JP6835298B1 - Film and film manufacturing method - Google Patents

Abstract

Provided are a transparent film having high slidability and suppressed turbidity, and a method for producing the film. Aromatic polycarbonate (B) having a weight average molecular weight of 45,000 or more and 0.5 parts by mass or more and 15 parts by mass or less and an aromatic polycarbonate (B) having a weight average molecular weight of 45,000 or less 99.5 parts by mass or less and 85 parts by mass or more. A film formed from a composition containing the above, wherein the thickness of the film is 10 μm or more and 300 μm or less.

Description

The present invention relates to films and methods for producing films.

A transparent conductive film is used for a film sensor of a touch panel, electronic paper, a dye-sensitized solar cell, a touch sensor, and the like. As shown in FIG. 1, for example, the transparent conductive film 10 is known to be composed of an electrode layer (transparent conductive film) 11, a base film 12, an adhesive layer 13, and a protective film 14. ing.
For example, Patent Document 1 describes a transparent conductive film laminate having an adhesive layer, a film substrate, and a transparent conductive film in this order on a protective film, and at least one of the film substrate and the protective film. Has an uneven portion on the surface on the adhesive layer side in each end region from one end portion in the width direction and the other end portion to 100 mm inside in the width direction, respectively. The effective roughness R1 of the surface of the uneven portion in each end region is 0.1 to 20 μm, and the pressure-sensitive adhesive layer has an uneven portion in one end region and the other in the width direction. From the position where the separation distance from the uneven portion of the one end region is 0 to 10 mm from the uneven portion of the end region, the separation distance from the uneven portion of the other end region is 0 to 10 mm. A transparent conductive film laminate is disclosed, which is characterized by being provided over such positions. Further, it is described that a polycarbonate resin is used as the protective film.

On the other hand, Patent Document 2 describes a polycarbonate resin (A-1) having a polystyrene-equivalent weight average molecular weight (Mw) of 70,000 or more and less than 200,000 and a polystyrene-equivalent weight average molecular weight (Mw) as a resin composition composed of a polycarbonate resin and a polyarylate resin. Mw) A resin composition composed of a polycarbonate resin (A) composed of a polycarbonate resin (A-2) of 40,000 or more and less than 70,000 and a polyarylate resin (B) is disclosed. It is described that such a resin composition is used for a flat panel display for a portable device exposed to an impact or the like and a film for a flat panel having excellent repeated bending resistance of a touch panel display.

JP-A-2018-152187 Japanese Unexamined Patent Publication No. 2014-015509

A protective film is usually used as the transparent conductive film. Such a protective film is used to protect the base film when transporting the laminate of the electrode layer and the base film. That is, a protective film is used for anti-blocking on the opposite side of the electrode layer.
This protective film is required to have slidability to the extent that it does not stack in order to improve the transportability of the film and prevent winding wrinkles. Further, since the in-line defect inspection is performed on the transparent conductive film with the protective film attached, a transparent film in which turbidity is suppressed is required.
An object of the present invention is to solve such a problem, and an object of the present invention is to provide a transparent film having high slidability and suppressing turbidity, and a method for producing a transparent film.

As a result of the study by the present inventor based on the above problems, by using a specific polyarylate and a specific aromatic polycarbonate and adjusting the content ratio thereof, the transparency is not deteriorated and the transparency is not deteriorated. We have succeeded in improving the slidability by deteriorating the compatibility, and have completed the present invention. Specifically, the above problem was solved by the following means.
<1> Aromatic polycarbonate (B) having a weight average molecular weight of 45,000 or more, 0.5 parts by mass or more and 15 parts by mass or less, and an aromatic polycarbonate (B) having a weight average molecular weight of 45,000 or less, 99.5 parts by mass or less 85 A film formed from a composition containing parts by mass or more, wherein the thickness of the film is 10 μm or more and 300 μm or less.
<2> The dynamic friction coefficient with a film having a root mean square roughness of 0.093 μm, and the dynamic friction coefficient measured under the conditions of a thread of 100 mm / min and a load cell of 10 N is 2.0 or less, according to <1>. Film.
<3> The film according to <1> or <2>, wherein the haze is 10% or less.
<4> The film according to any one of <1> to <3>, wherein the polyarylate (A) has a weight average molecular weight of 80,000 or less.
<5> The film according to any one of <1> to <4>, wherein the aromatic polycarbonate (B) has a weight average molecular weight of 20,000 or more.
<6> A transparent conductive film having the film according to any one of <1> to <5>, an adhesive layer, a film base material, and an electrode layer in this order.
<7> Aromatic polycarbonate (B) having a weight average molecular weight of 45,000 or more, 0.5 parts by mass or more and 15 parts by mass or less, and an aromatic polycarbonate (B) having a weight average molecular weight of 45,000 or less, 99.5 parts by mass or less 85 A method for producing a film produced by extruding a composition containing a mass portion or more into a sheet in a molten state and pressure-bonding the composition with a pair of rolls, which is a type A type of at least one roll surface of the pair of rolls. A method for producing a film having a durometer hardness of 10 to 99.
<8> The film has a dynamic friction coefficient with a film having a root mean square roughness of 0.093 μm, and the dynamic friction coefficient measured under the conditions of a thread of 100 mm / min and a load cell of 10N is 2.0 or less. > The method for producing a film.
<9> The method for producing a film according to <7> or <8>, wherein the haze of the film is 10% or less.
<10> The method for producing a film according to any one of <7> to <9>, wherein the thickness of the film is 10 μm or more and 300 μm or less.
<11> The method for producing a film according to any one of <7> to <10>, wherein the weight average molecular weight of the polyarylate (A) is 80,000 or less.
<12> The method for producing a film according to any one of <7> to <11>, wherein the aromatic polycarbonate (B) has a weight average molecular weight of 20,000 or more.

INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a transparent film having high slidability and suppressing turbidity, and a method for producing a film.

FIG. 1 is an example of a schematic cross-sectional view showing a layer structure of a transparent conductive film. FIG. 2A is a schematic view showing a state in which the smooth polycarbonate film is slid on the smooth polycarbonate film, and FIG. 2B is a schematic view showing a state in which the smooth polycarbonate film is slid on the polycarbonate film having fine irregularities on the surface. , A schematic diagram showing a state in which a polycarbonate film having fine irregularities on the surface is slid is shown. FIG. 3 shows an example of a schematic view of the film of the present invention as viewed from the cross-sectional direction. FIG. 4 is an example of a schematic diagram showing a method for producing a film of the present invention.

The contents of the present invention will be described in detail below. In addition, in this specification, "~" is used in the meaning that the numerical values described before and after it are included as the lower limit value and the upper limit value.

The film of the present invention has a weight average molecular weight of 45,000 or more, a polyarylate (A) of 0.5 parts by mass or more and 15 parts by mass or less, and an aromatic polycarbonate (B) having a weight average molecular weight of 45,000 or less, 99.5% by mass. It is a film formed from a composition containing 85 parts by mass or less, and the thickness of the film is 10 μm or more and 300 μm or less.
With such a configuration, it is possible to provide a transparent film having high slidability and suppressing turbidity (low haze). Furthermore, the total light transmittance can be increased. That is, the film of the present invention is required to suppress adhesion between films (anti-blocking property) from the viewpoint of improving the transportability of the film and preventing winding wrinkles. Anti-blocking refers to making it easy to peel off even if the films are in close contact with each other. That is, the film formed from the composition of the present invention is required to have slidability to the extent that it does not stack. FIG. 2A is a schematic view showing a state in which the smooth polycarbonate film is slid on the smooth polycarbonate film. When the smooth polycarbonate film is placed on the smooth polycarbonate film as described above, there is no slidability. In order to impart slidability to such a polycarbonate film, it is conceivable to provide fine irregularities on the surface of the film as shown in a schematic diagram in FIG. 2 (b). When the surface of the film is provided with fine irregularities, the contact area between the films is reduced and high slidability is achieved. In FIG. 2, 21 is a polycarbonate film having a smooth surface, and 22 is a polycarbonate film having fine irregularities on the surface.
As a means for providing fine irregularities on the surface of the film as described above, a known method is already known. For example, a method of forming fine irregularities on the surface of a film by using a roll having fine irregularities on the surface can be mentioned. In this method, a molten film is passed between rolls having fine irregularities on the surface to form fine irregularities. However, in the method using a roll having fine irregularities on the surface, the shape of the fine irregularities transferred to the film surface may change due to wear of the roll due to long-term use. Further, as another method, there is also a method of adding fine particles to the film and forming fine irregularities on the surface of the film by the fine particles. However, in the method of adding fine particles, transparency may be impaired due to the difference in refractive index between the fine particles and the resin.
Therefore, in the present invention, as a new method, it is decided to form fine irregularities on the surface of the film by polymer blending. Specifically, it is presumed to be due to the following mechanism.
That is, FIG. 3 is a schematic view of the film 30 of the present invention as viewed from the cross-sectional direction, where X represents polyarylate (A) and Y represents aromatic polycarbonate (B). That is, in the film of the present invention, polyarylate (A) and aromatic polycarbonate (B) are used, and the compatibility between the two is intentionally deteriorated to produce a sea-island structure and enhance the slidability. More specifically, by adopting polyarylate (A) having a weight average molecular weight of 45,000 or more and aromatic polycarbonate (B) having a weight average molecular weight of 45,000 or less, compatibility between the two is suppressed. , Fine irregularities are formed on the surface of the film. Further, by setting the amount of polyarylate (A) to 15 parts by mass or less with respect to 99.5 parts by mass or less and 85 parts by mass or more of the aromatic polycarbonate (B), turbidity is suppressed and a highly transparent film can be obtained. It is presumed that it was done.

The composition used in the present invention includes polyarylate (A) and aromatic polycarbonate (B), as well as an antioxidant (C), a transesterification inhibitor (D), and a mold release agent (E), which are blended as necessary. ), And other components.

<Polyarylate (A)>
The composition used in the present invention contains polyarylate (A) having a weight average molecular weight of 45,000 or more. By blending the relatively high molecular weight polyarylate with the relatively low molecular weight aromatic polycarbonate (B) in this way, the compatibility between the polyarylate (A) and the aromatic polycarbonate (B) does not become too high. It is adjusted to.
The weight average molecular weight of the polyarylate (A) is preferably 50,000 or more, more preferably 55,000 or more, and even more preferably 60,000 or more. The weight average molecular weight of the polyarylate (A) is preferably 80,000 or less, more preferably 75,000 or less, further preferably 70,000 or less, and less than 70,000. Is more preferable, and 66,000 or less is even more preferable.
The weight average molecular weight of the polyarylate (A) is measured according to the description of Examples described later.
When the composition contains two or more kinds of polyarylate (A), the weight average molecular weight is the weight average molecular weight of the mixture of polyarylate (A) (hereinafter, the same applies to other physical properties, and other resin components). Is the same.).

The ultimate viscosity of the polyarylate (A) is preferably 0.49 dL / g or more, more preferably 0.55 dL / g or more, further preferably 0.59 dL / g or more, and 0. It is more preferably 62 dL / g or more. By setting the lower limit of the ultimate viscosity of the polyarylate (A) to 0.49 dL / g or more, slidability is more effectively exhibited when a film is produced. The ultimate viscosity of polyarylate (A) is preferably 0.84 dL / g or less, more preferably 0.79 dL / g or less, and even more preferably 0.74 dL / g or less. By setting the upper limit of the ultimate viscosity of the polyarylate (A) to 0.84 dL / g or less, it becomes possible to more effectively suppress the increase in haze of the film.
The ultimate viscosity of polyarylate (A) is measured according to the description of Examples described later.

The polyarylate (A) used in the present invention is preferably an aromatic polyester composed of a structural unit derived from an aromatic dicarboxylic acid and a structural unit derived from bisphenol.
Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, and 4,4'-diphenyldicarboxylic acid. , 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid and the like.
Examples of the bisphenol include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and 2,2-bis (4-hydroxy-3,). 5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfide , 4,4'-Dihydroxydiphenylketone, 4,4'-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1, Examples thereof include 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane. These compounds may be used alone or in combination of two or more.

The method for producing the polyarylate (A) is not particularly limited, and a method obtained by a known method can be used. The polyarylate (A) obtained by the interfacial polymerization method and the melt polymerization method can be preferably used.

<Aromatic Polycarbonate (B)>
The composition used in the present invention contains an aromatic polycarbonate (B) having a weight average molecular weight of 45,000 or less. By blending the aromatic polycarbonate having a relatively low molecular weight with the polyarylate having a relatively high molecular weight in this way, the compatibility between the polyarylate (A) and the aromatic polycarbonate (B) is adjusted so as not to become too high. ing.
The weight average molecular weight of the aromatic polycarbonate (B) is preferably 40,000 or less, more preferably 35,000 or less, further preferably 30,000 or less, and 25,000 or less. It is more preferable to have. Further, the lower limit of the weight average molecular weight of the aromatic polycarbonate (B) is preferably 20,000 or more.
The weight average molecular weight of the aromatic polycarbonate (B) is measured according to the description of Examples described later.

In the present invention, the ultimate viscosity of the aromatic polycarbonate (B) is preferably 0.30 dL / g or more, more preferably 0.35 dL / g or more, and 0.40 dL / g or more. More preferred. The upper limit is preferably 1.0 dL / g or less, more preferably 0.50 dL / g or less, and further preferably 0.48 dL / g or less.
The ultimate viscosity is measured by the method described in Examples described below.

The glass transition temperature (Tg) of the aromatic polycarbonate (B) is preferably 140 ° C. or higher, more preferably 145 ° C. or higher. The upper limit is preferably 160 ° C. or lower. The higher the upper limit is, the more preferable it is, but for example, even if the temperature is 155 ° C or lower, or even 150 ° C or lower, the performance requirement is sufficiently satisfied.
The glass transition temperature (Tg) of the aromatic polycarbonate (B) is raised and lowered in two cycles according to the following DSC measurement conditions, and the glass transition temperature at the time of raising the temperature in the second cycle is measured.
The intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line of the inflection point is the starting glass transition temperature, and the intersection of the straight line extending the baseline on the high temperature side to the low temperature side and the tangent line of the inflection point is The end glass transition temperature is defined, and the intermediate point between the start glass transition temperature and the end glass transition temperature is defined as the glass transition temperature (Tg). The measurement start temperature is 30 ° C., the temperature rise rate is 10 ° C./min, the ultimate temperature is 250 ° C., and the temperature decrease rate is 20 ° C./min.
As the measuring device, a differential scanning calorimeter (DSC, manufactured by Hitachi High-Tech Science Corporation, "DSC7020") can be used.

式（１）中、Ｘ^１は下記構造を表す。

Ｒ^５およびＲ^６は、アルキル基または水素原子であり、少なくとも一方がメチル基であることが好ましく、両方がメチル基であることがより好ましい。
式（Ｂ−１）は下記式（Ｂ−２）で表されることが好ましい。

The aromatic polycarbonate (B) is preferably a bisphenol A type polycarbonate. The bisphenol A type polycarbonate refers to a resin having a carbonate structural unit derived from bisphenol A and its derivative, and preferably has a structural unit represented by the following formula (B-1). * In the formula represents the bonding position with other structural units or end groups.

In formula (1), X ¹ represents the following structure.

R ⁵ and R ⁶ are alkyl groups or hydrogen atoms, preferably at least one is a methyl group, and more preferably both are methyl groups.
The formula (B-1) is preferably represented by the following formula (B-2).

The content of the structural unit represented by the formula (B-1) in the bisphenol A type polycarbonate is preferably 70 mol% or more, preferably 80 mol% or more, of all the structural units excluding both ends. More preferably, it is 90 mol% or more. The upper limit value is not particularly limited, and 100 mol% may be a structural unit represented by the formula (B-1). As the bisphenol A type polycarbonate, a resin in which substantially all the structural units excluding both ends are composed of the structural units of the formula (B-1) can be mentioned. Here, substantially all the constituent units excluding both ends mean that the total constituent units excluding both ends are 99.0 mol% or more, preferably 99.5 mol% or more, and 99.9 mol. % Or more is more preferable.
The bisphenol A type polycarbonate may have a structural unit other than the carbonate structural unit derived from bisphenol A and its derivative. Examples of the dihydroxy compound constituting such another structural unit include the aromatic dihydroxy compound described in paragraph 0014 of JP-A-2018-154819, and the contents thereof are incorporated in the present specification. ..

The method for producing the bisphenol A type polycarbonate is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

<Blend of polyarylate (A) and aromatic polycarbonate (B)>
The composition used in the present invention contains 0.5 parts by mass or more of polyarylate (A) and 15 parts by mass or less, and 99.5 parts by mass or less of aromatic polycarbonate (B) and 85 parts by mass or more. With such a blend ratio, it becomes possible to form fine irregularities on the surface of the film.
In the composition used in the present invention, the blend ratio of polyarylate (A) and aromatic polycarbonate (B) is more preferably 3 to 15 parts by mass: 97 to 85 parts by mass.
The composition used in the present invention also preferably contains polyarylate (A) in a proportion of 0.5 to 15% by mass in the composition. The composition used in the present invention also preferably contains aromatic polycarbonate (B) in a proportion of 85 to 99.5% by mass in the composition. However, the total of polyarylate (A) and aromatic polycarbonate (B) does not exceed 100% by mass.
As one embodiment of the composition used in the present invention, the total content of the polyarylate (A) and the aromatic polycarbonate (B) is 95% by mass or more of the composition, and further, 97% by mass of the composition. Examples of the above-mentioned aspects, particularly those in which the composition is 98% by mass or more.
The composition used in the present invention may contain only one type of polyarylate (A), or may contain two or more types. When two or more types are included, the total is preferably in the above range.
The composition used in the present invention may contain only one type of aromatic polycarbonate (B), or may contain two or more types. When two or more types are included, the total is preferably in the above range.

The difference (Mwa-Mwb) between the weight average molecular weight of the polyarylate (A) and the weight average molecular weight of the aromatic polycarbonate (B) is preferably 10,000 or more, and more preferably 20,000 or more. It is preferable, and more preferably 30,000 or more. The difference (Mwa-Mwb) is preferably 60,000 or less, and more preferably 50,000 or less.

（式（１）中、Ｒ^１およびＲ^２はそれぞれ独立に、炭素原子数１〜３０のアルキル基または炭素原子数６〜３０のアリール基を表す。）

（式（２）中、Ｒ^３〜Ｒ^７は、それぞれ独立に、水素原子、炭素原子数６〜２０のアリール基または炭素原子数１〜２０のアルキル基を表す。）<Antioxidant (C)>
The composition used in the present invention preferably contains an antioxidant.
Examples of the antioxidant include a phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, and the like, and a phosphorus-based antioxidant and a phenol-based antioxidant (more preferably hinder). At least one of (dophenol-based antioxidants) is preferable, and phosphorus-based antioxidants are particularly preferable. It is also preferable to use both in combination.
As the phosphorus-based antioxidant, a phosphite compound represented by the following formula (1) or (2) is preferable.

(In the formula (1), R ¹ and R ² independently represent an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.)

(In the formula (2), R ^{3 to} R ⁷ independently represent a hydrogen atom, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.)

In the above formula (1), the ^{alkyl groups represented by R 1} and R ² are preferably linear or branched alkyl groups having 1 to 10 carbon atoms, respectively. When R ¹ and R ² are aryl groups, an aryl group represented by any of the following general formulas (1-a), (1-b), or (1-c) is preferable.

（式（１−ａ）中、Ｒ^Ａは、それぞれ独立に、炭素原子数１〜１０のアルキル基を表す。式（１−ｂ）中、Ｒ^Ｂは、それぞれ独立に、炭素原子数１〜１０のアルキル基を表す。）

(In the formula (1-a), ^{R A} is independently, in represents an alkyl group having 1 to 10 carbon atoms. Formula (1-b), ^{R B} are each independently, 1 to carbon atoms Represents an alkyl group of 10.)

Examples of the phenolic antioxidant include hindered phenolic antioxidants. As the phenolic antioxidant, the phenolic antioxidant described in paragraph 0041 of JP-A-2019-002023 and the phenol-based antioxidant described in paragraphs 0033 to 0034 of JP-A-2019-0506035 are preferably used. These contents are incorporated herein by reference.
In addition, the details of the antioxidant can be referred to in paragraphs 0057 to 0061 of JP-A-2017-031313, and these contents are incorporated in the present specification.

When contained, the content of the antioxidant in the composition is preferably 0.005 part by mass or more, more preferably 0.005 part by mass or more, based on 100 parts by mass of the total of polyarylate (A) and aromatic polycarbonate (B). Is 0.007 parts by mass or more, more preferably 0.01 parts by mass or more. The upper limit of the content of the antioxidant is preferably 4 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the total of polyarylate (A) and aromatic polycarbonate (B). It is preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less.
By setting the content of the antioxidant to 0.005 parts by mass or more, the transparency of the film tends to be further improved. Further, by setting the content of the antioxidant to 4 parts by mass or less, the moist heat stability tends to be improved.
When a phosphorus-based antioxidant and a phenol-based antioxidant (preferably a hindered phenol-based antioxidant) are used in combination as the antioxidant, the contents thereof are polyarylate (A) and aromatic polycarbonate (preferably hindered phenolic antioxidant). It is preferable that the phosphorus-based antioxidant is contained in the range of 0.001 to 0.2 parts by mass and the phenol-based antioxidant is contained in the range of 0.001 to 0.2 parts by mass with respect to a total of 100 parts by mass of B). ..
Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

<Transesterification inhibitor (D)>
The composition used in the present invention preferably contains a transesterification inhibitor.
Examples of the transesterification inhibitor include a phosphorus-based transesterification inhibitor and a sulfur-based transesterification inhibitor.
Examples of the phosphorus-based ester exchange inhibitor include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, and esters thereof.
As the transesterification inhibitor, the descriptions in paragraphs 0035 to 0039 of International Publication No. 2015/190162, paragraphs 0037 of JP-A-2019-002023, and paragraphs 0041 of JP-A-2018-199745 can be referred to. Is incorporated herein.

The content of the transesterification inhibitor in the composition, when contained, is preferably 0.001 part by mass or more with respect to 100 parts by mass in total of the polyarylate (A) and the aromatic polycarbonate (B). It is preferably 0.005 parts by mass or more, and more preferably 0.007 parts by mass or more. The upper limit of the content of the transesterification inhibitor is preferably 1.0 part by mass or less, more preferably 0.5 part by mass or less, and further preferably 0.3 part by mass with respect to 100 parts by mass of the thermoplastic resin. Parts or less, more preferably 0.1 parts by mass or less.
The transesterification inhibitor may contain only one type, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

<Release agent (E)>
The composition used in the present invention preferably contains a mold release agent.
The release agent is at least one selected from the group consisting of an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, and a polysiloxane-based silicone oil. Compounds can be mentioned, and esters of aliphatic carboxylic acids and alcohols are preferable.
Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (mixture containing myricyl palmitate as the main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, and glycerin monostearate. , Glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.
In addition, as the release agent, the release agent described in paragraph 0032 of JP-A-2017-226848 and paragraph 0056 of JP-A-2018-199745 can be used, and the contents thereof are incorporated in the present specification. ..

When contained, the content of the release agent in the composition is preferably 0.001 part by mass or more, more preferably 0, based on 100 parts by mass of the total of polyarylate (A) and aromatic polycarbonate (B). It is .005 parts by mass or more, preferably 2 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.5 parts by mass or less.
Only one type of release agent may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

<Other ingredients>
In addition to the above, the above composition includes other thermoplastic resins, heat stabilizers, flame retardants, flame retardants, ultraviolet absorbers, colorants, antistatic agents, fluorescent whitening agents, antifogging agents, and fluidity improving agents. It may contain an agent, a plasticizer, a dispersant, an antibacterial agent, an antiblocking agent, an impact improving agent, a sliding improving agent, a hue improving agent, an acid trapping agent and the like. One type of these components may be used, or two or more types may be used in combination.
When contained, the total amount of the other components is preferably 0.001 to 5% by mass, more preferably 0.001 to 2% by mass, and 0.01 to 1% by mass. Is more preferable.

<Film characteristics>
The film of the present invention has a thickness of 10 μm or more and 300 μm or less. By setting the thickness to 300 μm or less, a transparent film can be obtained. If it is less than 10 μm, there are too many polyarylate (A) regions (islands) formed on the surface, and the haze becomes high.
The thickness of the film of the present invention is preferably 20 μm or more, and may be 25 μm or more. Further, it is preferably 250 μm or less, more preferably 200 μm or less, further preferably 150 μm or less, further preferably 100 μm or less, further preferably 80 μm or less, and even more preferably 60 μm or less. It is even more preferable to have.

The film of the present invention also preferably has a coefficient of kinetic friction with a film having a root mean square roughness of 0.093 μm of 2.0 or less, and more preferably 1.8 or less. The lower limit is, for example, 0.1 or more.
The coefficient of kinetic friction is a value measured under the conditions of a thread of 100 mm / min and a load cell of 10N, and more specifically, it is measured by the method described in Examples described later.

The film of the present invention has a total light transmittance of preferably 80% or more, more preferably 85% or more, and even more preferably 88% or more under the condition of a D65 light source 10 ° field of view. Ideally, the upper limit of the light transmittance is 100%, but even if it is 94% or less, the required performance is sufficiently satisfied.
The total light transmittance is measured by the method described in Examples described later.

The film of the present invention preferably has a haze of 10% or less, more preferably 8% or less, further preferably 6% or less, and even more preferably 5% or less. The ideal lower limit is 0%, but even if it is 0.1% or more, it is a practical level.
Haze is measured by the method described in Examples described below.

<Use>
The film of the present invention is preferably used as a masking film. More preferably, it is used as a protective film for a transparent conductive film. In particular, it is preferably used as a transparent conductive film having the film of the present invention, an adhesive layer, a film base material, and an electrode layer in this order.
Further, the transparent conductive film is preferably used as a transparent conductive film used for a film sensor of a touch panel, electronic paper, a dye-sensitized solar cell, a touch sensor, and the like.
In addition to the above, the film of the present invention is preferably used as a film for applications that require high slidability and transparency.

<Film manufacturing method>
The method for producing a film of the present invention is an aromatic polycarbonate (B) 99 having a weight average molecular weight of 45,000 or more, 0.5 parts by mass or more and 15 parts by mass or less, and a weight average molecular weight of 45,000 or less. A method for producing a film produced by extruding a composition containing 0.5 parts by mass or less and 85 parts by mass or more into a sheet in a molten state and pressure-bonding it with a pair of rolls, wherein at least one roll of the pair of rolls is produced. The surface is characterized by having a type A durometer hardness of 10 to 99.
With such a configuration, a film in which the islands of polyarylate (A) are formed in the aromatic polycarbonate (B) can be obtained.
Hereinafter, the details of the production method of the present invention will be described.
FIG. 4 is an example of a schematic diagram showing a method for producing a film of the present invention. In the production method of the present invention, for example, as shown in FIG. 4, the composition 41 containing the polyarylate (A) and the aromatic polycarbonate (B) is extruded from the die 42 in a molten state into a sheet. The melted and sheet-like composition 41 is pressure-bonded by the pair of rolls 43 as it passes between the pair of rolls 43 (the first roll 43a and the second roll 43b). At this time, for at least one of the first roll 43a and the second roll 43b, a roll having a type A durometer hardness of 10 to 99 on the roll surface is used.
In FIG. 4, the first roll 43a is a roll having a surface durometer hardness of 10 to 99. That is, as the first roll 43a, a roll having a soft surface is used. By using a roll having a surface durometer hardness of 10 to 99, a portion of the polyarylate (A) that is not compatible with the aromatic polycarbonate (B) appears on the surface of the film and is fine on the surface of the film. Form unevenness. As a result, high slidability can be achieved. The durometer hardness of the roll surface is preferably 30 or more, more preferably 50 or more, and more preferably 80 or less, more preferably 75 or less. By setting the range in such a range, the roll has an appropriate softness. Examples of rolls having a surface durometer hardness of 10 to 99 include mirrored rubber rolls.
The temperature of the roll having a surface durometer hardness of 10 to 99 is preferably 30 to 90 ° C, more preferably 40 to 70 ° C.

In FIG. 4, the composition passes between the pair of rolls 43 (first roll 43a and second roll 43b) and then further passes through the transport roll 44.
Rolls other than rolls having a surface durometer hardness of 10 to 99, for example, in FIG. 4, the second roll 43b and the transport roll 44 include metal rolls. The metal roll reaches a durometer hardness of 100, which is the measurement limit. Examples of the metal roll include a mirror rigid body roll and a metal elastic roll. The surface temperature of rolls other than rolls having a surface durometer hardness of 10 to 99 is preferably 70 to 170 ° C, more preferably 100 to 160 ° C.

In the present invention, the durometer hardness of at least one roll surface of the first roll and the second roll may be in the above range, but the surfaces of both the first roll and the second roll may satisfy the above durometer hardness. .. In this case, desired fine irregularities are formed on the surface of the film.

The film after passing between the pair of rolls 43 (first roll 43a and second roll 43b) is cooled while passing through the transport roll 44, or by passing through a cooling zone or a cooling roll. To. After cooling, it may be further wound up. That is, in the present invention, a wound body having the core material and the film of the present invention wound around the core material can be obtained.
The film obtained by the above film manufacturing method preferably has a film thickness of 10 μm or more and 300 μm or less. In addition, the details of the film obtained by the method for producing the film of the present invention are the same as those of the above-mentioned film of the present invention.
Further, a transparent conductive film can also be produced by laminating the film of the present invention obtained above, the pressure-sensitive adhesive layer, the film base material, and the electrode layer.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Raw materials>
・ Polyarylate (A)
(A1) Aromatic polyarylate obtained by interfacial polymerization method (manufactured by Unitika Ltd., U-powder D type, weight average molecular weight 63,000, ultimate viscosity 0.65 dL / g)
(A2) Aromatic polyarylate obtained by interfacial polymerization method (manufactured by Unitika Ltd., U-powder L type, weight average molecular weight 40,800, ultimate viscosity 0.48 dL / g)

・ Polycarbonate (B)
(B1) Aromatic polycarbonate obtained by an interfacial polymerization method using bisphenol A as a starting material (manufactured by Mitsubishi Engineering Plastics, E-2000F, weight average molecular weight 52,800, viscosity average molecular weight 27,000, ultimate viscosity 0. 54 dL / g, Tg 151 ° C.)
(B2) Aromatic polycarbonate obtained by an interfacial polymerization method using bisphenol A as a starting material (manufactured by Mitsubishi Engineering Plastics Co., Ltd., S-3000F, weight average molecular weight 41,300, viscosity average molecular weight 21,000, ultimate viscosity 0. 43 dL / g, Tg 148 ° C.)

・ Antioxidant (C)
(C1) Tris (2,4-di-tert-butylphenyl) phosphite (phosphorus antioxidant, manufactured by ADEKA Corporation, ADEKA STAB 2112)
(C2) Tetrakis [3- (3', 5'-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol (hindard phenolic antioxidant, ADEKA Corporation ADEKA STAB AO-60)

-Transesterification inhibitor (D)
(D1) Octadecylphosphite (manufactured by ADEKA Corporation, AX-71)

・ Release agent (E)
(E1) Glycerin monostearate (manufactured by RIKEN Vitamin Co., Ltd., Rikemar S-100A)

<Measurement method of weight average molecular weight>
The measurement of the weight average molecular weight (Mw) of the polyarylate (A) and the aromatic polycarbonate (B) by gel permeation chromatography was specifically carried out as follows.
An LC-20AD system (manufactured by Shimadzu Corporation) was used as a gel permeation chromatography apparatus, and LF-804 (manufactured by Shodex) was connected and used as a column. The column temperature was 40 ° C. As the detector, an RI detector of RID-10A (manufactured by Shimadzu Corporation) was used. Chloroform was used as the eluent, and the calibration curve was prepared using standard polystyrene manufactured by Tosoh Corporation.
If the gel permeation chromatography device, column, or detector is difficult to obtain, the measurement is performed using another device having the same performance.

<Measurement method of extreme viscosity>
The ultimate viscosity [η] (unit: dL / g) of the resin was measured using methylene chloride as a solvent. The measurement temperature was 25 ° C. _{The specific viscosity [η sp} ] at each solution concentration [C] (g / dL) was measured with an Ubbelohde viscometer. The ultimate viscosity was calculated from the obtained specific viscosity values and concentrations by the following formula.

Examples 1-5, Comparative Examples 1-3
<Manufacturing of resin pellets>
Each of the above-mentioned components was weighed so as to have the content shown in Table 1 or Table 2 (the content of each component is a mass part). Then, after mixing with a tumbler for 15 minutes, melt-kneading was performed at a cylinder temperature of 300 ° C. by a twin-screw extruder with a vent having a screw diameter of 32 mm (“TEX30α” manufactured by Japan Steel Works, Ltd.), and pellets were obtained by strand cutting.

<Manufacturing of film>
Using the obtained pellets, a film was produced by the following method.
The pellets obtained above were subjected to a T-die melt extruder consisting of a twin-screw extruder (manufactured by Japan Steel Works, Ltd., "TEX30α") with a barrel diameter of 32 mm and a screw L / D = 31.5. The film was extruded in a molten state under the conditions of a discharge rate of 10 kg / h and a screw rotation speed of 63 rpm, crimped with a first roll and a second roll, and then cooled and solidified to prepare a film. The cylinder / die head temperature was 280 ° C.
The final film thickness was adjusted by changing the roll speeds of the first roll and the second roll so as to have the values shown in Table 1 or Table 2.

Details of the first roll and the second roll used are as follows.
-First roll: Silicone rubber roll (IT68S-MCG) manufactured by Mochida Shoko Co., Ltd.
Dimensions Diameter: Outer diameter 260 mm x Width 600 mm
Durometer hardness of roll surface (type A type): 70
Roll temperature: 50 ° C
-Second roll: JSW, metal rigid body roll (surface: hard chrome treatment)
Core metal diameter: outer diameter 250 mm x width 600 mm
Durometer hardness of roll surface (type A type): Roll temperature reached the measurement limit of 100: 130 ° C

<Measurement of dynamic friction coefficient>
The dynamic friction coefficient of the obtained film was measured using a friction coefficient measuring machine. Specifically, the bisphenol A type polycarbonate film having a root mean square roughness of 0.093 μm and the obtained film were placed so as to overlap each other, and the threads were placed on the polycarbonate film under the conditions of 100 mm / min and a load cell of 10N. The film was slid and the dynamic friction coefficient was measured.
A friction coefficient measuring machine manufactured by Toyo Seiki Seisakusho Co., Ltd. (“friction tester”) was used.
As the bisphenol A type polycarbonate film having a root mean square roughness of 0.093 μm, a bisphenol A type polycarbonate film with a single-sided masking film (manufactured by Mitsubishi Gas Chemical Company, FE-2000, 100 μm thick) was used. In this embodiment, the unmasked side of the bisphenol A type polycarbonate film with a single-sided masking film is turned to the upper surface, and fixed to the right end of the test table with tape so that the long axis coincides with the long axis of the test table, 63 mm × The obtained film was attached to the underside of a 63 mm, 200 g thread, and the polycarbonate film and the obtained film were placed so as to overlap each other. As described above, the obtained film was slid and the dynamic friction coefficient was measured. In the comparative example, the film did not slip and the coefficient of dynamic friction could not be measured.

<Measurement of root mean square roughness Rq>
The surface roughness of the bisphenol A type polycarbonate film used for measuring the dynamic friction coefficient was specifically measured by the following method using a surface roughness measuring machine. The detector of the device was made "integrated", and a "standard drive unit" was attached to the drive unit of the detector. The film was fixed in the shape of a glass plate with tape, and the surface roughness measuring machine was installed on it so that it would not move. After that, the measurement was performed under the standard "JIS B 0601-2001", the measurement speed was 0.5 mm / s, the cutoff value was 0.8, and the number of sections was 3, and the root mean square roughness Rq was measured. The root mean square roughness Rq was measured three times at different locations of the film and used as the average value.
As the measuring machine, "SJ-210" manufactured by Mitutoyo Co., Ltd. was used.

<Measurement of total light transmittance and haze>
Using a haze meter, the total light transmittance (%) and haze (%) of the obtained film were measured under the condition of a D65 light source 10 ° field of view.
As the haze meter, "HM-150" manufactured by Murakami Color Technology Research Institute was used.

The results are shown in Tables 1 and 2 below.

10 Transparent conductive film 11 Electrode layer (transparent conductive film)
12 Base film 13 Adhesive layer 14 Protective film 21 Polycarbonate film with a smooth surface 22 Polycarbonate film with fine irregularities on the surface 30 Film 41 Composition 42 Dice 43 Pair of rolls 44 Conveying rolls

Claims (11)

Aromatic polycarbonate (B) having a weight average molecular weight of 45,000 or more and 0.5 parts by mass or more and 15 parts by mass or less and an aromatic polycarbonate (B) having a weight average molecular weight of 45,000 or less 99.5 parts by mass or less and 85 parts by mass or more. A film formed from a composition containing
The coefficient of dynamic friction with a film having a root mean square roughness of 0.093 μm, and the coefficient of dynamic friction measured under the conditions of a thread of 100 mm / min and a load cell of 10 N is 2.0 or less.
A film having a thickness of 10 μm or more and 300 μm or less. The film according to claim 1, wherein the haze is 10% or less. The film according to claim 1 or 2 , wherein the polyarylate (A) has a weight average molecular weight of 80,000 or less. The film according to any one of claims 1 to 3 , wherein the aromatic polycarbonate (B) has a weight average molecular weight of 20,000 or more. A transparent conductive film having the film according to any one of claims 1 to 4 and an adhesive layer, a film base material, and an electrode layer in this order. Aromatic polycarbonate (B) having a weight average molecular weight of 45,000 or more, 0.5 parts by mass or more and 15 parts by mass or less, and an aromatic polycarbonate (B) having a weight average molecular weight of 45,000 or less, 99.5 parts by mass or less and 85 parts by mass or more. A method for producing a film produced by extruding a composition containing the above into a sheet in a molten state and crimping it with a pair of rolls, wherein the type A durometer hardness of the surface of at least one roll of the pair of rolls is high. A method for producing a film, which is 10 to 99. The film has a coefficient of dynamic friction with a film having a root mean square roughness of 0.093 μm, and the coefficient of dynamic friction measured under the conditions of a thread of 100 mm / min and a load cell of 10 N is 2.0 or less, according to claim 6 . Film manufacturing method. The method for producing a film according to claim 6 or 7 , wherein the haze of the film is 10% or less. The method for producing a film according to any one of claims 6 to 8 , wherein the thickness of the film is 10 μm or more and 300 μm or less. The method for producing a film according to any one of claims 6 to 9 , wherein the polyarylate (A) has a weight average molecular weight of 80,000 or less. The method for producing a film according to any one of claims 6 to 10 , wherein the aromatic polycarbonate (B) has a weight average molecular weight of 20,000 or more.

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