TWI302870B - Polycarbonate film-based optical film, process for producing it, optical film having adhesive layer, and process for producing it - Google Patents

Description

1302870 IX. Description of the Invention: [Technical Field] The present invention relates to a polycarbonate film having no substantial defects for use in optical applications such as a cover layer of an optical disk or a surface protective layer of a display. An optical film as a substrate, in particular, an optical hard coat film. Further, the present invention relates to an optical film with an adhesive layer, an optical hard coat film with an adhesive layer, and a compact disc. Further, the present invention relates to an optical film comprising a polycarbonate film having no substantial defect, and a method for producing an optical film having an adhesive layer. [Prior Art] Polycarbonate has excellent transparency, is lightweight, and has excellent impact properties, and thus can be widely used in various industries, building materials, decorative materials, optical materials, and household materials as materials for replacing glass. In particular, a polycarbonate film obtained by a casting method (solvent casting method) is used as a substrate of an optical functional film because of its extremely low optical anisotropy, and is used as a substrate for an optical functional film. The amount is expanding year by year.

In particular, in recent years, a plastic cover film of about 100 micrometers has been discussed as a cover layer of a high-density optical disk using a blue-violet laser light source, but it preferably has a coefficient of thermal expansion similar to that of a substrate, and thus is generally used with the substrate. For the homogenous material. For this reason, the resin substrate of the optical disk is generally made of a polycarbonate resin. Therefore, the light-transmitting substrate film is also being reviewed for practical use centering on the polycarbonate film. When a polycarbonate film obtained by a casting method (solvent casting method) is used as an optical functional film, the functional layer is formed by containing a functional material 1302870, a curable resin, and an organic solvent. The composition was coated on a polycarbonate film and hardened to form. A hard coat film having a polycarbonate film as a base material will be further described below as an example. Polycarbonate films have the disadvantage of low surface hardness and poor scratch resistance. Therefore, a method of imparting a hard coat layer to the surface of a polycarbonate film to increase the surface hardness is generally employed. On the other hand, a method of forming a hard coat layer on a plastic film substrate is mainly composed of a curable organic compound such as a polyfunctional (meth)acrylic monomer or a photo-coupling initiator, and is used for improving coating properties. The ultraviolet curable resin composition to which an organic solvent as a diluent is added is continuously applied to a plastic film in a roll-to-roll manner, and subjected to a drying step, and the method of ultraviolet irradiation is widely used because of its high productivity. Further, in the organic solvent, since methyl ethyl ketone has a strong dissolving power and a high boiling point and a low vapor pressure, it is widely used as a diluent. The patent documents relating to the present invention are explained below. There has been a proposal for a solvent for a curable composition for a polycarbonate film. For example, in the prior patent document 1, there has been proposed a method of controlling the ratio of the solvent which erodes the polycarbonate β to the solvent which does not erode in the step of laminating the hard coat layer on the substrate of the polycarbonate film. - In Patent Document 2, it is proposed to disclose that a solvent for a curable composition for a polycarbonate resin is displayed by adding a solvent having a boiling point of 120 ° C to 160 ° C and capable of dissolving a polycarbonate resin. Adhesion of the carbonate resin substrate. 1302870 In Patent Document 3 and Patent Document 4, the side of the optical film formed by casting a resin solution of polycarbonate on a support of polyethylene terephthalate to the support is indicated. A number of surface defects of about 3 () to 1 〇〇 micron are generated. CITATION LIST Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

CITATION LIST Patent Document 3: Japanese Patent Application Laid-Open No. 2003- 326542 (Patent Document No. 2003-326543) SUMMARY OF THE INVENTION [Technical Problem to be Solved] However, by the present invention The inventors of the present invention have found that the ultraviolet light-curable composition using methyl ethyl ketone as a diluent solvent is continuously applied in a roll-to-roll manner on a polycarbonate film substrate by a coating and drying step. When a hard coat film is produced by a method of ultraviolet irradiation, a bump-like defect of about 50 to 100 μm which is mainly composed of polycarbonate is generated. As a result of review by the inventors of the present invention, it has been found that the number of point defects can be drastically reduced by setting the content of the solvent which causes the polycarbonate to swell. However, even if the solvent is set, the defect at this point remains. However, up to now, it has been proposed to set the physical properties of the organic solvent in the curable composition coated on the polycarbonate film substrate, and it is intended to reduce the surface defect by 1302870, and the countermeasures may remain. The report on the causes of the point defects and the countermeasures were not disclosed. For example, in the method disclosed in Patent Document 1, although the solvent which erodes the polycarbonate is contained in the total solvent in an amount of 70% by weight or more in order to improve the adhesion, the purpose of reducing the bump defect is In terms of it, it is counterproductive. Further, the proposal disclosed in Patent Document 1 is that the reduction of the bump-like defect is an inverse effect as described above, and the definition of the solvent which dissolves the polycarbonate resin is ambiguous, and When the thickness is 30 μm, the result is that point defects on the surface of the polycarbonate substrate are buried in the hardened layer without being a problem. Further, as disclosed in Patent Document 3 and Patent Document 4, a specific method capable of reducing point defects has not been disclosed. In view of the above circumstances, an object of the present invention is to provide an optical film which is used as a substrate with a polycarbonate film and which is laminated with a hard layer which is substantially free from point defects, and an optical hard coat film, and provides an attachment There are such optical hard coating films. % [Technical means for solving the problem] That is, the optical film of the present invention is characterized in that an average film thickness of 1.0 to ^ 8.0 is formed on a film substrate made of polycarbonate and obtained by a casting method. a micron hardened layer, and the number of bumps having a diameter of 50 μm or more from the polycarbonate of the film substrate in the hardened layer (inclusive of the inner package β) is every 10 cm square It is an average of 1 or less. Further, in the optical film of the present invention, the film substrate obtained by casting a coating liquid on a casting tape by a casting die is used. Further, in 1302870 - when a film substrate is produced, a casting tape having a number of pinholes of 50 μm or more in the welded portion of the casting tape is used. Further, a casting belt having a number of pinholes of 40 to 50 μm in the welded portion of the casting belt of 5 or less is used. Further, the number of pinholes having a diameter of 70 μm or more on the general surface other than the casting portion of the casting tape is used. Further, the number of pinholes having a normal surface diameter of 40 to 70 μm is 5/m2 or less. Further, in the optical film of the present invention, the hardened layer is a curable composition for a transparent polycarbonate film substrate containing a curing agent and an organic solvent, and the solubility parameter (SP値) is 8.3 or more and 10.5. The following organic solvent is a layer formed of a curable composition having a content of 60% by weight or less in an all organic solvent. Further, the hardened layer is a layer formed of a curable composition containing no organic solvent having a solubility parameter (SP値) of 9.0 or more and 10.0 or less. Further, in the optical film of the present invention, the average thickness of the hardened layer is preferably 1.0 to 4.0 μm, more preferably 2.5 to 4.0 μm. Further, the optical film with an adhesive layer of the present invention is as described above. On the surface of the un-hardened layer of the thin Φ film substrate, an adhesive layer having a film thickness of 10 μm or more is laminated. Further, in the optical film with an adhesive layer of the present invention, the surface of the film-substrate having an unlaminated hardened layer is an air surface of the film substrate which is formed on a casting tape, and a laminated adhesive is used. The surface of the layer is the surface. Further, the present invention is an optical hard coat film having a hard coat layer which is scratch resistant to steel wool or an optical hard coat film having an adhesive layer. Further, the present invention is a disc having the above-mentioned optical hard coat film with an adhesive layer attached thereto. Further, the present invention relates to a method for producing an optical film by casting a coating liquid on a casting tape by a casting die to produce a film substrate composed of polycarbonate, and then laminating an average film on the film substrate. The hardened layer has a thickness of 1.0 to 8.0 μm, and the number of pinholes having a diameter of 50 μm or more in the welded portion of the casting tape is one. Further, it is a manufacturing method of an optical film in which the number of pinholes having a diameter of 70 μm or more on a general surface other than the welded portion of the casting tape is zero. Further, the present invention is a method for producing an optical film with an adhesive layer, characterized in that a casting liquid is cast on a casting tape by a casting die to produce a film substrate composed of polycarbonate, The film substrate has a hardened layer having an average film thickness of 1.0 to 8.0 μm formed on the air surface when the film substrate is produced on the casting tape, and the film thickness of the film substrate is 10 μm when the film substrate is formed on the casting tape. The above adhesive layer. More specifically, the above technical problem can be solved by the following method. Φ 1. An optical film characterized in that it is composed of an aromatic polycarbonate composed of bisphenol A as an aromatic dihydroxy component and is casted by a casting method (solvent casting method). The hardened layer having an average film thickness of 1.0 to 8.0 μm is formed, and the number of bumps having a diameter of 50 μm or more in which the polycarbonate derived from the film substrate is contained in the hardened layer is one per one turn. The square is equal to one or less. 2. The optical film of item 1, wherein the portion of the polycarbonate which is derived from the film substrate is bonded to the thin film of the polycarbonate -10-1302870 film. 3. The optical film of items 1 to 2 above, wherein the number of raised point defects is an average of 〇5 or less per 10 cm square. 4. The optical film according to items 1 to 2 above, wherein the number of the raised point defects is an average of less than one square per 10 cm square. The optical film according to any one of items 1 to 4, wherein the hardened layer has a thickness of 1.0 to 4.0 μm. 6.

The optical film of any one of items 1 to 4, wherein the hardened layer has a thickness of 2.5 to 4.0 μm. The optical film according to any one of items 1 to 6, wherein the plastic film substrate has a thickness of 50 to 1 μm. The optical film according to any one of items 1 to 6, wherein the plastic film substrate has a thickness of 70 to 90 μm. The optical film according to any one of items 1 to 8, wherein the plastic film substrate has a thickness of 4 μm or less.

The optical film according to any one of items 1 to 9, wherein the plastic film substrate has a thermal dimensional change rate of 〇. 〇 7 % or less. The optical film according to any one of items 1 to 10, wherein the in-plane retardation of the plastic film substrate is 15 nm or less. The optical film according to any one of items 1 to 11, wherein the plastic film substrate has a total light transmittance of 90% or more. The optical film according to any one of items 1 to 12, wherein the residual amount of the solvent of the plastic film substrate is 0.3% by weight or less. The optical film according to any one of items 1 to 13, wherein the plastic -11 - 1302870 film substrate has a retardation 値 (Rth 値) in the thickness direction of 100 nm or less. The optical film according to any one of items 1 to 14, wherein the surface roughness Ra of the plastic film substrate (without surface protection film) is 5.0 nm or less on both sides. The optical film according to any one of items 1 to 15, wherein the plastic film is cast on the casting tape by a casting die to produce a film.

The number of pinholes having a diameter of 50 μm or more in the welded portion of the casting tape used at that time is one. The optical film according to any one of items 1 to 16, wherein the number of pinholes having a diameter of 40 to 50 μm in the welded portion is 5 or less. The optical film according to any one of items 1 to 17, wherein in the method of casting a coating liquid on a casting tape by a casting die to produce a film, a general surface other than the welded portion is used. The number of pinholes having a diameter of 70 μm or more is one of the casting zones. 19. The optical film of item 18, wherein the number of pinholes having a diameter of 40 to 70 μm in the general surface is 5/m2 or less. The optical film of any one of items 16 to 19, wherein the casting tape is made of metal. The optical film of item 20, wherein the casting tape is made of stainless steel, and the optical film of any one of items 16 to 21, wherein the casting tape is an endless belt. The optical film according to any one of the items 16 to 22, wherein the hard layer of the flat film of -12-1302870 having a film thickness of 1·0 to 8·0 μm is laminated on the surface of the plastic film. The optical film according to any one of the items 1 to 23, wherein the hardened layer is a hardenable composition for a transparent polycarbonate film substrate containing a hardener and an organic solvent, and the organic solvent is The solvent (S) which erodes the polycarbonate film at 25 ° C in a total organic solvent content of 60% by weight or less is formed by a hardenable composition for a polycarbonate film. The optical film in which the solvent (S) of the curable composition which erodes the polycarbonate film is contained in an organic solvent content of 50% by weight or less. The optical film of item 24, wherein the solvent (S) of the hardenable composition which erodes the polycarbonate film is 40% by weight or less in the total organic solvent.

The optical film according to any one of the items 24 to 26, wherein the solubility parameter (SP値) of the solvent (S) which erodes the polycarbonate film of the curable composition is 8.3 or more and 10.5 or less. . The optical film according to any one of the items 24 to 27, wherein the solubility parameter (SP値) in the solvent (S) of the curable composition which erodes the polycarbonate film is 9.0 or more and 10.0 or less. The content in the total organic solvent is 20% or less. 29. The optical film of item 28, wherein the solubility parameter (SP値) in the solvent (S) of the hardenable composition erodes the polycarbonate film is 9.0 or more and 10.0 or less in the total organic solvent. It is -13 - 1302870 1 〇% or less. The optical film according to item 28, wherein the solubility parameter (SP値) in the solvent (S) which erodes the polycarbonate film is 9.0 or more and 10.0 or less, and the content in the total organic solvent is 5% or less. 3. The curable composition for a polycarbonate film according to item 28, which does not contain an organic solvent having a solubility parameter (SP値) of 9.0 or more and 10.0 or less.

The optical film according to any one of the items 24 to 31, wherein the hardening composition contains 2 to 40% by volume of the inorganic oxide fine particles with respect to the solid portion. The optical film of any one of items 1 to 32, wherein the hardened layer is formed of an active energy ray hardening composition. The optical film with an adhesive layer according to any one of items 1 to 33 above, wherein an adhesive layer is laminated on the surface of the unhardened layer of the plastic film. 35. The optical film of claim 34, wherein the surface of the hardfacing layer of the plastic film is an air surface, and the surface of the layer of the adhesive layer is a belt surface. 36. The optical film of claim 35, wherein the adhesive layer has a film thickness of 1 Å or more. 37. An optical film comprising an adhesive layer according to item 36 above, wherein the layer of the adhesive layer is applied by directly applying an adhesive layer coating liquid to the plastic film. The optical film of any one of the above-mentioned items 1 to 33, or the optical hard coat film with an adhesive layer according to any one of items 34 to 37, which has When the functional surface was made of steel wire of #0000, a hard coating having a scratch resistance characteristic of a mark was not observed while applying a load of 1.96 N/cm 2 and rubbing back and forth for 10 times. 39. An optical hard coat film having an adhesive layer as described in item 38 above, which is used as a cover layer for a disc which is read and written by blue laser light having a wavelength of 400 to 432 nm. 40. A kind of optical disc, attached to the optical disc of item 38 as described above with adhesive

The optical hard coat film of the agent layer serves as a cover layer. [Effect of the Invention] According to the present invention, an optical film which is substantially suitable for use in a cover layer for an optical disk and which has no point defects on the hardened layer, an optical film with an adhesive layer, and an optical hard coat can be provided. A film, an optical hard coat film with an adhesive layer, and a disc having scratch resistance. [Embodiment] [Best Mode for Carrying Out the Invention]

The optical film of the present invention which uses a polycarbonate film as a substrate and which forms a hardened layer substantially free of point defects will be described in detail below. In the present specification, when the number is a physical property, a characteristic, or the like, for example, "(number 値1) to (number 値2)" means "(number 値1) or more, (number 値) 2) The following". In addition, in the present specification, for example, "(meth)acrylonitrile", "(meth)acrylate", "(meth)acrylic acid" and the like mean "acryloyl group and/or methyl group", respectively. Acrylsulfonyl, "acrylate and/or methacrylate", "acrylic acid-15-1302870, and/or methacrylic acid". [Current Review Status] When a functional layer is formed on a polycarbonate film substrate, in order to control the physical properties of the coating liquid and improve the coating property, a diluent such as methyl ethyl ketone is generally used. The solvent such as methyl ethyl ketone is immersed in the polycarbonate film after being applied through the coating liquid until it is dried, and the surface thereof is unevenly swollen, and the interface between the film and the coating liquid is about A size of 50 μm to 1 μm and a ridge-like point defect of 10 or more squares (hereinafter also referred to simply as a point defect). As a result of the review by the inventors of the present invention, it is understood that the number of point defects can be greatly reduced by setting the content of the organic solvent which causes the polycarbonate in the coating liquid to swell. However, even if a solvent which does not swell the polycarbonate is used, such defects are not completely eliminated, so that there are still a plurality of ridge-like defects having a diameter of 50 μm or more, which may remain in a few of 10 cm square. For example, when the functional film is used as an optical film for image display device Φ such as a liquid crystal display, attention is paid to the formation of a dot defect, and the quality of the image display device is lowered. Further, when the optical film is used as a coating layer for an optical recording material such as a compact disc, a point defect is a cause of noise. Therefore, the use of a hard coat film for optical use, particularly when used in an image display device such as a display or a compact disc, is strongly required to reduce the number of such defects and to make it as close as possible. Therefore, in the case of a functional film using a polycarbonate film as a substrate, the measure of reducing the bump-like defects or infinitely close to zero is extremely heavy -16 - 1302870. In particular, regarding the optical disc, in recent years, although a high-density optical disc having a blue-violet laser light source and a plastic cover film of about 100 μm is being reviewed, the pit length tends to be short due to high density, and the pit is pitted. The interval becomes narrow, and the thickness of the cover layer is about 1.2 mm with respect to the CD (disc), and about 0.6 mm of the DVD (digital versatile disc), so that the surface such as about 0.1 mm is close to the recording layer, The reduction in the projected area of the laser light on the surface of the cover layer corresponds to this portion, so the influence of the point defect is large, and the importance of removing the point βρ defect is increasing. For example, if a point defect completely obstructs the transmission of the laser light, then [(the projection area of the laser light) - (the projected area of the point defect)] / the projection surface of the laser light will become the signal intensity, and the signal intensity will follow the point defect. The size is reduced, and when the size of the point defect exceeds the projected area of the laser light, the signal will completely disappear. In addition, in terms of specifications, a defect having a diameter of 50 μm or more is regarded as a cause of noise for recording. Even if the point defect does not exceed the projected area of the laser light, the higher the intensity of the Φ signal, the easier it is to recognize the high reflectance portion/low reflectance portion, so that the probability of picking up as a signal will increase. Therefore, the smaller the size of the point defect, the better. Λ On the other hand, if the point defect is such that light is scattered or reflected, the low reflectance portion is affected, and as a result, it is difficult to recognize as described above. [Analysis of the cause of the dot defect] In order to analyze the point defect existing after the content of the solvent which swells the polycarbonate by setting the restriction, the cross-sectional observation of the defect using the electron microscope -17-1302870^ was performed. As a result, the point defect was increased by about 50% in the film thickness near the apex thereof, and the film thickness was slowly decreased. A characteristic phenomenon is that a plate-like foreign matter having a thickness of several micrometers is contained inside, and the end portion thereof is bonded to the surface of the base film. It is caused by a spot-like convex failure on the polycarbonate film produced by the pinholes of the tape used for the production of the film. The internal polycarbonate foreign matter of the bump-like defect is flat because the slight convex fault caused by the pinhole of the belt is subsequently crushed by the reel (see [Fig. 6]). . • [Pinholes in the belt] The polycarbonate film used in the present invention is produced by a solution film forming method, and is produced, for example, by a film forming apparatus as shown in Fig. 1. In Fig. 1, 10 is a casting step of casting a coating liquid on a support, 20 is an extension drying step of stretching a film formed by a casting step 10 by a tenter, and 30 is drying the stretched film. The drying step. The casting step 10 is such that the casting die 1 is provided, and the coating liquid in which the cellulose ester is dissolved in the solvent is cast by the casting die 1 1 on the casting tape 12 provided below. The extension step % 20 is to set the tenter 2 1 to extend the film in the width direction while drying it. The drying step 30 is such that the conveying roller 31 is provided to dry the film conveyed by the conveying roller 31 with the drying wind 32. The 40 series is used to take up the take-up portion of the finished film. The casting tape 12 is formed by welding a long strip of stainless steel into an endless loop as shown in Fig. 2, and can be divided into a welded portion 12a to which welding is applied, and a general surface 12b other than the welded portion 12a. The corner 0 of the welded portion 12a is generally formed at 90 degrees. The casting belt is manufactured by an endless belt and an opening 180-1302870*. The endless belt is welded to an endless loop, and is installed in the film forming device. The plate wound into a coil shape is attached to the film forming apparatus, and is formed into an endless loop by welding. When the coating liquid is cast by the casting tape 1 2 as described above to form a film, if the defect of the pinhole 50 or the like is present in the casting tape 12, the surface quality of the film deteriorates. In particular, in the case of an optical film having a hardened layer having a relatively thin film thickness of 1 〇 to 8 μm, the defect portion is enlarged when compared with the case where the hardened layer is not formed. For example, the foreign matter of the polycarbonate containing the inside of the 1 〇〇 micron ridge-like defect is about 10 μm. Therefore, the defect will be enlarged to about 10 times due to the presence of the hardened layer. [Improvement of pinholes] It has been found that the ridge-like defects which are considered to be problems in the present invention can be solved by eliminating the pinholes of the casting tape to eliminate the disadvantages of the constituent polycarbonate. These pinholes can be improved by using a solution film forming method disclosed in Japanese Laid-Open Patent Publication No. 2002-234041. That is, the % of the solution film forming method usable in the production of the optical film of the present invention is used in a method of casting a film by casting a coating liquid on a casting tape by a casting die, and is used in a welded portion. A casting zone having a number of pinholes having a diameter of 50 μm or more is composed of zero. Further, a solution film forming method which can be used in the production of the optical film of the present invention or the like is a method of producing a film by casting a coating liquid on a casting tape by a casting die, and is used in a general state other than the welded portion. The number of pinholes having a surface diameter of 70 μm or more is composed of one of the casting zones. . In other words, the solution -19-1302870^ which is available for use in the production of the optical film of the present invention is a pinhole which is set in the general portion of the welded portion of the casting tape. The so-called welded portion is a portion to which the welded portion is applied when the casting tape is formed into an endless loop shape, and generally has a width of about 6 mm and a length of about 1.5 to 2.0 m. The general surface is the welding part of the casting belt " Further, in general, since the pinholes generated in the welded portion are deeper than the pinholes generated in the general surface, and the maintenance is difficult, the required specifications of the welded portion are stricter than the general surface. That is, in the present invention, it is necessary to use a casting tape having a diameter of 50 μm in the welded portion and a number of pinholes in the §§, preferably a needle having a diameter of 40 to 50 μm in the welded portion. The number of holes is 5 or less. The pinholes having a diameter of 40 to 50 μm are 5 or less as described above, but the pinholes having a deeper depth (about 50 μm or more) are preferably 0. A pinhole having a diameter of less than 40 μm is preferably within a permissible range because of the adverse effect on the surface quality of the film formed film, but it is of course less preferred. Further, in the present invention, it is necessary to use a casting tape having a number of pinholes having a diameter of 70 μm or more on a general surface other than the welded portion, preferably a number of pinholes having a diameter of 40 to 70 μm. 5 or less casting tapes. Pinholes having a diameter of less than 40 μm are preferably within the allowable range, although the adverse effects on the surface quality of the film formed film are within the allowable range, but it is of course less preferred. The diameter of the pinhole is the average 値 of the diameter of the orthogonal length direction and the width direction. That is, as shown in Fig. 3, when the length of the pinhole 50 in the longitudinal direction is a and the length in the width direction is b, the diameter of the pinhole 50 will be (a + b) / 2. If you want to determine the diameter and number of pinholes, you can use the judgment according to the microscope -20 - 1302870 - break ' according to the reproduction method. According to the judgment of the microscope, the pinholes on the casting tape are visually observed through a microscope, and judged according to the replica method. After applying the solvent on the casting tape, the cellulose triacetate film is pressed to make the pinholes turn. This is carried out by printing on a film and then observing the transfer marks on the film. The judgment according to the reproduction method is judged more accurately than the judgment based on the microscope. Therefore, it is usually judged by a microscope, and it is judged by the reproduction method in a subtle situation close to the specification. By using the judgment according to the microscope and the judgment according to the replica method as appropriate, it is possible to make an accurate judgment every time. [Use of polycarbonate air surface] If the polycarbonate film cannot eliminate the disadvantage of the pinhole caused by the surface, it is possible to avoid this problem as long as the hardened layer is not laminated on the belt surface. For example, when the cured film is used as a cover layer for an optical disk, a hard coat layer is laminated on one surface of the polycarbonate film, and an adhesive layer is laminated on the other surface. In general, the film thickness of the adhesive layer is 10 μm or more, and the defects on the polycarbonate film resulting from the pinholes are completely buried therein without being noticed. When the film is formed on the belt by the casting method, the dust caused by the film forming environment will fall on the air surface side, and a part thereof will be taken into the undried film to become a foreign matter of the surface. Therefore, in general, one of the belt faces is caused by dust and foreign matter, so that the hardened layer is laminated on the belt surface. A hardened layer of 1.0 to 8.0 μm is provided on one surface of the polycarbonate film, and a layer of 1 μm or more is provided on the other surface, particularly in the structure of the laminated adhesive layer, and the film forming environment is reduced by an individual method. After the dust, the hardened layer is distributed. 21 - 1302870 „ The air surface on the polycarbonate film is placed on the surface of the polycarbonate film to solve the above problem. The dustproof method that can be used is not particularly limited, and conventional dustproof technology can be used. The degree of cleanliness is preferably 1,000 or less, and particularly preferably 1 or less. The adhesive layer is laminated on the hard coat film. The method includes a method in which an adhesive layer is directly applied to a hard coat film, and a method in which an adhesive layer is laminated on a release paper or a release film in advance, and an adhesive is laminated on a hard coat film to laminate. The direct coating method is preferable because it is less likely to cause bubbles to get caught in the vicinity of the polycarbonate, and therefore, if the hard coat film with the adhesive layer is used as a cover layer of a high-density optical disc, the plastic film is used. Set sticky The surface of the agent layer is close to the recording layer, and it is because the defect is likely to cause noise that cannot be repaired. Therefore, careful attention should be paid to the removal of defects such as bubbles. [Polycarbonate film substrate] In the present invention The polycarbonate film substrate used is a plastic film composed of an aromatic polycarbonate having a bisphenol A as an aromatic dihydroxy component, and has a thickness of preferably 20 to 300 μm, more preferably 30. ~200 micron, especially preferably 70~120 micron. Moreover, if the optical film is used as a cover layer of the optical disc, the thickness of the base film is preferably 70 to 90 micrometers. When thin, the film strength is weak, and when it is too thick, the rigidity is too large. The "transparent" of the transparent substrate means that the light transmittance in the visible light region is 80% or more, preferably 90% or more. Although the film forming method includes a melting method and a casting method (solvent casting method), -22-1302870. In the present invention, a casting method is used. In general, the casting method is low in optical anisotropy and is suitable for use as an optical film, particularly as a substrate for a cover film for optical discs. (Material of Polycarbonate Film) The polycarbonate used in the plastic film of the present invention is preferably an aromatic dihydroxy component containing 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) as a main component. Polycarbonate. In this context, the term "polycarbonate" means an aromatic dihydroxy compound containing 2,2-bis(4-hydroxy•Iphenyl)propane as the main component and is combined with carbonyl dichloride and diphenyl carbonate. A polymer obtained by reacting a carbonate-bonding forming compound of an ester in a solution state, a bulky state, a molten state, or the like. The ratio of 2,2-bis(4-hydroxyphenyl)propane in the aromatic dihydroxy compound to be used is at least 80 mol%, preferably 90 mol% or more, and more preferably 100 mol%. . Examples of the above aromatic dihydroxy compound used below 20 mol%, specifically, include the following compounds: 1,1-bis(4-hydroxy-3-tris-butylphenyl)propane, 2, 2-bis(%4-hydroxy-3-tris-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3) - bis(hydroxyaryl) alkane such as bromophenyl)propane or 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane; 1,1 -bis(4-hydroxybenzene) a bis(hydroxyaryl) ring of cyclohexane, 1,1 -bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 9, 9 · bis ( 4 -hydroxyphenyl)anthracene, 9,9-bis(3-methyl-4-hydroxyphenyl)anthracene or the like; 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxyl a dihydroxyaryl ether such as -3,3-dinonylphenyl ether; 4,4'-dihydroxydi-23-1302870 phenyl sulfide, 4,4'-dihydroxy-3,3'- Dihydroxyaryl sulfides such as dimethylphenyl sulfide; 4,4'-dihydroxydiphenylarylene, 4,4,-dihydroxy-3,3'-dimethylphenylarylene Wait for Aryl sulfoxide class; 4, 4, - Sa-dihydroxydiphenyl, 4,4 '- dihydroxy-3,3' - dimethylphenyl etc. Sa Sa dihydroxyaryl the like. These aromatic dihydroxy compounds may be used singly or in combination. Further, a polycarbonate in which a part of the above aromatic dihydroxy compound is substituted with a terephthalic acid and/or an isophthalic acid component can also be used. As long as these constituent units are used for a part of the constituents of the polycarbonate composed of bisphenol A, properties such as heat resistance and solubility of the polycarbonate can be improved. These copolymers can also be used in the present invention. (Molecular Weight of Polycarbonate) The molecular weight of the polycarbonate of the present invention, although not particularly limited, is determined by a viscosity measurement at 20 ° C in a dichloromethane solution having a concentration of 5.0 g / Torr. The viscosity average molecular weight is 30,000 or more and 200,000 or less, and preferably 30,000 or more and 120,000 or less.

If the viscosity average molecular weight is too small, when the film is punched into a thin-walled disk shape, there is a possibility that a small cut mark or a punching chip is likely to be generated at the punched end face, which is not preferable. On the other hand, when the viscosity average molecular weight is too high, it is difficult to form a flat liquid film when the solution is formed into a film, so that the thickness unevenness (non-uniformity) of the film is deteriorated. (Production of Film) The plastic film of the present invention is preferably obtained by film-forming a polycarbonate by a solution casting method. It is preferable that the film formation by the solution casting method is not easy -24-1302870 A fine thickness unevenness or a foreign matter is unlikely to occur in the plastic film. (A: Solvent) A solvent which can be used in the case of producing a polycarbonate film of the present invention by a casting method is not particularly limited, and a conventionally known solvent can be used. For example, the solvent for the solvent for producing the aromatic polycarbonate includes methylene chloride, 1,3 -dioxane, or a mixture thereof or a solvent mainly composed of the same. In the manufacture of the film, the solvents are preferably as free from water as possible. When the solvent is dichloromethane, the water content is preferably set to 50 ppm or less, and more preferably 30 ppm or less. The dehydration (drying) of the solvent can be carried out by a conventional dehydration apparatus for a full-size sieve. (B: solution film formation) A solution in which an aromatic polycarbonate was dissolved in the above solvent was produced. This solution is usually adjusted to 15 to 35 mass% of polycarbonate. The resin solution adjusted as described above was extruded in an extrusion die and cast on a support. (C: Dry)

The cast liquid film is divided into a plurality of zones and dried in an oven which changes the drying conditions (hot air temperature, wind speed, etc.) of each zone. In the present invention, the drying step is divided into five zones. In the first zone, the liquid film which has just been cast on the support body is dried so as not to cause surface disorder as much as possible, so that uniform coating unevenness does not occur. In order to improve the drying efficiency, the heating method is a method of drying the liquid film by hot air drying or heating the surface of the belt with a heat medium. From the viewpoint of ease of operation, it is preferable to use a hot air method. -25- 1302870 The temperature of the belt surface immediately after casting, and the temperature of the atmosphere are preferably controlled so as not to be higher than the boiling point of the dissolved solvent of the polycarbonate. If the temperature of the liquid film is raised above the boiling point, the result of bubbles which are caused by the sudden boiling of the solvent will appear in the film. If the solvent is dichloromethane, the temperature should be 4 ° C or less, more preferably 3 (TC or less. If the solvent is dichloromethane, then the second zone is controlled to 45 to 5 〇. t, drying until the concentration of methylene chloride in the liquid film reaches about 30 to 40% by mass, so that the liquid film is not deformed.

If the solvent is methylene chloride, the control is carried out at 45 to 50 ° C in the third zone, and the amount of the solvent in the film is preferably controlled to be about 23 to 27 mass%. Further, the drying temperature in the fourth zone is controlled at 50 to 55 ° C, and the amount of the solvent in the film is preferably controlled to be about 18 to 20 mass%. In the fifth zone, it was cooled to about 15 ° C, and then the film was peeled off from the support. (D = post-drying) Next, the film is post-dried, and then dried, depending on the use for use without stretching or the use for extension. In the case of %, it is preferred to control the optical properties (refractive index) of the film while drying. The drying is preferably carried out by appropriately using a needle-clamping tenter in which both ends of the film width direction are held for transport. The optical properties of the film can be controlled by conventional drying methods such as a machine, a roll suspension dryer or an air suspension dryer. The film obtained by such a method is taken up as an aromatic polycarbonate film for optical use. The film thickness at the final stage of film formation is preferably from 50 to 130 μm. -26- 1302870 (E: Winding of film forming step) In the film winding step, a surface protective film (also referred to as "film") is a polyethylene terephthalate film. The film end was pulled out from the reel and laminated with the polycarbonate film, and then clamped by a nip roll to extrude air between the films, and the two were co-rolled in a wrinkle-free manner. The plastic film reel body of the present invention is produced in this manner. [Evaluation method of polycarbonate film substrate] 1) Method for measuring thickness of film

A full width sample was taken in a winding direction of the polycarbonate film of the uncovered protective film of 1 m. The film is divided into its width direction (direction orthogonal to the winding direction) and the winding direction is 10 cm X 10 cm square (if the number of ends in the width direction is more than 50 mm, the part is also taken as The sample was measured, and then the thickness was measured at a substantially central portion of the square using a micrometer manufactured by Mitsutoyo Co., Ltd. Then, the thickness average 値 at 100 points of the measurement point was obtained and expressed as the thickness of the film. 2) Method for measuring film thickness spot (non-uniformity) According to the measurement method of the micrometer according to the above 1), since it is possible to miss a thickness spot which may exist outside the measurement point, for example, a thin stripe-like thickness spot, etc., it is used. A film thickness gauge KG60 1 A manufactured by Anritz Co., Ltd. was used to continuously measure thickness spots. The sampling of the film was measured as follows. Namely, 10 samples of the full width of the sample were continuously cut at a distance of 5 cm in the film winding direction (total 50 mm in the winding direction of the film). The thickness distribution of -27 - 1302870 of each sample was measured by the above film thickness meter and recorded on recording paper. Then, the difference between the maximum thickness of the recorded thickness (the range of the thickness) is determined for the film of the above-mentioned one cymbal sheet, and the thickness unevenness of the film is expressed by the maximum thickness of the film. 3) Thermal dimensional change rate

A mother sample of an appropriate size was taken by dividing the width direction of the polycarbonate film (the film width was approximately 1 m) into three portions. Then, 10 samples for measuring the thermal dimensional change rate were produced from each of the master samples, and a total of 30 samples were used. Regarding the size of the sample for measuring the thermal dimensional change rate, for five of the ten samples from each of the mother samples, the winding direction of the film was 150 mm, and the positive direction was 1 mm, and the remaining 5 The film is wound in a direction of 1 mm and the direction of the film is 150 mm. Further, for each sample, the punctuation required for the measurement of the thermal dimensional change rate was made at intervals of 1 mm in the longitudinal direction of 150 mm. By this method, the sample for measurement in which the winding direction of the film is 15 points and the direction perpendicular thereto (width direction) is 15 points is prepared. After the measurement sample was suspended in a thermostat at 14 ° C for 1 hour under no load, taken out and cooled to room temperature, the punctuation interval was measured. The measurement of the size was carried out under a constant temperature and humidity at 23 ° C and 65% RH using a reading microscope. The dimensional change rate was determined from the dimensions before and after heat treatment at 40 °C in the following manner to obtain 15 points in the winding direction and 15 points in the width direction. Then, the maximum enthalpy is expressed as the thermal dimensional change rate: Thermal dimensional change rate = {(pre-treatment size) one (post-processed ruler -28-1302870 inches)} / (pre-treatment size) X 100%. 4) Total light transmittance A sample of about 300 mm square was taken from the width direction of the polycarbonate film (the width of the film was approximately 1 m). The total light transmittance of the sample was measured using a color difference turbidity meter COH-300A manufactured by Nippon Denshoku Industries Co., Ltd. Five points were measured for each sample, and the average 値 of the total of 1 5 points of the sample in the width direction was taken as the total light transmittance.

5) Determination of the solvent content in the polycarbonate film: About 5 g of the solvent-containing polycarbonate film was taken and cooled to room temperature after drying for 1 hour in a TC hot air dryer. At this time, the chemical scale was used for accurate weighing. The mass before and after the drying, and the rate of change thereof, from which the solvent content based on the solid portion is determined. Specifically, the polycarbonate film (having a width of about 1 m) is equally divided into 5 in the width direction. In the same manner, the method was carried out three times in the respective width directions, and then the average enthalpy was determined (the average enthalpy measured at 15 points was expressed as the solvent content). It is assumed that the mass before drying is a, dry cooling When the mass is b, the determination of the solvent content based on the solid fraction can be represented by the following formula: { (a-b) / b} X 100%. 6) In-plane retardation 値Re is measured in the winding direction At the interval of 50 cm, a Japanese-style strip-shaped sample of a polycarbonate film having a length of 40 mm in a winding direction at a full width was used. Next, the strip-shaped film was cut into 40 mm to -29 - 1302870 to prepare a 40 mm square sample for measurement. In other words, since there are 25 lengths of 1,000 mm in the full width direction of the film and three samples of the long strips, a total of 75 samples for measurement are obtained. The in-plane retardation 値Re was measured for the samples. The representation of the number is the range of Re 値 and is expressed by its minimum 値 to maximum 値. The measuring device was a composite refractive index measuring instrument manufactured by Oji Scientific Instruments Co., Ltd. under the trade name of KOBRA-2 1ADH, and the light was incident perpendicularly to the direction of the surface of the polycarbonate film to measure the in-plane retardation Re値. • 7) Determination of the retardation 厚度 (Rth値) in the thickness direction

Sampling was carried out in the same manner as in the measurement of the above item 6), and measured by KOBRA-2 1 ADH. The retardation was measured by rotating the polycarbonate film sample with its slow axis or the phase axis and changing the angle of incidence, and then the refractive indices nx, ny and nz were calculated from the data. And, from these calculations, Rth 値 = | ( ( nx + ny) / 2 - nz ) X d | (2 vertical lines means "absolute 値"). Here, nx represents the refractive index in the winding direction, ny represents the refractive index in the direction orthogonal to the winding direction, nz represents the refractive index in the thickness direction, and d represents the thickness (in micrometers) of the measured film. Further, the unit of Rth値 can be calculated in micrometers (micrometers) in the above calculation, but when expressed, it is converted into nanometer (nm) units. In the present specification, the largest relationship of Rth値 means the biggest flaw in these. Measurement of the average surface roughness (Ra) of the center line The average surface roughness (Ra) of the center line is defined by JIS-B0601. In the case of this manual, the small research institute (-30-8) is used. 1302870 strands of contact surface roughness meter (Surfc〇rder, SE_3〇c) for measurement. The measurement conditions of Ra are as follows: Tip tip radius: 2 μm Measurement pressure·· 30 mg (2.94×10·4 N) Cutting: 0.08 mm Measuring length: 1.0 mm

The sample was sampled in the full width direction of the film for measurement in the same manner as the mother sample of the above item 3). The measurement was repeated five times for the same sample, and the enthalpy (based on the fourth decimal place of the micron unit) was removed, and the largest 値 was removed to obtain the remaining four data, and then all three were The fifth decimal place below the decimal point of the average 値 of the data is rounded off, and the fourth digit below the minority point is expressed in nm units. [Cured layer] The curable composition of the present invention may be a thermosetting composition or an active energy ray-curable composition % as long as it contains a curing agent and an organic solvent. If the polycarbonate film is soft and the hardened layer is too thick, it will cause curling, and therefore it is preferably 10 μm or less. In the optical film having a relatively thin film thickness of 1.0 to 8 μm, the defect portion is enlarged as compared with the case where the film is not cured. Further, the point defect is likely to occur below 4.0 μm, so the present invention can exert a special effect at 4.0 μm or less. If the thickness of the hardened layer is thicker than 4.0 μm, the point defects may be easily embedded in the hardened layer. Further, if the thickness of the hardened layer is thinner than 2.5 μm, the number of point defects will easily increase, so that it is particularly preferably 2.5 μm or more -31 to 1302870 . [Hard Coating Layer] ^ The function of the hard coat layer of the present invention includes a hard coat layer having scratch resistance. In this case, the hard coat layer preferably has a scratch-resistant hard layer which cannot be visually observed to have a rubbing mark when the surface is rubbed with a weight of 1.96 N/cm 2 for 50 times using steel wool of #0000. . Further, when the transparent plastic film substrate is a polycarbonate film, since the rigidity is low, if the cured film is too thick, curling is likely to occur, and if it is too thin, the function of hard coating is hard to be displayed. Therefore, the film thickness is preferably from 1.0 to 10.0 μm, more preferably from 1.0 to 4.0 μm, and particularly preferably from 2.5 to 4.0 μm. A preferred method of forming the hard coat layer of the present invention is to apply a UV curable composition which is hardened by ultraviolet irradiation to a transparent plastic film substrate, and to dry it, and to cure the composition by irradiation with ultraviolet rays. The ultraviolet curable composition is preferably a compound containing two or more of the ethyl storage-unsaturated groups in the same molecule which is cured by ultraviolet irradiation or polymerization. The "ultraviolet curable composition" which can be suitably used in the present invention and which is suitable for use in the present invention, and which is suitable for use in the present invention, is described as " * The above "ethylenically unsaturated group" is preferably an acryl fluorenyl group, a methyl fluorenyl group, a phenethyl group or an ethyl phenyl group, and particularly preferably a propyl group. The compound containing an ethyl unsaturation group may have two or more ethylenically unsaturated groups in the molecule, and more preferably three or more. Among them, a compound called a "polyfunctional acrylate monomer" having a compound having -32·1302870 acryl fluorenyl group and having 2 to 6 acrylate groups in the molecule is preferably used. An ester acrylate, a polyester acrylate, or an epoxy acrylate having a plurality of acrylate groups having a molecular weight of several hundreds to several thousands of oligomers having "more than two ethylene groups in the molecule" Preferred specific examples of the compound of the unsaturated group include: divinylbenzene, ethylene glycol diacrylate, trimethylolpropane triacrylate, bis-trimethylolpropane tetraacrylate, neopentyl alcohol Polyol polyacrylates such as triacrylate, neopentyl alcohol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc.; bisphenol A diglycidyl ether diacrylate An epoxy acrylate such as diacrylate of hexanediol diglycidyl ether; a urethane acrylate obtained by a reaction of a polyisocyanate with a hydroxy group-containing acrylate such as hydroxyethyl acrylate. In addition, these compounds also include: commercial grade E B - 600,

EB-40, EB-140, EB-1150, EB-1290K, IRR214, EB-2220, TMPTA, TMPTMA (all of which are manufactured by DAICEL UCB); UV-6 3 00, UV-1700B (above Japanese synthetic chemical industry (stock) manufacturing). Among the "compounds having two or more ethylenically unsaturated groups in the molecule" as exemplified above, a particularly preferred compound includes three propylene groups in the molecule and an acryl oxime equivalent of 120. Specific examples of the following compounds include: trimethylolpropane triacrylate, bis-trimethylolpropane tetraacrylate, neopentyl alcohol triacrylate, neopentyl alcohol tetrapropyl-33-1302870 enoate , dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like. In addition to the above-mentioned compound having two or more ethylenically unsaturated groups in the molecule, it can be suitably used as the "compound of the ultraviolet curable composition" of the present invention, and includes a curable resin containing a ring-opening polymerizable group. The "curable resin containing a ring-opening polymerizable group" is a curable resin having a ring structure which undergoes ring-opening polymerization reaction by the action of a cation, an anion or a radical, and preferably contains a heterocyclic group. Sclerosing tree • Fat. These curable resins include an epoxy group-containing compound, an oxetanyl-containing compound, a tetrahydrofuranyl-containing compound, a cyclic lactone compound, a cyclic carbonate compound, and an oxazoline group. A cyclic imine ether or the like such as a compound, and particularly preferably an epoxy group-containing compound, an oxetane group-containing compound, or an oxazoline group-containing compound. In the present invention, the curable resin having a ring-opening polymerizable group preferably has two or more ring-opening polymerizable groups in the same molecule, and more preferably has three or more. Further, in the present invention, the curable resin having a ring-opening polymerization-based group may be used in two or more types. In this case, if necessary, a ring-opening polymerizable group may be used in the same molecule. Curable resin. The curable resin having a ring-opening polymerizable group used in the present invention is not particularly limited as long as it is a curable resin having a cyclic structure as described above. Preferred examples of such curable resins include, for example, monofunctional glycidyl ethers, monofunctional alicyclic epoxides, difunctional alicyclic epoxides, diglycidyl ethers (for example). Glycidyl ether-34-1302870 ^ class includes: ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, trimethylolethane triglycidyl ether]; trifunctional or higher glycidol Ethers [trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl hydroxyethyl isomeric cyanurate Etc.: polyglycidyl ethers of four or more functional groups (sorbitol tetraglycidyl ether, neopentyltetraethylene tetraglycidyl ether, polyglycidyl ether of cresol novolac resin, phenol novolac resin) Glycidyl ether, etc.; polyacrylic acid glycidyl ester, polyglycidyl methacrylate, etc., acrylic polymer having an epoxy group in a side chain; alicyclic epoxy type [Celloxide 2021P, Celloxide 208 1 , Eporide GT-3 01, Eporide GT-401 (above manufactured by Daicel Chemical Industry Co., Ltd.); EHPE (manufactured by Daicel Chemical Industry Co., Ltd.); polycyclohexyl epoxy methyl ether of phenol novolac resin, etc.; oxetane OX-SQ, PNOX-1009 (the above is manufactured by East Asia Synthetic Co., Ltd.), etc., but the present invention is not limited thereto. In the present invention, a curable composition including both a curable compound containing an ethylenically unsaturated group and a curable resin containing a ring-opening polymerizable group can also be used. A curable compound (curable resin) # containing an ethylenically unsaturated group and a curable composition containing a curable resin having a ring-opening polymerizable group (hereinafter, unless otherwise added, a "curable composition" contains When the composition of the curable resin is hardened, it is preferred to carry out a crosslinking reaction of the curable resin. The preferred crosslinking reaction of the ethylenically unsaturated group is a radical polymerization reaction, and a preferred crosslinking reaction of the ring-opening polymerizable group is a cationic polymerization -35 - 1302870 ^ reaction. In any case, the polymerization reaction can also be carried out by the action of active energy rays. Usually, a small amount of a radical generating agent called a polymerization initiator and a cation generating agent (or an acid generator) may be added and decomposed by an active energy ray to generate a radical and a cation to carry out a polymerization reaction. The radical polymerization can be carried out separately from the cationic polymerization, but it is preferred to simultaneously carry out the photoacid generator which generates a cation by ultraviolet rays, and includes ionic hardening such as a triarylsulfonium salt or a diaryl iodine salt. A non-ionic curable resin such as a resin or a sulfonic acid nitrate-based benzyl ester, which can be used in the Organic Electron Materials Research Society, "Organic Materials for Imaging", Wenxin Publishing House (1 997) Various conventional photoacid generators such as curable resins. Among them, from the viewpoint of less yellow coloration, it is particularly preferably a diaryl iodine salt, and a diionic ion is preferably PF6·, SbF6_, AsF6·, B(C6F5)4· or the like. Further, a combination of a triarylsulfonium salt and a diaryliodonium salt is also preferred. An example of a "polymerization initiator" which generates a radical by ultraviolet rays can be used: acetophenone, benzophenone, rice. Miller's ketone, benzhydryl benzoate, benzoin, α-decyloxym ester, tetramethylthiuram monosulfide and oxysulfide star • A conventional free radical generator such as thioxanthone). Examples of "sensitizers" include n-butylamine, triethylamine, tri-n-butylphosphine, and oxysulfanyl star compounds. The amount of the polymerization initiator added is preferably based on the total mass of the curable resin containing an ethylenically unsaturated group in the curable composition and the curable tree-36-1302870^ fat containing a ring-opening polymerizable group. It is used in the range of 0.1 to 15% by mass, and more preferably in the range of 1 to 10% by mass. Further, in the present invention, it is preferred to add fine particles to the curable composition. The swelling caused by the solvent of the transparent plastic film substrate can be suppressed by adding inorganic fine particles. Further, since the amount of hardening shrinkage of the hardened film can be reduced by adding the fine particles, it is also preferable to improve the adhesion to the substrate or to reduce the curl. As the fine particles, any of inorganic fine particles, organic fine particles, and organic-inorganic composite fine particles can be used. However, in general, particles have a tendency to cause an increase in haze, so it is necessary to measure the balance of the necessary characteristics to adjust the filling method. The inorganic fine particles include, for example, cerium oxide particles, titanium oxide particles, zirconium oxide particles, alumina particles, and the like. These inorganic crosslinked particles are generally hard, and as long as they are impregnated into the hard coat layer, not only the shrinkage at the time of hardening but also the surface hardness can be improved. In general, the affinity between the inorganic fine particles and the organic component such as the above-mentioned curable resin used in the present invention is low, so that simply mixing Φ may form aggregates or cause hardening of the hardened film after hardening. Open situation. In the present invention, in order to increase the affinity of the inorganic fine particles and the organic component, the surface of the inorganic fine particles may be treated with a surface modifying agent containing an organic segment. The surface modifying agent preferably has a functional group capable of forming a bond with or adsorbing to the inorganic fine particles in the same molecule, and a functional group having a high affinity with the organic component. The surface modifier having a functional group capable of forming a bond with the inorganic fine particles or adsorbing to the inorganic fine particles is preferably a surface modifier having a metal alkoxy-37-1302870 compound of decane, aluminum, titanium, pin, or the like, or A surface modifier of an anionic group such as a phosphate group, a sulfate group, a sulfonic acid group or a carboxylic acid group. As for the functional group having high affinity with an organic component, although it is also possible to simply combine the organic component with the hydrophilic or hydrophobic property, it is preferably a functional group which can be chemically bonded to the organic component, and is particularly preferably ethylenic. An unsaturated group or a ring-opening polymerizable group. In the present invention, a preferred inorganic particulate surface modifier is a metal alkoxide or a curable resin having an anionic group and an ethylenically unsaturated group, or an anionic group and a ring-opening polymerizable group in the same molecule. . Representative examples of such surface modifiers include the following: a coupling agent containing an unsaturated double bond, an organic curable resin containing a phosphoric acid group, an organic curable resin containing a sulfuric acid group, an organic curable resin containing a carboxylic acid group, or the like. . S-l H2C = C ( X) COOC3H6Si ( OCH3 ) 3 S-2 H2C = C ( X ) COOC2H4OTi ( OC2H5 ) 3 S-3 H2C = C ( X ) COOC2H4OCOC5H10OPO ( OH ) 2

S-4 ( H2C = C ( X) COOC2H4OCOC5H10O ) 2POOH

S-5 H2C = C ( X) COOC2H4OSO3H

S-6 H2C = C ( X) COO ( C5H10COO) 2H

S-7 H2C = C ( X) COOC5H10COOH S-8 3 -(glycidoxy)propyltrimethoxydecane (X = Η, or CH3) The surface modification of these inorganic particles is preferably carried out in solution . When the inorganic fine particles are mechanically dispersed finely, the surface modifier may be present together, or the inorganic fine particles may be finely dispersed, and then the surface modifier may be added and stirred, or may be taken. The surface modification is carried out before the inorganic fine particles are finely dispersed (if necessary, heating is applied after heating, drying, or pH is changed), and then fine dispersion is carried out. A solution which dissolves the surface modifier, preferably a highly polar organic solvent. Specifically, it includes a conventional solvent such as an alcohol, a ketone, or an ether. Although the organic fine particles are not particularly limited, it is preferred to use polymer particles composed of a monomer having an ethylenically unsaturated group, for example, polymethyl methacrylate, polyethyl methacrylate, and polyethyl acrylate. Polymer particles composed of polybutyl acrylate, polyethylene, polypropylene, polystyrene, etc.; other materials include: polyoxyalkylene, melamine resin, benzoguanamine resin, polytetrafluoroethylene, polycarbonate Resin particles such as nylon, polyvinyl alcohol, polytetrafluoroethylene, polyethylene terephthalate, polyvinyl chloride, cellulose acetate, nitrocellulose, gelatin, and the like. The particles are preferably crosslinked. Microparticle finer dispersing machine, preferably using ultrasonic wave, disperser, homogenizer, dissolver, polytron, paint shaker, sand honing machine, kneading machine, Eiger grinding machine, Dinomill , Cobowl mill, etc. Further, as the dispersion medium, the above solvent for surface modification can be used. The volume of the fine particles is preferably from 2 to 40% by volume, more preferably from 3 to 30% by volume, and most preferably from 5 to 20% by volume, based on the volume of the hardened film after charging. When the hard coat film is used for optical use, the haze is preferably lower. In the present invention, the cured film (hard coat layer) has a haze of 5% or less, preferably 2% or less, and most preferably 1.0% or less. -39- 1302870 ^ In the present invention, the hardened film obtained by the same is made to contain an antifouling agent, or a low surface energy hardening resin which is laminated to contain fluorine and/or antimony, and is irradiated with active energy. The hardenable composition which is hard to be irradiated is the antifouling layer of the main body, whereby the antifouling hardening film can be obtained. The antifouling agent used in the present invention is for imparting antifouling properties such as water repellency and oil repellency to a substrate having curability. These antifouling agents are not inconvenient for the preparation of the energy ray-curable resin composition and coating on the substrate, and can exhibit water repellency and oil repellency on the surface of the cured film when the cured film is formed. , anyone can use it. These antifouling agents include hardening resins containing fluorine and/or cerium. Further, the antifouling layer of the hardened film used in the present invention may be formed of a composition containing a curable resin containing fluorine and/or antimony. The curable resin containing fluorine and/or cerium contained in the hardened film or the antifouling layer used in the present invention includes a conventional fluororesin resin or cerium curable resin, or has fluorine and cerium. A hardening resin of a block, and a hardening resin which preferably has a segment which is compatible with a resin or a metal oxide compound or the like and a segment containing fluorine or ruthenium is added to the cured film or the antifouling layer. , so that fluorine or ruthenium is unevenly biased on the surface. The specific curable resins include block copolymers containing a monomer of fluorine or hydrazine and other hydrophilic or lipophilic monomers, or a graft copolymer. The fluorine-containing single system includes perfluorocarbon represented by hexafluoroisopropyl acrylate, heptafluorodecyl acrylate, perfluoroalkyl sulfonamide ethyl acrylate, perfluoroalkyl decyl acrylate, and the like. Alkyl (meth) acrylate. The single system containing ruthenium includes a monomer having a ruthenoxyalkyl group which is reacted with polydimethyl siloxane and (meth) propyl - 40 - 1302870 - enoic acid or the like. The hydrophilic or lipophilic single system includes a (meth) acrylate such as methyl acrylate, a polyester having a hydroxyl group at the terminal, an ester of (meth)acrylic acid, a hydroxyethyl (meth)acrylate, and a polyethylene glycol. An alcoholic (meth)acrylic acid ester or the like. Commercially available graded curable resins include Defensa MCF-300, 312, 323, etc., which have an acrylic oligomer having a microdomain structure of a peroxyalkyl chain; and oligomers containing a peroxyalkyl group and a lipophilic group. Megafac F-1 70, F-173, F-175, etc.; Megafac F-171 containing a peroxyalkyl group/hydrophilic group oligomer, etc. (manufactured by Dainippon Ink Chemical Co., Ltd. or having superior surface migration property) The MODIPER F-200, 220, 600, 820, etc. of the fluorinated alkyl group of the ethylene monomer block polymer which is compatible with the resin segment, and the polyoxygenated MODIPER FS-700, 710 (manufactured by Nippon Oil & Fats Co., Ltd.). When an antifouling layer is provided on the cured film, it is preferably a low surface energy curable resin containing fluorine atoms, specifically, it is contained in the Japanese invention patent special opening. A fluorinated hydrocarbon group-containing polyoxynoxy resin, a fluorinated hydrocarbon group-containing polymer, or the like disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. The coating liquid is diluted in a ketone system, an alcohol system, an ester system, etc. _ organic solvent The polyfunctional monomer and the polymerization initiator are mainly prepared by dissolving and dissolving. Further, a surface-modified hard inorganic fine particle dispersion and a soft fine particle dispersion may be further added to prepare a second hardening composition. In the present invention, the organic solvent is preferably a ratio of an organic solvent having a solubility parameter (SP値) of 8.3 or more and 10.5 or less in an all organic solvent of 60% by mass. In the following, it is more preferably 50% or less, and particularly preferably 40% or less. Further, the organic solvent having an SP値 of 9.0 or more and 10.0 or less is contained in the all-organic solvent in the cured composition for a polycarbonate film. The ratio is preferably 20% or less, more preferably 10% or less, still more preferably 5% or less, and most preferably no.

In the present invention, the "solubility parameter (SP値)" is determined by σ = [(AH - RT) / VL] 1/2 (where σ: solubility parameter, ΔΗ: heat of vaporization, VL: molar volume, R:气体 Η Η Η Η Η Η Η Η Η 298 = 23·7 Tb + 0·02 0 Tb2 — 2,950 値 (where Tb : t fulcrum) according to the Hildebrand criterion. Therefore, the solubility parameter is also 298 °K. In addition, specific examples of the solubility parameters obtained by the Hildebrand criteria are, for example, J. BRANDRUP, Ε·H. IMMERGUT and EAGRULKE, "Molecular Handbook", Fourth Edition, Chapter VII, 688 ~ 694 Page (1998), part of the detailed disclosure in JOHN WILEY & SONS, INC. In addition, based on

The calculation method for the solubility parameter of the Hildebrand criterion is described in 〗· Hildebrand, “Solubility of Non-Electrolytes”, pp. 424-427 (1950), Reinhold Publishing Company. The s p値 of representative compounds is shown in Table 1. -42- 1302870

I® Oh 00 r- ο 00 ο σ\ ο ^t; τ—Η 寸 · rH in rH tH r-; rH t~H On τ-Η ▼-H rH cs rH (Ν rH r- cs m Ό· $ in vd r—Η 寸 CO CN g 锲η 氍Η CN 1 Η 黻Η7 1 rH s ίΰ m moth pr (N Λ secret s- 1 r—H gg N3 11 twist 11 黻K] 黻11 Ν] 氍 HI Ph 00 00 00 00 00 Ο as Οί Ον m Os m cK 〇\ C\ On cK Ο 〇〇 〇〇τ-Η Ο CN Ο CO ο inchο v〇〇锲擀Μ 擗fr u ύ 浒KK1 枨匾N3 W ffi- 匾E 遁ID 擀 擀 ύ ύ & chain & ύ m genus m & 卜 in Oh ϋΟ in ui cn vd 〇\ vd Ο v〇00 〇00 CN 00 00 00 00 οό VO 00 VO 00 Secret δ & 11 遁13⁄4 m Slightly 11 m N] 11 Dance 1 匾 卜 € 11 K] 11 遁ΓΏ 11 匾Η ή ή Π Νm (Ν s 龅磐 US枨Λ ΙΕ 1302870. According to the inventors of the present invention, a point defect originating from a functional layer formed of a hardenable composition, the organic solvent of the composition is impregnated into the polycarbonate film to make the surface uneven Swelling and bonding between film and coating liquid When the functional film is used as an optical film for an image display device such as a liquid crystal display, the protrusions are formed to be point defects and can be recognized. The solubility parameter (SP 値) is generated when the functional film is used as an optical film for an image display device such as a liquid crystal display. The organic solvent of 8.3 or more and 10.5 or less, particularly 9.0 or more and 10.0 or less, can be easily impregnated into the polycarbonate film, and the surface is not uniformly swollen to cause the above-mentioned protrusions. In the following, it is easy to penetrate into the polycondensation. The solvent for the non-uniform swelling of the surface of the carbonate film is referred to as the solvent (S) which invades the uranium polycarbonate. That is, the organic solvent used to dilute the hardened composition of the present invention can be etched at 25 ° C. The ratio of the organic solvent (S) of the polycarbonate contained in the total organic solvent is 60% by mass or less, preferably 50% or less, and particularly preferably 40% or less. The so-called 25 ° C will not The judgment that the polycarbonate is eroded is immersed in a 50 cc solvent at 25 ° C in a polycarbonate film sheet (1 cm X 2 cm) used as a substrate for forming a hardened layer. The mixture was stirred, and after 5 minutes, it was observed and visually observed. The solvent that will erode the polycarbonate film will dissolve or whiten the polycarbonate film. Therefore, the degree of erosion can be assessed by observing the rate of dissolution or clouding. In addition, a greater degree of erosion of the polycarbonate film completely dissolves the polycarbonate film. The solvent which does not erode the polycarbonate film does not cause the polycarbonate film to become cloudy and remains transparent. -44- 1302870 . [Solvent for invading uranium polycarbonate at 25 ° C] It includes, for example, cyclohexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, acetonitrile, toluene , ethyl acetate, methyl acetate and the like. [solvent which does not attack polycarbonate at 25 ° C] It includes, for example, methanol, isopropanol, 1-propanol, ethanol, cyclohexane, 1-butanol, 1-methoxy-2 - Propanol and the like. The solvent which does not erode the polycarbonate at 25 ° C, in addition to the above, includes: alcohols other than the above, pentane, n-hexane, isohexane, n-heptane·I, n-octane , isooctane, decane, decane, 2-methylhexane, 3-methylhexane, 3-methylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane Alkane, 3,3-dimethylpentane, 2,3-dimethylbutane, 2,2,3-trimethylpentane, 2,2,4-trimethylpentane, 2, 2, a saturated aliphatic hydrocarbon such as 3,3-tetramethylpentane; pentene, hexene and its heterologous body, hexadiene and its heterogeneous body, hexatriene, heptene and its heterogeneous body, heptadiene and Hetero, heptane, octene and its heterogeneous, octadiene, octylene, decene, decadiene, ninhydrene, decene, undecene, dodecene and other unsaturated aliphatic hydrocarbons ; cyclohexane φ, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, isopropylcyclohexane, cycloheptane, cyclopentane, methyl ring Pentane, dimethylcyclopentane, ethylcyclopentane, diethylcyclopentane, isopropylcyclopentane, cyclooctane, etc. a saturated alicyclic hydrocarbon system; cyclopentene, cyclopentadiene, cyclohexene, methylcyclohexene, dimethylcyclohexene, methylcyclohexene, cyclohexadiene, methylcyclohexane An unsaturated alicyclic hydrocarbon system such as an alkene or a cycloheptene; a chain of diethyl ether, dibutyl ether, diisobutyl ether, dipropyl ether, diisopropyl ether or diamyl ether; A non-polar solvent such as ether. -45- 1302870 . [Coating] The hardened layer of the present invention can be produced by a immersion method, a spin coating method, a spray coating method, a roll coating method, or a gravure coating on a polycarbonate film substrate. A conventional film forming method such as a method, a bar coating method, a slit die extrusion coating method (single layer, multi-layer), or a slide coater method is applied to apply a hard coating liquid, and then dried. It is manufactured by irradiating ultraviolet rays to harden them. The drying condition is preferably such that the concentration of the organic solvent in the applied liquid film is 5% by mass or less, more preferably 2% by mass or less, and further more preferably 1% by mass or less. The drying conditions are of course affected by the heat strength or the conveying speed of the substrate, the length of the drying step, and the like. However, from the viewpoint of improving the polymerization rate, the content of the organic solvent is preferably low. Further, the ultraviolet curable composition which is preferably used in the acrylate monomer as the main component of the present invention, when irradiated with ultraviolet rays in an oxygen atmosphere, causes poor hardening, so that it is likely to cause scratches when rubbed with steel wool. To prevent this, it is necessary to reduce the oxygen concentration in the ultraviolet irradiation atmosphere. The oxygen concentration at the time of irradiation is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.3% or less. [Adhesive Layer] When the optical hard coat film as described above is used as a light-transmitting layer of an optical disk, it is preferable to bond the support or the substrate containing the recording layer via an adhesive layer. In the step of providing the adhesive layer, the adhesive layer may be continuously provided on a surface different from the hard coat coating surface of the light-transmitting film which has been previously formed on one surface of the hard coat layer. The method of providing the adhesive layer can be roughly divided into a method of attaching the adhesive layer formed (hereinafter referred to as "indirect method"), and applying an adhesive directly on the surface of the transparent film, and then applying the adhesive. Two methods of drying to form an adhesive layer (hereinafter referred to as "direct method"). _ In the "indirect method", "the method of attaching the adhesive layer formed" means that the adhesive is continuously applied to the surface of the release film having the same size as the light-transmissive film, for example, and dried. A method of providing an adhesive layer on one side of the release film and then attaching the adhesive layer to the light-transmitting film. As a result, an adhesive layer with a release film can be provided over the entire surface of the light-transmissive film.

In the "direct method", the front end of the light transmissive film wound in a roll shape is continuously fed to a specific application region, and the adhesive is continuously applied from the front end to the end of one surface of the light transmissive film. After the coating film is formed, the coating film is sequentially dried to provide an adhesive layer over the entire surface of the light-transmitting film. In the above indirect method and direct method, the coating method of the adhesive can be carried out by a conventionally known coating method. Specifically, it includes a spray coating method, a roll coating method, a knife coating method, a doctor roll method, a screen printing method, and the like. Further, the drying unit can be a conventionally known method such as heat drying, air drying, or the like. An acrylic, rubber or polyoxygenated adhesive can be used as the adhesive, but an acrylic adhesive is preferred from the viewpoint of transparency and durability. As the acrylic adhesive, it is preferred to use 2-ethylhexyl acrylate, n-butyl acrylate or the like as a main component, and to improve cohesive force with a short-chain alkyl acrylate or methacrylic acid. Base esters, such as methyl acrylate, ethyl acrylate, methyl methacrylate, and acrylic acid, methacrylic acid, acrylamide derivative, which can be used as a crosslinking point with a crosslinking agent, -47- 13〇287 〇 A copolymerization of enedic acid, hydroxyethyl acrylate, glycidyl acrylate or the like. The glass transition temperature (Tg) or crosslink density can be changed by appropriately adjusting the mixing ratio and type of the main component, the short chain component, and the components required to add the parent point. The crosslinking agent which can be used for the above-mentioned adhesive includes an isocyanate crosslinking agent, an epoxy resin crosslinking agent, a melamine resin crosslinking agent, a urea tree ruthenium crosslinking agent, and a chelate crosslinking. The agent, but more preferably an isocyanate parent agent. As the isocyanate crosslinking agent, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, monomethyl diisocyanate, and naphthyl-1,5- can be used. Isocyanates such as diisocyanate, o-toluidine isocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, polyisocyanates formed by condensation of such isocyanates with polyhydric alcohol products and isocyanates. Commercial grades of such isocyanates include: Coronate L, Coronate HL, Coronate 2030, Coronate 203 1 manufactured by Japan Polyurethane Co., Ltd.

Milionate MR, Milionate HTL; Takenate D-102, Takenate D-110N, Takenate D-200, Takenate D-202 manufactured by Takeda Pharmaceutical Co., Ltd.; Dismodule L, Dismodule IL, Dismodule N, Dismodule manufactured by Sumitomo Bayer HL, etc. The adhesive layer is formed on the surface of the light-transmitting film other than the hard coat layer, but it is preferable to prevent the hard coat layer from adhering to the adhesive layer due to being wound into a roll in the subsequent step. In order to attach the release film to the surface of the adhesive layer. As described above, in the case of the indirect method, the release film may be pre-attached to the state of -48-1302870 _. On the other hand, in the case of the direct method, it is preferred to newly add a release film to the surface of the adhesive layer after forming an adhesive layer on the surface of the light-transmitting film. The release film which can be attached to the surface of the adhesive layer includes: polyethylene film, polyethylene terephthalate film, polyethylene naphthalate film, polycarbonate film, triacetate cellulose Films, etc. [Embodiment] Next, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. [Manufacture of long rolled polycarbonate film with surface protective film] (Manufacture of long rolled polycarbonate film (s-0) and (sl) with surface protective film) Aromatic polycarbonate Ester resin pellets (Panlight (registered trademark grade C-1400QJ) manufactured by Teijin Chemical Co., Ltd.), viscosity average molecular weight of 38,000, hot air drying at 120 ° C for 16 hours, followed by dehumidification Cool to 30 ° C in air. The aromatic polycarbonate resin diced pellet was dissolved in a dichloromethane solvent to prepare a solution of 18% by mass. The solution was subjected to removal of foreign matter by a sieve. Further, the temperature of the solution was adjusted to 15 ± 0.5 ° C, and then a coat hanger type head having a width of 1,200 mm was introduced, and then a liquid film of about 560 μm was cast on the support. The support temperature (surface temperature) immediately before the start of casting was set to 9 °C. The casting belt is made of stainless steel and has a width of 2 m and a length of 56 m (area of 112 m2). The welded portion of the belt forms an angle of 80 degrees for the casting direction and a width of 1.5 mm for the casting portion. -49 - 1302870 Welding is carried out by laser welding. The result of inspecting the casting tape by the replica method is that the number of pinholes having a pinhole diameter of 50 μm or more in the welded portion is one, and the number of pinholes having a diameter of 40 to 50 μm is three, and is in the general surface. The number of pinholes having a diameter of 70 μm or more is one, and the number of pinholes having a diameter of 40 to 70 μm is 0.5/m 2 . The film forming conditions are as follows. Film forming speed: 30 m/min Film (substrate) thickness = 80 μm The cast polycarbonate film was applied by drying as follows. (1st zone) In the initial stage of drying, 30 ° C warm air is blown on the back side of the support to heat, and the atmosphere temperature of the polycarbonate film is set to 20 ° C and care is taken not to cause deformation of the polycarbonate film. (poor uniformity) and dried. (Second Division) Next, the atmospheric temperature was set to 45 t by blowing a warm air, and the drying was continued until the concentration of methylene chloride in the polycarbonate film was about 35 mass%. (3rd zone) Next, drying was performed by blowing a warm air at an atmospheric temperature of 50 ° C so that the amount of the solvent in the polycarbonate film was 25% by mass. (4th zone) In this zone, drying is applied at an ambient temperature of 55 °C. The amount of the solvent in the polycarbonate film at this time was set to 20% by mass. (Fifth Division) In this zone, the polycarbonate film was cooled together with the support at an atmosphere of 15 °C. The amount of the solvent in the polycarbonate film at the end of this step was 18% by mass. - The polycarbonate film is then peeled off from the support, and the peeled polycarbonate film is fed again into a dryer of the needle clamp tenter type, and dried while being applied -50-1302870. In the needle clamp tenter, the polycarbonate film is conveyed by holding the both ends of the polycarbonate film with a needle holder. The needle clamp tenter is used in a manner that is divided into 6 zones. " In the needle clamp tenter, the drying of the polycarbonate film is carried out by the inlet

And the width will shrink with it, so the track width of the needle clamp tenter is also narrowed to shrink according to the width to dry. That is, the hot air temperature is raised to promote the drying of the polycarbonate film as it enters the needle clamp tenter step. At this time, the track width of the needle clip tenter is set as much as possible so as not to cause molecular alignment of the polycarbonate film. The hot air temperature in the first half is set to 90 ° c, 110 ° c, 120 ° c, so that the temperature in the middle of the 4th and 5th zones is set to 1 3 (TC, in the 5th section, the polycarbonate is partially opened by the needle. Further, the hot air temperature was set to 135 ° C in the sixth zone. At the exit of the pinch tenter, the coiling tension of the polycarbonate film was set to 0.49 MPa at approximately room temperature to be taken up.

And, the film is then conveyed to a roller suspension type dryer. The roller suspension type dryer was divided into two compartments, and the hot air temperature at the front portion was 135 ° C, the hot air temperature at the rear portion was 145 ° C, and the take-up tension was set to 0.15 MPa to be taken up. The properties of the polycarbonate film produced by this method are as follows. The polycarbonate film obtained had a width of 1,000 mm. The polycarbonate film has a thickness of 80 μm and a thickness spot of 2 μm. The thermal dimensional change rate is 0.07%, the total light transmittance is 90%, the solvent content is 0.3% by mass, the in-plane retardation 値 is -51 - 1302870 4 to 8 nm, the surface roughness Ra is 1.8 nm, and Rth is The maximum 値 is 90 nm. Further, a 20-micron-thick polyethylene terephthalate film (a Young's modulus) is stacked on the surface of the polycarbonate film to be taken up by a coiler (the Young's modulus, both vertical and horizontal) 5.29 GPa, surface roughness Ra is 25 nm on both sides) and pressure-stacked to obtain a 500 m long roll-shaped polycarbonate film (s-1) with a surface protective film. (Modulation of coating solution for hard coating (h-Ι))

A mixture of 450 parts by mass of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) is dissolved in 2 10 parts by mass of isopropyl alcohol (IPA) and A mixed solvent of 140 parts by mass of methyl isobutyl ketone (MIBK). To the obtained solution, 12.0 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba-Geigy Co., Ltd.) was added, and after stirring until dissolved, 380 parts by mass of IPA-ST was added (average particle diameter was 10 to 20 nm). Rice, solid content of 30% by mass of SiO 2 sol isopropanol dispersion, manufactured by Nissan Chemical Co., Ltd.) and 257 parts by mass of MIBK-ST (average particle size of 10 to 20 nm, solid concentration is 30% by mass of a dispersion of methyl isobutyl ketone of SiO 2 sol, manufactured by Nissan Chemical Co., Ltd., and stirred to obtain a mixture, which was then filtered with a polypropylene filter (PPE-03) having a pore size of 3 μm. To prepare a coating liquid for a hard coat layer (h-Ι) 〇 (preparation of a hard coat coating liquid (h-2)) 450 parts by mass of dipentaerythritol pentaacrylate and dipentaerythritol Acrylate mixture (DPHA, manufactured by Nippon Kayaku Co., Ltd.), dissolved -52-1302870 _ 426 parts by mass of methyl isobutyl ketone (MIBK) and 6 parts by mass of methyl ethyl ketone (ΜΕΚ a mixed solvent. After adding 12.0 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba-Geigy Co., Ltd.) to the obtained solution and stirring until dissolved, 514 parts by mass of MIBK-ST (average particle diameter of 10 to 20) was added. Nano, isobutyl ketone dispersion of SiO 2 sol having a solid concentration of 30% by mass, manufactured by Nissan Chemical Co., Ltd.) and 129 parts by weight of ΜΕΚ-ST (average particle diameter of 10 to 20 nm, solid a concentration of 30% by weight of a SiO 2 sol methyl ethyl ketone dispersion, manufactured per day (manufactured by the company), and stirred to obtain a mixture, and then a polypropylene filter having a pore size of 3 μm (PPE- 03) Filtration to prepare a coating liquid (h-2) for a hard coat layer. The hard coat liquid (h-2.) is a solvent for changing the coating liquid for hard coat layer (h-Ι), and (h-2) contains only a solvent which erodes the polycarbonate. Table 2 shows the SP値 of the solvent used to modulate the hard coat coating liquid. Table 2 Name Representation symbol SP値 PC tablet Isopropyl alcohol IPA 11.5 No change Methyl ethyl ketone MEK 9.3 White turbidity Methyl isobutyl ketone MIBK 8.4 White turbid

(Production of Hard Coating Film) [Example 1] The coating speed was set to 10 m/min, and the surface protection obtained by the above-mentioned width of 1, 〇〇〇 mm and thickness of 80 μm was obtained by co-winding. The surface protective film of the polycarbonate film (s-1) of the film is continuously fed while being taken up, and the hard coating liquid is applied to the belt to a thickness after drying by using a bar coater. 3.3 μm, coating width of 980 mm, and then drying at 70-53-1302870 for 1 minute, using a 160 W/cm air-cooled metal halide lamp (Eye) under nitrogen purge (0.1% oxygen concentration) Graphics (manufactured by the company) to illuminate the hard coat with an illuminance of 400 mW/cm2 and an irradiation dose of 500 mJ/cm2, and then take up a hard coat of 1 〇〇m. [Example 2] The sample of Example 1 was produced by changing the coated surface from the belt surface to the air surface in Example 1. [Example 3]

A surface protective film of a polycarbonate film (Pureace 110-80 manufactured by Teijin Chemicals Co., Ltd.) having a thickness of 1 m, a thickness of 80 μm and a thickness of 20 μm as a surface protective film. The film was continuously taken out while being taken up, and a hard coat liquid was applied to the air surface by a bar coater to a thickness of 3.3 μm, a coating width of 980 mm, and then dried at 70 ° C. After 1 minute, under a nitrogen purge (oxygen concentration of 0% by%), an air-cooled metal halide lamp (manufactured by Eye Graphics) of 160 W/cm was used to irradiate an illumination of 400 mW/cm2 and an irradiation amount of 500. UV light of mJ/cm2, hardening the hard coat layer, and then coiling hard coat of 1〇〇m

[Example 4] The sample of Example 4 was produced under the same conditions except that the thickness of the hard coat layer was changed to 5.0 μm except that the thickness of the hard coat layer was changed to 5.0 μm. [Comparative Example 1] The sample of Comparative Example 1 was produced by changing the coated surface to the belt surface in Example 3. [Comparative Example 2] -54 - 13 〇 287 〇 Comparative Example 2 A sample of Comparative Example 2 was produced under the same conditions except that the thickness of the hard coat layer was changed to 5.0 μm. [Comparative Example 3] Comparative Example 3 was prepared under the same conditions except that the comparative example 1 was changed to the hard coat liquid (h-2). [Comparative Example 4] The sample of Comparative Example 4 was produced under the same conditions except that the Example 3 was changed to the hard coat liquid (h-2).

(1) Evaluation of bump-like defects The hard coating film obtained was removed from its both ends by 10 cm and the remaining width was 80 cm, which was 20 cm X 20 cm square.

Take a total of 4 pieces of 2 rows and a total of 8 pieces of sample, then make the back side painted black, and mark 10 cm X 10 cm square mark, the light perpendicular to the coated surface is incident on the mark, and is perpendicular to The direction of the coated surface (the direction of incidence of light) is magnified 30 times with an optical microscope to focus on the surface, and point defects of 50 μm or more are picked up according to the surface reflected light. The bulging portion is caused by the film thickness being changed to cause the focus to deviate. Also, the normal portion is separated from the ridge portion depending on the phenomenon that the incident light will be scattered on the surface and cannot be returned to the microscope. The section of the ridge-shaped defect of 50 μm or more which was picked up was cut and magnified by an electron microscope to 1,000 times, and the number of protrusion-shaped foreign objects displayed on the surface of the polycarbonate film was observed to be increased - 55- 1302870 to count and take the average of 8 samples. (2) Evaluation of the damage resistance The hard coating film obtained was subjected to a friction tester and the friction test was carried out under the following conditions: Sample conditioning conditions: 25T: 60% RH, 2 hours or more; _ Rubbing material: The friction front end of the test machine in contact with the sample (1 cm X 1 cm) is wound around steel wool (made of Japanese steel wool, grade #0000) and fixed by entrainment;

Moving distance (one-way): 13 cm; Friction speed: 13 cm/sec; Load: 1.96 N/cm2; Front end contact area: 1 cm X 1 cm; Number of rubs · Live for 1 〇. Oily black ink was applied to the back side of the rubbed sample, and the reflected portion was visually observed by the reflected light, and the abrasion of the rubbing portion was evaluated on the following basis: 〇: no damage was observed; X: wound was observed. Table 3 Example 1 - Substrate coated surface - belt surface - cliff cloth liquid h-1 hardened film thickness - 3 · 3 micron - scratch resistance point defect 〇 ~ 0 Example 2 s-1 hot surface h-1 3·3 micron 〇0 Example 3 Pureace: 3⁄43⁄4 face h-1 3·3 micron 〇0 Example 4 s-1 band surface h-1 5.0 micron 〇0 Comparative example 1 Pureace band surface h-1 3·3 Micron 〇5 Comparative Example 2 Pureace belt surface h-1 5.0 micron 〇1 2 Comparative Example 3 Pureace belt surface _Ji-2 3.3 micron 〇324 Comparative Example 4 Pureace air surface h-2 3·3 micron 〇315 -56- 1302870 From the results shown in Table 3, the following items are known. The hardenable composition (h-2) of the hard coat layer prepared by using only an organic solvent having an SP値 of 8·3 or more and 100.5 or less (invasive polycarbonate film) is used in the polycarbonate. When a film is formed into a hard coat layer, the point defects due to the polycarbonate film are often generated regardless of whether the coated surface is a belt surface or an air surface. (Comparative Examples 3 and 4) The hardenable composition (h-Ι) for hard coating layer prepared by reducing the ratio of the organic solvent to the total organic solvent to 60% or less was formed in Teijin In the case of a hard coat layer having a film thickness of 3.3 μm or 5.0 μm in the range of 1.0 to 8.0 μm on the surface of Pureace manufactured by the company, a bump-like defect is generated. (Comparative Examples 1 and 2) In addition, the number of ridge-like point defects in which the film thickness is 5.0 μm is 3.3 μm is increased, and the importance of countermeasures is increased. (Examples 1 and 4, Comparative Examples 1 and 2)

The hard coat film of the polycarbonate film obtained by using the set face pin hole of the present invention has no embossing defects in the form of face coating or air face coating. (Examples 1 and 2) The hard coat film in which the hard coat layer was laminated on the air surface of Pureace manufactured by Teijin Chemicals Co., Ltd. of the present invention had no ridge-like defects. (Embodiment 3) [Applicability to optical discs] (Manufacture of optical disc) In place of the comparative example disclosed in paragraphs (0048) to (0054) of Japanese Patent Laid-Open Publication No. 2003-263797, the present invention is a comparative example of the present invention. 20 , and replace the cover film disclosed in paragraph (005 1 ) (polycarbonate film -57-1302870 . , Teijin Pureace, thickness · 80 μm, one side with a second release film; second release film The surface roughness of the surface D: 250 nm) and the long roll-shaped hard coat films of the inventive examples 1 and 3 and the comparative example 1 shown above were used to obtain an optical recording body (disc). (Examples 21 and 23, respectively, Comparative Example 2 1) [Example 2 1] "Manufacture of optical information recording medium" There will be a spiral groove (depth of 100 nm, width of 120 nm, gauge distance) 320 nm), a polycarbonate resin having a thickness of 1.1 mm and a diameter of 120 mm (polycarbonate manufactured by Teijin Co., Ltd., trade name: Panlight AD5503) was injection molded into a substrate. On the grooved surface of the obtained substrate, Ag was sputtered to form a light reflecting layer having a thickness of 100 nm (light reflecting layer forming step). Thereafter, 20 g of Orazobl GN (anthraquinone-based pigment, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to 1 liter of 2,2,3,3-tetrafluoropropanol for 2 hours. The ultrasonic treatment is performed to dissolve the coating liquid for forming a recording layer. The prepared coating liquid was applied to the light-reflecting layer by a spin coating method while changing the number of revolutions in the range of 300 to 4,000 rpm, and was applied under the conditions of 23 ° C and 50 % RH. Thereafter, the film thickness of the recording layer formed by storage at 23 ° C and 50 % RH for 1 to 4 hours was 100 nm (recording layer forming step). Then put ZnS on the recording layer —

Si〇2 was sputtered to a thickness of 5 nm to form an intermediate layer. <<Manufacturing of Cover Layer>> [Preparation of Adhesive Coating Liquid] -58- 1302870 , Acrylic Copolymer (Solvent: Ethyl Acetate / Toluene = 1/1) and Isocyanate Crosslinking Agent (Solvent: Ethyl Acetate) /Toluene = 1/1) was mixed at 100:1 (mass ratio) to prepare an adhesive coating liquid A. [(a) a step of continuously providing an adhesive layer containing a *crosslinking agent on the surface of a hard coating film wound into a roll, and (b) a cover film provided with an adhesive layer, which is again wound into a roll Step of the shape] First, an adhesive layer having a thickness of 17 μm was provided on the surface of the hard coat film by using an adhesive layer setting device as shown in Fig. 1. The polyethylene release film wound in the roll 1 is continuously fed in the direction of the arrow mark, and the adhesive application liquid A is applied onto the surface of the release film by using the applied portion 2 (coating step). Thereafter, the release film of the formed adhesive coating layer was dried by a drying apparatus 3 disposed in a drying zone at 100 ° C (drying step) to obtain a release film having an adhesive layer. Then, the release film having the adhesive layer was further conveyed, and the cover film (the long roll-shaped hard coat film of Example 1: 83 μm, one side with a release film) was fed from the roll 4 The tube 6 is peeled off while peeling off the surface protective film, and in the bonding area a, the polycarbonate surface of the hard coating film after the peeling surface protective film Φ is bonded to the adhesive layer (adhesion step) . Then, the release film having the adhesive layer and the hard coat film are co-rolled on the reel 5 (winding step). -' [(c) the step until the crosslinking reaction of the adhesive layer is substantially completed], * thereafter, the roll 5 in a state in which the release film having the adhesive layer and the cover film are co-rolled, at 23 Under an atmosphere of °C and 50% RH, it was kept for 72 hours. The "72 hours" is that the adhesive layer of the present embodiment is measured with an infrared spectroscopy absorption spectrum over time under the above atmosphere, and the absorption wave of the isocyanate is present at -59-1302870 and is now around 2,275 to 2,250 cnT1. The elapsed time required for the summit to substantially disappear, that is, corresponds to the time "before the crosslinking reaction of the adhesive layer is substantially completed" in the present embodiment. Further, in this step, the infrared spectroscopy absorption spectrum was measured by the FT-IR-subreflection method under the following conditions. Measuring machine: Nexus 670 measuring aid manufactured by Thermo Nicore Japan: OMNI-Sampler - secondary reflection type horizontal ATR device

The total number of calculations: 4 cnT1 32 times detector: MCT-A (high sensitivity detector) [(d) the step of punching the cover film with the adhesive layer into a disk shape, and (e) the disk shape The step of laminating the cover film of the adhesive layer to be substantially horizontal and held] The release film and the cover film having the adhesive layer in a co-rolled state are continuously fed from the roll 5 and punched into the same shape as the above-mentioned substrate. A laminate having a release layer of a punched adhesive layer and a cover film, as shown in Fig. 2, is laminated in a manner of being placed in a storage sleeve shaft having an outer diameter smaller than the center hole. It is approximately horizontal and remains in this state for 1 hour. Thereafter, the film was taken out one by one, and the release film on the adhesive side was peeled off, and the intermediate layer and the adhesive layer were bonded together by a pressing device of a roll to obtain an optical disk. [Example 23] The long roll-shaped hard coat film of Example 21 was changed to Example 3 to obtain a sample of Example 23. [Comparative Example 2 1] -60-1302870. The sample of Comparative Example 21 was prepared by changing the long roll-shaped hard coat film of Example 21 to Comparative Example 1. (Evaluation of the sample) 1. The evaluation of the noise is evaluated by the evaluation according to paragraph (0055) <Evaluation> (1) C/N (carrier-to-noise ratio) in Japanese Patent Laid-Open Publication No. 2003-263797. As a result of Examples 21 and 23 and Comparative Example 21, it was found that the bump-like defect on the hard coat layer can be detected as noise, and it was confirmed that the noise can be greatly reduced by the present invention. <Evaluation> C/N (Carrier-to-Noise Ratio) The disc used is a recording and reproduction evaluation machine (Dul 1000 manufactured by Pulsetec) with a 405 nm laser and a NA: 0.85 pickup. Recording and regeneration were performed with a single frequency signal (2 T = 0.13 μm) at a frequency of 66 MHz/line speed of 5.6 m/s, and the following results were obtained using a spectrum analyzer to determine the C/N results =

Example 21: 52 dB Example 23: 49 dB Comparative Example 21: 32 dB 2. Scratch resistance The side surface of the light-transmitting layer of the sample was coated with a steel wool of #〇〇〇〇 to apply a load edge of 1.96 N/cm2. The damage at the time of rubbing is evaluated by visual observation (the state of the trace is not seen even if the friction is 1 〇〇 times; the state of the trace can be seen when X is less than 30 times) The following results were obtained: -61 - 1302870 Example 21: 〇 Example 23: 〇 Comparative Example 20: X Comparative Example 21: 〇 From the above results, the hard coat film of the present invention is greatly reduced in resistance to abrasion, and noise is greatly reduced. Therefore, it is also suitable for use as a cover layer for optical discs. [Simple description of the drawing] Fig. 1 is a schematic diagram of a solution film forming apparatus for solution film forming method

Figure 2 is a partial cutaway perspective view of the casting zone. Figure 3 is a diagram for setting the pin aperture pattern generated in the casting tape. Fig. 4 is a schematic cross-sectional view showing an adhesive layer setting device of an exemplary embodiment in which the adhesive layer is continuously provided while peeling off the surface protective film on the surface of the long roll-shaped hard coat film. Fig. 5 is a view showing a state in which a cover film in which a disk-shaped adhesive layer is provided is laminated in a substantially horizontal state in a holding device.

Figure 6 is an electron micrograph showing a section of the bump-like defect. -62-

32 40 50 70 80 fl 1302870 [Description of main components] 1, 4, 5, 6 Reel 2 Coating device 3 Drying device 10 Casting step 11 Casting die 12 Casting tape 20 Extension step 21 Tenter 30 Drying Step 3 1 Conveying roller Drying wind winding part Pinhole pedestal Storage sleeve shaft release film f2 Hard coating film f3 Set hard coating film of disc-shaped adhesive layer f4 Surface protection cover film-63-

Claims (1)

, 1302870, yue, yue, yue, yue, yue, yue, yin, yin, yin, yin, yin, yin, yin, yin, yin, yin, yin, yin, yin, yin, yin, yin, yin, yin, yin, yin Amendment on the 13th of the month) X. Patent application scope: An optical film comprising a hardened layer having an average thickness of 1.0 to 8.0 μm on a film substrate made of polycarbonate and formed by a casting method, and in the hardened layer The number of ridge-like point defects having a diameter of 50 μm or more in the middle of the polycarbonate containing the film substrate is an average of 1 or less per 10 cm square. 2. The optical film of claim 1, wherein the film substrate is a film obtained by casting a coating liquid on a casting tape by a casting die. 3. The optical film of claim 2, wherein the number of pinholes having a diameter of 50 μm or more in the welded portion of the casting tape is zero. 4. The optical film of claim 2, wherein the number of pinholes having a diameter of 40 to 50 μm in the welded portion of the casting tape is 5 or less. 5. The optical film of claim 2 or 3, wherein the number of pinholes having a diameter of 70 μm or more in a general surface other than the welded portion of the casting tape is one. 6. The optical film of claim 5, wherein the number of pinholes having a normal face diameter of 40 to 70 μm is 5/m2 or less. 7. The optical film of claim 1 wherein the hardened layer is a hardenable composition for a transparent polycarbonate film substrate comprising a hardener and an organic solvent, and has a solubility parameter (S p値) of 8 ·3 or more, 1 〇. 5 or less of the organic solvent in the total organic solvent content of 60 weights 1302870 months 3 osmosis (more) positive replacement 贞 '1% by weight or less of the hardening composition ΐ / formed 8. The optical film of claim 7, wherein the hardened layer is a layer formed of a curable composition containing no organic solvent having a solubility parameter (SP値) of 9.0 or more and 10.0 or less. 9. The optical film of claim 1, wherein the hardened layer has an average film thickness of from 1.0 to 4.0 microns. The optical film of claim 1, wherein the hardened layer has an average film thickness of 2.5 to 4.0 μm. An optical film with an adhesive layer, characterized in that an adhesive film having a thickness of 10 μm or more is laminated on the surface of the hardened layer of the optical film which is not laminated with the optical film of claim 1 of the patent application. Agent layer. 12. The optical film with an adhesive layer as claimed in claim 11, wherein the film substrate is a film obtained by casting a coating liquid on a casting tape by a casting die, and the film substrate The surface of the hardened layer which is not laminated is the air surface when the film substrate is produced on the casting tape, and the surface on which the adhesive layer is laminated is the tape surface when it is produced on the casting tape. An optical film according to claim 1, wherein the hardened layer is a hard coat having scratch resistance to steel wool. 14. An optical film having an adhesive layer as claimed in claim 11 or 12, wherein the hardened layer is a hard coat having scratch resistance to steel wool. 1 5 . An optical film with an adhesive layer as disclosed in claim 14 of the patent application, which is used for an optical disc. 16. A method of making an optical film, characterized by a casting die in a stream -2- 1302870 17. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> Further, the number of pinholes having a diameter of 50 μm or more in the welded portion of the casting tape is one. The method for producing an optical film according to claim 16 wherein the number of pinholes having a diameter of 70 μm or more on a general surface other than the welded portion of the casting tape is one. A method for producing an optical film with an adhesive layer, characterized in that a film substrate composed of polycarbonate is cast on a casting tape by a casting die, and then the film substrate is flowed a hardened layer having an average film thickness of 1.0 to 8.0 μm formed on the air surface at the time of manufacture, and an adhesive layer having a film thickness of 10 μm or more laminated on the tape substrate when the film substrate is produced on a casting tape . -3-