JP2008174694A - Thermoplastic resin film rolled web - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical film rolled web which causes no planar failure even when keeping a thermoplastic resin film for a long term and is excellent in productivity. <P>SOLUTION: The thermoplastic resin film rolled web comprises a winding core and a thermoplastic resin film comprising a lactone ring-containing polymer and wound on the winding core, wherein elastic modulus of the winding core is within a range of 10-40 GPa and the thermoplastic resin film has ≥1,350 mm film width and 20-80 μm film thickness. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin film raw material containing a lactone ring-containing polymer, and particularly used for a protective film for a polarizing plate, a retardation film, a viewing angle widening film and a plasma display used for a liquid crystal display device and the like. The present invention relates to a raw material for a thermoplastic resin film that can be used for various functional films such as an antireflection film and various functional films used in an organic EL display.

  In recent years, a large screen of a flat panel display represented by a liquid crystal television has been developed. Along with this, there is an increasing demand for larger-sized optical films for flat panel displays. In particular, demands for thinning, widening, and high quality of the protective film of the polarizing plate for liquid crystal display devices have become very strong. Here, the protective film for polarizing plates is usually wound around a core to form a film original, which is stored and transported.

  Along with the increase in the screen size of liquid crystal display devices, the original film becomes wider and longer, and the load on the original film tends to increase. It becomes easy. In addition, when installed on the outermost surface of the liquid crystal display, clear hard processing, anti-glare processing and anti-reflection processing are applied to the surface of the film. When these processes are performed, if there is a planar failure of the film, uneven coating or vapor deposition occurs, which causes a significant deterioration in product yield. Up to now, it has been known that the occurrence of such a film failure can be reduced by lowering the dynamic friction coefficient of the base surface or adjusting the height of annealing (embossing) on both sides. However, since a thermoplastic resin film containing a lactone ring-containing polymer has a high surface strength and a high mechanical strength, the problem of surface failure is serious when stored and transported in a raw film, and a solution is eagerly desired. It had been.

International Publication WO2006 / 025445A1 JP 2005-22766 A

  Therefore, the present invention has been made in view of the above-mentioned problems, and a thermoplastic resin film containing a lactone ring-containing polymer (hereinafter sometimes simply referred to as “thermoplastic resin film”) is stored for a long period of time. However, the present invention provides an optical film raw material excellent in productivity that does not cause a planar failure, and exhibits its effect particularly in a wide and thin optical film having a width of 1350 mm or more.

  As a result of our study, we found that it is effective to set the elastic modulus of the core of the thermoplastic resin film which is wide and long to be in a specific range in order to solve the above-mentioned failure. It was.

That is, the above object of the present invention is achieved by the following means.
(1) It has a core and a thermoplastic resin film containing a lactone ring-containing polymer wound around the core, and the core has an elastic modulus in the range of 10 GPa to 40 GPa, and the thermoplastic The resin film is a thermoplastic resin film raw material having a film width of 1350 mm or more and a film thickness of 20 μm to 80 μm.
(2) The thermoplastic resin according to (1), wherein the circumferential length of the central portion in the width direction is longer in the range of 0.5 mm to 10 mm than the circumferential length of both end portions in the width direction. Original film.
(3) The thermoplastic resin film raw material according to (1) or (2), wherein the elastic modulus of the core is in the range of 10 GPa to 20 GPa.

  According to the present invention, even when the thermoplastic resin film is stored for a long period of time, it is difficult to cause a surface failure of the original film of the thermoplastic resin film.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, a “group” such as an alkyl group may or may not have a substituent unless otherwise specified. Further, in the case of a group having a limited number of carbon atoms, the number of carbon atoms means a number including the number of carbon atoms that the substituent has.

  The original thermoplastic resin film containing the lactone ring-containing polymer of the present invention is a thermoplastic resin film containing a lactone ring-containing polymer on the outer peripheral surface of the core with the core (cylindrical core) as an axis. It is configured by winding.

  The winding core used in the present invention is a so-called FWP core made of fiber reinforced resin by a filler-winding (FW) method. The FW method is a method in which a reinforcing fiber such as glass, carbon, or aramid with a resin attached to the outer periphery of a core metal is wound, the resin is heated and cured in a curing furnace, and then the core metal is pulled out. A core is produced. This FWP core is excellent in accuracy, strength and lightness.

   FIG. 1 shows an example of a fiber reinforced resin-made core by the FW method in the present invention. As shown in FIG. 1, the core body 10 made of this FWP core includes a base material layer 12 formed by winding inorganic fibers such as glass and carbon impregnated with resin (prepreg), glass, carbon, and the like. The first winding layer 14 obtained by winding fibers 13 formed of a synthetic fiber such as inorganic fiber or nylon at a predetermined inclination angle is different from the crossing angle of the fibers 13 forming the first winding layer 14. A second winding layer 15 formed by winding fibers 13 at an intersecting angle, and a coating layer 16 are included.

   FIG. 1 shows a state where the cored bar 11 is inserted for the sake of explanation. The molded core 11 is removed after the core body 10 is completed, and is not a constituent element of the core in the present invention.

  The base material layer 12 is formed by winding a prepreg-made glass, inorganic fiber such as carbon, etc. in two layers around a cored core 11 as a central object. This is for smoothing the inner surface of the core body 10 and increasing the accuracy of the inner diameter. In this case, the cored bar 11 is of course close to a perfect circle, and a release agent is applied to the surface as necessary. The release agent is applied so that the work can be easily performed when the formed core 11 is removed from the core body 10 after completion.

  Further, in order to wind the base material layer 12 around the formed core metal 11, the cloth layer is arranged so as to be inclined with respect to the formed core metal 11. The reason is that when the first winding layer 14 is wound on the base material layer 12, the base material layer 12 is not unraveled during the winding.

  The base material layer 12 is intended to facilitate and ensure the subsequent winding operation of the first winding layer 14 and the second winding layer 15 rather than ensuring the strength after the core body 10 is completed. Yes, for example, when the diameter of the core body 10 itself is small, it may be performed once. On the other hand, when the diameter of the core body 10 is large, it may be wound three or more times.

  The first winding layer 14 is formed by sequentially winding (winding) the fibers 13 on the upper surface of the base material layer 12 that is rotated together with the molding core 11. The fibers 13 forming the first winding layer 14 are formed of inorganic fibers such as glass and carbon, or synthetic fibers such as nylon and aramid, and are prepreg before being wound. Of course, this winding is performed in a state where a predetermined tension is applied to each fiber 13. The inclination angle of the fibers 13 forming the first winding layer 14 with respect to the axis of the core 11 is 45 degrees in the case of FIG. The forming core 11 is wound at a predetermined gap from one end side to the other end side at this inclination angle, and when reaching the other end, similar winding operations are sequentially performed at a reverse inclination angle (135 degrees). To go. The layer formed by such winding (one turn of the fiber 13 is one layer) is, for example, six layers. Since the first winding layer 14 is a main tar portion that gives the strength of the core, etc., the number of layers formed by the fibers 13 may be further increased, but when forming a core having a small diameter. May be less.

  The second winding layer 15 is basically formed by the same method as that for forming the first winding layer 14, but differs in the inclination angle and the number of turns with respect to the molded core 11. That is, the inclination angle of the fibers 13 forming the second winding layer 15 is 75 degrees in FIG. 1, and the number of windings is, for example, 3 layers. At this inclination angle, similarly to the case of the first winding layer 14 described above, the molded cored bar 11 is wound with a predetermined gap from one end side to the other end side. The same winding operation is sequentially performed at an angle (105 degrees). Thus, it is preferable to change the inclination angle of the fibers 13 as compared with the case of the first winding layer 14 so as to fill in the gaps of the fibers 13 forming the first winding layer 14. The second winding layer 15 is for ensuring the smoothness of the surface of the finished core, rather than ensuring the strength of the core.

  For example, a coating layer 16 made of an epoxy resin having a thickness of 0.3 to 0.4 mm is applied to the outermost layer of the core, and the surface of the coating layer 16 is mechanically polished to finish the surface. Abrasive surface.

 In the core body 10 formed as described above, before the surface finish, that is, after each layer and each film is cured, the formed core metal 11 is extracted, and then the core body 10 is The surface finish is made, and unnecessary ends of the core body 10 are cut into a finished product.

  The extraction of the molded core 11 can be performed even better if a mold release agent is applied to the molded core 11 and the end of each layer is locked to the locking member. The molding core 11 is forcibly pulled out by a machine.

In general, in a thermoplastic resin film containing a lactone ring-containing polymer, before winding the formed long film around a winding core, the back and front surfaces of the wound films are completely face to face. In order to prevent adhesion, knurling is performed on the end portion of the film processing width by embossing or the like to place a pattern on a constant width composed of minute continuous irregularities. As a result, the wound films are completely or partially adhered to each other, affecting the surface condition of the film and preventing the failure. It is preferable to apply processing.
However, when a thermoplastic resin film containing a wide, thin lactone ring-containing polymer is wound on a long roll for storage and transportation, a surface failure occurs in the wound film only by knurling. End up.

  In the present invention, in the thermoplastic resin film raw material containing a lactone ring-containing polymer having a film width of 1350 mm or more and a film thickness of 25 μm to 80 μm, the elastic modulus of the core used for the film raw material is 10 GPa to When it is 40 GPa, the occurrence of planar faults is reduced, and it is more preferably 10 GPa to 20 GPa.

  If the elastic modulus of the core is too high, surface failure will occur mainly in the vicinity of the core, while if the elastic modulus of the core is too low, surface failure will tend to occur around the outside of the roll. there were. This is because there is a balance between the effect of the force concentrated on the hard core and the force concentrated near the core and the effect of the force concentrated on the outside of the roll due to the distortion of the core. This is thought to be because the preferable properties of the elastic modulus of the core are determined by overlapping the characteristics of the film.

  The effect of the present invention is significant when applied to a thermoplastic resin film containing a lactone ring-containing polymer having a film width of 1350 mm or more. Further, the longer the film length wound on the roll, the more remarkable the effect is obtained, and the film length wound on the roll tends to be more advantageous when the film length is 500 m or more. Furthermore, it is preferable to apply a knurling process for embossing or the like on both ends of the thermoplastic resin film containing the lactone ring-containing polymer of the present invention so as to give a pattern to a certain width composed of minute continuous irregularities.

  In the present invention, the elastic modulus of the core is obtained from the load-deflection ratio when the core to be measured is supported so that the distance between fulcrums is 1250 mm and a load is applied to the center of the core. To do.

  The method for adjusting the elastic modulus is not particularly limited, but for example, the type of the reinforcing fiber used in FWP is increased by using a large amount of carbon fiber or aramid fiber or increasing the amount of winding. Therefore, adjustment can be made as appropriate. Also, the selection of the base prepreg resin (matrix resin) (polyester resin, epoxy resin) and the selection of the core surface resin (thermoplastic resin, epoxy resin, epoxy conductive resin, acrylic paint, etc.) are appropriately combined. It is possible to make adjustments. When these are appropriately combined, the above elastic modulus range can be easily adjusted.

In the present invention, the circumferential length of the central portion is preferably longer in the range of 0.5 mm to 10 mm than the average of the circumferential lengths of both ends of the winding core. 0 mm is more preferable, and 1.0 mm to 3.0 mm is more preferable.
The core used in the present invention may be provided with a flat portion at the center. By adopting such a configuration, there is an advantage that planar failure is further reduced. Moreover, the flat part of a center part can be formed by grind | polishing a core. The ratio of the flat portion at the center is preferably 20 to 50%.

  Hereinafter, the thermoplastic resin film containing the lactone ring-containing polymer of the present invention will be described in detail, but the scope of the present invention is not limited to these explanations, and the gist of the present invention other than the following examples It can change suitably in the range which does not impair.

<Lactone ring-containing polymer>
The thermoplastic resin film containing the lactone ring-containing polymer used in the present invention has a film width of 1350 mm or more, preferably 1500 mm or more. Moreover, although the film thickness of this film is 20 micrometers-80 micrometers, Preferably it is 20-65 micrometers.
The thermoplastic resin film containing a lactone ring-containing polymer used in the present invention contains a lactone ring-containing polymer as a main component (a thermoplastic resin film (A) having a lactone ring-containing polymer) or a lactone ring-containing polymer. What contains a polymer and another thermoplastic resin (a thermoplastic resin film (B) having a lactone ring-containing polymer is preferred.

The lactone ring-containing polymer preferably has a lactone ring structure represented by the following formula (1).
Formula (1)

［式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ、水素原子または炭素原子数１〜２０の有機残基を表し、有機残基は酸素原子を含有していてもよい］
ここで、炭素原子数１〜２０の有機残基は、メチル基、エチル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基などが好ましい。

[Wherein R ¹ , R ² and R ³ each represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue may contain an oxygen atom]
Here, the organic residue having 1 to 20 carbon atoms is preferably a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group, or the like.

  The content of the lactone ring structure represented by the above formula (1) in the structure of the lactone ring-containing polymer is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 10 to 60% by mass. Especially preferably, it is 10-50 mass%. By setting the content ratio of the lactone ring structure to 5% by mass or more, the heat resistance, solvent resistance and surface hardness of the obtained polymer tend to be improved, and the content ratio of the lactone ring structure is 90% by mass or less. By doing so, the moldability of the obtained polymer tends to be improved.

The lactone ring-containing polymer may have a structure other than the lactone ring structure represented by the above formula (1). Examples of the structure other than the lactone ring structure represented by the above formula (1) include, for example, (meth) acrylic acid esters, hydroxy group-containing monomers, A polymer structural unit (repeating structural unit) formed by polymerizing at least one monomer selected from the group consisting of a saturated carboxylic acid and a monomer represented by the following formula (2) is preferred.
Formula (2)

［式中、Ｒ⁴は水素原子またはメチル基を表し、Ｘは水素原子、炭素原子数１〜２０のアルキル基、アリール基、−〇Ａｃ基、−ＣＮ基、−ＣＯ−Ｒ⁵基、または−ＣＯ−Ｏ−Ｒ⁶基を表し、Ａｃはアセチル基を表し、Ｒ⁵およびＲ⁶は水素原子または炭素原子数１〜２０の有機残基を表す。］
ここで、Ｘは、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、シクロヘキシル基、ベンジル基などが好ましい。

Wherein, R ⁴ represents a hydrogen atom or a methyl group, X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, -〇_Ac group, -CN group, -CO-R ⁵ group, or —CO—O—R ⁶ group, Ac represents an acetyl group, R ⁵ and R ⁶ represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms. ]
Here, X is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, cyclohexyl group, benzyl group or the like.

  The content ratio of the structure other than the lactone ring structure represented by the above formula (1) in the structure of the lactone ring-containing polymer is a polymer structural unit (repeated structural unit) formed by polymerizing (meth) acrylic acid ester. In this case, it is preferably 10 to 95% by mass, more preferably 10 to 90% by mass, still more preferably 40 to 90% by mass, particularly preferably 50 to 90% by mass, and the hydroxy group-containing monomer is polymerized. In the case of the polymer structural unit to be formed (repeating structural unit), it is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, further preferably 0 to 15% by mass, and particularly preferably 0 to 10% by mass. is there. In the case of a polymer structural unit (repeating structural unit) formed by polymerizing an unsaturated carboxylic acid, it is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and still more preferably 0 to 15% by mass. Especially preferably, it is 0-10 mass%. Furthermore, in the case of a polymer structural unit (repeating structural unit) formed by polymerizing the monomer represented by the above formula (2), preferably 0 to 30% by mass, more preferably 0 to 20% by mass, Preferably it is 0-15 mass%, Most preferably, it is 0-10 mass%.

  The method for producing the lactone ring-containing polymer is not particularly limited. For example, after the polymer (a) having a hydroxy group and an ester group in the molecular chain is obtained by a polymerization step, the obtained heavy polymer is obtained. It can be obtained by carrying out a lactone cyclization condensation step for introducing a lactone ring structure into the polymer by heat-treating the compound (a).

In the polymerization step, for example, a polymer having a hydroxyl group and an ester group in the molecular chain can be obtained by performing a polymerization reaction of the monomer component containing the monomer represented by the following formula (3). .
Formula (3)

［式中、Ｒ⁷およびＲ⁸は、互いに独立して、水素原子または炭素原子数１〜２０の有機残基を表す。］
ここで、炭素原子数１〜２０の有機残基としては、メチル基、エチル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基などが好ましい。

[Wherein, R ⁷ and R ⁸ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms. ]
Here, the organic residue having 1 to 20 carbon atoms is preferably a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group, or the like.

  Examples of the monomer represented by the above formula (3) include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, and 2- (hydroxy Examples include methyl) n-butyl acrylate and tert-butyl 2- (hydroxymethyl) acrylate. These monomers may be used alone or in combination of two or more. Among these monomers, 2- (hydroxymethyl) methyl acrylate and 2- (hydroxymethyl) ethyl acrylate are preferable, and since the effect of improving heat resistance is high, methyl 2- (hydroxymethyl) acrylate Is particularly preferred.

  The content ratio of the monomer represented by the formula (3) in the monomer component to be subjected to the polymerization step is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 10 to 60% by mass. %, Particularly preferably 10 to 50% by mass. When the content ratio of the monomer represented by the above formula (3) is 5% by mass or more, the obtained polymer tends to have improved heat resistance, solvent resistance and surface hardness. On the contrary, when the content ratio of the monomer represented by the above formula (3) is 90% by mass or less, gelation occurs in the polymerization step or the lactone cyclization condensation step, and the moldability of the obtained polymer is increased. Tend to improve.

You may mix | blend monomers other than the monomer shown by the said Formula (3) with the monomer component with which it uses for a superposition | polymerization process. Such a monomer is not particularly limited, and examples thereof include (meth) acrylic acid esters, hydroxy group-containing monomers, unsaturated carboxylic acids, and the following formula (4). And the like. These monomers may be used alone or in combination of two or more.
Formula (4)

［式中、Ｒ⁴は水素原子またはメチル基を表し、Ｘは水素原子、炭素原子数１〜２０のアルキル基、アリール基、−ＯＡｃ基、−ＣＮ基、−ＣＯ−Ｒ⁵基、または−ＣＯ−Ｏ−Ｒ⁶基を表し、Ａｃはアセチル基を表し、Ｒ⁵およびＲ⁶は水素原子または炭素原子数１〜２０の有機残基を表す］
ここで、Ｘは、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、シクロヘキシル基、ベンジル基などが好ましい。

[Wherein, R ⁴ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an —OAc group, a —CN group, a —CO—R ⁵ group, or — Represents a CO—O—R ⁶ group, Ac represents an acetyl group, R ⁵ and R ⁶ represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms]
Here, X is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, cyclohexyl group, benzyl group or the like.

  The (meth) acrylic acid ester is not particularly limited as long as it is a (meth) acrylic acid ester other than the monomer represented by the above formula (3). For example, methyl acrylate, ethyl acrylate Acrylates such as n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylic acid And methacrylic acid esters such as isobutyl, tert-butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. These (meth) acrylic acid esters may be used alone or in combination of two or more. Among these (meth) acrylic acid esters, methyl methacrylate is particularly preferable because the obtained polymer has excellent heat resistance and transparency.

  When (meth) acrylic acid ester other than the monomer represented by the above formula (3) is used, the content ratio in the monomer component to be subjected to the polymerization step is preferably 10 to 95% by mass, more preferably 10%. -90 mass%, More preferably, it is 40-90 mass%, Most preferably, it is 50-90 mass%.

  The hydroxy group-containing monomer is not particularly limited as long as it is a hydroxy group-containing monomer other than the monomer represented by the above formula (3). For example, α-hydroxymethylstyrene, α -2- (hydroxyalkyl) acrylic acid ester such as hydroxyethylstyrene and methyl 2- (hydroxyethyl) acrylate; 2- (hydroxyalkyl) acrylic acid such as 2- (hydroxyethyl) acrylic acid; and the like. These hydroxy group-containing monomers may be used alone or in combination of two or more.

  When using a hydroxyl group-containing monomer other than the monomer represented by the above formula (3), the content ratio in the monomer component to be subjected to the polymerization step is preferably 0 to 30% by mass, more preferably 0. -20% by mass, more preferably 0-15% by mass, particularly preferably 0-10% by mass.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-substituted acrylic acid, α-substituted methacrylic acid and the like. These unsaturated carboxylic acids may be used alone or in combination of two or more. Of these unsaturated carboxylic acids, acrylic acid and methacrylic acid are particularly preferred.

  When using unsaturated carboxylic acid, the content ratio in the monomer component to be subjected to the polymerization step is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, further preferably 0 to 15% by mass, particularly Preferably it is 0-10 mass%.

  Examples of the monomer represented by the formula (2) include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, and vinyl acetate. These monomers may be used alone or in combination of two or more. Of these monomers, styrene and α-methylstyrene are particularly preferable.

  When using the monomer shown by said Formula (2), the content rate in the monomer component with which it uses for a superposition | polymerization process becomes like this. Preferably it is 0-30 mass%, More preferably, it is 0-20 mass%, More preferably It is 0-15 mass%, Most preferably, it is 0-10 mass%.

  As a form of the polymerization reaction for polymerizing the monomer component to obtain a polymer having a hydroxy group and an ester group in the molecular chain, a polymerization form using a solvent is preferable, and solution polymerization is particularly preferable. .

  The polymerization temperature and polymerization time vary depending on the type and proportion of the monomer used, for example, preferably, the polymerization temperature is 0 to 150 ° C., the polymerization time is 0.5 to 20 hours, More preferably, the polymerization temperature is 80 to 140 ° C. and the polymerization time is 1 to 10 hours.

  In the case of a polymerization form using a solvent, the polymerization solvent is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone ketone; Examples thereof include ether solvents 1 such as tetrahydrofuran. These solvents may be used alone or in combination of two or more. Moreover, since the residual volatile matter of the lactone ring containing polymer finally obtained will increase when the boiling point of a solvent is too high, the solvent whose boiling point is 50-200 degreeC is preferable.

  During the polymerization reaction, a polymerization initiator may be added as necessary. The polymerization initiator is not particularly limited. For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-tert-butyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butylperoxyisopropyl Organic peroxides such as carbonate and tert-amylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2,2 Azo compounds such as' -azobis (2,4-dimethylvaleronitrile); These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the combination of monomers and reaction conditions.

  When performing the polymerization, it is preferable to control the concentration of the produced polymer in the polymerization reaction mixture to be 50% by mass or less in order to suppress gelation of the reaction solution. Specifically, when the concentration of the produced polymer in the polymerization reaction mixture exceeds 50% by mass, it is preferable that the polymerization solvent is appropriately added to the polymerization reaction mixture and controlled to be 50% by mass or less. . The concentration of the produced polymer in the polymerization reaction mixture is more preferably 45% by mass or less, and further preferably 40% by mass or less. In addition, since the productivity may be lowered if the concentration of the polymer produced in the polymerization reaction mixture is too low, the concentration of the polymer produced in the polymerization reaction mixture is preferably 10% by mass or more, more preferably It is 20 mass% or more.

  The form in which the polymerization solvent is appropriately added to the polymerization reaction mixture is not particularly limited, and for example, the polymerization solvent may be added continuously or the polymerization solvent may be added intermittently. By controlling the concentration of the polymer formed in the polymerization reaction mixture in this way, the gelation of the reaction solution can be more sufficiently suppressed, and in particular, to increase the lactone ring content and improve the heat resistance. Even when the ratio of the hydroxy group and the ester group in the molecular chain is increased, gelation can be sufficiently suppressed. The polymerization solvent to be added may be, for example, the same type of solvent used during the initial charging of the polymerization reaction or a different type of solvent, but the solvent used during the initial charging of the polymerization reaction. It is preferable to use the same type of solvent. Moreover, the polymerization solvent to be added may be only one kind of single solvent or two or more kinds of mixed solvents.

  The polymerization reaction mixture obtained when the above polymerization process is completed usually contains a solvent in addition to the obtained polymer, but the solvent is completely removed and the polymer is taken out in a circumferential state. It is not necessary, and it is preferably introduced into the subsequent lactone cyclization condensation step in a state containing a solvent. If necessary, after taking out in a solid state, a solvent suitable for the subsequent lactone cyclization condensation step may be added again.

  The polymer obtained in the polymerization step is a polymer (a) having a hydroxy group and an ester group in the molecular chain, and the mass average molecular weight of the polymer (a) is preferably 1,000 to 2,000. 5,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, and particularly preferably 50,000 to 500,000. The polymer (a) obtained in the polymerization step is subjected to heat treatment in the subsequent lactone cyclization condensation step, whereby a lactone ring structure is introduced into the polymer to become a lactone ring-containing polymer.

  The reaction for introducing a lactone ring structure into the polymer (a) is a reaction in which a hydroxy group and an ester group present in the molecular chain of the polymer (a) are cyclized and condensed to form a lactone ring structure by heating. The alcohol is by-produced by the cyclized condensation. High heat resistance is imparted by being formed in the molecular chain of the lactone ring structural force conjugate (in the main skeleton of the polymer). If the reaction rate of the cyclization condensation reaction leading to the lactone ring structure is insufficient, the heat resistance will not be improved sufficiently, or a condensation reaction will occur during the molding due to the heat treatment during molding, and the resulting alcohol will be contained in the molded product. May exist as bubbles or silver streaks.

 The lactone ring-containing polymer obtained in the lactone cyclization condensation step preferably has a lactone ring structure represented by the following formula (5).

［式中、Ｒ¹、Ｒ²およびＲ³は、互いに独立して、水素原子または炭素原子数１〜２０の有機残基を表す；なお、有機残基は酸素原子を含有していてもよい。］
炭素原子数１〜２０の有機残基としては、好ましくはメチル基、エチル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基などが挙げられる。 Formula (5)

[Wherein R ¹ , R ² and R ³ independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms; the organic residue may contain an oxygen atom. . ]
Preferred examples of the organic residue having 1 to 20 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, and a t-butyl group.

  The method for heat-treating the polymer (a) is not particularly limited, and a conventionally known method may be used. For example, you may heat-process the polymerization reaction mixture containing the solvent obtained by the superposition | polymerization process as it is. Or you may heat-process using a ring-closure catalyst as needed in presence of a solvent. Or heat processing can also be performed using the heating furnace and reaction apparatus provided with the vacuum apparatus or devolatilization apparatus for removing a volatile component, the extruder provided with the devolatilization apparatus, etc.

  In carrying out the cyclization condensation reaction, in addition to the polymer (a), another thermoplastic resin may coexist. Further, when performing the cyclization condensation reaction, if necessary, an esterification catalyst or a transesterification catalyst such as p-toluenesulfonic acid generally used as a catalyst for the cyclization condensation reaction may be used. Organic carboxylic acids such as propionic acid, benzoic acid, acrylic acid, and methacrylic acid may be used as a catalyst. Furthermore, as disclosed in, for example, Japanese Patent Application Laid-Open Nos. 61-254608 and 61-261303, basic compounds, organic carboxylates, carbonates, and the like may be used.

  Alternatively, an organophosphorus compound may be used as a catalyst for the cyclization condensation reaction. By using an organic phosphorus compound as a catalyst, the cyclization condensation reaction rate can be improved, and coloring of the resulting lactone ring-containing polymer can be greatly reduced. Furthermore, by using an organophosphorus compound as a catalyst, it is possible to suppress a decrease in molecular weight that can occur when a devolatilization step described later is used in combination, and to impart excellent mechanical strength.

  Examples of the organic phosphorus compound that can be used as a catalyst for the cyclization condensation reaction include alkyl (aryl) phosphonous acids such as methylphosphonous acid, ethylphosphonous acid, and phenylphosphonous acid (however, these are tautomers). Which may be an alkyl (aryl) phosphinic acid which is an active substance) and monoesters or diesters thereof; dialkyl (such as dimethylphosphinic acid, diethylphosphinic acid, diphenylphosphinic acid, phenylmethylphosphinic acid, phenylethylphosphinic acid) Aryl) phosphinic acids and their esters; alkyl (aryl) phosphonic acids such as methylphosphonic acid, ethylphosphonic acid, trifluoromethylphosphonic acid, phenylphosphonic acid and their monoesters or diesters; Alkyl (aryl) phosphinic acids such as acid, ethylphosphinic acid, phenylphosphinic acid and their esters; methyl phosphite, ethyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite Phosphorous acid monoester, diester or triester such as diphenyl phosphite, trimethyl phosphite, triethyl phosphite, triphenyl phosphite; methyl phosphate, ethyl phosphate, 2-ethylhexyl phosphate, phosphoric acid Octyl, isodecyl phosphate, lauryl phosphate, stearyl phosphate, isostearyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, di-2-ethylhexyl phosphate, diisodecyl phosphate, dilauryl phosphate, diphosphate Stearyl, diisostearyl phosphate, diphenyl phosphate, phosphorus Phosphoric monoesters, diesters or triesters such as trimethyl, triethyl phosphate, triisodecyl phosphate, trilauryl phosphate, tristearyl phosphate, triisostearyl phosphate, triphenyl phosphate; methylphosphine, ethylphosphine, phenylphosphine, Mono-, di- or tri-alkyl (aryl) phosphine such as dimethylphosphine, diethylphosphine, diphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine; methyldichlorophosphine, ethyldichlorophosphine, phenyldichlorophosphine, dimethylchlorophosphine, Alkyl (aryl) halogen phosphines such as diethyl chlorophosphine and diphenylchlorophosphine; Mono-, di- or tri-alkyl (aryl) phosphine oxides such as ethyl phosphine oxide, phenyl phosphine oxide, dimethyl phosphine oxide, diethyl phosphine oxide, diphenyl phosphine oxide, trimethyl phosphine oxide, triethyl phosphine oxide, triphenyl phosphine oxide; And halogenated tetraalkyl (aryl) phosphonium such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, and tetraphenylphosphonium chloride. These organic phosphorus compounds may be used alone or in combination of two or more. Among these organophosphorus compounds, since the catalytic activity is high and the colorability is low, alkyl (aryl) phosphonous acid, phosphorous acid monoester or diester, phosphoric acid monoester or diester, and alkyl (aryl) phosphonic acid Preferably, alkyl (aryl) phosphonous acid, phosphorous acid monoester or diester, phosphoric acid monoester or diester is more preferable, and alkyl (aryl) phosphonous acid, phosphoric acid monoester or diester is particularly preferable.

  Although the usage-amount of the catalyst used in the case of a cyclization condensation reaction is not specifically limited, For example, Preferably it is 0.001-5 mass% with respect to a polymer (a), More preferably, it is 0.01. -2.5 mass%, More preferably, it is 0.01-1 mass%, Most preferably, it is 0.05-0.5 mass%. By making the usage-amount of a catalyst 0.001 mass% or more, it exists in the tendency for the reaction rate of a cyclization condensation reaction to improve. On the contrary, when the amount of the catalyst used is 5% by mass or less, the obtained polymer tends to be difficult to be colored, and the polymer can be prevented from being cross-linked and causing melt shaping. It is in.

  The addition timing of the catalyst is not particularly limited. For example, the catalyst may be added at the beginning of the reaction, may be added during the reaction, or may be added in both of them.

  It is preferable to carry out the cyclization condensation reaction in the presence of a solvent and to use a devolatilization step in combination with the cyclization condensation reaction. In this case, a mode in which a devolatilization step is used throughout the cyclization condensation reaction, a mode in which the devolatilization step is not used over the entire cyclization condensation reaction, and only in the -part of the process are included. . In the method using the devolatilization step in combination, the alcohol produced as a by-product in the condensation cyclization reaction is forcibly devolatilized and removed, so that the equilibrium of the reaction is advantageous for the production side.

  The devolatilization process means a process of removing volatile components such as solvents and residual monomers and alcohol by-produced by a cyclization condensation reaction leading to a lactone ring structure under reduced pressure heating conditions as necessary. To do. If this removal treatment is insufficient, the residual volatile matter in the obtained polymer increases, and coloring due to alteration during molding, or molding defects such as bubbles and sill streaks may occur.

  In the case of using a devolatilization step throughout the cyclization condensation reaction, the apparatus to be used is not particularly limited. For example, in order to more effectively perform the present invention, a devolatilization step and devolatilization are performed. It is preferable to use a devolatilizing device or vented extruder consisting of a tank, or a devolatilizing device and an extruder arranged in series, and a devolatilizing device or vented extruder consisting of a heat exchanger and a devolatilizing tank More preferably, it is used.

  The reaction treatment temperature in the case of using a devolatilizer comprising a heat exchanger and a devolatilization tank is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. If the reaction treatment temperature is 150 ° C. or higher, the cyclization condensation reaction tends to be sufficient and the residual volatile matter tends to be reduced. If the reaction treatment temperature is 350 ° C. or lower, the resulting polymer is colored or decomposed. It tends to be difficult.

  The reaction treatment pressure in the case of using a devolatilization apparatus comprising a heat exchanger and a devolatilization tank is preferably 931 hPa to 1.33 hPa (700 mmHg to 1 mmHg), more preferably 798 hPa to 66.5 hPa (600 mmHg to 50 mmHg). By setting the reaction treatment pressure to 931 hPa (700 mmHg) or less, volatile components including alcohol hardly remain. Conversely, when the reaction treatment pressure is 1.33 hPa (1 mmHg) or more, it tends to be industrially easy to implement.

  When using an extruder with a vent, one or a plurality of vents may be used, but it is preferable to have a plurality of vents.

  The reaction treatment temperature when using an extruder with a vent is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. When the reaction treatment temperature is 150 ° C. or higher, the cyclization condensation reaction tends to proceed sufficiently and the residual volatile content tends to decrease. Conversely, by setting the reaction treatment temperature to 350 ° C. or lower, the obtained polymer tends to be less likely to be colored or decomposed.

 The reaction treatment pressure when using an extruder with a vent is preferably 931 hPa to 1.33 hPa (700 mmHg to 1 mmHg), more preferably 798 hPa to 13.3 hPa (600 mmHg to 10 mmHg). By setting the reaction treatment pressure to 931 hPa (700 mmHg) or less, it becomes difficult for volatile components including alcohol to remain, and when the reaction treatment pressure is 1.33 hPa (1 mmHg) or more, industrial implementation tends to be easily performed. .

  In the case of a form in which a devolatilization step is used throughout the cyclization condensation reaction, the physical properties of the lactone ring-containing polymer obtained may deteriorate under severe heat treatment conditions, as will be described later. It is preferable to carry out by using an extruder with a vent etc. on the conditions as mild as possible.

  In the case of using the devolatilization step throughout the cyclization condensation reaction, preferably, the polymerization holiday (a) obtained in the polymerization step is introduced into the cyclization condensation reactor system together with the solvent. If necessary, it may be passed once again through a cyclocondensation reaction apparatus such as a vented extruder.

  You may perform the form which does not use a devolatilization process over the whole process of cyclization condensation reaction, but uses together only in a part of process. For example, the apparatus for producing the polymer (a) is further heated, and if necessary, a part of the devolatilization step is used together to advance the cyclization condensation reaction to some extent in advance, followed by the devolatilization step. Is a form in which a cyclization condensation reaction is simultaneously used to complete the reaction.

  In the form of using the devolatilization step throughout the cyclization condensation reaction described above, for example, when the polymer (a) is heat-treated at a high temperature of about 250 ° C. or higher using a twin-screw extruder. Depending on the thermal history, partial decomposition or the like may occur before the cyclization condensation reaction occurs, and the physical properties of the resulting lactone ring-containing polymer may deteriorate. Therefore, if the cyclization condensation reaction is allowed to proceed to some extent before the cyclization condensation reaction using the devolatilization process at the same time, the latter reaction conditions can be relaxed, and the physical properties of the resulting lactone ring-containing polymer deteriorated. Is preferable. As a particularly preferred form, for example, a form in which the devolatilization step is started after a lapse of time from the start of the cyclization condensation reaction, that is, a hydroxy group present in the molecular chain of the polymer (a) obtained in the polymerization step Examples include a form in which an ester group is preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent, and then a cyclization condensation reaction in which a devolatilization step is simultaneously performed is performed. Specifically, for example, a cyclization condensation reaction is allowed to proceed to a certain reaction rate in the presence of a solvent in advance using a kettle reactor, and then a reactor equipped with a devolatilizer, for example, heat exchange Preferred is a mode in which the cyclization condensation reaction is completed with a devolatilizer comprising a vessel and a devolatilization tank, an extruder with a vent, or the like. In particular, in the case of this form, it is more preferable that a catalyst for the cyclization condensation reaction is present.

  As described above, the hydroxy group and the ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent, The method of carrying out the cyclization condensation reaction simultaneously using the volatilization process is a preferred form in obtaining the lactone ring-containing polymer in the present invention. With this form, a lactone ring-containing polymer having a higher glass transition temperature, a higher cyclization condensation reaction rate, and excellent heat resistance can be obtained. In this case, as a measure of the cyclization condensation reaction rate, for example, the mass reduction rate in the range of 150 to 300 ° C. in the dynamic TG measurement shown in the examples is preferably 2% or less, more preferably 1.5% or less. More preferably, it is 1% or less.

  The reactor that can be employed in the cyclization condensation reaction performed in advance before the cyclization condensation reaction using the devolatilization process at the same time is not particularly limited. For example, an autoclave, a kettle reactor, a heat exchanger And a devolatilizer comprising a devolatilization tank, and a vented extruder suitable for a cyclization condensation reaction using a devolatilization step at the same time can also be used. Of these reactors, an autoclave and a kettle reactor are particularly preferable. However, even when a reactor such as an extruder with a vent is used, the autoclave or kettle can be adjusted by adjusting the temperature conditions, barrel conditions, screw shape, screw operating conditions, etc. It is possible to carry out the cyclization condensation reaction in the same state as the reaction state in the type reactor.

  In the case of the cyclization condensation reaction carried out in advance before the cyclization condensation reaction using the devolatilization step at the same time, for example, a mixture containing the polymer (a) and the solvent obtained in the polymerization step is used as (i) a catalyst. And (ii) a method of performing a heat reaction without a catalyst, a method of performing the above (i) or (ii) under pressure, and the like.

  The “mixture containing the polymer (a) and the solvent” introduced into the cyclization condensation reaction in the lactone cyclization condensation step refers to the polymerization reaction mixture obtained in the polymerization step itself or once the solvent is removed. It means a mixture obtained by re-adding a solvent suitable for the cyclization condensation reaction later.

  The solvent that can be re-added in the cyclization condensation reaction that is carried out in advance before the cyclization condensation reaction using the devolatilization step at the same time is not particularly limited. For example, aromatic carbonization such as toluene, xylene, ethylbenzene, etc. Hydrogens; ketones such as methyl ethyl ketone and methyl isobutyl ketone; chloroform, dimethyl sulfoxide, tetrahydrofuran; and the like. These solvents may be used alone or in combination of two or more. It is preferable to use the same type of solvent as that used in the polymerization step.

  Examples of the catalyst to be added in the method (i) include commonly used esterification catalysts such as p-toluenesulfonic acid or transesterification catalysts, basic compounds, organic carboxylates, and carbonates. In the invention, it is preferable to use the aforementioned organophosphorus compound. The timing of addition of the sole solvent is not particularly limited. For example, it may be added at the initial stage of the reaction, may be added during the reaction, or may be added in both of them. The addition amount of the catalyst is not particularly limited, but for example, is preferably 0.001 to 5% by mass, more preferably 0.01 to 2.5% by mass with respect to the mass of the polymer (a). More preferably, it is 0.01-0.1 mass%, Most preferably, it is 0.05-0.5 mass%. Although the heating temperature and heating time of method (i) are not particularly limited, for example, the heating temperature is preferably room temperature to 180 ° C, more preferably 50 ° C to 150 ° C. Preferably it is 1 to 20 hours, more preferably 2 to 10 hours. By setting the heating temperature to room temperature or higher, or by setting the heating time to 1 hour or longer, the cyclization condensation reaction rate tends to be improved. Conversely, when the heating temperature is 180 ° C. or lower, or when the heating time is 20 hours or shorter, the resin is less likely to be colored or decomposed.

  In the method (h), for example, the polymerization reaction mixture obtained in the polymerization step may be heated as it is using a pressure-resistant kettle reactor or the like. Although the heating temperature and heating time of the method (h) are not particularly limited, for example, the heating temperature is preferably 100 to 180 ° C, more preferably 100 to 150 ° C, and the heating time is preferably 1 to 20 hours, more preferably 2 to 10 hours. When the heating temperature is 100 ° C. or higher, or the heating temperature is 1 hour or longer, the cyclization condensation reaction rate tends to be improved. Conversely, when the heating temperature is 180 ° C. or lower, or the heating time is 20 hours or shorter, the resin is less likely to be colored or decomposed.

  In any method, there is no problem even under pressure depending on conditions.

  In the case of the cyclization condensation reaction performed in advance before the cyclization condensation reaction using the devolatilization step at the same time, there is no problem even if part of the solvent volatilizes spontaneously during the reaction.

  The mass reduction rate within the range of 150 to 300 ° C. in the dynamic TG measurement at the end of the cyclization condensation reaction performed in advance before the cyclization condensation reaction simultaneously used in combination with the devolatilization step, that is, immediately before the start of the devolatilization step is Preferably it is 2% or less, More preferably, it is 1 or 5% or less, More preferably, it is 1% or less. By setting the mass reduction rate to 2% or more, the cyclization condensation reaction rate easily proceeds, and the physical properties of the resulting lactone ring-containing polymer tend to be improved. In addition, when performing said cyclization condensation reaction, in addition to a polymer (a), you may coexist other thermoplastic resins.

  The hydroxy group and the ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent. In the case of a form in which a combined cyclization condensation reaction is carried out, a polymer obtained by a cyclization condensation reaction carried out in advance (a polymer in which at least a part of a hydroxy group and an ester group present in a molecular chain is subjected to a cyclization condensation reaction) And the solvent may be introduced into the cyclization condensation reaction using the devolatilization step at the same time, and if necessary, the polymer (at least a part of the hydroxy group and ester group present in the molecular chain is present). It may be introduced into a cyclization condensation reaction in which a devolatilization step is used at the same time after other treatments such as re-addition of a solvent after the cyclization condensation reaction polymer is isolated.

  The devolatilization step is not limited to being completed at the same time as the cyclization condensation reaction, and may be completed after a lapse of time from the completion of the cyclization condensation reaction.

The mass average molecular weight of the lactone ring-containing polymer is preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, particularly preferably. 50,000 to 500,000.
The lactone ring-containing polymer preferably has a mass reduction rate in the range of 150 to 300 ° C. in dynamic TG measurement of 1% or less, more preferably 0.5% or less, and still more preferably 0.3% or less.

  Since the lactone ring-containing polymer has a high cyclization condensation reaction rate, it is possible to avoid the disadvantage that bubbles and silver streaks enter the molded product after molding. Furthermore, since the lactone ring structure is sufficiently introduced into the polymer due to the high cyclization condensation reaction rate, the obtained lactone ring-containing polymer has sufficiently high heat resistance.

  The lactone ring-containing polymer has a coloring degree (YI) of preferably 6 or less, more preferably 3 or less, still more preferably 2 or less, and particularly preferably 1 or less when a chloroform solution having a concentration of 15% by mass is used. . When the coloring degree (YI) exceeds 6, transparency may be impaired due to coloring, and may not be used for the intended purpose.

  The lactone ring-containing polymer has a 5% mass reduction temperature in thermal mass spectrometry (TG) of preferably 330 ° C. or higher, more preferably 350 ° C. or higher, and still more preferably 360 ° C. or higher. The 5% mass reduction temperature in thermal mass spectrometry (TG) is an indicator of thermal stability, and by setting it to 330 ° C. or higher, sufficient thermal stability tends to be exhibited.

  The lactone ring-containing polymer has a glass transition temperature (Tg) of preferably 115 ° C. or higher, more preferably 125 ° C. or higher, further preferably 130 ° C. or higher, particularly preferably 135 ° C. or higher, and most preferably 140 ° C. or higher. .

  The total amount of residual volatile components contained in the lactone ring-containing polymer is preferably 5,000 ppm or less, more preferably 2,000 ppm or less, still more preferably 1,500 ppm, and particularly preferably 1,000 ppm. When the total amount of residual volatile components is 5,000 ppm or more, molding defects such as coloring, foaming, and silver streak are unlikely to occur due to deterioration during molding.

  The lactone ring-containing polymer has a total light transmittance of 85% or more, more preferably 88% or more, and still more preferably measured by a method based on ASTM-D-1003 for a molded product obtained by injection molding. 90% or more. The total light transmittance is an index of transparency, and when it is 85% or more, the transparency tends to be improved.

<< Thermoplastic resin film (A) containing a lactone ring-containing polymer >>
Examples of the thermoplastic resin film containing the lactone ring-containing polymer in the present invention include a thermoplastic resin film (A).

  The content ratio of the lactone ring-containing polymer in the thermoplastic resin film (A) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass. 100% by mass.

  The thermoplastic resin film (A) may contain a polymer other than the lactone ring-containing polymer (hereinafter sometimes referred to as “other polymer”) as other components.

  Examples of other polymers include olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-1-pentene); halogens such as vinyl chloride, vinylidene chloride, and chlorinated vinyl resins. Acrylic polymers such as polymethyl methacrylate; Styrene polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer Polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamides such as nylon 6, nylon 66 and nylon 610; polyacetal; polycarbonate; polyphenylene oxide; Sulfides; polyetheretherketone; polysulfones; polyethersulfones; polyoxyethylene benzylidene alkylene; polyamideimide; polybutadiene rubber, rubber-like polymer such as ABS resin or ASA resin containing an acrylic rubber; and the like.

  The content of the other polymer in the thermoplastic resin film (A) is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, further preferably 0 to 30% by mass, and particularly preferably 0 to 20%. % By mass.

  The thermoplastic resin film (A) may contain various additives. Examples of additives include antioxidants such as hindered phenols, phosphorus, and sulfur; stabilizers such as light stabilizers, weather stabilizers, and heat stabilizers; reinforcing materials such as glass fibers and carbon fibers; phenyls UV absorbers such as salicylate, (2,2′-hydroxy-5-methylphenyl) benzotriazole, 2-hydroxybenzophenone; near infrared absorbers; tris (dibro-mopropyl) phosphate, triallyl phosphate, antimony oxide, etc. Flame retardants; antistatic agents such as anionic, cationic and nonionic surfactants; colorants such as inorganic pigments, organic pigments and dyes; organic fillers and inorganic fillers; resin modifiers; organic fillers and inorganics Fillers; plasticizers; lubricants; antistatic agents; flame retardants;

  The content of the additive in the thermoplastic resin film (A) is preferably 0 to 5% by mass, more preferably 0 to 2% by mass, and still more preferably 0 to 0.5% by mass.

  As a manufacturing method of a thermoplastic resin film (A), it can carry out according to the above-mentioned method, for example, a lactone ring containing polymer, and other polymers, additives, etc. are conventionally well-known mixing. It can be mixed well by the method and formed into a film.

  Since the thermoplastic resin film (A) has high transparency, the total light transmittance is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more, and particularly preferably 92% or more.

  The thermoplastic resin film (A) preferably has a tensile strength measured according to ASTM-D-882-61T of 10 MPa or more and less than 100 MPa, more preferably 30 MPa or more and less than 100 MPa. When the tensile strength is 10 MPa or more, sufficient mechanical strength tends to be obtained, and when the tensile strength is 100 MPa or less, workability tends to be improved.

  The thermoplastic resin film (A) preferably has an elongation percentage measured according to ASTM-D-882-61T of 1% or more. The upper limit of the elongation is not particularly limited, but is usually preferably 100% or less. By setting the elongation to 1% or more, the toughness tends to be excellent.

  The thermoplastic resin film (A) preferably has a tensile modulus measured according to ASTM-D-882-61T of 0.5 GPa or more, more preferably 1 GPa or more, and even more preferably 2 GPa or more. The upper limit of the tensile elastic modulus is not particularly limited, but is usually preferably 20 GPa or less. By setting the tensile modulus to 0.5 GPa or more, sufficient mechanical strength can be easily obtained.

  The thermoplastic resin film (A) has an antistatic layer, an adhesive layer, an adhesive layer, an easy-adhesion layer, an antiglare layer (non-glare) layer, a photocatalyst layer and other antifouling layers, and an antireflection layer, depending on the purpose. Various functional coating layers such as a hard coat layer, an ultraviolet ray shielding layer, a heat ray shielding layer, an electromagnetic wave shielding layer, and a gas barrier property may be laminated, or each individual functional coating layer may be coated. The processed member may be laminated via an adhesive or an adhesive. In addition, the stacking order of each layer is not particularly limited, and the stacking method is not particularly limited.

  The ultraviolet shielding layer is provided in order to prevent ultraviolet degradation of a material that degrades ultraviolet rays, such as a base material layer and a printing layer that are lower than the ultraviolet shielding layer. The UV shielding layer is composed of an UV absorber having a molecular weight of 1,000 or less, a thermoplastic resin such as an acrylic resin, a polyester resin, or a fluorine resin, or a thermosetting, moisture curable, ultraviolet curable, or electron beam curable resin. In particular, from the viewpoint of weather resistance, the ultraviolet absorption property disclosed in Japanese Patent No. 3081508, Japanese Patent No. 3404160, and Japanese Patent No. 2835396 can be used. Acrylic polymers obtained by polymerizing a monomer mixture that essentially contains a single monomer having a skeleton are preferred. Examples of commercially available products include “Hals Hybrid UV-G13” and “Hals Hybrid UV-G301” (manufactured by Nippon Shokubai Co., Ltd.) and “ULS-935LH” (manufactured by Yushi Kogyo Co., Ltd.). Can be mentioned.

  The heat ray shielding layer is provided, for example, to prevent malfunction of peripheral devices due to near infrared rays (particularly, 700 to 1,200 nm) generated with light emission of the display device. For the heat ray shielding layer, organic or inorganic heat ray shielding substances are thermoplastic resins such as acrylic resins, polyester resins, and fluorine resins, or thermosetting, moisture curable, ultraviolet curable, and electron beam curable. What was mix | blended with curable resin, such as, is used. The organic heat ray shielding material is not particularly limited as long as it is a substance having absorption in the near infrared region (700 to 1,800 nm) such as phthalocyanine dye, diimonium type, squarylium type, etc. A dye having absorption in the visible region (400 to 700 nm) such as a porphyrin dye or a cyanine dye can be used alone or in combination of two or more. Examples of the inorganic heat ray shielding material include metals, metal nitrides, and metal oxides. From the viewpoint of solubility in a dispersion medium and weather resistance, metal oxide fine particles are preferably used. Is done. As the metal oxide, indium oxide and zinc oxide are preferable, and those having an average particle size of 0.1 μm or less are preferable from the viewpoint of transparency.

 As the adhesive layer, acrylic resins, acrylate resins, or copolymers thereof, styrene-butadiene copolymers, rubbers such as polyisoprene rubber and polyisobutylene rubber, polyvinyl ethers, silicones, Maleimide-based and cyanoacrylate-based adhesives and the like can be mentioned, and these may be used alone, but a crosslinking agent and a tackifier can also be blended. From the viewpoint of optical properties, light resistance, and transparency, an acrylic resin that is a copolymer mainly composed of an acrylic acid alkyl ester monomer is preferable, and an aromatic tackifier is added to adjust the refractive index. A pressure-sensitive adhesive that is close to the refractive index of the thermoplastic resin film (A) containing the lactone ring-containing polymer is more preferable. If necessary, the heat-shielding substance, for example, a phthalocyanine dye or a cyanine dye can be mixed with the pressure-sensitive adhesive to form a functional pressure-sensitive adhesive layer, which is advantageous from the viewpoint of thinning and productivity as an optical laminate. It is.

 The electromagnetic wave shielding layer is provided, for example, in order to prevent an adverse effect on a living body or an electronic device due to an electromagnetic wave generated due to light emission from the display device. The magnetic wave shielding layer is made of a metal or metal oxide thin film such as silver, copper, indium oxide, zinc oxide, indium tin oxide, and antimony tin oxide. These thin films can be manufactured by using a conventionally known dry plating method such as a vacuum deposition method, an ion plating method, a sputtering method, a CVD method, a plasma chemical vapor deposition method or the like. The most commonly used electromagnetic shielding layer is a thin film of indium tin oxide (sometimes abbreviated as “ITO”), but a copper thin film with mesh holes, a dielectric layer and a metal. A laminate in which layers are alternately laminated on a substrate can also be suitably used. Examples of the dielectric layer include transparent metal oxides such as indium oxide and zinc oxide, and the metal layer is generally silver or a silver-palladium alloy. The laminated body is usually laminated so that it starts from a dielectric layer and becomes an odd number of layers of about 3 to 13 layers.

 The antireflection layer suppresses reflection of the surface and prevents reflection of external light such as a fluorescent lamp on the surface. The anti-reflective layer consists of a single layer of a resin with a different refractive index, such as an acrylic resin or a fluororesin, when it is made of an inorganic thin film such as a metal oxide, fluoride, silicide, boride, carbide, nitride, or sulfide. Or it may consist of what was laminated | stacked on the multilayer. Moreover, what laminated | stacked the thin film containing the composite fine particle of an inorganic type compound and an organic type compound as disclosed by Unexamined-Japanese-Patent No. 2003-292805 can also be used.

 The non-glare layer is provided to widen the viewing angle and scatter transmitted light. A fine powder such as silica, melamine resin, or acrylic resin is converted into ink, applied onto another functional layer by a conventionally known coating method, and formed by heat or photocuring. Further, the non-glare-treated film (A) may be pasted on another functional film.

 The hard coat layer is a coating solution in which an acrylate such as a silicone-based curable resin, an organic polymer composite inorganic fine particle-containing curable resin, urethane acrylate, epoxy acrylate, polyfunctional acrylate, and a photopolymerization initiator are dissolved or dispersed in an organic solvent. Is coated on the thermoplastic resin film (A) containing the lactone ring-containing polymer in the present invention by a conventionally known coating method, preferably in the outermost layer, dried and photocured. It is formed by. The silicone-based curable resin is a resin having a siloxane bond. For example, a partially hydrolyzed product of trialkoxysilane and tetraalkoxysilane or an alkylated product thereof, a mixture of methyltrialkoxysilane and phenyltrialkoxysilane is hydrolyzed. And partially hydrolyzed condensates of colloidal silica-filled organotrialkoxysilanes. Examples of commercially available products include “Si Coat 2” (manufactured by Eighth Chemical Industry Co., Ltd.), “Tosguard 510” and “UVHC8553” (above, GE Toshiba Silicone Co., Ltd.), “Solgard NP720” and “Solgard”. NP730 "or" Solgard RF0831 "(above, manufactured by Mekoku Dakurosha Lock). The organic polymer composite inorganic fine particles mean composite inorganic fine particles in which an organic polymer is fixed on the surface of the inorganic fine particles. By forming a surface protective layer with a curable resin containing the composite inorganic fine particles, the surface hardness can be reduced. Improvements are planned. Details of the composite inorganic fine particles and the production method thereof are described in, for example, JP-A-7-178335, JP-A-9-302257, JP-A-11-124467. The curable resin containing the composite inorganic fine particles is not particularly limited, and examples thereof include melamine resin, urethane resin, alkyd resin, acrylic resin, and polyfunctional acrylic resin. Examples of the polyfunctional acrylic resin include resins such as polyol acrylate, polyester acrylate, urethane acrylate, and epoxy acrylate. Examples of the commercially available curable resin containing composite inorganic fine particles include “U-Double C-3300” and “U-Double C-3600” (manufactured by Meiko Catalysts, Inc.).

<Optical protective film (A)>
The thermoplastic resin film (A) is used for, for example, an optical protective film (hereinafter sometimes referred to as “optical protective film (A)”).
The protective film for optics (A) is not particularly limited as long as it is a film that protects the transparent optical component, but preferred specific examples include a protective film for a polarizing plate for a liquid crystal display device. Moreover, it can also be set as the protective film for optics which served as the phase difference film.
The optical protective film (A) may be an unstretched film or a stretched film.
When the optical protective film (A) is an unstretched film, the retardation in the plane direction is preferably less than 20 nm, more preferably less than 10 nm.
When the optical protective film (A) is a stretched film, the retardation in the plane direction is preferably 20 to 500 nm, more preferably 50 to 400 nm.
When the protective film for optics (A) is a stretched film, it may have a retardation film function by giving a specific retardation (for example, λ / 2 or λ / 4). is there. In this case, (meth) acrylic acid and / or (meth) acrylic acid ester as the monomer represented by the above formula (3) is used as the monomer used for producing the lactone ring-containing polymer. preferable. Moreover, it is preferable that an acrylic polymer is included as another polymer in the thermoplastic resin film (A) containing a lactone ring-containing polymer.
The optical protective film (A) has a small wavelength dependency of the retardation, and the ratio (R / Re) of the retardation Re at 590 nm to the retardation R at each wavelength is preferably 0.9 to 1.2. More preferably, it is 0.95-1.1.
Optical protective film (A) has a small incident angle dependence of the phase difference, the difference between the phase difference R ₄₀ angle of incidence 40 ° and the phase difference R ₀ of the incident angle OQ (R ₀ -R ₄₀₎ is preferably Is less than 20 nm, more preferably less than 10 nm.
The protective film for optics (A) has a high surface hardness, and the pencil hardness is preferably H or higher, more preferably 2H or higher.

 The method for producing the optical protective film (A) is not particularly limited. For example, a lactone ring-containing polymer and, if necessary, other polymers and additives, a conventionally known mixing method. To obtain a film. Moreover, it is good also as a stretched film by extending | stretching.

As a film forming method, a conventionally known film forming method may be used, and examples thereof include a solution casting method (solution casting method), a melt extrusion method, a calendar method, and a compression molding method. Of these film forming methods, the solution casting method (solution casting method) and the melt extrusion method are particularly preferable.
Examples of the solvent used in the solution casting method (solution casting method) include chlorine solvents such as chloroform and dichloromethane; aromatic solvents such as toluene, xylene and benzene; methanol, ethanol, isopropanol, n-butanol, Examples include alcohol solvents such as 2-butanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, and diethyl ether. These solvents may be used alone or in combination of two or more.
Examples of the apparatus for performing the solution casting method (solution casting method) include a drum casting machine, a band casting machine, and a spin coater.
Examples of the melt extrusion method include a T-die method and an inflation method. In this case, the film forming temperature is preferably 150 to 350 ° C., more preferably 200 to 300 ° C.
As a method for stretching, conventionally known stretching methods can be applied. For example, uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, and the like can be used.
The stretching is preferably performed in the vicinity of the glass transition temperature of the polymer of the film raw material. The specific stretching temperature is preferably (glass transition temperature-30 ° C) to (glass transition temperature + 100 ° C), more preferably (glass transition temperature-20 ° C) to (glass transition temperature + 80 ° C). . By setting the stretching temperature to (glass transition temperature −30 ° C.) or higher, a sufficient stretching ratio tends to be obtained. By setting the stretching temperature to (glass transition temperature + 100 ° C.) or lower, the resin flows. And tend to perform stable stretching.
The draw ratio defined by the area ratio is preferably 1.1 to 25 times, more preferably 1.3 to 10 times. By setting the draw ratio to 1.1 times or less, an improvement in toughness due to drawing tends to be obtained, which tends to be cheap. Conversely, by setting the draw ratio to 25 times or more, the effect of only increasing the draw ratio tends to be recognized more easily.
The stretching speed (one direction) is preferably 10 to 20,000% / min, more preferably 100 to 10,000% / min. By setting the stretching speed to 10% / min or more, the time for obtaining a sufficient stretching ratio tends to be shortened, and the production cost can be suppressed. Conversely, by setting the stretching speed to 20,000% / min or more, the stretched film is less likely to break.
In order to stabilize the optical isotropy and mechanical properties of the film, heat treatment (annealing) or the like can be performed after the stretching treatment.

<Optical film (A)>
The thermoplastic resin film (A) can be used as, for example, an optical film (hereinafter sometimes referred to as “optical film (A)”).
The optical film (A) is not particularly limited as long as it is a film excellent in optical properties, but preferably a retardation film (hereinafter sometimes referred to as “retardation film (A)”), visual field. An angle compensation film (hereinafter sometimes referred to as “viewing angle compensation film (A)”).
The optical film (A) has a retardation in the plane direction of preferably 20 to 500 nm, more preferably 50 to 400 nm.
The optical film (A) may be an unstretched film or a stretched film, but is preferably a stretched film in order to develop a large retardation.
The retardation film (A) has a small wavelength dependency of retardation, and the ratio (R / Re) of the retardation Re at 590 nm to the retardation R at each wavelength is preferably 0.9 to 1.2. Preferably it is 0, 95-1.1.
The retardation film (A) has a small incident angle dependence of the phase difference, the difference between the incident angle of 0 ° phase difference R ₀ as the incident angle of 40 ° phase difference R ₄₀ of (R ₀ -R ₄₀₎ is preferably Is less than 20 nm, more preferably less than 10 nm.
The retardation film (A) has a high surface hardness and a pencil hardness of preferably H or higher, more preferably 2H or higher.

The method for producing the retardation film (A) is not particularly limited, but preferably, a lactone ring-containing polymer and, if necessary, other polymers and additives, are conventionally known mixing methods. To obtain a film. Moreover, it is good also as a stretched film by extending | stretching.
The film forming temperature and the film forming method are the same as the film forming temperature and the film forming method in the optical protective film described above.
As a method for stretching, conventionally known stretching methods can be applied. For example, uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, and the like can be used. Among these stretching methods, uniaxial stretching is particularly preferable in order to obtain a retardation film.
The stretching temperature, the stretching ratio, and the stretching speed are the same as the stretching temperature, the stretching ratio, and the stretching speed in the optical protective film described above.
In order to stabilize the optical isotropy and mechanical properties of the film, heat treatment (annealing) or the like can be performed after the stretching treatment.
If necessary, the surface of the retardation film (A) may be corona-treated. In particular, when surface treatment such as coating is applied to the film surface, or when another film is laminated with an adhesive, corona treatment of the film surface can be performed to improve mutual adhesion. preferable.

 The retardation film (A) may be laminated on the polarizing plate. Moreover, it is also possible to use retardation film (A) as a protective film of a polarizing plate.

The viewing angle compensation film (A) has a small wavelength dependency of the retardation, and the ratio (R / Re) of the retardation Re at 590 nm to the retardation R at each wavelength is preferably 0.9 to 1.2. More preferably, it is 0.95-1.1.
The viewing angle compensation film (A) has a high surface hardness, and the pencil hardness is preferably H or higher, more preferably 2H or higher.
The method for producing the viewing angle compensation film (A) is not particularly limited. For example, a lactone ring-containing polymer and, if necessary, other polymers and additives, a conventionally known mixing method. To obtain a film. Moreover, it is good also as a stretched film by extending | stretching.

The film forming temperature and the film forming method are the same as the film forming temperature and the film forming method in the optical protective film described above.
As a method for stretching, conventionally known stretching methods can be applied. For example, uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, and the like can be used. Of these stretching methods, biaxial stretching such as sequential biaxial stretching and simultaneous biaxial stretching is particularly preferable in order to obtain a viewing angle compensation film.
The stretching temperature, the stretching ratio, and the stretching speed are the same as the stretching temperature, the stretching ratio, and the stretching speed in the optical protective film (A) described above.
In order to stabilize the optical isotropy and mechanical properties of the film, a heat treatment (annealing) or the like can be performed after the stretching treatment.

<Optical sheet>
Yet another preferred form of the thermoplastic resin film (A) containing the lactone ring-containing polymer is an optical sheet (hereinafter sometimes referred to as “optical sheet (A)”).

The optical sheet (A) is not particularly limited as long as it is a sheet excellent in heat resistance and optical characteristics, but is preferably a diffusion plate or a light guide plate.
When the optical sheet (A) is a diffusion plate, the configuration thereof may be the same as the configuration of a conventionally known diffusion plate unless departing from the gist of the present invention.
When the optical sheet (A) is a light guide plate, the configuration thereof may be the same as the configuration of a conventionally known light guide plate without departing from the gist of the present invention.
The optical sheet (A) has a surface direction retardation of preferably less than 20 nm, more preferably less than 10 nm.
The optical sheet (A) has a high surface hardness, and the pencil hardness is preferably H or higher, more preferably 2H or higher.
The optical sheet (A) has particularly high heat resistance, and the Vicat softening temperature is preferably 110 ° C. or higher, more preferably 120 ° C. or higher.

The method for producing the optical sheet (A) is not particularly limited. For example, a lactone ring-containing polymer and, if necessary, other polymers and additives are mixed by a conventionally known mixing method. And obtained by molding into a sheet shape.
A conventionally known sheet forming method can be applied as the sheet forming method, and specific examples include extrusion molding, injection molding, inflation molding, and blow molding.
The molding temperature of the sheet molding is preferably 150 to 350 ° C, more preferably 200 to 300 ° C.

When the optical sheet (A) is a diffusion plate, it is preferable to contain an organic filler and / or an inorganic filler as an additive.
The total amount of the organic filler and / or the inorganic filler is preferably 0.01 to 50% by mass, more preferably 0, based on the lactone ring-containing polymer. 0.05 to 40% by mass, more preferably 0.1 to 20% by mass. By using an organic filler and / or an inorganic filler within this range, a diffusion plate having a good balance of properties such as light transmittance, diffusivity, strength, rigidity, heat distortion temperature and hardness can be obtained.
Examples of organic fillers include polymers and polymer crosslinked particles.
When polymer crosslinked product particles are used as the organic filler, the particle size of the polymer crosslinked product particles is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm.
Examples of the organic filler include acrylic resin, polyurethane, polyvinyl chloride, polystyrene, polyacrylonitrile, polyamide, polysiloxanes, and fluororesin. These organic fillers may be used alone or in combination of two or more.
Examples of the inorganic filler include silica, silica alumina, diatomaceous earth, alumina, calcium carbonate, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, sulfuric acid Examples include calcium, potassium titanate, barium carbonate, barium sulfate, calcium sulfite, tark, clay, mica, asbasate, glass flakes, glass beads, calcium silicate, montmorillonite, pentonite, graphite, aluminum powder, and molybdenum sulfide. These inorganic fillers may be used alone or in combination of two or more. Of these inorganic fillers, calcium carbonate, titanium oxide, alumina, silica, silica alumina, talc, and barium carbonate are particularly preferable.
The inorganic filler preferably has a mass average particle size of 0.5 to 50 μm, more preferably 1 to 30 μm. When the mass average particle size of the inorganic filler is within the above range, when the mass average particle size is increased, the total light transmittance of the obtained light diffusion plate is decreased, the diffusion transmittance is increased, and the display, glazing, blindfold plate, It can be suitably used as a light diffusing plate for lighting equipment or the like. On the contrary, when the mass average particle size of the inorganic filler is within the above range, when the mass average particle size is small, the total light transmittance of the obtained light diffusion plate is increased, the diffuse transmittance is decreased, and the screen of the large display It can use suitably for uses, such as.

By using the optical film (A) as a diffusion plate, a light diffusion sheet of a liquid crystal display device and a backlight unit using the same can be obtained by a conventionally known method.
The light guide plate in the present invention preferably has a fine uneven shape having a light reflecting function on one plane other than the side surface. Examples of the fine concavo-convex shape include a V-shaped groove shape and a continuous prism shape.
The light guide plate using the optical film (A) preferably has a light reflection preventing layer on one plane other than the side surface. As described above, when the light guide plate has a fine uneven shape having a light reflecting function in one flat image other than the side white, the light reflection preventing layer has a fine uneven shape having a light reflecting function. It is preferable that it is an opposite surface.
The light reflection preventing layer is not particularly limited as long as it is a layer having a function of preventing reflection of light such as visible light on the light incident surface, similarly to the light reflection preventing layer of a general optical component, For example, an inorganic thin film, a transparent resin film, etc. are mentioned.
By using a light guide plate using the optical film (A), a light guide plate of a liquid crystal display device and a backlight unit or front light unit using the same can be obtained by a conventionally known method.

<< Thermoplastic resin film (B) containing a lactone ring-containing polymer >>
In the present invention, the thermoplastic resin film is a thermoplastic resin film containing a lactone ring-containing polymer containing a lactone ring-containing polymer and another thermoplastic resin, and has a glass transition temperature of 120 ° C. or higher. A thermoplastic resin film having a retardation per 100 μm in the direction of 20 nm or less and a total light transmittance of 85% or more (hereinafter sometimes referred to as “thermoplastic resin film (B)”) can be used.

When the other thermoplastic resin used for the thermoplastic resin film (B) is blended with a lactone ring-containing polymer to form a film, the glass transition temperature is 120 ° C. or more, and the thickness per 100 μm in the surface direction. Any kind of thermoplastic resin can be used as long as it can exhibit the performance of a phase difference of 20 nm or less and a total light transmittance of 85% or more. This is preferable from the viewpoint of providing an optical film having low retardation and excellent mechanical strength.
The content ratio of the lactone ring-containing polymer and the other thermoplastic resin in the thermoplastic resin film (B) containing the lactone ring-containing polymer is preferably 60 to 99: 1 to 40% by mass, more preferably 70. -97: 3-30 mass%, More preferably, it is 80-95: 5-20 mass%.
Other thermoplastic resins include, for example, olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-1-pentene); halogen-containing polymers such as vinyl chloride and chlorinated vinyl resins. Acrylic polymer such as polymethyl methacrylate; styrene polymer such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer; polyethylene terephthalate, polybutylene terephthalate Polyester such as polyethylene naphthalate, polyamide such as nylon 6, nylon 66, nylon 610, polyacetal, polycarbonate, polyphenylene oxide, polyphenylenesulfur De; polyether ether ketone; polysulfone; polyether sulfone; polyoxyethylene benzylidene alkylene; polyamideimide; polybutadiene rubber, rubber-like polymer such as ABS resin or ASA resin containing an acrylic rubber; and the like. The rubbery polymer preferably has on its surface a graft portion having a composition that is compatible with the lactone ring-containing polymer, and the average particle size of the rubbery polymer is transparency when formed into a film. From the viewpoint of improving the thickness, it is preferably 100 nm or less, more preferably 70 nm or less.

Examples of the thermoplastic resin which is thermodynamically compatible with the lactone ring-containing polymer include a copolymer having a vinyl cyanide monomer unit and an aromatic vinyl monomer unit, specifically, acrylonitrile- Examples thereof include polymers containing 50% by mass or more of styrene-based copolymers, polyvinyl chloride resins, and methacrylic esters. Among these thermoplastic resins, when an acrylonitrile-styrene copolymer is used, the glass transition temperature is 120 ° C. or more, the phase difference per 100 μm thickness in the plane direction is 20 nm or less, and the total light transmittance is 85% or more. An optical film can be easily obtained. Note that the thermodynamic compatibility of the lactone ring-containing polymer and other thermoplastic resins should be confirmed by measuring the glass transition temperature of the thermoplastic resin composition obtained by mixing them. Can do. Specifically, only one point of the glass transition temperature measured by the differential scanning calorimeter is observed for the mixture of the lactone ring-containing polymer and the other thermoplastic resin, so that the thermodynamic compatibility is achieved. I can say that.
When an acrylonitrile-styrene copolymer is used as another thermoplastic resin, an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, or the like can be used as the production method. From the viewpoint of the transparency and optical performance of the resin film (B), it is preferable to use a solution polymerization method or a bulk polymerization method.

The thermoplastic resin composition (B) may contain various additives. Examples of additives include antioxidants such as hindered phenols, phosphorus, and sulfur; stabilizers such as light stabilizers, weather stabilizers, and heat stabilizers; reinforcing materials such as glass fibers and carbon fibers; phenyls UV absorbers such as salicylate, (2,2′-hydroxy-5-methylphenyl) benzotriazole, 2-hydroxybenzophenone; near infrared absorbers; tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide, etc. Flame retardants; antistatic agents such as anionic, cationic and nonionic surfactants; colorants such as inorganic pigments, organic pigments and dyes; organic fillers and inorganic fillers; resin modifiers; organic fillers and inorganics Fillers; plasticizers; lubricants; antistatic agents; flame retardants;
The content of the additive in the thermoplastic resin film (B) is preferably 0 to 5% by mass, more preferably 0 to 2% by mass, and still more preferably 0 to 0.5% by mass.
Production of the thermoplastic resin film (B) can be carried out according to the above-described method, for example, a lactone ring-containing polymer, other thermoplastic resin, and, if necessary, a conventionally known mixture. It can be mixed well by the method and formed into a film.

<Optical film (B)>
The thermoplastic resin film (B) is used as, for example, an optical film (hereinafter sometimes referred to as “optical film (B)”).
An optical film (B) is an optical film which can fully exhibit the characteristic according to various optical uses.
The optical film (B) has a glass transition temperature of 120 ° C. or higher, preferably 125 ° C. or higher, more preferably 130 ° C. or higher.
The optical film (B) preferably has a retardation per 100 μm thickness in the plane direction of 20 nm or less, more preferably 10 nm or less.
The optical film (B) preferably has a total light transmittance of 85% or more, more preferably 87% or more, and more preferably 90% or more.
The optical film (B) has a small incident angle dependency of the phase difference, and the difference between the phase difference R ₀ per 100 μm thickness at an incident angle of 0 ° and the phase difference R ₄₀ per 100 μm thickness at an incident angle of 40 ° ( R ₄₀ -R ₀ ) is preferably less than 20 nm, more preferably less than 10 nm.
The optical film (B) has a thickness of preferably 1 μm or more and less than 500 μm, more preferably 10 μm or more and less than 300 μm. By setting the thickness to 1 μm or more, mechanical strength tends to be improved, and breakage or the like hardly occurs when stretching.
The optical film (B) preferably has a tensile strength measured according to ASTM-D-882-61T of 10 MPa or more and less than 100 MPa, more preferably 30 MPa or more and less than 100 MPa. By setting the tensile strength to 10 MPa or more, sufficient mechanical strength tends to be easily developed, and by setting the tensile strength to 100 MPa or more, workability tends to be improved.
In the optical film (B), the elongation measured according to ASTM-D-882-61T is preferably 1% or more, more preferably 3% or more. The upper limit of the elongation is not particularly limited, but is usually preferably 100% or less. It is preferable that the elongation is 1% or more because the toughness tends to be improved.
The optical film (B) preferably has a tensile modulus measured in accordance with ASTM-D-882-61T of 0.5 GPa or more, more preferably 1 GPa or more, and even more preferably 2 GPa or more. The upper limit of the tensile elastic modulus is not particularly limited, but is usually preferably 20 GPa or less. It is preferable that the tensile elastic modulus is 0.5 GPa or more because mechanical strength tends to be improved.

Although the manufacturing method of an optical film (B) is not specifically limited, For example, a lactone ring containing polymer, another thermoplastic resin, and an additive etc. with a conventionally well-known mixing method as needed. The optical film (B) can be produced after mixing and preparing a thermoplastic resin composition in advance. As a method for producing this thermoplastic resin composition, for example, a method of pre-blending with a mixer such as an omni mixer and then extruding and kneading the obtained mixture can be employed. In this case, the kneader used for extrusion kneading is not particularly limited. For example, a conventionally known kneader such as an extruder such as a single screw extruder or a twin screw extruder or a pressure kneader can be used. .
As a film forming method, a conventionally known film forming method may be used, and examples thereof include a solution casting method (solution casting method), a melt extrusion method, a calendar method, and a compression molding method. Of these film forming methods, the solution casting method (solution casting method) and the melt extrusion method are particularly preferable. At this time, a thermoplastic resin composition that has been extruded and kneaded in advance as described above may be used, or a lactone ring-containing polymer and other thermoplastic resins, and if necessary, additives and the like may be separately added to the solution. After being dissolved to obtain a uniform mixed solution, it may be subjected to a film forming process such as a solution casting method (solution casting method) or a melt extrusion method.
Examples of the solvent used in the solution casting method (solution casting method) include chlorine solvents such as chloroform and dichloromethane; aromatic solvents such as toluene, xylene and benzene; methanol, ethanol, isopropanol, n-butanol, Examples include alcohol solvents such as 2-butanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, and diethyl ether. These solvents may be used alone or in combination of two or more.
Examples of the apparatus for performing the solution casting method (solution casting method) include a drum casting machine, a band casting machine, and a spin coater.
Examples of the melt extrusion method include a T-die method and an inflation method. In this case, the film forming temperature is preferably 150 to 350 ° C., more preferably 200 to 300 ° C.
When the film is formed by the T-die method, a T-die is attached to the tip of a known single-screw extruder or twin-screw extruder, and the film extruded into a film shape can be obtained as a roll-like film. At this time, it is possible to adjust the temperature of the winding roll as appropriate and apply stretching in the extruding direction to achieve a uniaxial stretching step. Moreover, it is also possible to add processes, such as a sequential biaxial stretching and simultaneous biaxial stretching, by adding the process of extending | stretching a film in the direction perpendicular | vertical to an extrusion direction.
The optical film in the present invention may be an unstretched film or a stretched film. When stretching, a uniaxially stretched film or a biaxially stretched film may be used. When a biaxially stretched film is used, it may be biaxially stretched simultaneously or sequentially biaxially stretched. In the case of biaxial stretching, the mechanical strength is improved and the film performance is improved. The optical film in the present invention can suppress an increase in retardation even when stretched by mixing other thermoplastic resins, and can maintain optical isotropy.
The stretching is preferably performed in the vicinity of the glass transition temperature of the thermoplastic resin composition of the film material. The specific stretching temperature is preferably (glass transition temperature-30 ° C) to (glass transition temperature + 100 ° C), more preferably (glass transition temperature-20 ° C) to (glass transition temperature + 80 ° C). . If the stretching temperature is less than (glass transition temperature-30 ° C.), a sufficient stretching ratio may not be obtained. Conversely, when the stretching temperature exceeds (glass transition temperature + 100 ° C.), the resin may flow and stable stretching may not be performed.

The draw ratio defined by the area ratio is preferably 1.1 to 25 times, more preferably 1.3 to 10 times. When the draw ratio is 1.1 times or more, the toughness due to drawing tends to be improved. Conversely, when the draw ratio is 25 times or less, the effect of increasing the draw ratio tends to be exhibited.
The stretching speed (one direction) is preferably 10 to 20,000% / min, more preferably 100 to 10,000% / min. When the stretching speed is 10% / min or more, the time for obtaining a sufficient stretching ratio tends to be shortened, and the production cost can be easily suppressed. Conversely, by setting the stretching speed to 20,000% / min or more, the stretched film tends to be less likely to break.
In order to stabilize the optical isotropy and mechanical properties of the film, heat treatment (annealing) or the like can be performed after the stretching treatment.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Example 1
(Production of core)
With the shape shown in Table 1, cores A-1 to A-3 and comparative cores-A1 and A2 were produced by the FW method. The size of the winding core was set to an inner diameter of 150 mm, an outer diameter of 166 to 168 mm, and a length of 1620 mm. The core was formed by winding a prepreg resin layer using epoxy resin as glass, carbon fiber, and matrix resin for the base material layer, the first winding layer, and the second winding layer, respectively. About the formed core preform, the ratio of the glass fiber and carbon fiber of each layer and the number of turns were adjusted so that the elastic modulus of the finished core was the value shown in Table 1. The core surface is coated with an epoxy conductive resin, and the surface is polished so that both end portions and the center portion of the core have the circumferential length shown in Table 1, respectively. Each core was adjusted so that the ratio (%) was as shown in Table 1.

(Circumferential circumference)
The circumference of the core was measured by using a strip scale (JIS class 1) with an accuracy of 0.1 mm and measuring the circumference of the center and both ends of the core.

(Elastic modulus of the core)
The elastic modulus of the core was obtained from the load-deflection ratio after the core was supported so that the distance between the fulcrums was 1250 mm, and a load was applied to the center of the core.

(Surface roughness)
The surface roughness Ra value was measured according to JIS B 0601, using a surface roughness meter Surfcom 111A from Tokyo Seimitsu Co., Ltd., and measuring the centerline average roughness at 3 points with a cutoff of 0.25 mm. The average value was defined as the surface roughness.

Example 2
(Production of lactone ring-containing polymer)
<Preparation of lactone ring-containing polymer pellet (A)>
A lactone ring-containing polymer pellet (A) was obtained according to the synthesis method described in International Publication WO2006 / 025445A1 Pamphlet [0230] to [0232].

<Preparation of lactone ring-containing polymer pellet (B)>
A lactone ring-containing polymer pellet (B) was obtained according to the synthesis method described in International Publication WO2006 / 025445A1 Pamphlet [0245] to [0247].

Example 3
(Production and roll winding)
The lactone ring-containing polymer pellets (A) prepared in Example 2 were melt extruded to produce 2500 rolls of 1450 mm and an average thickness of 80 μm of resin film 2500 m, and the cores A-1 to A-1 prepared in Example 1, respectively. A-3 and comparative cores-A1 and A2 were wound at 25 ° C. and 55% RH under a condition in which a tension of 130 N was applied.

  The wound film original sample is placed on a pedestal so that the film original film does not touch the floor, etc., and the film original film is wrapped twice with a polyethylene sheet, under conditions of 25 ° C. and 50% RH. And stored for 30 days. Thereafter, the polyethylene sheet was opened, the film was rewound from the roll, and 10 samples of 2450 m in width and 1450 mm in width were taken at 300 m, 1200 m, and 2400 m from the outside, and the number of surface faults was counted visually. .

  In the film raw material using the winding core of the present invention, preferable results with few planar failures were obtained.

Example 4
(Production and roll winding)
The lactone ring-containing polymer pellet (B) produced in Example 2 was subjected to acrylonitrile-styrene (manufactured by Asahi Kasei Co., Ltd., Stylac (R) -AS783) according to the method described in [0311] of International Publication WO2006 / 025445A1. ) (AS resin) was kneaded at a mass ratio of lactone ring-containing polymer / AS resin = 90/10 using a single screw extruder to obtain transparent pellets of the thermoplastic resin composition.

  This thermoplastic resin composition was dissolved in methyl ethyl ketone, and 5 rolls of unstretched film having a thickness of 40 μm, a width of 1450 mm, and a length of 4100 m were prepared by a solution casting method. -A-3 and comparative winding cores-A1 and A2 were wound up under the same conditions as in Example 3.

  The wound film original sample is placed on a pedestal so that the film original film does not touch the floor, etc., and the film original film is wrapped twice with a polyethylene sheet, under conditions of 25 ° C. and 50% RH. And stored for 30 days. Thereafter, the polyethylene sheet was opened, the film was rewound from the roll, 10 samples of 1450 mm in width and 1450 mm in width were taken at 300 m, 2000 m, and 3800 m from the outside, and the number of surface faults was counted visually. .

  In the film raw material using the winding core of the present invention, preferable results with few planar failures were obtained.

An example of the winding core in this invention is shown. The shape of the core produced in the example of the present application is shown. The shape of the core produced in the example of the present application is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Core body 11 Core 12 Base material layer 13 Fiber 14 First winding layer 15 Second winding layer 16 Coating layer

Claims (3)

  A core and a thermoplastic resin film containing a lactone ring-containing polymer wound around the core, and the core has an elastic modulus in the range of 10 GPa to 40 GPa, and the thermoplastic resin film is An original thermoplastic resin film having a film width of 1350 mm or more and a film thickness of 20 μm to 80 μm.  2. The thermoplastic resin film raw material according to claim 1, wherein a circumferential length of a central portion in the width direction is longer in a range of 0.5 mm to 10 mm than a circumferential length of both end portions in the width direction.   The thermoplastic resin film original fabric according to claim 1 or 2, wherein the core has an elastic modulus in a range of 10 GPa to 20 GPa.

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