, it is preferable that it is 50 pieces/cm< ² > or less, and, as for the number of the foreign material whose longest diameter is 5 micrometers or more and less than 30 micrometers, it is more preferable that it is 30 pieces/cm< ² > or less.

The number and magnitude|size of the foreign material contained in the cyclic olefin resin film which concerns on this indication can be measured by the method in the Example mentioned later.

(composite film)

The composite film which concerns on this indication has the cyclic olefin resin film which concerns on this indication.

The composite film which concerns on this indication may further have a polarizing plate, and may further have functional layers, such as a liquid crystal layer, the layer which controlled the refractive index (for example, low reflection layer), and a hard-coat layer.

The composite film which concerns on this indication may be manufactured using the above-mentioned multilayer film forming apparatus, for example, and may be manufactured by another well-known method.

Example

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 unless departing from the gist thereof. In addition, unless otherwise indicated, "part" is based on mass.

<Production method>

In the Example and the comparative example, the cyclic olefin resin film was manufactured basically according to the following procedure. However, in each example, the screw flight spacing W of the screw, the supply part groove depth Hf, the cylinder inner diameter D of the extruder, a compression ratio, and Q/N were respectively changed as shown in the separate table, and the supply part resin transport efficiency was adjusted.

In Table 1, as Q and N of Comparative Example 3, the set values of the apparatus were described. In reality, extrusion was not possible due to resin clogging.

In addition, as the density (rho) of the raw material resin used for calculation of the resin transport efficiency of a supply part, the value of "the specific gravity of the whole film" described in Table 2 was used.

[Master pellet production]

The cyclic olefin resin described in the matrix material column of Table 2 was pre-dried at 100 degreeC for 5 hours.

The elastomers described in the matrix material column of Table 2 were pre-dried at 80°C for 12 hours.

Into the extruder, pellets of the cyclic olefin resin described in the matrix material column of Table 2 and the elastomer described in the matrix material column of Table 2 are put in a ratio such that the elastomer is 30% by mass, and melt-extruded at 285 ° C., A master pellet was obtained.

[Unveiling]

Cyclic olefin resin and the master pellet obtained by the said method were pre-dried at 100 degreeC for 5 hours.

After preliminary drying, the cyclic olefin resin and the master pellet were put into the hopper provided in the extruder so that the elastomer concentration in the cyclic olefin resin film obtained became the density|concentration shown in Table 1, and it melted at 285 degreeC with the extruder. In addition, the said temperature is the temperature of the cylinder after a compression part.

The molten resin (melt) extruded from the extruder and transported to the gear pump through the pipe was sent out again from the gear pump and filtered with a leaf disk filter having a filtration accuracy of 5 µm.

After filtration, a melt (molten resin) is extruded from a coat hanger die with a slit spacing of 1.0 mm and a 285 ° C. on the casting roll 1 (CR1) set at 137 ° C, and a touch roll (metal made, set at 133 ° C.) was brought into contact with Subsequently, after passing through the casting roll 2 (CR2) and the casting roll 3 (CR3), the film of arbitrary thickness was obtained.

About the example in which "None" was described in the "Touch roll presence/absence" column in Table 1, the said touch roll was not used.

<Measurement, evaluation>

The following measurement and evaluation were performed about the cyclic olefin resin film obtained above.

[Number of foreign bodies]

About the number of foreign substances per 100 micrometers in thickness of the obtained film, using the differential interference microscope (200x) made by Nikon Corporation, the center part of the film was measured in the range of 10 cm x 10 cm. In the measurement, the number of foreign substances having the longest diameter of 30 µm or more and the number of foreign substances of 5 µm or more and less than 30 µm were recorded, respectively, and the value obtained by dividing 100 µm by the thickness of the film multiplied by the number of recorded foreign substances was taken as the number of foreign substances.

The measurement results are shown in Table 2.

[MFR of elastomer]

From the obtained film, the elastomer powder was extracted by the following method, and the MFR (melt flow rate) of the elastomer was measured. The value of MFR was based on JISK7210 (2014), and the temperature measured with Tg+50 degreeC measured by the following method, and the load measured by 49N (5kgf).

The elastomer powder was extracted from the film by the following method. 10 cm x 10 cm, multiple sheets of the center part of the obtained film are sampled, and it is immersed in methyl isobutyl ketone (MIBK) which is a solvent which melt|dissolves cyclic olefin resin but does not melt|dissolve an elastomer. At this time, the amount of solvent is set to be 1,000 times or more of the film to be treated. The dissolved elastomer remaining and precipitated elastomer is collected by filtration, dried at room temperature to remove solvent content, and a single elastomer powder is obtained.

[MFR of cyclic olefin resin film]

The MFR (melt flow rate) of the obtained cyclic olefin resin film was measured, without extracting an elastomer powder by the said method. The value of MFR was based on JISK7210 (2014), and the temperature measured with Tg+50 degreeC measured by the following method, and the load measured by 49N (5kgf).

[Glass Transition Temperature Tg]

The center part of the obtained film was sampled, and the glass transition temperature was measured by DSC (Differential scanning calorimeter, Shimadzu Corporation DSC-60A).

[Concentration of elastomer]

10 cm x 10 cm of the center part of the obtained film was sampled, and the mass was measured. Then, from the sampled film, the elastomer powder was extracted by the said method, and the mass was measured. A value obtained by dividing the mass of the elastomer powder by the mass of the film and multiplying by 100 was defined as the concentration of the elastomer. The measurement results are shown in Table 2.

[Average particle diameter of elastomer]

A scanning electron microscope was used for observation of the elastomer disperse|distributed in the film. In 10 different parts of the sample, a cleavage section parallel to the width direction of the film (direction perpendicular to the transport direction of the film on the film plane) and perpendicular to the film plane was observed. Observation was performed at an appropriate magnification of 100 to 10,000 times, and the image was taken so that the dispersion state of the elastomer particles in the width of the entire thickness of the film could be confirmed. For 200 randomly selected elastomer particles, the outer periphery of each particle is traced, the equivalent circle diameter of the particles is measured from these trace images with an image analysis device, and the arithmetic average value is obtained, and this is the average particle diameter of the elastomer. defined The equivalent circle diameter refers to the diameter of a circle equal to the area on the trace. The measurement results are shown in Table 2.

[Surface Roughness Ra]

The surface roughness Ra of the film can be measured using a stylus type roughness meter according to JIS B 0601 (2013). The measurement of Ra was calculated|required as an arithmetic mean by performing the measurement of 5 places selected at random within 10 cm x 10 cm of the center of a film. About the obtained Ra, it evaluated based on the following index|index. It can be said that it is excellent in the surface smoothness of cyclic olefin resin, so that the value of Ra is small. The evaluation result was described in Table 2.

A: Ra is more than 5 nm and less than 15 nm

B: Ra is 15 nm or more and less than 20 nm

C: Ra of 20 nm or more and less than 50 nm

D: Ra of 50 nm or more

[Impact strength]

The impact strength of the obtained film was measured using the film impact tester (made by Toyo Seiki Seisakusho). About the measured impact strength, it evaluated based on the following index|index. The evaluation result was described in Table 2.

A: The impact strength is 1.5N·m or more

B: Impact strength is 1.2N·m or more and less than 1.5N·m

C: Impact strength 0.8N·m or more and less than 1.2N·m

D: impact strength less than 0.8 N·m

[Table 1]

[Table 2]

Details of the abbreviations listed in Table 2 are as follows.

COP: Cyclic olefin resin, JSR Corporation make Arton (trademark), glass transition temperature Tg: 151 degreeC

SEBS: Styrene-ethylene-butylene-styrene copolymer, Asahi Kasei Toughtech

MBS: methyl methacrylate-butadiene-styrene copolymer, Denkaze TH polymer

TPO: Olefin-based elastomer, EXCELINK made by JSR

As shown in Table 2, using raw material resin containing a cyclic olefin resin and an elastomer, the supply part resin transport efficiency performs melt extrusion on the conditions which satisfy|fill 0.75 or more and 1.0 or less, Furthermore, the glass transition temperature Tg of a cyclic olefin resin film In each Example in which the melt flow rate of the elastomer at +50°C and a load of 49N is 0.3 cm ³ /10 min or more and less than 9.0 cm ³ /10 min, the generation of foreign matter is suppressed, the surface smoothness is excellent, and the impact strength An excellent cyclic olefin resin film was obtained.

10 Film making device
12 Hopper
14 extruder
16 gear pump
18 filters
20 die
22, 24, 26 cooling rolls
28 contact roll
40 plumbing
44 cylinder
46 screw shaft
48 Flights (Screw Flights)
50 screw
52 inlet
54 extruder
100 raw resin
Groove depth of Hf supply (A)
Hm Depth of groove of metering part (C)
d1 Outer diameter of the screw shaft of the supply part (A)
d2 Outer diameter of screw shaft of metering part (C)
A supply
B compression section
C Weighing part
D cylinder inner diameter
L cylinder length
Screw flight spacing in the W supply
Ψ Screw flight angle at the supply
As for the indication of the JP Patent application 2018-029132 for which it applied on February 21, 2018, the whole is taken in into this specification by reference.
All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference. is introduced

Claims (12)

A cylinder having a supply port to which a raw material resin containing a cyclic olefin resin and an elastomer is supplied and an extrusion port through which a molten resin in which the raw resin is melted is extruded;
having a screw shaft and a flight spirally arranged around the screw shaft,
and a screw rotating in the cylinder;
In the cylinder, an extruder having a supply part, a compression part, and a metering part in order from the side of the supply port along the screw shaft is used,
Supply and melting of the raw material resin is performed under the condition that the supply part resin transport efficiency calculated by the following formula satisfies 0.75 ≤ supply part resin transport efficiency ≤ 1.0,
having a process of melt-extruding the molten resin extruded from the extrusion port into a film form from a die,
When the glass transition temperature of the obtained cyclic olefin resin film is Tg ° C, the melt flow rate of the elastomer at Tg + 50 ° C and a load of 49 N is 0.3 cm ³ /10 min or more and less than 9.0 cm ³ /10 min,
The ratio of the melt flow rate of the cyclic olefin resin film obtained at the Tg+50°C and load 49N to the melt flow rate of the elastomer at the Tg+50°C and load 49N is 80% or more and 120% or less , a method for producing a cyclic olefin resin film.
[Equation 1]

W: Spacing of screw flights in the supply section (mm)
Hf: Groove depth at the feed (mm)
D: inner diameter of cylinder (mm)
Ψ: screw flight angle at the supply (°)
Q: Extrusion amount of molten resin (kg/h)
ρ: specific gravity of the raw resin (g/cm ³ )
N: number of screw revolutions per minute (rpm)
Compression ratio: volume per pitch of screw flights in the feed section/volume per pitch of screw flights in the metering section The method according to claim 1,
The manufacturing method of the cyclic olefin resin film whose density|concentration of the said elastomer contained in the cyclic olefin resin film obtained is 1 mass % or more and less than 20 mass % with respect to the total mass of the cyclic olefin resin film obtained. The method according to claim 1,
The manufacturing method of the cyclic olefin resin film whose said elastomer is a styrene-type thermoplastic elastomer. delete The method according to claim 1,
The manufacturing method of the cyclic olefin resin film which introduce|transduces the molten resin obtained by the process of melt-extruding into a film form into the clamping part formed in the clearance gap of a pair of smooth rolls, and further includes the process of clamping. A cyclic olefin resin film comprising:
a cyclic olefin resin and an elastomer;
Per 100 µm in thickness of the cyclic olefin resin film, the number of foreign substances having a longest diameter of 30 µm or more is 0.3 pieces/cm ² or less, and the number of foreign substances having a longest diameter of 5 µm or more and less than 30 µm is 100 pieces/cm ² or less,
When the glass transition temperature of the cyclic olefin resin film is Tg°C, the melt flow rate of the elastomer at Tg+50°C and a load of 49N is 0.3 cm ³ /10 min or more and less than 9.0 cm ³ /10 min,
The ratio of the melt flow rate of the cyclic olefin resin film at Tg+50°C and load 49N to the melt flow rate of the elastomer at Tg+50°C and load 49N is 80% or more and 120% or less, Cyclic olefin resin film. 7. The method of claim 6,
The cyclic olefin resin film whose content of the said elastomer is 1 mass % or more and less than 20 mass % with respect to the total mass of a cyclic olefin resin film. 7. The method of claim 6,
The cyclic olefin resin film whose said elastomer is a styrene-type thermoplastic elastomer. delete 7. The method of claim 6,
The cyclic olefin resin film whose average particle diameters of the said elastomer are 100 nm or more and less than 1000 nm. 7. The method of claim 6,
Said Tg degreeC is 130 degreeC or more and less than 170 degreeC, The cyclic olefin resin film. The composite film which has the cyclic olefin resin film of Claim 6.

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