WO2007138785A1

WO2007138785A1 - Hard coat film and optically functional film

Info

Publication number: WO2007138785A1
Application number: PCT/JP2007/057404
Authority: WO
Inventors: Naoki Mizuno; Hideki Sugihara; Shigenori Iwade; Yasuhiro Nishino; Katsuhiko Nose; Toshitake Suzuki; Chikao Morishige
Original assignee: Toyo Boseki Kabushiki Kaisha
Priority date: 2006-05-29
Filing date: 2007-04-02
Publication date: 2007-12-06
Also published as: KR100898255B1; CN101460308B; JP4029356B2; TWI360477B; TW200810924A; JP2007313865A; KR20080111173A; CN101460308A

Abstract

A hard coat film having an adherence modifying substratum film consisting of adherence modifying layer (B) containing copolymerized PEs and PU superimposed on one major surface or both major surfaces of thermoplastic resin film (A) and having, superimposed on the surface of the adherence modifying layer (B) on either one major surface of the substratum film, hard coat layer (C) containing inorganic microparticles, characterized in that the adherence modifying layer (B) has a micro phase separation structure or nano phase separation structure of PEs phase and PU phase, and that when a cut plane of the hard coat film is observed in a phase measurement mode by the use of a scanning probe microscope, the ratio of area of PU phase of adherence modifying layer (B) in the zone from interface of the adherence modifying layer (B) with the hard coat layer (C) to a depth of 20 nm is in the range of 30 to 60%.

Description

Specification

Hard coat film and optical functional film

[0001] The present invention relates to a hard coat film and an antireflection film, a light diffusion sheet, a prismatic lens sheet, a near-infrared ray shielding film, a transparent conductive film, an antireflection film, which are mainly used for display members, and the film. It relates to optical functional films such as glare films. Specifically, adhesion between the base film and the hard coat layer containing inorganic fine particles, and other optical functional layers (hard coat layer, light diffusion layer, prism layer, infrared absorption layer, transparent conductive layer, antiglare layer, etc.) The present invention relates to a hard coat film having excellent properties and excellent scratch resistance, and an optical functional film using the same.

Background art

[0002] In general, hard coat films used for display components such as liquid crystal displays (LCDs) and plasma display panels (PDPs) are made of thermoplastic resin films and hard coat (HC) layers that have improved adhesion. It is laminated via a resin layer. Furthermore, the optical functional film for display is generally used by bonding optical functional films having different functions through an adhesive layer. On the other hand, demands for large flat displays have been increasing in recent years due to low-price market power. Therefore, composite films in which other optical functional layers are laminated on one hard coat film are being developed for display materials. For example, in a liquid crystal display (LCD), a hard coat film has an antireflection layer (AR layer) that prevents reflection of external light, a prism-like lens layer that is used to collect and diffuse light, and light that improves brightness. Examples include an optical composite functional film in which optical functional layers such as a diffusion layer are laminated.

[0003] The thermoplastic resin film used as the base material of the hard coat film includes a transparent film having polyethylene terephthalate (PET), polyamide, acrylic, polycarbonate (PC), triacetyl cellulose (TAC), cyclic polyolefin, etc. Is used. Among these substrate films, in particular, the biaxially oriented polyester film is used as a thermoplastic resin film for various optical functional films from the viewpoint of excellent transparency, dimensional stability, and chemical resistance. Widely used.

[0004] Generally, in the case of a biaxially oriented thermoplastic film such as a biaxially oriented polyester film or a biaxially oriented polyamide film, the film surface is highly crystallized, so that it can be used with various paints, adhesives, inks, etc. There is a drawback of poor adhesion. For this reason, conventionally, methods for imparting easy adhesion to the surface of a biaxially oriented thermoplastic resin film by various methods have been proposed.

[0005] In addition, the film does not have a polar group like a polyolefin film! /, And the film has very poor adhesion to various paints, adhesives, inks, etc., so corona discharge treatment, flame treatment, etc. in advance There have been proposed methods for imparting easy adhesion to the film surface by various methods after the physical treatment and chemical treatment.

[0006] For example, by providing an adhesive modified layer containing an adhesive modified resin such as film, polyester, acrylic, polyurethane, and acrylic graft polyester on the surface of a thermoplastic resin film by a coating method, A method for imparting easy adhesion to a plastic resin film is generally known. Among these coating methods, the thermoplastic resin film before completion of crystal orientation was subjected to corona discharge treatment directly or as needed, and then the above-mentioned solution or resin was dispersed with a dispersion medium. A method in which an aqueous coating solution containing a dispersion is applied to a substrate film, dried, stretched at least in a uniaxial direction, and then subjected to a heat treatment to complete the crystal orientation of the thermoplastic resin film (so-called inline A coating method) and a method of drying a water-based or solvent-based coating liquid after manufacturing a thermoplastic resin film (so-called off-line coating method) are widely used industrially.

[0007] Displays such as LCDs and PDPs are increasing in size and cost each year, and the production speed is increased in the manufacturing process of optical functional films used as the members. With such high-speed manufacturing processes, stresses due to curing shrinkage are more likely to occur at the interface between the functional layer such as the hard coat layer, the diffusion layer, and the prism layer and the base film. For this reason, when the optical functional film is cut to a specific size in order to produce a display, if the adhesion at the interface is insufficient, the end portion is particularly easily peeled off. This tendency is more pronounced as the roll-up film becomes larger and the production speed increases in the manufacturing process. The impact of interfacial delamination due to impact during casting becomes more prominent, and the conventional level of adhesion has become insufficient.

[0008] Further, the processing agent used for forming the functional layer such as the prism layer or the diffusion layer described above is directly applied to the base film without being diluted with an organic solvent from the viewpoint of reducing the environmental load. Is often applied. For this reason, since the effect of improving the wettability of the adhesion modified layer by the organic solvent may not be sufficiently obtained, higher adhesion is required. On the other hand, in applications such as hard coating where emphasis is placed on smoothness, the processing agent is often diluted with an organic solvent in order to reduce the viscosity of the processing agent and obtain a good leveling effect. In this case, an appropriate solvent resistance is required for the adhesion modified layer of the adhesion modified substrate film.

[0009] In order to improve the adhesion between the functional layer and the base film, a method of using a resin having a low glass transition temperature as the resin constituting the adhesive property modification layer is generally used. However, when a resin having a low glass transition temperature is used, the blocking resistance decreases when the adhesive modified base film is continuously wound into a roll and the film is rolled. Tend.

[0010] Further, in recent years, due to low cost, the processing machine for laminating functional layers such as a hard coat layer and a diffusion layer on a base film has been increased in size, so that it can be easily used as a base film. The roll diameter of the adhesive film is also increasing. Along with this, when winding with high tension in order to prevent roll misalignment, blocking is more likely to occur, especially because the core of the roll is pressed with high pressure.

[0011] In order to improve the blocking resistance, a method is generally employed in which irregularities are imparted to the surface of the adhesive modified base film to reduce the contact area. In order to give unevenness to the film surface, a method of increasing the content of inorganic particles or organic particles contained in the adhesive modified layer or the substrate film, or using particles having a large particle size is used. The method is common. However, the refractive index of commercially available particles is generally different from the refractive index of the resin used for the adhesive reforming layer, and voids are formed around the particles as the film is stretched. Therefore, in these methods, the light transmittance of the film is lowered and the haze is raised. In particular, the transparency required for the base film of the optical functional film is lowered. In other words, in the conventional method, the high speed of the process is low. Due to new problems associated with the increase in the diameter of the rod, it was extremely difficult to improve the adhesion and the blocking resistance while maintaining transparency while maintaining the transparency.

Furthermore, in recent years, the optical functional film is provided with a hard coat layer on both sides of the base film for the purpose of preventing adhesion with the light guide plate, increasing the transmittance, or reducing the curl. In many cases, a hard coat layer is also laminated on the surface opposite to the optical functional layer such as a prism lens layer or a light diffusion layer. In particular, a hard coat film is usually a thin cured film having a thickness of 3 to 10 μm on a thermoplastic resin film using an ionizing radiation curable resin such as a thermosetting resin or an ultraviolet curable resin. A coating film (node coat layer) is formed.

However, since the thickness of the hard coat layer is thinner than that of the base film, the hardness of the hard coat film itself is affected by the base film and does not become sufficiently high. Therefore, in order to further improve the scratch resistance of the node coat, it has been studied to contain inorganic particles in the hard coat layer.

[0014] On the other hand, when the hard coat layer contains inorganic particles, the ratio of the curable resin in the hard coat layer decreases, so the adhesive modified base film and the hard coat layer of the adhesive modified base film Adhesiveness at the interface decreases.

[0015] In particular, it is known that the biaxially oriented polyester film has poor adhesion to a coating agent mainly composed of an acrylic resin used for prism lenses, hard coats, and the like! . For this reason, various proposals have been made in which an adhesive modified layer made of polyurethane or the like is formed on the surface of a polyester film (see, for example, Patent Document 1). However, when an adhesion modified layer made of polyurethane is formed, the adhesion to a functional layer such as a hard coat layer is improved, but the adhesion to the polyester film as the substrate is insufficient. As a result, the adhesiveness is insufficient at the interface between the adhesive modified layer and the functional layer. In particular, the adhesion at the interface between the adhesion modified layer and the hard coat layer containing inorganic particles is remarkably inferior. Patent Document 1: JP-A-6-340049

[0016] In addition, a resin composition comprising a copolymer film and polyurethane as main components on a base film made of biaxially oriented polyethylene terephthalate by an in-line coating method. A method for improving the adhesion between the base polyester film and the functional layer such as ink has been proposed (see, for example, Patent Document 2). More specifically, the polyester film is uniaxially stretched in a longitudinal direction, copolymerized polyester and polyurethane; after coating the aqueous dispersion coating solution containing (= 20/80 by weight ^_0/0), introduced into a tenter, drying, horizontal After stretching, it is heat-set at 220 ° C to obtain an easy-adhesive biaxially oriented polyester film.

Patent Document 2: Japanese Patent Publication No. 64-6025

However, although the adhesion is improved by the method described in Patent Document 2, the substrate film and the hard coat layer are recently required as a substrate film for use in an optical functional film. The adhesiveness at the interface between the functional layer such as the diffusion layer, particularly the adhesion modified layer and the hard coat layer containing inorganic particles is insufficient.

[0018] The applicant provided a resin composition layer in which a copolyester, polyurethane, and inorganic particles having an appropriate particle diameter were added on a base film made of biaxially oriented polyethylene terephthalate, and further optical We have proposed a laminated polyester film that can sufficiently satisfy the required level of adhesion while maintaining transparency, which is an extremely important property for a substrate film for use in a film, and has few optical defects (for example, , See Patent Documents 3 and 4). More specifically, the polyester film is uniaxially stretched in a longitudinal direction, copolyester, polyurethane (= 20Z80; Mass ^_0/0) and two different average particle sizes of silica particles, the Ryoji on surfactant An easy-adhesive biaxially oriented polyester film obtained by applying a water-dispersible coating solution containing it, guiding it to a tenter, drying, transverse stretching, and heat setting at 240 ° C. was disclosed.

[0019] The easy-adhesive biaxially oriented polyester film obtained in Patent Documents 3 and 4 has excellent adhesion, blocking resistance, transparency, and optical defects such as foreign matter and scratches. It was greatly improved and satisfied the conventionally required characteristics. However, as mentioned above, the substrate film, hard coat layer, diffusion layer, prism layer, which are required as a substrate film for optical functional films, due to the recent reduction in cost and the increase in the display screen. The required level of adhesion to functional layers and blocking resistance is becoming stricter year by year. In particular, the adhesiveness at the interface between the adhesion modified layer and the hard coat layer containing inorganic particles is not fully satisfactory at the required quality of the current factory. Patent Document 3: Japanese Patent Laid-Open No. 11 323271

Patent Document 4: Japanese Patent Laid-Open No. 2000-246855

[0020] Further, the applicant of the present invention has proposed an invention relating to an easy-adhesive film roll in which the variation in coating amount is reduced in order to improve the uniformity of adhesion (see, for example, Patent Document 5). The Examples of Patent Document 5, the polyester film is uniaxially stretched in a longitudinal direction, copolymerized poly ester and polyurethane (= 50Z50; Mass ^_0/0), silica particles having an average particle size of 1. 4 m, and a fluorine-based An easy-adhesive biaxially oriented polyester film obtained by applying a water-dispersible coating solution containing a surfactant, drying in a drying oven at 120 ° C, laterally stretching, and then heat-setting at 220 ° C Is described. The obtained film roll had excellent adhesion uniformly throughout the film roll, and satisfied the required level from the factory. However, the adhesion at the interface between the adhesion modified layer and the hard coat layer containing inorganic particles is not fully satisfactory.

Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-10669

[0021] For the purpose of improving scratch resistance, an ionizing radiation curable hard disk containing about 40 parts by mass of ultrafine silica particles having a particle size of about 50 nm or less on 100 parts by mass of a resin on an easily adhesive polyethylene terephthalate film. A hard coat film in which a coating agent is applied to a dry thickness of about 15 m and cured with an electron beam has been proposed (for example, see Patent Document 6). However, this hard coat film has high hardness in the hard coat layer and excellent scratch resistance. However, the hard coat film has good resistance to adhesion at the interface between the adhesive modified layer and the hard coat layer containing inorganic particles. As a result, the required quality of the current factory will not be fully satisfied.

Patent Document 6: Japanese Unexamined Patent Publication No. 2000-112379

[0022] On the other hand, a hard coat film in which a hard coat layer not containing particles is laminated on an easily adhesive polyethylene terephthalate film having an adhesive modified layer composed of a copolyester and a melamine crosslinking agent has been proposed (for example, (See Patent Document 7). However, this hard coat film is not satisfactory in terms of adhesion to the hard coat layer and hardness of the hard coat layer.

Patent Document 7: Japanese Unexamined Patent Application Publication No. 2004-160774 That is, in the prior art, while maintaining high hardness, a hard coat film excellent in adhesiveness that can withstand high-speed cutting required in recent years, in particular, adhesiveness with a hard coat layer containing inorganic particles. Is obtained. Disclosure of the invention

Problems to be solved by the invention

[0024] An object of the present invention is to provide a hard coat film having a high hardness and a high hardness at the interface between the adhesion modified layer and the hard coat layer containing inorganic particles, and an optical functional film using the same. Is to provide.

Means for solving the problem

[0025] The above-described problems can be achieved by the following solution means.

That is, the first invention in the present invention is an adhesive modified base film in which an adhesive modified layer B containing a copolymerized polyester and polyurethane is formed on one side or both sides of a thermoplastic resin film A, and A hard coat film having a layer structure of AZBZC or BZAZBZC, in which a hard coat layer C containing inorganic fine particles is laminated on the surface of an adhesive modified layer B on one side of the film, the adhesive modified Layer B has a micro phase separation structure or a nano phase separation structure of a polyester (PEs) phase and a polyurethane (PU) phase, and the cutting surface of the hard coat film was observed in a phase measurement mode using a scanning probe microscope. At this time, the interface force between the adhesive modified layer B and the hard coat layer C is within the range of a depth of 20 nm, and the polyurethane phase (phase image) of the adhesive modified layer B is defined by the following formula (1). Show light hue Area ratio of) is a hard coat film, characterized in that 60% or less than 30%.

PU phase area ratio (%) = (PU phase area Z measurement area) X 100 · · · (1)

[0026] The second invention is an adhesive modified base film in which an adhesive modified layer B containing a copolymerized polyester and polyurethane is formed on one or both sides of a thermoplastic resin film A, and the film A hard coat film having a layer structure of AZBZC or BZAZBZC, in which a hard coat layer c containing inorganic fine particles is laminated on the surface of one of the adhesive modified layers B, the adhesive modified layer B , Having a micro phase separation structure or a nano phase separation structure of polyester (PEs) phase and polyurethane (PU) phase, and using a scanning probe microscope When the surface of the adhesive modified layer B is observed in the phase measurement mode, the polyester phase on the surface of the adhesive modified layer B defined by the following formula (2) (shows a dark hue in the phase image) The hard coat film is characterized by having an area ratio of 35% or more and less than 90% in the range of 5 m × 5 m.

PEs phase area ratio (%) = (PEs phase area Z measurement area) X 100 · · · (2)

[0027] A third invention is the hard coat film according to the first or second invention, wherein the content of inorganic fine particles in the hard coat layer C is 20 to 80% by mass.

[0028] Further, in the fourth invention, the thermoplastic resin film does not contain particles or contains 50 ppm or less, and the adhesive modified layer contains 0.1 to 20% by mass of particles. The hard coat film according to claim 1 or 2.

[0029] A fifth invention is the hard coat film according to the fourth invention, wherein the particles are silica particles.

[0030] The sixth invention provides a hard coat layer, a light diffusing layer, a prismatic lens layer, an electromagnetic wave absorbing layer, a near-surface on the surface opposite to the hard coat layer C of the hard coat film described in the first or second invention. An optical functional film in which at least one optical functional layer selected from an infrared ray blocking layer and a transparent conductive layer is laminated.

[0031] A seventh invention is an optical functional film in which an antireflection layer or an antifouling layer is laminated on the hard coat layer C of the hard coat film described in the first or second invention.

It is.

The invention's effect

[0032] The hard coat film of the present invention has a specific microphase separation structure or nanophase separation structure in the polyester phase and the polyurethane phase as an intermediate layer between the thermoplastic resin film and the hardcoat layer, and is bonded. The area ratio of the polyurethane phase in the vicinity of the interface with the hard coat layer on the cut surface of the property modified layer is in a specific range. Therefore, even when a hard coat layer containing inorganic fine particles is laminated, adhesion to the hard coat layer can be improved while maintaining high hardness. Furthermore, the adhesiveness with optical function layers, such as a diffusion layer and a prism layer, is also excellent.

[0033] Furthermore, a specific amount of particles having a specific particle size is contained only in the adhesive modified layer, or particles are formed in either the polyester phase or the polyurethane phase on the surface of the adhesive modified layer. By making the material unevenly distributed, it is possible to improve blocking resistance, handling property, and scratch resistance while maintaining high transparency. Therefore, it is useful as a hard coat film or an optical functional film requiring high transparency. In particular, when silica particles are contained in the adhesion modified layer, the silica particles can be unevenly distributed in the polyurethane phase, so that the disadvantage of polyurethane having poor blocking resistance can be compensated.

Brief Description of Drawings

FIG. 1 is an explanatory diagram of a phase image obtained by observing the surface of an adhesion modified layer of an adhesion modified substrate film used in the hard coat film of the present invention in a phase measurement mode of a scanning probe microscope.

FIG. 2 is an explanatory diagram of a phase image in which the contour of the interface between the light hue and the dark hue is emphasized by image processing software in the phase image of FIG.

3 is an explanatory diagram of a phase image in which the outline of the interface between the light hue and the dark hue in FIG. 2 is emphasized and the dark hue is filled with image processing software.

4 is an explanatory diagram showing a boundary line between a light hue and a dark hue in the phase image in which the outline of the interface between the light hue and the dark hue in FIG. 2 is emphasized.

FIG. 5 is an explanatory diagram showing the difference in level of scratches when the surface shape of a scratch attached to the surface of an adhesive modified layer is measured in a wave mode using a three-dimensional non-contact surface shape measuring device.

[Fig. 6] In Examples 1-23 and Comparative Examples 1, 4-6, 8-14, the area ratio of the PE s phase on the surface of the adhesive modified layer and the PEs in the slag component of the adhesive modified layer It is explanatory drawing which shows that mass ratio does not respond | correspond.

FIG. 7 is an explanatory diagram showing a coating liquid receiving tray, a circulation tank of a circulation tank, an arrangement of a preparation tank, and a circulation path of the coating liquid.

[FIG. 8] The cut surface of the adhesive modified layer when the hard coat film of the present invention was cut was observed in a phase measurement mode of a scanning probe microscope, and the color was equalized to enhance the contrast. It is explanatory drawing of a phase image.

FIG. 9 is an explanatory diagram showing the range in which the phase separation structure is to be observed with two red lines in the phase image subjected to the color homogenization process in FIG. FIG. 10 is an explanatory diagram of a phase image obtained by binarizing the phase image of FIG. 8 with image processing software.

FIG. 11 is an explanatory diagram of a phase image in which the two red lines in FIG. 9 are pasted at the same position on the binary phase image in FIG.

FIG. 12 is an explanatory diagram of a phase image in which the portion surrounded by two red lines is painted red with an image processing software.

Explanation of symbols

1: Dark hue (polyester phase mainly composed of copolymer polyester)

2: Light hue (polyurethane phase mainly composed of polyurethane)

3: Protrusions caused by particles

4: Line that emphasizes the outline of the interface between light and dark hues

5: Profile curve of unevenness on the surface of the adhesion modified layer

6: Valley of scratches

7: The top of the scratch

8: Example 1 23

9: Comparative examples 1, 4 6, 8-14

10: Coater

11: Application liquid tray

12: Die

13: Tank for circulation

14: Mixing tank

15: Base film

16: pinchiro nore

17: Hard coat layer C

18: Adhesion modified layer B

19: Thermoplastic resin film A

20: Line indicating the interface between the hard coat layer C and the adhesion modified layer B

21: A line moved from the interface 20 in parallel to the depth of 20 nm from the vertical direction inside the adhesive modified layer BEST MODE FOR CARRYING OUT THE INVENTION

[0036] In the present invention, the definitions of adhesion and hardness described in the problem will be described first.

[0037] In the hard coat film of the present invention, adhesion refers to a hard coat layer after repeating a cross-cut peel test (100 squares) with an adhesive tape on a hard coat layer containing inorganic fine particles 10 times. It means the adhesion at the interface between the substrate and the adhesion modified layer of the substrate film. In the present invention, an adhesive having an adhesion of 80% or more defined by the following formula is accepted. It is preferably 85% or more, particularly preferably 90% or more.

Adhesion (%) = (1—Number of peeled Z100) X 100

[0038] Further, in the adhesion-modified base film used in the present invention, the adhesion refers to a hard coat layer obtained by curing a solvent-diluted photocurable acrylic resin with ultraviolet rays, and the adhesion of the film. Means the adhesion of the interface between the acrylic hard coat layer and the film adhesion modified layer after 10 times of cross-cut peel test (100 squares) with adhesive tape. To do. In the present invention, an adhesive having an adhesion defined by the following formula of 80% or more is considered acceptable. Preferably it is 85% or more, particularly preferably 90% or more.

Adhesion (%) = (1—Number of peeled Z100) X 100

[0039] The hardness in the present invention means "pencil hardness" evaluated by a pencil hardness test in accordance with JIS-K5400. For the pencil hardness, the pencil hardness test was repeated 5 times on the surface of the hard coat layer of the hard coat film. If any abnormalities such as scratches were observed in any test, the pencil used for the test The hardness of the pencil is the pencil hardness. For example, using a 3H pencil, perform 5 test operations, and if there is no appearance abnormality even once, set the pencil hardness of the material to 3H.

[0040] Further, the anti-blocking property of the adhesive modified base film used in the present invention is that two film samples are laminated so that the adhesive modified layers face ^each other, and a pressure of lkgfZcm ² is applied thereto. After adhering for 24 hours in an atmosphere of 50 ° C and 60% RH, the film is peeled off, and the peeled state is “those that can be peeled lightly with no adhesion-modified layer transition”.

[0041] Further, the film having high transparency in the present invention means a film having a haze of 1.5% or less. Preferably, the haze is 1.0% or less. [0042] In order to obtain excellent adhesion and blocking resistance in the adhesive modified base film used in the present invention, a microphase separation structure or nanostructure specific to the surface of the adhesive modified layer. It is important to develop a phase separation structure. Furthermore, in the hard coat film of the present invention, in order to improve the adhesion between the adhesive modified layer of the adhesive modified base film and the hard coat layer containing inorganic fine particles, It is important to develop a specific microphase separation structure or nanophase separation structure on the surface, that is, the interface with the hard coat layer.

[0043] However, in the hard coat film of the present invention, the adhesion modified layer B becomes an intermediate layer between the thermoplastic resin film A and the hard coat layer C. That is, the phase separation structure on the surface of the adhesion modified layer B cannot be observed from the surface of the hard coat film. Therefore, in the present invention, the hard coat film was cut, and the phase separation structure of the adhesion modified layer near the interface with the hard coat layer was observed from the cut surface.

[0044] The specific phase separation structure of the adhesion modified layer in the present invention includes the composition of the coating liquid used for forming the adhesion modified layer, the type and concentration of the surfactant, the coating amount, the adhesion It can be formed by selectively adopting and controlling the drying conditions and heat setting conditions of the property-modified layer.

[0045] First, an outline of the method for producing an adhesion-modified base film used in the present invention will be described using polyethylene terephthalate (hereinafter abbreviated as PET) as a representative example. Not limited.

[0046] Substantially containing particles for the purpose of imparting slipperiness, the PET pellets were sufficiently vacuum-dried, then fed to an extruder, melt-extruded into a sheet at 280 ° C, Cool and solidify to form an unoriented PET sheet. At this time, high-precision filtration is performed at any place where the molten resin is kept at about 280 ° C. in order to remove foreign substances contained in the resin. The obtained unoriented sheet is stretched in the longitudinal direction 2.5 to 5.0 times with a roll heated at 80 to 120 ° C. to obtain a uniaxially oriented PET film.

[0047] Thereafter, the copolymer polyester and polyurethane aqueous solution is applied to one side or both sides of the uniaxially oriented PET film. In order to apply the aqueous coating solution, for example, reverse roll 'coating method, gravure' coating method, kiss' coating method, roll brushing method, Examples include a play coat method, an air knife coat method, a wire barber coat method, a pipe doctor method, an impregnation 'coat method, and a curtain' coat method, and these methods can be performed alone or in combination.

[0048] Next, the end of the film is gripped with a clip, guided to a hot air zone heated to 80 to 180 ° C, and stretched 2.5 to 5.0 times in the width direction after drying. Next, lead to a heat treatment zone of 220-240 ° C and heat-treat for 1-20 seconds to complete crystal orientation. In this heat treatment process, if necessary, apply a 1 to 12% relaxation treatment in the width direction or longitudinal direction.

[0049] First, the phase separation structure of the adhesion modified layer of the adhesion modified substrate film used in the present invention will be described. Next, the raw materials and production conditions used for the hard coat film and optical functional film of the present invention will be described in detail, including the condition factors for controlling the phase separation structure.

[0050] (1) Phase separation structure of adhesion modified layer

In the present invention, the adhesion-modified layer is composed of a polyester phase mainly composed of a copolyester (hereinafter sometimes abbreviated as PEs phase) and a polyurethane phase mainly composed of polyurethane (hereinafter PU phase). A microphase separation structure or a nanophase separation structure).

[0051] In the hard coat film of the present invention, the adhesive modification layer B is used for the purpose of improving the adhesion between the hard coat layer containing inorganic fine particles and the thermoplastic resin film. Furthermore, when the same coating layer or other optical functional layer is laminated on the surface opposite to the hard coat layer, it is also used for the purpose of improving the adhesion between these layers and the thermoplastic resin film. It is done.

[0052] In the present invention, the adhesive modification layer B has a structure in which a polyester (PEs) phase and a polyurethane (PU) phase are microphase-separated or nanophase-separated, and is hard-coated using a scanning probe microscope. When the cutting surface of the film is observed in the phase measurement mode, the interface force between the adhesion modified layer B and the hard coat layer C is defined by the following formula in the range up to a depth of 20 nm. It is an important feature that the area ratio (PU area ratio) of the polyurethane phase (showing a light hue in the phase image) is 30% or more and 60% or less. PU phase area ratio (%) = (PU phase area Z measurement area) X 100

[0053] The area ratio of the PU phase is determined as follows.

To calculate the area ratio of the PU phase of the adhesive modified layer of the intermediate layer in the hard coat film of the present invention having the thermoplastic resin film Z adhesive modified layer Z hard coat layer as a structural unit It is necessary to expose the adhesive modification layer embedded in the surface.

[0054] As a method for exposing the adhesive modified layer to the surface, a method of cutting a film from an oblique direction using a surface interface property analyzer (SAICAS, manufactured by Dybla Wintes Co., Ltd.) is preferable. Next, using a scanning probe microscope (SPM), the phase separation structure is observed from the phase image of the adhesive modified layer in the phase measurement mode (phase mode), and the area ratio of the PU phase in the vicinity of the hard coat layer is obtained.

[0055] The area ratio of the polyurethane phase in the vicinity of the interface with the hard coat layer on the cut surface of the adhesive modified layer has the following technical significance.

When the area ratio of the polyurethane phase exceeds 60%, the ratio of the polyurethane phase on the surface of the adhesive modified layer becomes relatively large during the production of the adhesive modified base film, and the frequency with which blocking resistance decreases. Will increase. On the other hand, when the area ratio of the polyurethane phase is less than 30%, the frequency of decrease in adhesion increases. In particular, the adhesiveness to solventless hard coat agents and lens forming resins is significantly reduced.

[0056] The upper limit of the area ratio of the polyurethane phase in the adhesion modified layer near the interface with the hard coat layer is preferably 50% from the viewpoint of blocking resistance. On the other hand, the lower limit of the area ratio of the PU phase is preferably 35% from the viewpoint of adhesion to the hard coat layer and other optical functional layers made of acrylic resin.

[0057] In addition, a microphase separation structure or a nanophase separation structure of PEs phase and PU phase is observed on the surface of the adhesion modified layer of the adhesion modified substrate film before laminating the hard coat layer. . When the scanning probe microscope is observed in the phase measurement mode, the area ratio of the polyester phase (indicating a dark hue in the phase image) on the surface of the adhesive modified layer defined by the following formula is 5 m X It is 35% or more and less than 90% within the range of 5 m. In addition, in this invention, when providing an adhesive property modification layer on both surfaces of a thermoplastic resin film, any adhesive property modification layer has the area ratio of the polyester phase similar to the above. PEs phase area ratio (%) = (PEs phase area Z measurement area) X 100

[0058] The area ratio of the PEs phase on the surface of the adhesion modified layer has the following technical significance. When the area ratio of the PEs phase is less than 35%, the area ratio of the polyurethane phase on the surface of the adhesive modified layer becomes relatively large, and the frequency of the decrease in blocking resistance increases. On the other hand, when the area ratio of the PEs phase is 90% or more, the frequency of decrease in adhesion increases. In particular, the adhesion with respect to the solventless hard coat agent is significantly reduced.

[0059] The lower limit of the area ratio of the PEs phase on the surface of the adhesive modified layer is preferably 40%, more preferably 45%, and particularly preferably 50%, from the viewpoint of blocking resistance. On the other hand, the upper limit of the area ratio of the PEs phase on the surface of the adhesive modified layer is preferably 85%, more preferably 80%, particularly preferably, from the viewpoint of adhesion to the functional layer made of acrylic resin. 75%.

In the present invention, a phase measurement mode (phase mode) using a scanning probe microscope (SPM) was used for the evaluation of the phase separation structure on the surface of the adhesive modified layer. The phase mode is a phase lag measurement mode that is usually performed simultaneously with surface morphology observation in the dynamic force mode (DFM mode; using SII NanoTechnology SPM).

[0061] The principle of measurement of the phase separation structure of the modified adhesive layer by the phase measurement mode (phase mode) of the scanning probe microscope (SPM) will be briefly described.

In phase mode, it detects the phase lag of cantilever vibration when DFM operation is performed. In DFM operation, the shape is measured by controlling the distance between the probe and the sample so that the vibration amplitude of the resonated cantilever is constant. Here, when a signal that vibrates a nomorph (piezoelectric element) for vibrating the cantilever is called an “input signal”, an effective cantilever vibration signal for this “input signal” is used in the phase measurement mode. The phase lag is detected simultaneously with the vibration amplitude. The phase delay responds sensitively to the effects of surface properties, and the softer the sample surface, the greater the delay. By visualizing the magnitude of this phase lag, it is possible to observe the distribution of surface properties (called a phase image or phase image). Therefore, when a plurality of rosin phases having different physical properties are present on the surface, the phase separation structure can be evaluated by this measurement method. [0062] However, the evaluation of the phase separation structure of the adhesion modified layer is not limited to the phase measurement mode, but the friction force measurement mode, the viscosity measurement mode, etc. It is important to select an observation mode that can evaluate the phase-separated structure with the highest sensitivity, which is acceptable in other modes. In the phase measurement mode, it is possible to detect the phase lag due to the difference in surface properties such as the magnitude of the adsorption force as well as the phase lag due to the difference in viscoelasticity of the adhesive modified layer.

[0063] When observing the phase separation structure of the cutting surface of the adhesive modified layer, in order to facilitate the observation of the phase separation structure, a phase image is obtained with SPIP software (Image Metrology, Version 4.1). It is preferable to increase the contrast by reading and performing color equalization. The reason is as follows.

[0064] When using a surface interface property analyzer (SAICAS) to cut the hard coat film from the base film side to the inside, completely avoid deformation of the cutting surface of the adhesive modified layer with respect to the cutting direction. It is difficult. In addition, since the inorganic particles contained in the adhesive modified layer cannot be cut, it is inevitable that voids appear around the inorganic particles as a result of damage during cutting. By such cutting, the interface between the adhesion modified layer exposed on the surface, the thermoplastic resin film or the hard coat layer, and other functional layers becomes dominant as compared with the PU component force PEs component. This is because the PU component is more susceptible to deformation compared to the PEs component, the difference between the physical properties of the PEs component and the thermoplastic resin film adjacent to the adhesive modified layer is small, and cutting is performed from an oblique direction. The difference in contrast is estimated to be small because the thickness of the adhesive modified layer is extremely thin.

In the present invention, the phase separation structure of the adhesion modified layer corresponds to a micro phase separation structure or a nano phase separation structure from the viewpoint of size. When the phase contrast image of the surface of the adhesive modified layer (interface with the node coat layer) in the adhesive modified substrate film used in the present invention is observed, it has the following phase separation structure. I understand that

[0066] When the PEs phase is regarded as a continuous structure having a major axis and a minor axis, the width in the minor axis direction is at most 1

It is mainly composed of IX m and continuous structure whose major axis length exceeds 1 μm. That is, the area of the portion having the continuous structure is 80% or more, preferably 85% or more, and more preferably 90% or more with respect to the entire area of the PEs phase. Also, in the above definition Even in the PEs phase dispersed in islands, which does not correspond to the continuous structure described, there are some which have a continuous structure inside the adhesive modified layer, but the ends appear on the surface.

[0067] The size of the continuous structure of the PEs phase is preferably 1 m at the maximum in the minor axis direction, more preferably 0.8 μm, and even more preferably 0.6 μm. m, particularly preferably 0. The width in the minor axis direction is not particularly limited, but in order to maintain a continuous structure, the narrowest part is preferably 0.01 m, particularly preferably 0.05 μm. On the other hand, the size of the continuous structure of the PEs phase is preferably 1 or more, more preferably 2 or more, and particularly preferably 2 or more, preferably the length in the major axis direction exceeds 1 μm. More than 5 m.

[0068] In the adhesion-modified base film used in the present invention, the phase separation structure on the surface of the adhesion-modified layer is seen in nature, as shown by the representative example shown in FIG. It shows a complex structure that cannot be defined, and it is difficult to uniquely define the form of phase separation. The phase separation structure can also be expressed in many ways as follows.

[0069] For example, when the form of the phase separation structure is expressed as a pattern, it is described in the literature as “pied structure” (“Dictionary of Chemical Languages”, page 226, June 1979 15 Japan, Sankyo Publishing Co., Ltd.), “Rippled Structure” (“Pattern”, pp. 168-169, published by Nobara Inc., 2002. 10.1), “Camouflage” .

[0070] The phase separation structure on the surface of such an adhesion modified layer is similar to what is expressed as a co-continuous structure in the field of morphology in a polymer blend system. Furthermore, it can also be expressed as an inter-network intrusion structure formed by co-polyester and self-crosslinking polyurethane.

[0071] In terms of morphology, the self-similarity of the PEs phase can also be quantitatively expressed using the fractal dimension. For example, as shown in Fig. 3, the surface of the adhesive modified layer is observed in the phase measurement mode of a scanning probe microscope, and the phase outline that emphasizes the interface between the light hue (polyurethane phase) and the dark hue (polyester phase). As an index indicating the complexity of the boundary between light and dark hues (interface contour), the image is quantified using the box counting method and the fractal dimension obtained from the interface contour. Can be expressed.

[0072] When the fractal dimension in the unit area is 1, it means a straight line (one dimension), 2 is a solid surface Means (two-dimensional). In other words, the closer the fractal dimension is to 2, the denser the structure. On the other hand, a fractal dimension closer to 1 means a sparse structure

[0073] Specifically, the surface of the adhesion-modified layer of the adhesion-modified base film is emphasized to emphasize the outline of the interface between the light hue (polyurethane phase) and the dark hue (polyester phase). In the obtained phase image, the fractal dimension of the boundary line (interface contour) between the light hue and the dark hue is preferably 1.60 to L95 in the measurement area of 5 / ζ πιΧ 5 / ζ πι. The upper limit of the fractal dimension is more preferably 1.93, particularly preferably 1.90. On the other hand, the lower limit of the fractal dimension is more preferably 1.65, and particularly preferably 1.70.

[0074] For example, the fractal dimension of the boundary line (interface contour) between the light hue (polyurethane phase) and the dark hue (polyester phase) on the surface of the modified adhesive layer shown in Fig. 4 is 1.89 and 1 respectively.

90. FIG. 4 is a phase image of FIG. 1 showing a typical phase separation structure on the surface of the adhesive modified layer in the present invention, with the outline of the interface between the light hue and the dark hue emphasized, and the light hue and the dark hue. It is the figure which showed the boundary line.

[0075] In the present invention, in order to maximize the functions of the copolyester and polyurethane used as the raw material of the adhesive modified layer, the adhesive modified layer has a micro phase separation structure. It is important to have a nanophase separation structure. This is because when the two resins are completely compatible, the properties of the two resins are offset, and overall, excellent properties of the copolyester or polyurethane cannot be expected. Other phase separation structures that can be adopted by the PEs phase and PU phase in the adhesion modified layer include those in which the PU phase is dispersed in the PEs phase, and so-called composite forms in which the PES phase is dispersed in the PU phase. It is also possible to show a typical sea-island structure. Of course, this sea-island structure is an incompatible state of coconut resin. If one cocoon phase is increased, the other inevitably decreases, and so-called islands are formed. Also in the present invention, if the production conditions are controlled, it is possible to provide an adhesion modified layer composed of a separated phase having such a sea-island structure.

[0076] However, in consideration of the nonuniformity of the size of the resin phase forming the island structure and the nonuniformity of the distribution state, the influence of the shape, number, and distribution state of the island phase may be ignored. Can not. For this reason, there is a concern that the properties of the oils that make up the sea structure will have a significant impact. Then In order to maintain the uniformity of the material, it is considered to form a phase separation structure in which the PEs phase and the PU phase of the present invention are intertwined with each other. A phase separation structure showing the sea-island structure of the P Es phase and the PU phase can also be cited as one of the typical embodiments of the present invention.

[0077] Further, as another phase separation structure of the adhesion modified layer in the present invention, a core-shell structure can be formed. For example, the PEs phase is surrounded by a PU phase, which is further surrounded by a P Es phase. However, in order to form such a core-shell structure, very high control is required. Also, because of its core 'shell structure', it seems that it cannot be expected to show excellent material behavior.

[0078] Furthermore, as an aspect of the phase separation structure, a laminated structure in which PEs phases and PU phases are regularly arranged alternately can be adopted. However, it is ideal that the phases are arranged in parallel at approximately equal intervals. If the width of the force phase increases, it becomes difficult to uniformly distribute the PEs phase and the PU phase at the interface of the adhesive reforming layer. In this case, the quality of the adhesion-modified base film may be affected. Due to subtle disparity in manufacturing conditions, they may take the form of a sea-island structure, a core-shell structure, and a laminated structure, but they may be mixed. However, the adhesion modified layer has a certain size of PEs phase and PU phase 1S, and it is important to keep them uniformly mixed to maintain quality.

[0079] It should be noted that a structure in which the PEs phase and the PU phase force adhesion modified layer are phase-separated into two layers in the thickness direction is not preferable in the present invention. This is because, in the present invention, the PEs phase and the PU phase are uniformly distributed at an appropriate area ratio on the surface of the adhesive modified layer (interface with the hard coat layer) from the viewpoint of the effect of the present invention. is important.

[0080] The phase separation structure on the surface or the cutting surface of the adhesive property-modified layer has an irregular form in each of the polyester phase mainly comprising a copolyester and the polyurethane phase mainly comprising a polyurethane. . These rosin phases form a complex array structure in which the surface of the adhesive reforming layer and the inside thereof are irregularly and densely arranged. Further, a structure in which the surface of one rosin phase is bitten in an incompatible state with the other rosin phase may be employed. In FIG. 3, the black portion indicates the polyester phase and the white portion indicates the polyurethane phase. [0081] On the surface of the adhesion modified layer of the adhesion modified substrate film! In the case where two types of resin phases are uniformly arranged with respect to a unit area (for example, 5 δ δ, α πι), if the size of one resin phase increases, The size of the rosin phase is constrained. Therefore, a large bias occurs in the presence of the resin phase. As a result, it becomes difficult to maintain a state in which both oleaginous phases are separated and uniformly dispersed, and unevenness occurs in the material of the adhesive modification layer, which is not preferable for quality control.

[0082] In order to cause both oleaginous phases to be phase-separated and to be present in the adhesion-modified layer in a uniformly mixed state, the PEs phase has a short axis width of 1 μm at maximum. The length in the axial direction is preferably 1 μm or more. Of course, if there is no high quality requirement, a relatively large structure with a maximum width of 6 μm in the minor axis direction is possible. The phase separation structure of this continuous phase (PEs phase) consists of the resin composition of the coating solution used to form the adhesion modified layer, the type and concentration of the surfactant, the coating amount, the drying conditions of the coating layer, and the heat By selectively adopting and controlling the fixing conditions and the like, it can be expressed as a microphase separation structure or a nanophase separation structure specific to the adhesion modified layer. In any case, the mode force of the phase separation structure of the polyester phase and the polyurethane phase on the surface of the adhesive reforming layer shown in FIG. 1 is a representative model for expressing the effect of the adhesive modified base film of the present invention. It is.

[0083] Further, the importance of the phase separation structure will be described in detail.

The adhesive modified layer in the adhesive modified base film used in the present invention is composed of a copolymer polyester component and a polyurethane component as a resin component, and a PEs phase mainly composed of a copolymer polyester and a polyurethane as a major component. It is preferable that the phase is separated into PU phases and each phase has a continuous structure. It is possible to phase-separate the above two types of resin without uniformly mixing them, thereby having excellent adhesion to a base film that has thermoplastic resin film strength and relatively good solvent resistance. The copolyester having the property and polyurethane with excellent adhesion to many types of resin such as hard coat layer, diffusion layer, and attalylate type resin are inferior to each other. This makes it possible to make full use of the characteristics of each coconut oil.

[0084] constituting the adhesive modifying layer, and the polyester phase, co the polymerization polyester is preferably composed solely may a 0.01 to 40 mass ^_0/0 comprise polyurethane. More In addition, the polyester phase may contain 0.001 to 20 mass% of particles. Further, in the polyester phase, a surfactant may be attached to or contained in the above-mentioned rosin. Similarly, the polyurethane phase can contain particles, surfactants, and the like that are preferably composed solely of polyurethane in an amount as described in the above-mentioned copolymer polyester. In particular, in the case of particles having a high affinity for polyurethane, it can be preferentially unevenly distributed in the polyurethane phase rather than the polyester phase in the process of forming the adhesive modification layer.

[0085] In general, in a composition that can also be a mixture of a copolyester and a polyurethane, the chemical supplementary function is usually that both are chemically uniform materials and complement each other's properties or functions. Often manifests. On the other hand, the adhesion modified layer composed of the polyester phase and the polyurethane phase of the present invention is largely related to the presence of the resin phase by physically separating the polyester phase and the polyurethane phase as described above. As a result, the structure of a state in which both oleaginous phases are separated and uniformly dispersed is maintained. The properties of each rosin can be controlled through the surface of each rosin phase. Sharing. In other words, it is a manifestation of a physical supplementary function, and this function or principle is completely recognized in the prior art! It can be said that it is a new technical matter.

[0086] In the present invention, the detailed generation mechanism of the phase separation structure of the adhesion modified layer is not clear. However, the composition ratio of the copolyester and polyurethane, the ratio of water / alcohol dispersion medium, the type of surfactant, the impurities in the surfactant, the pH of the aqueous coating solution, the coating amount, etc. Depending on the balance of delicate conditions such as drying and heat setting time, temperature, and wind speed in the material composition and properties, a specific micro phase separation structure or nano phase separation structure appears in the adhesion modified layer. This can be easily understood from the comparison between each example and the comparative example.

[0087] Furthermore, it is considered that the reaction initiation temperature of the isocyanate group possessed by the polyurethane has a subtle effect. In this context, the phase separation structure means that the so-called PEs phase and PU phase are in contact with each other without taking a distance. A large amount of copolyester gathers in the PEs phase and is biased. It should be seen that a lot of tongues are gathered and biased, and the boundaries between the two layers appear to be separated as if the force is clearly distinguishable. In the case of the present invention, there is a possibility that an isocyanate group of polyurethane reacts at the boundary, indicating a complicated separation structure.

[0088] Adhesive modified base film force used in the present invention Having an adhesive reformed layer composed of a PEs phase and a PU phase means that, for example, a base material that also has thermoplastic film strength, a hard coat layer, It plays the role of an interfacial function that acts equally on both the base material surface and the functional layer surface, which is interposed between the functional layer such as the diffusion layer. As a result, both the PEs phase and the PU phase have a separate structure, and the PEs phase exhibits the excellent properties of the copolyester inherent to both sides of the adhesive modified layer (the base material and the adhesive modified layer). It is in a state where it is exerted to the maximum extent with respect to the interface and the interface between the adhesion modified layer and the functional layer such as the hard coat layer. In other words, the PU phase is in a state where the excellent properties of the inherent polyurethane are fully exerted on both sides.

[0089] This is an adhesive modified base film having an adhesive modified layer! The surface of the adhesive modified layer has a microphase separation structure or nanophase separation composed of PEs phase and PU phase. Due to the structure, the PEs phase copolyester is exposed and performs the properties or functions of the copolyester to the maximum, and similarly, the PU phase polyurethane is exposed and the polyurethane is inherently This is to maximize the properties or functions possessed. Therefore, if each of the PEs phase and the PU phase on the surface of the adhesion modified layer is distributed within a specific range, the properties or functions of the both resins can be maximized. This is because of the unique structure of the laminate, it acts rationally at the interface between the base material and the adhesive modified layer and at the interface between the adhesive modified layer and the functional layer.

[0090] Further, in the present invention, when particles are contained in the rosin composition constituting the PEs phase and the PU phase, for example, silica particles can be unevenly distributed in the PU phase. This is presumably because the surface energy is closer to the silica particles in the PU phase than in the PEs phase. By making silica particles unevenly distributed in the PU phase, it is possible to improve the blocking resistance, which is a disadvantage of polyurethane, and to reduce the particle content of the entire adhesive modification layer, thus maintaining transparency. It is a useful structure to fulfill the function of [0091] Similarly, it is suggested that if particles having a surface energy closer to that of the copolyester are selected, the particles can be selectively unevenly distributed in the PEs phase. The prior art ability to unevenly distribute particles in either the PEs phase or the PU phase phase separation structure is an unprecedented technique that can improve slipperiness and blocking properties while maintaining transparency. Can do. Therefore, the present invention is also meaningful in that the application range of the material design of the micro phase separation structure or the nano phase separation structure can be expanded.

[0092] (2) Thermoplastic resin film

As the thermoplastic resin film used in the present invention, an unoriented sheet obtained by melt extrusion or solution extrusion of thermoplastic resin is stretched in the longitudinal direction or the uniaxial direction in the width direction, or two as required. A biaxially stretched thermoplastic resin film that is successively biaxially stretched in the axial direction or simultaneously biaxially stretched and subjected to heat setting treatment is preferable.

[0093] Further, the thermoplastic resin film does not detract from the object of the present invention! The film is subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation within the range of You can also apply surface activation treatments such as treatment and ozone treatment!

[0094] The thickness of the thermoplastic resin film used in the present invention can be arbitrarily determined in the range of 30 to 300 μm according to the specification of the application to be used. The upper limit of the thickness of the thermoplastic resin film is preferably 250 μm, particularly preferably 200 μm. On the other hand, the lower limit of the film thickness is preferably 50 μm, particularly preferably 75 μm. If the film thickness is less than 50 μm, rigidity and mechanical strength tend to be insufficient. On the other hand, if the film thickness exceeds 300 m, the absolute amount of foreign matter present in the film increases, and the frequency of optical defects increases. In addition, the slitting property when the film is cut to a predetermined width is deteriorated, and the manufacturing cost is increased. Furthermore, since the rigidity is increased, it is difficult to wind a long film into a roll.

[0095] Thermoplastic resin includes polyethylene (PE), polypropylene (PP), polymethylpentene (TPX) and other polyolefins, polyethylene terephthalate (PET), polyethylene 2,6-naphthalate (PEN), polytetramethylene Polyester resin such as terephthalate (PTT), polybutylene terephthalate (PBT), polyamide (PA) resin such as nylon 6, nylon 4, nylon 66, nylon 12, polyimide (PI), polyamideimide (PAI) , Polyether Sulphone (PES), Polyetheretherketone (PEEK), Polycarbonate (PC), Polyarylate (PAR), Cellulose propionate, Polychlorinated butyl (PVC), Polyvinylidene chloride, Polybutylalcohol (PVA), Poly Examples include ether imide (PEI), polyphenylene sulfide (PPS), polyphenylene oxide, polystyrene (PS), syndiotactic polystyrene, and norbornene polymers. In addition to using these polymers alone, a copolymer containing a small amount of a copolymer component may be used, or one or more other thermoplastic resins may be blended.

[0096] Among these thermoplastic resins, polyethylene terephthalate, polypropylene terephthalate, polyethylene 2,6 naphthalate, syndiotactic polystyrene, norbornene polymer, polycarbonate, polyarylate and the like are preferable. In addition, a resin having a polar functional group such as polyester or polyamide is preferable from the viewpoint of adhesion to the adhesive property modified layer.

[0097] Among them, polyethylene terephthalate, polyethylene 2,6 naphthalate, polybutylene terephthalate, polypropylene terephthalate, or a copolymer mainly composed of these resin components is more preferable, and particularly formed from polyethylene terephthalate. A biaxially oriented film is particularly suitable.

[0098] For example, when a polyester copolymer having polyethylene terephthalate as a basic skeleton is used as the resin forming the thermoplastic resin film, the ratio of the copolymer component is preferably less than 20 mol%. If it is 20 mol% or more, the film strength, transparency, and heat resistance may be poor. Dicarboxylic acid components that can be used as copolymerization components include aliphatic dicarboxylic acids such as adipic acid and sebacic acid, isophthalic acid, phthalic acid, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, trimellilot Examples thereof include polyfunctional carboxylic acids such as acids and pyromellitic acid. Examples of the glycol component that can be used as a copolymer component include fatty acid glycols such as diethylene glycol, 1,4 butanediol, propylene glycol, and neopentyl glycol; aromatic glycols such as p-xylene glycol; 1,4-cyclohexene. Examples include alicyclic glycols such as sandimethanol; polyethylene glycol having an average molecular weight of 150 to 20000, and the like.

[0099] In addition to the catalyst, each of the above-described thermoplastic resins is not limited to the effects of the present invention. Seed additives can be included. As additives, for example, inorganic particles, heat-resistant high molecular particles, alkali metal compounds, alkaline earth metal compounds, phosphorus compounds, antistatic agents, ultraviolet absorbers, light resistant agents, flame retardants, heat stabilizers, antioxidants, Examples thereof include an antigelling agent and a surfactant.

[0100] The particles described above may be handled in the production of a thermoplastic resin film, when wound into a roll, or handled when unrolled (sliding property, running property, blocking property, associated air in winding) From the standpoint of exfoliation, etc., it is used to impart moderate surface irregularities to the film surface.

[0101] Inorganic particles include calcium carbonate, calcium phosphate, amorphous silica, crystalline glass filler, kaolin, talc, titanium dioxide, alumina, silica-alumina composite oxide particles, barium sulfate, calcium fluoride, Examples include lithium fluoride, zeolite, molybdenum sulfate, and my power. The heat-resistant polymer particles include crosslinked polystyrene particles, crosslinked acrylic resin particles, crosslinked methyl methacrylate particles, benzoguanamine 'formaldehyde condensate particles, melamine' formaldehyde condensate particles, polytetrafluoroethylene particles. Etc.

[0102] When a polyester film is used as the thermoplastic resin film, among the above particles, the silica particles are relatively close to the polyester resin and have a high refractive index, so that high transparency is easily obtained. It is most suitable for certain applications. On the other hand, white pigments such as titanium oxide are preferred for applications that require concealment. In addition, the particles contained in the thermoplastic resin film may be used alone or in combination.

[0103] From the viewpoint of the balance between transparency and handling properties, the average particle size is 0.01-2 / ζ πι, and the content of particles in the film is 0. In the range of 01 to 5.0% by mass, it may be determined according to the use of the film. In addition, when the adhesion-modified base film used in the present invention is used for applications in which transparency is highly required, particles that cause a decrease in transparency are substantially contained in the thermoplastic resin film. It is preferable that the adhesive modified layer contains particles without containing them.

[0104] The above-mentioned "substantially free of particles" means, for example, in the case of inorganic particles, when inorganic elements are quantified by key X-ray diffraction, 50 ppm or less, preferably 10 ppm or less, most preferably Means the content that is below the detection limit. This is because even if particles are not actively added to the base film, contaminants derived from foreign substances, raw material grease, or dirt attached to lines and equipment in the film manufacturing process can be peeled off. This is because it may be mixed in.

[0105] The layer structure of the thermoplastic resin film used in the present invention may be a single layer, or may be a laminated structure having a function that cannot be obtained with a single layer. In the case of a laminated structure, a coextrusion method is preferable.

[0106] As a representative example, the case where polyester is used as a raw material for the thermoplastic resin film, a method for producing the base material film will be described in detail below.

[0107] The intrinsic viscosity of the polyester pellets used as the film raw material is preferably in the range of 0.45 to 0.70 dl / g. If the intrinsic viscosity is less than 0.45 dlZg, breakage tends to occur frequently during film production. On the other hand, if the intrinsic viscosity exceeds 0.70 dlZg, the filtration pressure increases greatly, making it difficult to perform high-precision filtration, and the productivity tends to decrease.

[0108] Further, in the hard coat film of the present invention or the optical functional film using the film, it is preferable to remove foreign matters contained in the raw material polyester which cause optical defects. In order to remove foreign substances in the polyester, high-precision filtration is performed at any place where the molten resin is kept at about 280 ° C during melt extrusion. The filter medium used for high-precision filtration of molten resin is not particularly limited, but in the case of a sintered stainless steel filter medium, the removal performance of aggregates and high-melting-point organic substances mainly composed of Si, Ti, Sb, Ge, Cu Excellent and suitable.

[0109] The filter particle size (initial filtration efficiency 95%) of the filter medium used for high-precision filtration of the molten resin is preferably 15 µm or less. When the filter particle size of the filter medium exceeds 15 μm, the removal of foreign matters of 20 μm or more tends to be insufficient. Productivity may be reduced by high-precision filtration of molten resin using a filter medium with a filtration particle size (initial filtration efficiency 95%) of 15 m or less.To obtain a film with few optical defects is important.

[0110] In the extrusion process of the molten resin, even fine foreign matter that passes through the filter medium, crystallization proceeds around the foreign matter in the cooling process of the sheet-like melt, and this causes non-uniform orientation in the orientation step. If there is a slight difference in thickness, the lens will be A place arises. Here, light is refracted or scattered as if it were a lens, and when viewed with the naked eye, it appears larger than the actual foreign object. This minute difference in thickness can be observed as the difference between the height of the convex part and the depth of the concave part.The height of the convex part is 1 m or more and the depth of the concave part adjacent to the convex part is 0. If this is the case, due to the lens effect, an object with a size of 20 / zm is recognized visually as a size of 50 m or more, and further as an optical defect of a size of 100 m or more. In some cases.

[0111] In order to obtain a highly transparent film, it is preferable not to contain particles in the thermoplastic resin film. However, the lower the particle content and the higher the transparency, the clearer the optical defects due to minute irregularities. It tends to be. In addition, since the surface of a thick film is less likely to be cooled more rapidly than a thin film and tends to proceed with crystallization, it is necessary to rapidly cool the entire film when manufacturing an unoriented sheet. As a method for cooling the unoriented sheet, molten resin is extruded into a sheet form from a slit portion of a die on a rotating cooling drum, and the sheet-like melt is brought into close contact with the rotating cooling drum and rapidly cooled to form a sheet. Is preferred. As a method for cooling the air surface (the surface opposite to the surface in contact with the cooling drum) of this unoriented sheet, a method of cooling by blowing a high-speed air stream is effective.

[0112] (3) Adhesive modified layer

The adhesive property-modified base film used in the present invention is a thermoplastic resin that travels with an aqueous coating liquid mainly composed of a resin containing a copolyester and polyurethane, a dispersion medium containing water and alcohol, and a surfactant. Coating process for continuous coating on one or both sides of the grease film, drying process for drying the coating layer (adhesive modified layer), stretching process for stretching in at least uniaxial direction, and heat-fixing treatment for the stretched coating film An adhesive modified substrate film provided with an adhesive modified layer having a microphase separation structure or a nanophase separation structure, which is obtained by continuously forming through a heat setting treatment step is manufactured. Also, at least one crosslinking agent selected from epoxy-based crosslinking agents, melamine-based crosslinking agents, and oxazoline-based crosslinking agents is mixed in the coating liquid and heat-treated to form a crosslinked structure in the copolymerized polyester. Also good.

[0113] In the method for producing an adhesive modified substrate film provided with an adhesive modified layer having a micro phase separation structure or a nano phase separation structure, the copolymer polyester (PEs) and the polyester The mass ratio (PEsZPU) of letane (PU) is 30Z70 to 70Z30, and it is preferable to satisfy the following conditions (a) to (f). The same applies when the coating solution contains a crosslinking agent.

(a) The film transit time from immediately after coating of the coating solution to the entrance of the drying process is less than 2 seconds

(b) Drying process at a temperature of 120-150 ° C for 0.1-5 seconds

(c) During the drying process, the wind speed of the drying air is 30mZ seconds or more.

(d) Heat setting process power The first heat setting zone through which the film passes is divided into a plurality of heat setting zones, and each zone is partitioned so that the temperature can be controlled independently. The temperature of the heat setting zone set at the maximum temperature is 190 to 200 ° C, and the heat fixing zone set at the maximum temperature from the outlet of the first heat setting zone is S210 to 240 ° C. (If there is more than one heat transfer zone on the most entrance side), the film transit time is 10 seconds or less.

(e) 0.01 to 0.18% by mass of a non-ionic surfactant or a cationic surfactant based on the coating solution

(f) The final coating amount of the adhesion modified layer is 0.005-0.20 g / m ²

[0114] In the production of the above-mentioned adhesion-modified base film, it is more preferable that the following conditions (g) to (i) are satisfied.

(g) The film transit time from immediately after application of the coating solution to the entrance of the drying process is less than 1.5 seconds.

(h) 0.5 to 3 seconds at a temperature of 130 to 150 ° C in the drying process

(i) In the heat setting treatment process, the temperature of the heat setting zone set to the maximum temperature is 225 to 235 ° C, and the heat setting zone set to the maximum temperature from the outlet of the first heat setting zone (note that If there are several, the passage time of the film to the heat setting zone on the most inlet side) is 5 seconds or less

[0115] In addition, the adhesive modified layer laminated by the in-line coating method contains fine particles having an appropriate particle size to form appropriate irregularities on the surface of the adhesive modified layer, It can provide slipping property, winding property, and scratch resistance. For this reason, the high transparency which does not need to contain microparticles | fine-particles in a thermoplastic resin film can be hold | maintained.

[0116] The adhesive modified base film used in the present invention has a three-dimensional center on the surface of the adhesive modified layer. The surface average surface roughness (SRa) is preferably smoothed to 0.002 to 0.001 m. The upper limit of SRa is more preferably 0.0080 μm force, particularly preferably 0.0060 μm, based on the point of transparency. On the other hand, the lower limit of SRa is preferably more than 0.0025 m force S, particularly preferably 0.030 m, and more preferably a handling force such as sliding property and rollability, and scratch resistance.

[0117] When the surface of the adhesive modified layer has a smooth surface with an SRa of less than 0.002 μm, blocking resistance when winding the adhesive modified substrate film into a roll, or during film production or processing Handling properties such as slipping and winding properties and scratch resistance are reduced, which is not preferable. On the other hand, if the SRa on the surface of the adhesion modified layer exceeds 0.000 / zm, the haze increases and the transparency deteriorates. Therefore, the base of the hard coat film or the optical functional film using the hard coat film is deteriorated. Preferred as a material film.

[0118] In the adhesive modified base film used in the present invention, the adhesive modified layer has the following four structural and structural characteristics, and can be obtained by the following means.

(a) Microphase separation or nanophase separation into a polyester phase and a polyurethane phase, and they have a specific area ratio

(b) It is possible to change the composition ratio of the resin component of the adhesive modified layer on the surface and inside

(c) When particles are included in the adhesion modified layer, the particles are unevenly distributed in the polyester phase or the polyurethane phase.

[0119] In addition, the polyester phase mainly composed of a copolyester observed on the surface of the adhesive modified layer may have a continuous structure having a maximum width of 1 μm and a length exceeding 1 m. More preferably, the copolymer polyester phase and the polyurethane phase have a co-continuous structure. Within the range of the area ratio of the PEs phase on the surface of the adhesive reforming layer, a fine continuous structure with a maximum polyester interfacial width of 1 μm and a length exceeding 1 μm based on copolymer polyester By having this, microscopically uniform adhesion can be obtained.

[0120] In a polyester phase composed mainly of a copolyester, the phase separation structure where the width exceeds 1 μm at the maximum is locally functioning as a hard coat layer, diffusion layer, or prism layer. The location inferior to adhesiveness arises with respect to a layer. If there is a location with poor adhesion on the surface of the modified adhesive layer, it may lead to macroscopic peeling starting from that location. In order to obtain a fine continuous structure with a maximum width of 1 μm, It is important to appropriately select the time required for the drawing zone force to reach the maximum temperature in the heat setting zone and the heat setting conditions. In particular, if the time required from the transverse stretching zone to the zone where the maximum temperature is reached in the heat setting zone is too long, the phase separation of the adhesive modified layer proceeds too much, resulting in a polyester mainly composed of a copolyester. The narrowest part of the phase is scattered with the part exceeding 1 μm. Specific heat setting conditions for producing the adhesive modified substrate film will be described later.

[0121] In order to control the phase separation structure on the surface of the final adhesion modified layer, the evaporation rate of the solvent in the drying step described later and the subsequent heat treatment are extremely important. By controlling the solvent evaporation rate in the drying process, the composition ratio of the polyester component and the polyurethane component on the surface of the adhesive modified layer can be changed.

[0122] For example, when a mixed solvent of water and Z-isopropyl alcohol is used, the ratio of water increases in the solvent remaining on the surface in the late drying process under mildly dry conditions. For this reason, the proportion of polyurethane having relatively high hydrophilicity existing on the surface of the adhesive modified layer is higher than when the adhesive modified layer is dried under strong conditions. Also, changing the coating amount has the same effect as controlling the evaporation rate of the solvent. In other words, when the coating amount is increased, drying takes time, and the residual solvent existing on the coating surface immediately before drying increases the ratio of water. That is, the ratio of the polyurethane component on the surface of the adhesive property modification layer can be increased compared to when the coating amount is small.

[0123] In the stretching step and the heat setting treatment step, phase separation of the polyester component and the polyurethane component proceeds. However, when thermal crosslinking of either one of the coconut resins begins, the mobility of each phase is greatly reduced and the progress of phase separation is suppressed. That is, the phase separation structure can be controlled by controlling the heating conditions in the stretching process and the heat setting process.

[0124] As described above, by controlling the ratio existing near the surface of the adhesive modified layer of polyester Z polyurethane in the drying process and by controlling the progress of phase separation in the stretching process and heat setting process. It is possible to strictly control the surface phase separation structure of the adhesive modified layer and the ratio of each phase existing near the surface of the adhesive modified layer. In addition, by controlling the surface energy of the particles to be included in the adhesive modification layer, either the polyester phase based on the copolyester or the polyurethane phase based on the polyurethane is used. In addition, the particles can be selectively localized.

[0125] The adhesion modified layer contains a copolymerized polyester and polyurethane as the main resin component. The copolyester alone has sufficient adhesion to the polyester-based substrate film, but is inferior to adhesion to the hard coat layer containing inorganic fine particles. In addition, since it is a relatively brittle resin, it tends to cause cohesive failure due to impact during cutting.

[0126] On the other hand, polyurethane alone is relatively excellent in adhesion to a hard coat layer containing inorganic fine particles. It is inferior in adhesiveness with a polyester-type base film, although it is strong. Furthermore, it is inferior in blocking resistance when the adhesive modified substrate film is wound into a roll. Therefore, the quality of hard coat films and optical functional films produced using an adhesive modified base film having an adhesive modified layer of a polyurethane alone system is remarkably lowered. In order to avoid such a problem, it is necessary to include a large amount of particles, a particle having a large particle size, or an increase in the content of particles in the adhesive property-modified layer. As a result, the haze of the film is increased, which is not preferable as a base film for a hard coat film or an optical functional film that is particularly demanding for transparency.

[3-1] (1) Preparation of coating solution used to form adhesion modified layer

In the present invention, the adhesion modified layer is formed using a coating method. The material used for the coating solution is a resin and a dispersion medium or a solvent. In the present invention, it is preferable that the coating solution used for forming the adhesion modified layer is aqueous. Moreover, in this invention, it is preferable embodiment to use particle | grains and surfactant together in addition to a resin component. Furthermore, additives such as antistatic agents, ultraviolet absorbers, organic lubricants, antibacterial agents and photooxidation catalysts can be used as necessary. In addition, a catalyst may be added to the coating solution to promote the thermal crosslinking reaction of the resin, such as inorganic substances, salts, organic substances, alkaline substances, acidic substances and metal-containing organic compounds. Various chemical substances can be used. Further, an alkaline substance or an acidic substance may be added to adjust the pH of the aqueous solution. The coating liquid disperses or dissolves the resin in a dispersion medium or solvent under stirring, and then, in addition to the particles and surfactant, various additives are used in combination as required to obtain the desired solid content concentration. Dilute until adjusted.

[0128] Further, in order to uniformly disperse the resin component and particles in the coating solution, coarser particle agglomeration is performed. In order to remove foreign substances such as collected materials and dust in the process, it is preferable to finely filter the coating solution.

[0129] The type of filter medium for microfiltration of the coating solution is not particularly limited as long as it has the above-mentioned performance. Examples thereof include a filament type, a felt type, and a mesh type. The material of the filter medium for finely filtering the coating solution is not particularly limited as long as it has the above-described performance and does not adversely affect the coating solution. Examples thereof include stainless steel, polyethylene, polypropylene, and nylon.

[0130] The filter medium for microfiltration of the coating solution is preferably a filter medium having a filtration particle size (initial filtration efficiency: 95%) of 25 μm or less, more preferably a filter medium having a filtration performance of 5 μm or less, particularly Preferably, the filter medium has a filtration performance of 1 μm or less. Most preferred is a method of using a combination of filters having different filtration performance. When filter media with a filter particle size exceeding 25 m is used, removal of coarse aggregates tends to be insufficient. Therefore, coarse agglomerates that could not be removed by filtration spread due to orientation stress in the uniaxial or biaxial orientation process after coating and drying, and are recognized as agglomerates of 100 m or more, which is likely to cause optical defects. .

[0131] The raw materials used for the coating solution will be described in detail below.

(a) Resin

In the present invention, copolymerized polyesters (PEs) and polyurethane (PU) are used as the resin constituting the adhesive modification layer. The mass ratio of the copolymerized polyester (PEs) and polyurethane (PU) based on the solid content in the coating solution is preferably (PEs) Z (PU) = 70Z30 to 30Z70, particularly preferably 60 to 40 to 40 to 60. The resin constituting the adhesive modified layer can be used in combination with the above-described copolymer polyester and a third resin other than polyurethane. In addition, a cross-linking agent is not used together.

[0132] In the present invention, the area ratio of the polyester phase on the surface of the adhesive modified layer and the mass ratio of the copolyester to the resin component of the adhesive modified layer are as shown in FIG. Not done. In Fig. 6, the PEs surface fraction of the surface of the adhesive modified layer varies from 30 to 91% even when the mass ratio of the copolyester to the resin component of the adhesive modified layer is 50%. Is clearly shown. This suggests that the composition ratio of the copolyester and polyurethane is different between the surface and the inside of the adhesive modified layer. That is, This suggests that the composition ratio of the copolyester and the polyurethane can be arbitrarily controlled in the thickness direction of the adhesive modified layer.

[0133] Further, by setting the ratio of the copolyester and polyurethane in the adhesive modified layer within the above-mentioned range, the surface hardness index of the adhesive modified layer is set to 3.0 15. Onm. S can. When the hardness index of the surface of the adhesive modified layer is less than 3. Onm, the adhesive modified layer becomes brittle. Therefore, after forming functional layers such as hard coat layer, diffusion layer, prism layer, etc. containing acrylic resin as a constituent component, in the processing process of high-speed cutting to a predetermined size, the shearing force during high-speed cutting is reduced. Thus, sufficient adhesion is obtained. Also. When the hardness index of the surface of the adhesion modified layer exceeds 15. Onm, the blocking resistance tends to decrease. Furthermore, there is a tendency that the coating property, adhesion and solvent resistance to the substrate film are insufficient.

In the present invention, it is presumed that the phase separation structure of the water-dispersed copolyester component and the hydrophilic polyurethane component is formed as follows. Both rosin components mixed with a common solvent are in a state of being uniformly dispersed or dissolved in the coating solution. After coating on the PET film, the coated surface after the drying process is in a uniform state without a clear phase separation structure. After that, the phase separation structure is developed by heat treatment in the stretching process and the heat setting process. That is, it is separated into a phase mainly composed of copolymer polyester and a phase mainly composed of polyurethane. As the phase separation progresses, it is considered that the ratio of the copolymerized polyester component having a lower surface energy is increased near the surface of the adhesive modified layer.

[0135] (Copolyester)

The copolyester used in the adhesive modification layer used in the present invention preferably comprises an aromatic dicarboxylic acid component and a glycol branched with ethylene glycol as the glycol component. Examples of the branched glycol component include 2,2-dimethyl 1,3 propanediol, 2-methyl-2-ethyl-1,3-propanediol, 2-methyl-2-butyl-1,3-propanediol, 2-methyl-2-propyl 1, 3 Propanediol, 2-methyl-2-isopropyl 1, 3 Propanediol, 2-Methyl-2-n Xylou 1, 3 Propanediol, 2, 2 Jetyl 1,3 Pro Pandiol, 2 ethyl 2-n-butyl-1,3 propanediol, 2 ethyl 2-n xylu 1,3 propanediol, 2,2 di-n-butyl-1,3 propanediol, 2-n-butyl-2-propyl 1,3 propanediol, and 2,2-di-n-xylu 1,3 propanediol.

[0136] The molar ratio of the branched glycol component is preferably 20 mol%, with the lower limit being preferably 10 mol% with respect to the total glycol component. On the other hand, the upper limit is preferably 80 mol%, more preferably 70 mol%, and particularly preferably 60 mol%. If necessary, diethylene glycol, propylene glycol, butanediol, hexanediol, or 1,4 cyclohexanedimethanol may be used in combination!

[0137] As the aromatic dicarboxylic acid component, terephthalic acid and isophthalic acid are most preferable. Addition of other aromatic dicarboxylic acids, especially aromatic dicarboxylic acids such as diphenylcarboxylic acid and 2,6-naltalenedicarboxylic acid, within a range of 10 mol% or less to the total dicarboxylic acid component Moyo!

[0138] The copolyester used as the resin component of the adhesive modified layer in the present invention is preferably a water-soluble or water-dispersible resin. Therefore, it is preferable to use 5-sulfoisophthalic acid or an alkali metal salt thereof in the range of 110 mol% in order to impart water dispersibility to the polyester in addition to the dicarboxylic acid component. Mention may be made of terephthalic acid, 5-sulfoisophthalic acid, 4 sulfonaphthalene isophthalic acid 2,7 dicarboxylic acid and 5- (4-sulfophenoxy) isophthalic acid or alkali metal salts thereof.

[0139] (Polyurethane)

As the polyurethane used for the adhesive modification layer, it is preferable to use water-soluble or water-dispersible resin. For example, it is a resin containing a block type isocyanate group, in which the terminal isocyanate group is blocked with a hydrophilic group (hereinafter abbreviated as “block”), a heat-reactive water-soluble urethane, and the like.

[0140] Examples of the blocking agent for the isocyanate group include bisulphites and sulfonic acid group-containing phenols, alcohols, ratata oximes, or active methylene compounds. Blocked isocyanate groups are urethane precursors Is made hydrophilic or water-soluble. In the drying process or heat setting process during film production, when thermal energy is applied to the above-mentioned resin, the blocking agent is detached from the isocyanate group, so that the resin is mixed with a water-dispersible oil mixed into a self-cross-linked stitch. While immobilizing the copolymerized polyester, it reacts with the end groups of the above-mentioned resin. The resin used during preparation of the coating solution is poor in water resistance because it is hydrophilic.However, when the thermal reaction is completed after application, drying, and heat setting, the hydrophilic group of the urethane resin, i.e., the blocking agent, is released. A good coating film can be obtained.

[0141] Among the blocking agents described above, the blocking agent is released from the isocyanate group at the heat treatment temperature and heat treatment time in the film production process, and is commercially available.

Bisulfites are most preferred. The chemical composition of the urethane prepolymer used in the above-mentioned resin includes (1) organic polyisocyanate having two or more active hydrogen atoms in the molecule, or at least two active hydrogen atoms in the molecule. (2) an organic polyisocyanate having two or more isocyanate groups in the molecule, or (3) at least two active hydrogen atoms in the molecule. It is a compound having a terminal isocyanate group, which is obtained by reacting a chain extender.

[0142] Generally known as the compound (1) is a compound containing two or more hydroxyl groups, carboxyl groups, amino groups or mercapto groups at the terminal or in the molecule. Examples of the compound include polyether polyol and polyether ester polyol. Examples of the polyether polyol include ethylene oxide and alkylene oxides such as propylene oxide, or compounds obtained by polymerizing styrene oxide and epichlorohydrin, or random polymerization, block polymerization or the like. Examples include compounds obtained by addition polymerization to polyhydric alcohols.

[0143] Examples of the polyester polyol and the polyether ester polyol include mainly linear or branched compounds. Polyvalent saturated or unsaturated carboxylic acids such as succinic acid, adipic acid, phthalic acid, and anhydrous maleic acid, or carboxylic acid anhydrous, ethylene glycol, diethylene glycol, 1,4 butanediol, neopentyl Multivalents such as glycol, 1, 6 hexanediol and trimethylolpropane It can be obtained by condensing with a saturated and unsaturated alcohol, polyalkylene ether glycols such as polyethylene glycol and polypropylene glycol having a relatively low molecular weight, or a mixture of these alcohols.

[0144] Further, examples of the polyester polyol include latatones and polyesters capable of obtaining hydroxy acidity. Further, as the polyether ester polyol, polyether esters obtained by adding ethylene oxide or propylene oxide or the like to previously produced polyesters can be used.

[0145] Examples of the organic polyisocyanate (2) include isomers of toluylene diisocyanate, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, and xylylene diisocyanate. Alicyclic diisocyanates such as aromatic aliphatic diisocyanates, isophorone diisocyanate, and 4,4-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and 2, 2, 4 to trimethyl Aliphatic diisocyanates such as xamethylene diisocyanate, or polyisocyanates obtained by intensive addition of these compounds with trimethylolpropane, etc.

[0146] Examples of the chain extender having at least two active hydrogens in (3) above include dalicols such as ethylene glycol, diethylene glycol, 1,4 butanediol, and 1,6 hexanediol, glycerin, Polymethyl alcohols such as trimethylolpropane and pentaerythritol, diamins such as ethylenediamine, hexamethylenediamine, and piperazine, amino alcohols such as monoethanolamine and diethanolamine, thiojetylene Examples include thiodiglycols such as dalcole, or water.

[0147] In order to synthesize a urethane prepolymer, it is usually at a temperature of 150 ° C or less, preferably 70 to 120 ° C, by a single-stage or multi-stage isocyanate polyaddition method using the chain extender described above. React for 5 minutes to several hours. If the ratio of isocyanate groups to active hydrogen atoms is 1 or more, it is necessary for free isocyanate groups to remain in the urethane prepolymer obtained. Furthermore, the content of free isocyanate groups may be 10% by mass or less, but considering the stability of the urethane polymer aqueous solution after being blocked, it is preferably 7% by mass or less. [0148] The obtained urethane prepolymer is preferably blocked using bisulfite. Mix with an aqueous bisulfite solution and allow the reaction to proceed with good agitation for about 5 minutes to 1 hour. The reaction temperature is preferably 60 ° C or lower. Then, it is diluted with water to an appropriate concentration to obtain a heat-reactive water-soluble urethane composition. When used, the composition is prepared to an appropriate concentration and viscosity. However, when heated to about 80 to 200 ° C, the bisulfite of the blocking agent is dissociated and the active isocyanate group is regenerated. A polyurethane polymer is produced by a polyaddition reaction that occurs within or between molecules of the prepolymer, or has the property of causing addition to other functional groups.

[0149] As an example of the resin (B) containing the block type isocyanate group described above, a trade name Elastron manufactured by Daiichi Kogyo Seiyaku Co., Ltd. is typically exemplified. Elastolone is a water-soluble because the isocyanate group is blocked with sodium bisulfite, and there is a strong rubamoyl sulfonate group with strong hydrophilicity at the molecular end.

[0150] (b) Solvent

In the present invention, the term “solvent” broadly includes a dispersion medium used to disperse the resin in a particulate form, which is not only the liquid that dissolves the resin. In order to carry out the present invention, various solvents such as an organic solvent and an aqueous solvent can be used.

[0151] The solvent used in the coating solution is preferably a mixed solution in which water and alcohols such as ethanol, isopropyl alcohol, and benzyl alcohol are mixed within a range of 30 to 50% by mass in the total coating solution. Furthermore, if it is less than 10% by mass, an organic solvent other than alcohols may be mixed in a range that can be dissolved. However, the total of alcohols and other organic solvents in the coating solution should be less than 50% by mass.

[0152] When the addition amount of the organic solvent is less than 50% by mass with respect to the total solvent, there is an advantage that the drying property is improved during coating and drying, and the appearance of the coating layer is improved as compared with the case of water alone. . When the addition amount of the organic solvent is 50% by mass or more based on the total solvent, the evaporation rate of the solvent is increased and the concentration of the coating solution is likely to change during coating. As a result, the viscosity of the coating solution increases and the coating property is lowered, which may cause a poor appearance of the coating film. Furthermore, due to the volatilization of the organic solvent, the risk of fire and the like increases. Also, the organic solvent When the added amount is less than 30% by mass with respect to the total solvent, the ratio of water is relatively increased, and the highly hydrophilic polyurethane component segregates near the surface of the adhesive modified layer. As a result, it is difficult to make the area ratio of the PEs phase on the surface of the adhesive modified layer, or the area ratio of the PU phase near the interface with the hard coat layer in the cutting surface of the adhesive modified layer within an appropriate range. .

[0153] (c) pH adjustment of coating solution

The coating solution used for forming the adhesive modified layer in the present invention preferably has a pH in the range of 5 or more and less than 8. When the pH of the coating solution is less than 5, the area ratio of the PEs phase on the surface of the adhesive modified layer increases, or the area ratio of the PU phase near the interface with the hard coat layer on the cut surface of the adhesive modified layer increases. It tends to be small and inferior in adhesion. On the other hand, if the pH of the coating solution is 8 or more, depending on the type of particles, significant aggregation occurs, haze increases, and transparency becomes poor. The pH adjuster is not particularly limited as long as it does not adversely affect adhesion, blocking resistance, and coatability or can be ignored. For example, sodium bicarbonate or sodium carbonate can be used to increase pH, and acetic acid or the like can be used to lower pH.

[0154] (d) Concomitant use of surfactant

When the aqueous coating solution is applied to the surface of the thermoplastic resin film, a surfactant is generally used to improve the wettability of the film and uniformly apply the coating solution. In the present invention, a surfactant can be used as one of means for controlling the surface of the adhesive modified layer and the internal phase separation structure.

[0155] The type of the surfactant is not particularly limited as long as it has good coatability and an appropriate phase separation structure can be obtained on the surface or inside of the adhesion-modified layer. Among the surfactants, a fluorosurfactant is preferable in order to obtain good coatability by adding a small amount. Furthermore, in order to make the area ratio of the PEs phase on the surface of the adhesive modified layer, or the area ratio of the PU phase near the interface with the hard coat layer in the cutting surface of the adhesive modified layer, within an appropriate range, It is preferable to add 0.01 to 0.18% by mass of a surfactant or a non-ionic surfactant with respect to the coating solution.

[0156] When a ionic surfactant is used, the compatibility with the above-mentioned copolymerized polyester and polyurethane may be increased, and the phase separation structure defined in the present invention may not be obtained. Peg. The addition amount of the surfactant can be appropriately selected as long as it does not inhibit the adhesion with a functional layer such as a hard coat layer or a diffusion layer and can provide good coating properties. For example, in the case of a fluorinated surfactant, the critical micelle concentration force with respect to pure water is preferably 30 times or less. When the critical micelle concentration is 30 times or more, the particles contained in the coating solution are easily aggregated, so that the haze of the obtained laminated film is increased, which is not preferable as a base film for an optical functional film. In addition, the surfactant component may bleed out on the surface of the adhesion modified layer, and adversely affect the adhesion. On the other hand, good coatability cannot be obtained at a critical micelle concentration or less. In addition, the area ratio of the PEs phase on the surface of the adhesive modified layer, or the area ratio of the PU phase near the interface with the hard coat layer on the cutting surface of the adhesive modified layer can be controlled within an appropriate range. It becomes difficult.

[0157] (Surfactant purification)

The surfactant used in the present invention is preferably a purified one. In general, the surfactants listed above often contain a small amount of impurities. In particular, impure polyethylene glycol may inhibit obtaining a good phase separation structure depending on the content thereof. To prevent this, it is preferable to use a purified surfactant that has been pretreated to remove impurities from the surfactant.

[0158] The pretreatment process for removing impurities is not particularly limited as long as the impurities can be removed without altering the surfactant. For example, the following method is mentioned.

Dissolve at least the surfactant and polyethylene glycol in an organic solvent that can be dissolved, let stand at low temperature, saturate and precipitate the surfactant as the main component, and then filter out the surfactant with improved purity A method is mentioned. In the case of perfluoroalkylethylene oxide adduct surfactants, heat dissolve in isopropyl alcohol on a 30 ° C hot bath, leave it at 0 ° C for about 24 hours, and filter out the precipitate. A surfactant with improved purity can be obtained.

[0159] (e) Particle

Adhesive modified base film has a haze of 1.5% or less, but for applications that require a high degree of transparency, a node coat film should be used as an optical functional film. Especially preferred. The haze is more preferably 1.0% or less. Heichi If the film thickness exceeds 1.5%, it is not preferable because the sharpness of the screen will be reduced if the film is used for LCD lens film or backlight substrate film.

[0160] In order to reduce the haze of the adhesive modified base film to 1.5% or less, it is preferable not to include particles in the thermoplastic resin film. When particles are not included in the thermoplastic resin film, scratch resistance and handling properties when squeezed into rolls (sliding property, running property, blocking property, air escape from the air during removal) In order to improve the property, it is preferable to include a specific amount of particles having an appropriate size in the adhesive modified layer to form appropriate irregularities on the surface of the adhesive modified layer.

[0161] As the particles, particles having a high affinity with copolymerized polyester or polyurethane are preferable, and it is preferable that there is a difference that the affinity for both is unevenly distributed in either phase. By making the particles unevenly distributed in one of the phase-separated waxes, the particles are gathered moderately, and by adding relatively few particles, that is, without significantly increasing haze, excellent blocking resistance can be obtained. It can be done.

[0162] Particles to be included in the adhesion modified layer include calcium carbonate, calcium phosphate, amorphous silica, crystalline glass filler, kaolin, talc, titanium dioxide, alumina, silica monoalumina composite oxide particles, Inorganic particles such as barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfate, My power, crosslinked polystyrene particles, crosslinked acrylic resin particles, crosslinked methyl methacrylate particles, benzoguanamine 'formaldehyde condensate particles And heat-resistant polymer particles such as melamine 'formaldehyde condensate particles and polytetrafluoroethylene particles.

[0163] Among these particles, silica particles are suitable for the following point power.

The first advantage is that a highly transparent film can be easily obtained because the refractive index of the adhesive modified layer is relatively close to that of the resin component. The second advantage is that silica particles tend to be unevenly distributed in the phase-separated polyurethane phase, and the polyurethane phase existing on the surface of the adhesive modified layer has poor blocking resistance. It is a point that can complement the nature of. This is presumably because the surface energy between the silica particles and the polyurethane is closer to that of the copolymer polyester and has a higher affinity.

[0164] In addition, the shape of the particles is not particularly limited. Particles are preferred.

[0165] The content of particles in the adhesive modified layer is preferably 20% by mass or less, more preferably 15% by mass or less, particularly preferably 10% by mass or less, based on the adhesive modified layer. Make it. If the content of particles in the modified adhesive layer exceeds 20% by mass, the transparency will deteriorate and the film adhesion will tend to be insufficient. On the other hand, the lower limit of the content of particles is preferably 0.1% by mass, more preferably 1% by mass, and particularly preferably 3% by mass with respect to the adhesive modified layer.

[0166] Further, two or more kinds of particles having different average particle diameters may be contained in the adhesion modified layer.

Moreover, you may contain the same kind of particle | grains from which an average particle diameter differs. In any case, the average particle size and the total content of the particles may be in the above ranges. When applying the coating solution, it is preferable to arrange a filter medium so that the coating solution is precisely filtered immediately before coating in order to remove coarse aggregates of particles in the coating solution.

[0167] The average particle size of the particles is preferably 20 to 150 nm, more preferably 40 to 60 nm. If the average particle size is less than 20 nm, it is difficult to obtain sufficient blocking resistance, and scratch resistance tends to deteriorate. On the other hand, if the average particle diameter of the particles exceeds 150 nm, the haze increases and the particles easily fall off.

[0168] In the present invention, sufficient blocking resistance and scratch resistance may not be obtained with only particles A having an average particle diameter of 20 to 150 nm. Therefore, in order to further improve the blocking resistance and scratch resistance, it is preferable to use a small amount of particles B having a larger average particle size. The average particle size of particles B having a large average particle size is preferably 160 to 1000 nm, more preferably 200 to 800 nm. When the average particle size of the particle B is less than 160 nm, scratch resistance, slipping property and winding property may be deteriorated. On the other hand, when the average particle size of the particle B exceeds 1 OOOnm, the haze tends to increase. In addition, it is preferable that the particle B is an aggregate particle in which primary particles are aggregated, and it is preferable to use a particle having a ratio of the average particle size in the aggregated state to the average particle size of the primary particle of 4 times or more. U, who also likes the point of scratch.

[0169] When two types of particles are used, for example, the content ratio (P1ZP2) of particle A (average particle size: 20 to 15 Onm) and particle B (average particle size: 160 to 1000 nm) in the adhesive modified layer 5 to 30 and the content of the particles B is 0.1 to 1% by mass with respect to the solid content of the adhesive modified layer. Two kinds Controlling the content of particles with a specific particle size within the above range optimizes the three-dimensional center plane average surface roughness of the surface of the adhesive modified layer, and achieves both transparency and handling resistance and blocking resistance. It is suitable for making it. When the content of the particle B exceeds 1% by mass with respect to the adhesion modified layer, the haze tends to increase remarkably.

[0170] The average primary particle diameter and the average particle diameter of the particles are measured by the following method.

Take a picture of the particles with an electron microscope and measure the maximum diameter of 300-500 particles at a magnification such that the size of one of the smallest particles is 2-5 mm. Is the average particle size. In addition, when obtaining the average particle size of the particles in the adhesion modified layer of the laminated film, a cross section of the laminated film is photographed at a magnification of 120,000 using a transmission electron microscope (TEM) to improve the adhesion. The maximum diameter of the particles existing in the cross section of the quality layer can be determined. The average particle size of particle B, which has agglomeration force, is measured by taking 300-500 cross sections of the adhesive-modified layer of the laminated film at a magnification of 200 using an optical microscope and measuring the maximum diameter. .

[0171] (f) Crosslinking agent

Opportunities to use information terminals outdoors, such as mobile phones, PDAs, and mopile computers, are increasing. In addition, materials used in cars, such as touch panels used in car navigation systems, are becoming hot during summer. Therefore, there is a demand for a hard coat film with little change in quality even under such harsh environments of high temperature and high humidity, that is, film strength having excellent wet heat and heat adhesion.

[0172] When the hard coat film of the present invention is used for such an application, a crosslinking agent is added to the coating solution and then heat treatment is performed in order to improve the wet heat resistance of the adhesive modified layer. Thus, an adhesion modified layer containing rosin having a crosslinked structure is formed. As the crosslinking agent, at least one selected from an epoxy crosslinking agent, a melamine crosslinking agent, and an oxazoline crosslinking agent is used. The cross-linking agent can be selected in consideration of the affinity with the copolymerized polyester resin used in the coating solution and the moisture and heat resistance required for the adhesion-modified layer.

[0173] In particular, when a high degree of wet heat resistance is required, an epoxy-based crosslinking agent or a melamine-based crosslinking agent is preferable among the above-mentioned crosslinking agents. The epoxy-based crosslinking agent is not particularly limited. For example, a water-soluble epoxy crosslinking agent manufactured by Nagase Kasei Kogyo Co., Ltd. (Deconal series; EX-521, EX-512, EX-421, EX-810, EX-811, EX—85 1) etc. are available as commercial products. Examples of melamine-based cross-linking agents include Sumitomo Chemical's Smitex Resin Series (M-3, MK, M-6, MC, etc.) and Miwa Chemical Co., Ltd. methylated melamine rosin (MW-22). MX-706, etc.) are commercially available. As oxazoline-based cross-linking agents, Nippon Shokubai Co., Ltd. Epocros series (WS-700), Shin-Nakamura Igaku Kogyo Co., Ltd. NX Linker FX, etc. are commercially available.

[0174] The crosslinking agent is preferably 5 to 40% by mass, more preferably 10 to 30%, based on the total amount (100% by mass) of the copolymerized polyester resin and the crosslinking agent in the adhesive property-modified layer. It is preferable that it be contained in the coating solution for forming an adhesive modification layer so as to be mass%. If the content of the cross-linking agent exceeds 40% by mass, the adhesion-modified layer becomes brittle, and high-speed processing is required after forming a functional layer such as a hard coat layer or a diffusion layer made of attalylate resin. Adhesion sufficient to withstand cutting may not be obtained. On the other hand, if the content of the crosslinking agent is less than 5% by mass, it may be difficult to obtain the durability required in recent years. In the coating solution, a catalyst may be added as necessary to promote crosslinking.

[0175] (3-2) Application process

The step of applying the aqueous coating solution is preferably an inline coating method applied during the production process of the film. More preferably, it is applied to the base film before crystal orientation is completed. The solid content concentration in the aqueous coating solution is preferably 30% by mass or less, particularly preferably 10% by mass or less. The lower limit of the solid content concentration is preferably 1% by mass, more preferably 3% by mass, and particularly preferably 5% by mass. Coating amount of the aqueous coating solution The film coated with the aqueous coating solution is guided to a tenter for orientation and heat setting, and heated there to form a stable film by a thermal crosslinking reaction. It becomes a film.

[0176] (Coating amount)

The coating amount when not dried (hereinafter abbreviated as wet coating amount) is preferably ² gZm ² or more and less than lOgZm ² . In order to obtain the designed dry coating amount (the coating amount of the final adhesion modified layer) when the wet coating amount is less than ² gZm ² , it is necessary to increase the solid content concentration of the coating solution. When the solid content concentration of the coating solution is increased, the viscosity of the coating solution increases. Is likely to occur. On the other hand, when the wet coating amount is lOgZm ² or more, coating spots are easily generated due to the influence of the drying air in the drying furnace. In order to prevent defects due to the adhesion of dust, it is preferable to apply the coating solution in a clean environment with a cleanness of class 5000 or less.

[0177] The coating amount of the final adhesive modifying layer (solid content per film unit area) is preferably managed to 0. 005-0. 20g / m ^2. In the prior art, if the coating amount is less than 0.05 g Zm ^2, it is difficult to obtain sufficient adhesion. However, since the adhesive modified layer has a specific phase separation structure, a laminated film having excellent adhesion to the functional layer and the substrate can be obtained even when the coating amount is less than 0.05 gZm ² . is there. If the coating amount is less than 0.005 g / m 2, adhesion will be insufficient. When the coating amount is less than 0.05 gZm ^2, it is preferable to use particles having an average particle size of 60 nm or less. When the average particle diameter exceeds 60 nm, the particles easily fall off the adhesive modified layer during the production or processing of the adhesive base film. When the particles are unevenly distributed in the polyurethane phase, the particles are unlikely to fall off if the coating amount is 0.005 gZm ² or more. On the other hand, when the coating amount exceeds 0.20 gZm ² , the polyurethane component that segregates on the surface of the adhesive modified layer increases, and the blocking resistance decreases.

[0178] The thickness of the adhesive modified layer can be measured by cutting the cross section of the adhesive modified layer with a microtome and observing with an electron microscope. There is a case. For simplicity, if the coating amount is known, the density force of the adhesive modified layer can be converted into thickness. For example, if the density of the adhesion modified layer is lgZcm ³ and the coating amount is lgZm ² , the thickness corresponds to 1 μm. The density of the adhesive modified layer is obtained by calculating the density of each material from the types of the resin and particles constituting the adhesive modified layer, and multiplying the density of each material by the mass ratio of the material to obtain the sum. Thus, the thickness of the adhesion modified layer can be estimated.

[0179] (3-3) Drying process

According to the method for producing an adhesive modified base film, a coating solution is applied to a thermoplastic resin film, and then a thinly applied coating film is dried. In general, when a coating film is dried after applying a coating solution, it is often dried using a preheating zone of a tenter. In this case, film formation The force that depends on the running speed of the size of the film Generally, the coating force It takes at least about 5 seconds to start drying. During this time, the balance between water and alcohol as the solvent of the coating solution is lost, and the highly hydrophilic polyurethane component segregates on the surface of the adhesive modified layer. Therefore, in the final modified adhesive base film, the area ratio of the PEs phase on the surface of the adhesive modified layer or the PU phase near the interface with the hard coat layer on the cut surface of the adhesive modified layer It is difficult to control the area ratio within an appropriate range. In the present invention, it is important that a drying oven (pre-dryer) dedicated to drying the coating film is disposed as close as possible to the exit of the coating apparatus in the film traveling direction, and the coating liquid is applied to the polyester film and dried immediately. It is.

[0180] In the drying furnace, the temperature of the drying air on the coating surface is preferably 120 ° C or higher and lower than 150 ° C. The wind speed is preferably 30 mZ seconds or more. A more preferable drying temperature is 130 ° C or higher and lower than 150 ° C. When the drying temperature is less than 120 ° C. or the wind speed is less than 30 mZ seconds, the drying speed becomes slow, the balance between water and alcohol as the solvent of the coating solution is lost, and the ratio of water is relatively likely to increase. Therefore, the highly hydrophilic polyurethane component segregates on the surface of the adhesive modified layer. Therefore, in the final modified adhesive base film, the area ratio of the PEs phase on the surface of the adhesive modified layer, or the PU phase near the interface with the hard coat layer on the cutting surface of the adhesive modified layer It becomes difficult to control the area ratio of the area within an appropriate range. On the other hand, when the drying temperature is 150 ° C or higher, crystallization of the thermoplastic resin film tends to occur, and the frequency of breakage during transverse stretching increases.

[0181] Further, in the drying furnace, it is preferable to dry for 0.1 to 5 seconds while maintaining the temperature at 120 ° C or higher and lower than 150 ° C. The drying time is more preferably 0.5 to 3 seconds. If the drying time is less than 0.1 second, the coating film will be insufficiently dried, and when passing through the roll disposed between the drying process and the transverse stretching process, the roll is applied with an insufficiently dried coating surface. Dirty. On the other hand, if the drying time exceeds 5 seconds, the thermoplastic resin film tends to crystallize and the frequency of breakage during transverse stretching increases.

[0182] After drying the coating film at a temperature of 120 ° C or higher and lower than 150 ° C in the drying furnace, the adhesive modified base film having an adhesively modified layer may be immediately cooled to near room temperature. Preferred し. Drying oven is maintained with the surface temperature of the adhesive modified substrate film at a high temperature of 100 ° C or higher. When the adhesive modified substrate film comes out of contact with a roll near room temperature, scratches are likely to occur due to film shrinkage.

[0183] If the wind speed in the drying furnace is usually 30 mZ seconds or more, strong drying air is applied to the undried coated surface in the drying furnace, and drying unevenness is likely to occur. However, in the present invention, it is possible to perform at a wind speed of 30 mZ seconds or more by exhausting an air volume equal to or greater than the air volume to be blown out of the drying furnace. It is also important that the exhaust air flow to the opposite side of the coater to prevent unevenness on the coating surface due to the exhaust air from the coater.

[0184] The transit time of the film from immediately after coating to entering the drying oven is less than 2 seconds, preferably 1.

It is important to make it less than 5 seconds. If the coating force takes more than 2 seconds to enter the drying furnace, the balance between water and alcohol, which are the solvent of the coating solution, will be lost during this time, and this will cause the highly hydrophilic polyurethane component to adhere to the modified adhesive layer. Segregated on the surface of the surface. Therefore, the finally obtained adhesion-modified base film is close to the area ratio of the PEs phase on the surface of the adhesion-modified layer or the interface with the hard coat layer on the cutting surface of the adhesion-modified layer. It becomes difficult to control the area ratio of the PU phase within an appropriate range.

[0185] In order to maintain the film transit time from immediately after coating to entering the drying furnace to less than 2 seconds, it is necessary to select the traveling speed of the film as appropriate. Move the coater and the drying furnace inlet as close as possible. It is preferable. In the drying furnace, it is preferable to use air that has been cleaned with a HEPA filter in order to prevent contamination of dry wind power. For the HEPA filter used at this time, it is preferable to use a filter capable of cutting 95% or more of dust with a nominal filtration accuracy of 0.5 / zm or more.

[0186] It is preferable that the drying process also includes a drying zone force divided into V, so-called 2 to 8 zones, in which the conditions of the drying temperature and the drying time are sequentially changed. Particularly preferably, a multistage drying apparatus divided into 3 to 6 zones is employed. For example, when the coating solution is applied to one or both sides of a uniaxially oriented thermoplastic resin film and dried in a multi-stage drying furnace arranged just above the coater, the following method is suitable.

[0187] For example, when drying in four stages, drying is performed in a drying furnace divided into four drying zones. In the first drying zone, at a temperature of 125-140 ° C for 0.1-4 seconds, the second drying zone At a temperature of 55-100 ° C for 0.1-4 seconds, in the third drying zone at a temperature of 35-55 ° C for 0.1-4 seconds, in a fourth drying zone at a temperature of 25-35 ° C. A method of drying for 1 to 4 seconds is mentioned.

[0188] The numerical range of the drying conditions varies somewhat depending on the solid content concentration of the coating solution, and is not limited to the above typical conditions. In addition, when performing hot air drying, it is important to change the air volume at each stage.

[0189] For example, the following method is suitable.

In the 1st drying zone, the wind speed of the drying wind is set to 20 to 50mZ seconds, the supply air volume of the drying wind is set to 100 to 150m ³ / sec, and the exhaust air volume is set to 150 to 200m ³ / sec. For the second drying zone, the supply air volume is set to 60 to 140 m ³ Z seconds and the exhaust air volume to 100 to 180 m ³ Z seconds until the fourth drying zone. In any drying zone, set so that the drying air does not flow to the coater side, and then grip the edge of the film with a clip, hot air at a temperature of 100 to 140 ° C and a wind speed of 10 to 20 mZ seconds. Lead to the zone and stretch 2-6 times in the width direction.

[0190] Further, while maintaining the temperature from 120 ° C to 150 ° C, the drying temperature and the total drying time are appropriately adjusted within a period of 0.1 to 5 seconds, preferably 0.5 to less than 3 seconds. do it. Each stage (zone) in the drying process is determined at the manufacturing site in consideration of various conditions such as the concentration of the dispersion, the coating amount, the traveling speed of the coated traveling film, the temperature of the hot air, the wind speed, and the amount of air. Appropriate values can be determined as appropriate.

[0191] (3-4) Heat setting process

In the method of manufacturing an adhesive modified base film, the transverse stretching process, heat setting process, and cooling process are divided into 10 to 30 zones continuously, and each zone can be controlled independently. Designed so that there is no sudden temperature change between zones. In particular, a rapid temperature change between adjacent zones can be suppressed by raising the temperature stepwise from the latter half of the transverse stretching zone to the heat setting maximum temperature setting zone. In the present invention, temperature control is very important particularly in the drying process and the heat setting process when producing an adhesive-modified base film having a specific phase separation structure on the surface or inside of the adhesive modified layer. is there. In addition, the temperature in the heat setting process is very important in order to form a crosslinked structure in the resin constituting the adhesive modified layer, and this temperature is the speed of the crosslinking reaction. Greatly affects the degree.

Hereinafter, the embodiment will be described in detail.

[0192] As described above, in the heat setting treatment step, the heat treatment condition affects the phase separation state of the adhesive property modified layer. That is, the maximum temperature in the heat-fixing treatment step is reached from the maximum temperature in the heat-fixing treatment step, the time required to reach the maximum temperature, and the temperature at which the phase separation of the adhesive property modified layer starts to proceed remarkably. It is important to set the time required.

[0193] The temperature in each heat setting zone in the heat setting process may vary slightly depending on the type of the resin constituting the thermoplastic resin film, and may be set appropriately within a temperature range of 100 to 260 ° C. Good. Hereinafter, a case where polyethylene terephthalate, which is a typical thermoplastic resin, is used as a thermoplastic resin film will be described as an example.

[0194] The maximum temperature in the heat setting treatment step is preferably controlled to 210 to 240 ° C, more preferably the lower limit is 225 ° C and the upper limit is 235 ° C. In general, heat fixing is performed at a relatively high temperature of 210 to 240 ° C in the initial stage of the heat setting treatment, and the temperature is gradually decreased to 100 to 200 ° C in the subsequent stage. ,.

[0195] When the maximum temperature in the heat setting treatment step is less than 210 ° C, it is difficult to form a mixed phase separation structure or a nanophase separation structure in the adhesive modified layer. Therefore, it is difficult to obtain sufficient adhesion between the base material and the functional layer, which can withstand the peeling of the interface due to impact during high-speed cutting, which has been demanded in recent years. Furthermore, the heat-shrinkage rate of the obtained adhesive modified base film becomes large, which is not preferable.

[0196] When the maximum temperature in the heat setting process exceeds 240 ° C, the PEs surface fraction of the surface of the adhesive modification layer increases, and the hard coat layer, diffusion layer, prism layer, ultraviolet curing Adhesiveness to a functional layer such as a printed layer printed with mold ink tends to be lowered. Furthermore, since the time required to reach the maximum temperature of the heat setting treatment from the temperature at which the phase separation of the adhesive reforming layer starts to proceed remarkably increases, the narrowest part of the polyester phase composed mainly of the copolyester It is in a state where spots with a width exceeding 1 _μm are scattered. As a result, there are locations with poor adhesion to functional layers such as hard coat layers, diffusion layers, prism layers, and printing layers printed with UV-curable ink, and that portion is the starting point. It may lead to macroscopic peeling.

[0197] Specifically, the time required to reach the maximum temperature of the heat setting treatment from the temperature at which the phase separation of the adhesive property modified layer starts to proceed remarkably is preferably set as follows.

In the present invention, the passage time of the film from the temperature setting zone where the phase separation of the adhesive reforming layer starts to proceed remarkably to the maximum temperature setting zone entrance of the heat setting process is 3 seconds or more and less than 20 seconds. Particularly preferred is 4 seconds or more and less than 15 seconds.

[0198] If the passage time is less than 3 seconds, the time for developing the phase separation structure defined in the present invention may be insufficient. On the other hand, when the passage time is 20 seconds or more, the phase separation proceeds excessively, and the thinnest part of the phase mainly composed of the copolyester tends to be scattered in places where the width exceeds 1 μm. As a result, a part having poor adhesion to a functional layer such as a hard coat layer, a diffusion layer, a prism layer, or a printing layer printed with UV ink is locally generated, which may lead to macroscopic peeling starting from that part. is there.

[0199] In the present invention, the temperature at which phase separation of the adhesive modified layer starts to proceed remarkably is estimated to be about 200 ° C within the composition range of the coating liquid shown in the examples of the present invention. Yes. However, the temperature is naturally not limited to this temperature because it varies depending on the resin component of the adhesive modified layer.

[0200] The heat setting treatment step will be described more specifically.

In general, the transverse stretching process, heat setting process, and cooling process are divided into 10 to 30 zones in the tenter to suppress rapid temperature changes in adjacent zones, and temperature control is independent in each zone. Has been made. In particular, the second half force of the transverse stretching zone is also set to the zone where the maximum temperature of the heat setting treatment process is set. It is preferable to prevent a sudden temperature change between the two.

[0201] In the present invention, the temperature setting zone force at which the phase separation starts to progress remarkably can be rapidly and uniformly increased in the passage time of the film to the maximum temperature setting zone inlet of the heat setting treatment step. is important. In order to quickly raise the temperature, it is effective to increase the heat transfer efficiency in each heat setting zone, for example, to increase the velocity of hot air blown onto the film. However, this method generally causes temperature spots. Because it is easy to produce, when the phase separation state of the adhesive reforming layer is uneven, or foreign matters such as oligomers slightly adhering to the inside of the device in the heat setting zone rise, and the raised foreign matter adheres to the film This may lead to optical defects.

[0202] On the other hand, if the wind speed is too low, a sufficient rate of temperature increase cannot be obtained. Therefore, in the present invention, the wind speed is preferably 10 mZ seconds or more and less than 20 mZ seconds. In order to raise the temperature of the laminated film quickly and uniformly, it is effective to arrange the nozzles for blowing hot air at relatively short intervals of 500 mm or less. When the nozzle spacing for blowing hot air is set to 500 mm or less, for example, when the nozzle spacing is set to 300 mm, 350 mm, or 400 mm, it is an unfavorable force for equipment maintenance. is there. The number of nozzles per zone corresponding to one stage is about 6 to 12, and the number is determined in consideration of the state of nozzle spacing, ventilation rate, and ventilation time. The wind speed described in the present invention means the wind speed on the film surface facing the outlet of the hot air blowing nozzle and is measured using a thermal anemometer (manufactured by Nippon Kanomax, Anemo Master Model 6161).

[0203] A preferred embodiment of the heat setting treatment step for producing an adhesive modified substrate film will be described.

The heat setting process is divided into a plurality of heat setting zones continuously, and each zone is partitioned so that the temperature can be controlled independently. The heat setting zone is divided into 2 to: processes where LO heat setting zones are continuously arranged, preferably 4 to 8 steps, and this multi-stage heat setting zone is used to improve adhesion. It is preferable to control the temperature of the base film.

[0204] For example, in the case of a polyester film having an adhesion modified layer, the heat setting zone divided into six steps as shown below is successively passed, and a subtle temperature difference is given to each step. An example is a method in which heat fixing treatment is performed, and both ends of the film are coated and trimmed. The heat setting temperature is 200 ° C in the first heat setting zone, 225 ° C in the second heat setting zone, 230 ° C in the third heat setting zone, 230 ° C in the fourth heat setting zone, The temperature is 210 ° C in the 5th heat setting zone, 170 ° C in the 6th heat setting zone, and 120 ° C in the 7th heat setting zone. In addition, 3% relaxation treatment is performed in the width direction in the sixth heat setting zone. [0205] The above-mentioned stage corresponds to one heat setting zone. As described above, it is preferable that the temperature of the thermosetting zone at each stage has a subtle temperature difference, that is, a temperature difference of about 5 to 40 ° C. The setting of this temperature difference is arbitrarily determined in consideration of various factors such as the running speed, the air volume, and the thickness of the adhesive modified layer of the thermoplastic resin film having the adhesive modified layer.

[0206] When used as a base film of an optical functional film such as a lens film or a diffusion plate, the film length is usually at least 1000 m or more, even if it is a relatively thick film having a film thickness of 100 m or more. Sometimes it is used in the process of laminating a prism layer and a diffusion layer in the form of a roll of 2000 m or more.

[0207] In the present invention, the area ratio of the PEs phase (indicating a dark hue in the phase image) on the surface of the adhesive modified layer, or the hard coat layer on the cutting surface of the adhesive modified layer. When measuring the area ratio of the PU phase near the interface (indicating a bright hue in the phase image) at 100 m intervals in the longitudinal direction of the film, the difference between the maximum and minimum area ratios in the longitudinal direction is 15% or less More preferably, it is 10% or less. By setting the difference between the maximum value and the minimum value of the area ratio in the longitudinal direction to 15% or less, an adhesive modified base film roll having stable adhesion and blocking resistance can be obtained.

[0208] In order to control the difference between the maximum value and the minimum value of the area ratio in the longitudinal direction to 15% or less, the film forming conditions such as the composition of the coating liquid, the coating conditions, the drying conditions, and the heat setting conditions It is important to keep the same constant when continuously manufacturing the long adhesive modified base film roll used in the present invention. However, in particular, the ratio of the mixed solvent used in the coating solution fluctuates, and it is easy to keep the ratio of the mixed solvent constant. However, the area ratio of the surface PEs phase in the longitudinal direction of the film roll and the PU phase of the cutting surface It is important to reduce the fluctuation of the area ratio. For example, the range of fluctuation of the area ratio of the PEs phase on the surface of the adhesive modified layer and the area ratio of the PU phase on the cutting surface can be controlled to 15% or less by the following means. The means for keeping the ratio of the mixed solvent constant is not limited to the following method.

[0209] Increasing the capacity of the circulation tank (13 in Fig. 7) relative to the volume of the coating solution tray (11 in Fig. 7) is effective in stabilizing the concentration ratio of the mixed solvent. It is. In particular, As shown in FIG. 7, when the capacity of the coating liquid receiving tray is 1, the ratio of the capacity of the circulation tank is preferably 10 or more, particularly preferably 50 or more. If the volume ratio (circulation tank capacity Z coating liquid tray capacity) is less than 10, that is, the circulation tank capacity is too small, the concentration ratio fluctuation of the mixed solvent tends to increase.

[0210] Furthermore, when the capacity of the circulation tank is 1, the ratio of the capacity of the mixing tank (14 in Fig. 7) is preferably 10 or more, and particularly preferably 20 or more. As a result, the capacity of the circulation tank can be kept constant during operation when supplying the coating liquid to the circulation tank.

[0211] Increasing the accuracy (roundness and cylindricity) of the applicator roll in the coating apparatus is also effective from the viewpoint of reducing coating thickness unevenness of the adhesive modified layer in the longitudinal direction of the film roll. Furthermore, it is also effective in reducing fluctuations in characteristics due to fluctuations in the area ratio of the PEs phase on the surface of the adhesive reforming layer or the PU phase of the cutting surface in the longitudinal direction of the film roll.

[0212] As described in JIS B 0621, the roundness of the applicator roll is the difference between the radii of two concentric circles determined by the minimum area method determined using a recording roundness measuring instrument. It is an index represented by The unit of roundness of the roll is mm. The applicator roll cylindricity can be measured in various measurement planes over the entire length by placing the roll on a surface plate, moving the stand with a measuring instrument in the axial direction, and placing a probe on the upper surface of the cylinder. This is an index expressed by 1Z2 of the maximum difference in reading at the time of measurement. The unit of cylindricity is mm.

[0213] In the present invention, variation in the thickness of the coating layer in the lengthwise direction can be reduced by improving the roll accuracy (roundness and cylindricity). Specifically, the roll accuracy (roundness and cylindricity) is preferably less than 5ZlOOOmm.

[0214] Also, when applying the coating liquid, the surface finish of each roll of the reverse coater should be 0.3S or less, and the accuracy of the applicator roll and metering roll (roundness and cylindricity) should be less than 5ZlOOOmm, 2Zl000mm By doing so, fluctuations in the amount of wet coating can be suppressed, and fluctuations in the thickness of the coating film can also be suppressed. Preferably, the applicator roll and metering roll have a precision (roundness and cylindricity) of 3ZlOOOmm A roll should be used.

[0215] In addition, by setting the film tension to 4,000 to 10,000 NZ original fabric width (original fabric width is 1 to 2 m), the flatness of the film is maintained on an industrial scale, and the transfer amount of the coating liquid becomes uniform. The Note that the tension of the film varies depending on the thickness of the film, and the flatness is maintained by applying a lower tension to a relatively thin film.

[0216] If the tension of the film exceeds the width of 10000 NZ, the film may be deformed or broken. On the other hand, when the film tension is less than 4000 NZ original fabric width, the flatness of the film during application may be insufficient, or the film may meander. As a result, the transfer amount of the coating liquid becomes non-uniform in the length direction of the film, and the variation in the thickness of the coating layer becomes larger due to the large variation in the wet coating amount of the film.

[0217] In addition, the change in the area ratio of the PEs phase on the surface of the adhesion modified layer or the PU phase on the cutting surface (difference between the maximum and minimum values) is controlled to 10% or less in the width direction of the film roll. In order to achieve this, it is important to reduce the variation in the thickness of the coating layer with respect to the width direction of the film roll. For this purpose, it is effective to improve the flatness in the width direction during coating. Specifically, just after coating with a reverse roll, grip only the both end faces of the film using a pinch roll (16 in FIG. 7). By holding the both ends of the film with the pinch roll, the flatness in the width direction of the film is improved on an industrial scale, and the wet coating amount in the width direction of the film is stabilized. Thereby, the fluctuation | variation of the thickness of the coating layer in the width direction of a film roll can be reduced. When the both ends of the film are not gripped with a pinch roll, the wet coating amount in the width direction and the length direction of the film varies greatly, and the variation in the thickness of the coating layer also increases.

[0218] (4) Hard coat layer and other optical functional layers

The hard coat film of the present invention comprises an adhesive modified base film in which an adhesive modified layer B containing a copolymerized polyester and polyurethane is formed on one side or both sides of a thermoplastic resin film A, and the adhesion of the film. This is a hard coat film having a layer structure of AZBZC or BZAZBZC in which a hard coat layer C containing inorganic fine particles is laminated on one side of the property-improving layer B. As curable resin constituting the hard coat layer, ionizing radiation hard Chemicalized rosin is preferred. Examples of the ionizing radiation curable resin include the following resins.

[0219] The ionizing radiation curable resin is preferably a resin having an acrylate functional group, and particularly preferably a polyester acrylate or a urethane acrylate. Polyester acrylate is also composed of polyester polyol oligomer acrylate or methacrylate (hereinafter, acrylate and Z or metatalate may be referred to as (meth) acrylate), or a mixture thereof. Urethane (meth) acrylate is composed of (meth) acrylated oligomers that also have the ability to produce poly-poly and di-isocyanate compounds.

[0220] Monomers constituting (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, Examples include methoxy shetil (meth) acrylate, butoxy chill (meth) acrylate, and phenol (meth) acrylate.

[0221] If it is necessary to further increase the hardness of the hard coat layer, it is preferable to use a polyfunctional monomer in combination. For example, the polyfunctional monomers include trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri ( Examples thereof include meta) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl dallicol di (meth) acrylate.

[0222] Polyester polyol oligomers include adipic acid and glycol (ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, etc.) and triol (glycerin, trimethylolpropane, etc.), sebacic acid and glycol And polyadipate polyol, which is a condensation product with triol, and polysebacate polyol. In addition, some or all of the aliphatic dicarboxylic acids can be substituted with other organic acids. For example, isophthalic acid, terephthalic acid, or phthalic anhydride can be used as a component that increases the hardness of the hard coat layer.

[0223] When applying the hard coat agent to the surface of the adhesion modified layer of the base film, leveling is performed. In order to improve property, you may dilute using a diluent as needed. Diluents include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane, heptane, octane, nonane, and decane, and ketones such as methyl ethyl ketone, jetyl ketone, and disopropyl ketone. Is mentioned. The blending amount of the diluent should be selected as appropriate so as to obtain an appropriate viscosity.

[0224] The inorganic fine particles to be contained in the hard coat layer C include, for example, amorphous silica, crystalline glass filler, inorganic oxides such as silica, zirconium oxide, titanium dioxide, alumina, and silica-alumina composite. Oxide particles, magnesium carbonate, aluminum hydroxide, barium sulfate, calcium carbonate, calcium phosphate, kaolin, talc, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfate, My strength It is done.

[0225] When the antireflective layer composed of the high refractive index layer Z low refractive index layer or the high refractive index layer Z medium refractive index layer Z low refractive index layer is laminated on the surface of the hard coat layer C, the hard coat layer C By providing layer C with a high refractive index, the antireflective layer strength high refractive index layer can be omitted. As a result, cost can be reduced. In order to increase the refractive index of the hard coat layer C, it is effective to include inorganic fine particles having a high refractive index in the hard coat layer. Examples of the inorganic fine particles having a high refractive index include zirconium oxide and titanium oxide.

[0226] The content of the inorganic fine particles in the hard coat layer is important to be 20% by mass or more and 80% by mass or less. When the content of the inorganic fine particles is less than 20% by mass, the scratch resistance is insufficient. On the other hand, when the content of the inorganic fine particles exceeds 80% by mass, the transparency tends to decrease. Moreover, the average particle diameter of the inorganic fine particles is preferably 5 to: LOOnm from the viewpoint of transparency. However, such inorganic fine particles having a small average particle diameter are easy to aggregate and are unstable. Therefore, in order to increase the dispersion stability of the inorganic fine particles, it is preferable to add a photosensitive group to the surface of the inorganic fine particles to increase the affinity with the curable resin.

[0227] Commercially available hard coat agents containing such inorganic fine particles are available. For example, ultraviolet curable resin (Desolite; Z7400A, Z7410A, Z7400B, Z7410B, Z7400C, Z7410C, Z7410D, Z7410E, Z7501, Z7503, Z7521, Z7527) manufactured by JSR Corporation may be mentioned. [0228] The ionizing radiation curable resin is cured by irradiation with ultraviolet rays or electron beams. Case of irradiation with ultraviolet rays, ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, a metal halide lamp, 100 to 400 nm, preferably, irradiated in the wavelength area of 200 to 400 nm, the ultraviolet energy 100～3000MjZm ² To do. When irradiating an electron beam, a scanning or curtain type electron beam accelerator is used to irradiate an electron beam having an acceleration voltage of lOOOOkeV or less, preferably 100 to 300 keV and having a wavelength region of lOOnm or less.

[0229] The thickness of the hard coat layer may be determined in the range of 0.1 to 30 / ζ πι depending on the application. More preferably, it is 1 to 15 m. When the thickness of the hard coat layer is within the above range, the surface of the hard coat layer has a high hardness and is hardly damaged. Furthermore, when the hard coat film is bent, the hard coat layer does not easily become brittle.

[0230] Next, the optical functional film described in the present invention is a film in which an optical functional layer is laminated on the surface opposite to or on the surface of the hard coat film C of the hard coat film of the present invention. There are two embodiments.

( _a ) At least one optical function selected from a hard coat layer, a light diffusion layer, a prismatic lens layer, an electromagnetic wave absorption layer, a near-infrared shielding layer, and a transparent conductive layer on the surface opposite to the hard coat layer C An optical functional film in which layers are laminated.

(b) An optical functional fine layer in which an antireflection layer or an antifouling layer is laminated on the hard coat layer C.

[0231] A lens film using a lens layer as an optical functional layer and a light diffusion film using a light diffusion layer will be described below as representative examples.

[0232] (Lens Finorem)

A prism lens film or a Fresnel lens film is an ionizing radiation curable hard coat containing inorganic fine particles on one side of an adhesive modified base film having an adhesive modified layer mainly composed of copolymer polyester and polyurethane. The layers are laminated, and a prism lens layer or a Fresnel lens layer is laminated on the opposite surface. The lens film may be called a lens sheet. In the present invention, a sheet is also included in the film. [0233] Next, the active energy ray-curable resin component constituting the prism lens layer will be described.

As the active energy ray-curable resin component, at least one of radically polymerizable monomer or oligomer determines the performance of the produced lens sheet, and is appropriately selected according to the performance of the target lens film. .

[0234] The resin component is a radically polymerizable monomer or oligomer used alone or in combination of two or more. In particular, when two or more types of rosin are used, the mechanical strength, impact resistance, heat resistance, surface hardness, and chemical resistance required for the lens film can be imparted. In addition, by using 60 parts by mass or more of a compound having an attalyloyl group or a methacryloyl group as a radical polymerizable functional group with respect to the composition, when the active energy ray is irradiated, it partially copolymerizes and instantaneously To become fluidized. Therefore, optical distortion due to convection is reduced when the lens layer is formed.

[0235] The resin component includes an ester-type (meth) acrylate, a component obtained by a condensation reaction of an aliphatic, alicyclic, or aromatic mono- or polyalcohol with acrylic acid or methacrylic acid. Urethane poly (meth) acrylates and molecules obtained by urethane reaction of isocyanate compounds having two or more isocyanate groups in the element and (meth) acrylates containing hydroxyl groups or thiol groups Epoxy poly (meth) acrylate, saturated or unsaturated polyvalent carboxylic acid, polyhydric alcohol obtained by ring opening reaction of glycidyl group with compound having at least two epoxy groups and acrylic acid or methacrylic acid , And (meth) atallyloyl functional monomers such as polyester (meth) ate lylate obtained by condensation reaction with (meth) acrylate. And butyl compounds such as styrene, chlorostyrene, bromostyrene, dibutyl styrene, dibutylbenzene, and (meth) aryl compounds such as diethylene glycol bisallyl carbonate, diallyl phthalate, and diallyl biphosphate. .

[0236] Preferred examples are shown below. The following various types of resin components may be used alone or in combination of two or more. Commercially available products are available for prism lenses or Fresnel lens resins. For example, UV curable resin (Desolite; Z9590, Z9502) manufactured by JSR Corporation can be mentioned. [0237] (a) Aliphatic mono (meta) attalylate

Methyl (meth) acrylate, butyl (meth) acrylate

[0238] (b) Alicyclic mono (meth) acrylate

Cyclohexyl (meth) acrylate, dicyclopental (meth) acrylate, dicyclopentale (meth) acrylate, isobornyl (meth) acrylate, born (meth) ate relay

[0239] (c) Aromatic mono (meth) acrylate

Phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxychetyl (meth) acrylate, phenoxy 2-methylethyl (meth) acrylate, 3 phenoxy 2 hydroxypropyl (meth) acrylate, 2-phenol phe -Lu (meta) attalylate, 2-Fuel

2 Phenol Phenol 2—Methyloxychetyl (Meth) Atalylate, 2 —Naphthyl (Meth) Atalylate, 2 Bromo Phenol (Meth) Atalylate, 4 Bromo Phenol (Meth) Atalylate, 2 , 4 Dibromophenol (meth) acrylate, 2, 4, 6 Tribromophenol (meth) acrylate, Phenolthioethyl (meth) acrylate, Phenolthioethoxyethyl (meth) acrylate

[0240] (d) Aromatic skeleton ester di (meth) acrylate

Bis (4— (meth) atalyloxyethoxyfile) methane, Bis (4— (meth) atarioxydiethoxyphenol) methane, 2, 2 Bis (4— (meth) ataryloxyethoxyfile) propaline 2, 2 bis (4- (meth) atari-oxydiethoxyphenyl) propane, 2,2 bis (4- (meth) acryloxypentaethoxyphenyl) propane, 2,2 bis (4- (Meth) Ataryloxypropoxyphenyl) propane, 2, 2 bis (4— (Meth) Atarioxydipropoxyphenyl) propane, 2,2 bis (4— (Meth) Ataryloxyethoxy 1,3,5 Dibromophenol) propane, 2, 2 bis (4- (meth) atarioxydiethoxy-3,5 dibromophenol) Propane, 2,2 bis (4- (meth) atalyloxypentaethoxy-1,3,5 dibromophenol ) Propane, bis (4- (meth) Ataliro Shietokishifuwe - Le) sulfone, bis (4- (meth) Atari port carboxymethyl diethoxy Hue - Le) sulfone, bis (4- (meth) Atari Roy Lucio Hue - Le) Sulfide, bis (4 (meth) atarilochechetyl alcohol) sulfide, etc.

[0241] (e) Alicyclic skeleton ester di (meth) acrylate

Bis (4- (meth) atarioxyxycyclohexyl) methane, bis (4- (meth) atoxyoxycyclohexyl) methane, bis (4- (meth) atoxydiethoxycyclohexyl) methane, bis (4- (meth) atarioxyxycyclohexyl) propane, bis (4- (meth) atarioxyxyxy) propane, bis (4 (meth) atarioxydiethoxycyclohexyl) propane, dicyclopentane Di (meta) Atarilate

[0242] (f) Aliphatic skeleton ester di (meth) acrylate

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol ( _n = 4 to 15) di (meth) acrylate, propylene glycol di (meth) Atalylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (n = 4-15) di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, polybutylene glycol (n = 2 -15) Di (meth) acrylate, neopentylglycol di (meth) acrylate, di (meth) acrylate of hydroxypentyl alcoholate, 1,6 hexanediol di (meth) acrylate, 1 , 9-nonanediol di (meth) atarylate

[0243] (g) Multifunctional (meth) atallylate

Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate

[0244] (h) Urethane poly (meth) acrylate

Tris (isocyanatohexyl) isocyanurate, isophorone diisocyanate, bis (4,4'-isocyanatocyclohexyl) methane, 1,3 bis (isocyanatomethyl) cyclohexane, metaxylylene diisocyanate, Polyisocyanate compounds such as 2,4 tolylene diisocyanate and 2,6 tolylene diisocyanate and 2-hydroxyethyl (meth) atrely

4-Hydroxybutyl (meth) atalylate, a reaction product with (meth) atalylate containing a hydroxyl group such as [0245] (i) Epoxy poly (meth) acrylate

2,2 bis (4-glycidinoleoxycyclocyclohexyl) propane, 2,2 bis (4-glycidyloxyphenol) propane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, Reaction products of (meth) acrylic acid with epoxy compounds such as tetrabromobisphenol A diglycidyl ether and tetrabromobisphenol S diglycidyl ether

[0246] (j) Polyester poly (meth) acrylate

Reaction of at least one of maleic acid, fumaric acid, phthalic acid or succinic acid with at least one of ethylene glycol, propylene glycol, butylene glycol, trimethylolpropane or pentaerythritol, and methacrylic acid or acrylic acid object

[0247] As the active energy ray-sensitive catalyst, a catalyst that generates a radical source mainly in response to an active energy ray having a wavelength of 200 to 400 nm is more preferable. Specific examples include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzil, benzophenone, p-methoxybenzophenone, methoxyacetophenone, benzyl dimethyl ketal, 2, 2-methoxyacetophenone, 1- Carboxylic compounds such as hydroxycyclohexylphenol ketone, methylphenol glyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenolpropanone, tetramethylthiuram monosulfide, tetramethyl Sulfur compounds such as thiuram disulfide, and acylphosphine oxides such as 2,4,6 trimethylbenzoyldiphenylphosphine oxide. These are used in one or a mixture of two or more. Among these, benzophenone, benzoin isopropyl ether, methyl phenol glycolate, 1-hydroxycyclohexyl phenol ketone, benzyl dimethyl ketal, and 2,4,6 trimethylbenzoyldiphenylphosphine oxide are more preferable.

[0248] The content of the active energy ray-sensitive catalyst is 0.005 to 5 parts by mass, and more preferably 0.02 to 2 parts by mass with respect to 100 parts by mass of the total amount of the resin components.

[0249] In the lens layer, the function as a lens is not impaired, and various additives within the range, for example, an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, a yellowing inhibitor , Organic lubricants, pigments, dyes, bluing agents, organic or inorganic fine particles, fillers, belts An antistatic agent, a surfactant, a leveling agent, a nucleating agent, a diffusing agent and the like may be blended.

[0250] The method of laminating the actinic radiation curable resin as a constituent component of the lens layer on the surface of the adhesive modified layer of the adhesive modified base film includes various methods depending on required characteristics and applications. Select a method. For example, a method of applying the resin with a bar cut into a prism shape, or pouring the resin into a mold having a lens layer shape such as a prism, Use the method of superimposing on the surface.

[0251] The actinic rays mean electromagnetic waves that polymerize acrylic vinyl groups such as ultraviolet rays, electron beams, and radiation (α rays, j8 rays, γ rays, etc.). In practice, ultraviolet light is convenient. As an ultraviolet ray source, for example, an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or a carbon arc lamp is used. In addition, the electron beam method is advantageous in that the apparatus is expensive and needs to be operated under an inert gas, but it does not need to contain a photopolymerization initiator or a photosensitizer.

[0252] The thickness of the lens layer is arbitrarily selected depending on the purpose of the lens film and the shape of the lens unit. In general, the thickness of the lens layer is preferably 0.1 to 5 mm, more preferably 0.2 to 3 mm. When the thickness of the lens layer is thinner than 0.1 mm, there is a tendency that the effect as the lens layer cannot be obtained. On the other hand, when the lens layer is thicker than 5 mm, it tends to be insufficient in terms of luminance.

[0253] Also, the pitch of the lens unit is arbitrarily selected depending on the purpose of the lens film and the shape of the lens unit. In general, the distance between the centers of the lens layers is preferably 0.03-0. 5 mm, more preferably 0.05-0.3 mm.

[0254] In particular, a prismatic lens film in which prismatic lens layers are laminated is preferable in terms of luminance and ease of formation. The apex angle of the prism is preferably 80 to 150 degrees, more preferably 85 to 130 degrees.

[0255] (Light diffusion film)

In the present invention, the light diffusing film is an ionizing radiation curable hard coat containing inorganic fine particles on one side of an adhesive modified base film having an adhesive modified layer mainly composed of copolymer polyester and polyurethane. There is also a constitutional force by laminating layers and stacking a light diffusion layer on the opposite side. The light diffusing film is sometimes called a light diffusing sheet. For clarity, sheets are also included in the film.

[0256] The light diffusion layer is composed of a composition containing a binder resin and a light diffusing agent. As the above-mentioned resin, an optically transparent resin is suitable. For example, acrylic resin, polyester resin, polychlorinated butyl, polyurethane, and silicone resin. The resin is commercially available, for example, from Mitsubishi Rayon Co., Ltd. under the trade name “Dianar Series”.

[0257] Further, as the particles used as the light diffusing agent, transparent particles are suitable, for example, silicone resin particles, acrylic resin particles, nylon resin particles, urethane resin particles, styrene resin particles. , Polyethylene resin particles, silica particles, and polyester resin particles. These particles may be used alone or in combination of two or more. The fine particles may be crosslinked on the entire surface or on the whole. The mixing ratio of the particles to the resin is preferably 5 to 150 parts by mass with respect to 100 parts by mass of the resin from the viewpoint of obtaining sufficient light diffusibility while ensuring light transmittance.

[0258] The average particle diameter of the above-mentioned particles is usually 1 to 70 µm, preferably 5 to 50 µm.

That is, when the average particle diameter of the particles is out of the above range, the balance between the light transmittance and the light diffusibility is lost, and the front luminance may not be increased. When spherical particles are used as the particles, each spherical particle acts as one kind of lens and can have a more effective light diffusion effect. In particular, spherical particles are effective. Spherical silica particles are commercially available, for example, from Nippon Shokubai Co., Ltd. under the trade name Eposta.

[0259] A typical method for producing a light diffusion film is shown below.

Surface of the adhesive modified layer of the adhesive modified base film (opposite to the surface on which the hard coat layer is laminated) with a coating liquid in which binder resin, solvent, and particles are mixed and dispersed at a specific ratio Further, it is applied by a known application method. Next, the coating layer is dried and cured by a drying method such as natural drying or hot air heating drying to form a light diffusion layer on the surface of the adhesive base film.

[0260] A suitable method for preparing the coating solution is as follows.

First, the binder resin is dissolved in a solvent at a specific ratio. Disperse particles and other subcomponents as necessary in this solution at a specific ratio to prepare a mixed dispersion. . At this time, the viscosity of the mixed dispersion is adjusted to be in the range of 1 to 500 boise. The viscosity of the liquid can be measured using a Brookfield viscometer (B type viscometer).

[0261] Next, the above-mentioned coating solution is applied to the surface of the adhesion-modified layer of the adhesion-modified base film and dried. The method for applying the coating solution is selected according to the viscosity of the solution and the desired thickness of the coating layer. For example, examples of the coating method include a comma direct method, a roll coating method, a dipping method, a knife coating method, a curtain flow method, a spray coating method, a spin coating method, and a laminating method.

[0262] The thickness of the adhesion-modified base film is preferably 50 to 200 µm from the viewpoint of use and workability. The thickness of the light diffusion layer is preferably 2 to 30 / ζ πι. Examples of the solvent include toluene, methyl ethyl ketone, xylene, cyclohexane, and ethyl acetate.

[0263] The mixing ratio of the solvent with respect to the binder resin is appropriately set depending on the coating method, workability, type of solvent, etc., but 50 to 500 parts by mass of the solvent with respect to 100 parts by mass of the binder resin. Is preferred.

[0264] Further, the mixing ratio of the solvent with respect to the particles is appropriately set in the range of 20 to 500 parts by mass of the solvent with respect to 100 parts by mass of the particles, depending on the coating method, workability, type of solvent, and the like. More preferably, it is 50-300 mass parts of solvent with respect to 100 mass parts of particle | grains. That is, when the mixing ratio of the solvent with respect to the particles is within the above range, the amount of the solvent with respect to the particles is an appropriate amount for softening the resin.

[0265] In addition, as a secondary component of the light diffusion layer, for example, an isocyanate compound, an epoxy resin, a methylolated melamine resin, a methylol urea resin, a metal salt, a metal hydroxide, or a crosslinking agent, Guazine derivatives, phosphate anion activators, sulfonic acids, quaternary ammonium salts, pyridinium salts, imidazoline derivatives, morpholine derivatives, polyoxyethylene alkylphenols, alkylamide ethers, sorbitan fatty acids Antistatic agents such as esters and silane coupling agents can be contained alone or in combination of two or more. Example

Next, the hard coat film of the present invention and the optical functional film using the same will be described using examples and comparative examples, but the present invention is naturally limited to these examples. It is not something. In addition, the physical properties and characteristics of the adhesion-modified base film, hard coat film, and optical functional film described in the examples were evaluated using the following methods.

[0267] (1) Phase separation structure of adhesion modified layer

(1-1) Surface of the adhesion modified layer of the adhesion modified substrate film

(1 1 1) Observation of phase image

Phase separation mode (phase mode) was evaluated using a scanning probe microscope (SPI3800N system ZSPA300, manufactured by SII Nano Technology) on the surface of the adhesive modified layer. I went there. In the phase image, the brighter the phase delay, the darker the phase delay. A small phase lag means that it is harder or has a relatively lower adsorption force than the other phases. In the adhesion modified layer of the adhesion modified substrate film used in the present invention, the dark hue is a polyester phase and the light hue is a polyurethane phase.

[0268] The measurement principle of the phase measurement mode in the scanning probe microscope is “1-2.Up” on the website of S'Nano Technology Co., Ltd. (http: ZZwww. Siint. Com / technology / probe—applications, html). It is described in the PDF file of “1. Phase measurement by SPM” in the Phase column in “Recations (by mode)”.

[0269] The cantilever used for the measurement was mainly DF3 (panel constant: about 1.6 NZm), and a new cantilever was always used to prevent deterioration of sensitivity and resolution due to probe contamination. The scanner used was FS-20A. The phase image was observed with a resolution of 512 x 512 pixels or higher, and the observation field of view was 5 m x 5 m. The measurement parameters such as the amplitude attenuation rate of the cantilever, the running speed, and the scanning frequency during the measurement were set to the conditions where the line was scanned and the sensitivity was highest and the resolution was good.

[0270] (1-1-2) Measurement of polyester phase area ratio

(a) Image analysis

The obtained phase mode image (bitmap format, 512 X 512 pixels) is read by image processing software (Adobe, Photoshop ver. 7.0) and displayed on the display so that the image size is 205 mm x 205 mm. Displayed (see Figure 1). Next, using the software's pencil tool (master diameter: 3px), a black A line was drawn to clarify the boundary between the two phases (see Figure 2). In addition, using the paint tool of the software, the dark hue was painted black and the light hue was painted white, giving a binary value (see Figure 3). At this time, dark portions with a diameter of 2 mm or less in the light hue with the size on the screen were judged to be unevenly distributed in the light hue, and were painted white. For example, when silica particles are used, it can be confirmed that they are unevenly distributed in a light hue.

[0271] Using this software, a histogram with the horizontal axis of brightness (black, white) and the vertical axis of frequency is displayed using the same software, and the area ratio of the black part (polyester phase) is obtained. The area ratio of the polyester phase on the surface of the adhesive modified layer in the adhesive modified base film was used.

[0272] (b) Paper weight method

The measurement of the area ratio of the polyester phase on the surface of the adhesive modified layer can be carried out using a paper weight method in addition to the image analysis method. The measurement procedure is as follows. The obtained phase mode image was stored as a digital image in bitmap format. Next, this image was printed out on A4 quality paper using a printer (Xerox, DocuPrintC830). For the output image (200mm x 200mm), the boundary between light and dark hues in the image was clarified with a 4B pencil in a bright room under 500 lux illumination. At this time, it has been confirmed that the dark color portion having a diameter of 0.1 m or less present in the light hue is a particle contained in the adhesive modified layer unevenly distributed in the light hue. Therefore, a line was not drawn between the light hue and the dark color area inside it, and this dark color area was included in the light hue. Then, it divided | segmented by cutting on the boundary line which clarified the light hue and the dark hue with the cutter knife. Next, the mass of the light hue (polyurethane phase) and dark hue (polyester phase) paper is measured, and the ratio of the mass of the dark hue (polyester phase) to the total mass of the light hue and dark hue paper is determined in units of%. The area ratio of the polyester phase on the surface of the adhesive modification layer

[0273] (c) Fluctuation width of polyester phase area ratio (difference between maximum and minimum values)

(c 1) Longitudinal direction of film roll

A roll made of an adhesive modified base film having a length of 1000 m or more and a width of 50 mm or more was unwound. With respect to the longitudinal direction (MD) of the film, the area ratio of the polyester phase (indicating a dark hue in the phase image) on the surface of the adhesive modified layer was measured at the following locations. Next At each location, the area ratio of the polyester phase on the surface of the adhesive modified layer was determined. Furthermore, the difference between the maximum value and the minimum value was obtained from these area ratios.

The area ratio of the polyester phase on the surface of the modified adhesive layer is measured by taking the first end as the first end and the second end as the first end of the steady region where the film properties are stable. The first measurement is performed at 2 m or less on the inner side, the final measurement is performed at 2 m or less on the inner side of the second end, and every 100 m from the first measurement point.

[0274] (c 2) Film roll width direction

An adhesive-modified base film roll having a length of 1000 m or more and a width of 50 mm or more was unwound, and the film was divided into four equal parts in the width direction (TD). Next, the area ratio of the polyester phase (indicating a dark hue in the phase image) on the surface of the adhesive modified layer was measured at each central portion. Next, the difference between the maximum value and the minimum value of the area ratio of the polyester phase on the surface of the adhesive modified layer in the width direction was determined. This measurement may be performed with a jumbo roll before slitting the width direction of the film into a small width size.

[0275] (1-2) Diagonal force cut surface of the adhesion modified layer in hard coat film

In the hard coat film of the present invention, the adhesive modification layer B is an intermediate layer between the thermoplastic resin film A and the hard coat layer C. Therefore, the phase separation structure of the resin should be observed directly at the interface between the adhesive modified layer B and the hard coat layer C (the surface of the adhesive modified layer in the adhesive modified substrate film). Is difficult. Accordingly, the present inventors have found that a hard coat film can be cut in the thickness direction, and the phase separation structure of the resin in the thickness direction of the adhesive modified layer can be measured from the cut surface. In addition, since the thickness of the adhesive modified layer is generally thin, it is difficult to observe the phase separation structure of the resin from the cut surface of the adhesive modified layer. Therefore, the hard coat film was cut obliquely and at a shallow angle with respect to the thickness direction. As a result, the observation area in the thickness direction of the adhesive modification layer could be expanded. By this technique, the phase separation structure of the resin constituting the adhesive modified layer in the vicinity of the interface between the adhesive modified layer B and the hard coat layer C could be observed.

[0276] Hereinafter, a method for preparing an evaluation sample and a method for evaluating the area ratio of the polyurethane phase on the cut surface of the adhesive reforming layer in the vicinity of the interface with the node coat layer C will be described in detail.

[0277] (1-2-1) Preparation of cutting specimen The hard coat film of the present invention has a layer structure of A / B / C or BZA / B / C, where A is the thermoplastic resin film, B is the adhesive modification layer, and C is the hard coat layer. It is a stacked body containing. The optical functional film using the hard coat film is a laminate including a layer structure of D (including C) ZBZAZBZC, where D is the other optical functional layer.

[0278] In the hard coat film or optical functional film, from the surface of thermoplastic resin film A or optical functional layer D, using cutting device 1 (SAICAS DN20-S type), diagonally under the conditions shown below Cut from. When the knife blade has reached the specified depth, press the button “Restrict cutting” and perform cutting at a certain depth. Moreover, when the thermoplastic resin film to be cut is thick, it is preferable to perform multiple cuttings at the same place.

(a) Cutting means: Diamond knife (rake angle: 40 degrees)

(b) Horizontal blade movement speed: 3000nmZs

(c) Vertical blade movement speed: 200nmZs

[0279] The above "predetermined depth" means a depth at which most of the thermoplastic resin film is cut and does not reach the adhesive property modified layer. “Incision limit” means that the moving speed of the blade in the vertical direction is set to zero and cutting is performed only in the horizontal direction.

[0280] Subsequently, the same location was cut with high precision from an oblique direction using a cutting device 2 (SAICAS NN-04 type) under the conditions shown below, and a cutting sample was prepared.

(d) Cutting means: Diamond knife (scoop, angle: 40 degrees)

(e) Horizontal blade movement speed: 500nmZs

(f) Vertical blade movement speed: 20nmZs

[0281] The above cutting conditions are typical conditions for cutting the node coat films obtained in the examples and comparative examples described in the present invention. Depending on the sample, a three-dimensional cutting method using a three-dimensional cutting tool may be effective. The blade width of diamond knives is usually lmm, but 0.3mm may be effective. In the examples and comparative examples described in the present invention, a diamond knife having a blade width of 1 mm was used.

[0282] Therefore, if the material strength of each layer of the hard coat film is different from the materials used in the examples and comparative examples described in the present invention, a preliminary test is performed to determine appropriate cutting conditions. Preferably.

[0283] Further, when the surface force of the optical functional layer D (including the hard coat layer C) is also cut, depending on the physical properties of the optical functional layer, it may be necessary to heat or cool during cutting. Caro For heat or cooling, use a low / high temperature gas spray device (TTFC-L type, Dybra “Wintes Co., Ltd.”). The temperature or gas flow rate when heating or cooling is appropriately adjusted according to the state of the cutting surface.

[0284] (1 2— 2) Observation of phase image

On the cutting surface of the obtained cutting sample, the phase separation structure of the resin of the adhesive modified layer B was obtained in the phase measurement mode (phase mode) using the scanning probe microscope (SPM) described above. Observe by phase image. The phase mode is a phase lag measurement mode that is usually performed simultaneously with the morphological observation in the dynamic force mode (DFM mode; when using SPM manufactured by SII Nanotechnology). In the phase image of the cut surface of the adhesive modification layer B, the dark hue is the polyester phase and the light hue is the polyurethane phase.

[0285] The cantilever used for the measurement was mainly DF3 (panel constant: about 1.6 NZm), and a new cantilever was always used to prevent deterioration of sensitivity and resolution due to probe contamination. The scanner used was FS-100A. The observation field of the phase image was 3 m × 3 m. Measurement parameters such as the amplitude attenuation rate of the cantilever, the scanning speed, and the scanning frequency during measurement were set to the conditions where line scanning was performed and the sensitivity was highest and the resolution was observable.

[0286] (1 2-3) Measurement of area ratio of polyurethane phase

Drawings attached to application documents include drawings that are displayed in color images, but for convenience of electronic filing, color images are saved in JPEG file format and displayed in grayscale. Yes. Black-and-white images are also saved in JPEG file format and displayed in grayscale to prevent image quality degradation.

[0287] (a) Reading of phase image

Use SPIP software (Image Metrology, Version 4.2.5) to read the obtained phase image in color.

[0288] (b) Enhancement of contrast in phase separation structure (see Figure 8)

Next, with this software, color equalization processing is performed, and the phase separation structure Enhance contrast so that is easily visualized.

[0289] (c) Determination of observation range of phase separation structure (see Fig. 9)

Copy the phase image that has undergone color uniformity processing and paste it onto the screen of the presentation software (Micros oft PowerPoint 2002). Next, a red line 20 is drawn at the interface (BZC) between the adhesion modified layer B and the hard coat layer C. At this time, if the interface is unclear, adjust the contrast.

[0290] Further, this interface (BZC) force is also directed to the adhesive modified layer B, and the red line indicating the above interface is copied and pasted in parallel at a depth of 20 nm in the vertical direction (Fig. 9 lines 21). In addition, when producing the cutting sample, the laminated body is cut from the diagonal direction. Therefore, in the cutting conditions shown above, the position at the depth of 2 Onm is equivalent to the position of 500 nm from the interface in FIG.

In this way, the range surrounded by these two red lines, that is, the range from the interface (BZC) to the depth of 20 nm of the adhesive modified layer B is reduced on the cutting surface of the adhesive modified layer B. The range for observation of the phase separation structure of fat.

[0291] (d) Image processing of phase separation structure

Save the image in Fig. 8 in JPEG file format and paste it on the screen of image processing software (Adobe, Photoshop ver6. 0. 1), and display it in two gray scales with a threshold value of 128 (see Fig. 10). ).

Next, the image of FIG. 10 is pasted on the screen of presentation software (Microsoft PowerPoint 2002). Then, the two red lines (20, 21) shown in Fig. 9 are displayed on the image of Fig. 10 so as to overlap with the image of Fig. 9 (see Fig. 11).

[0293] The image in Fig. 11 is displayed on the screen of image processing software (Adobe, Photoshop ver6. 0.1). In addition, use the brush tool to paint the area other than the adhesive modification layer B in red (see Figure 12). Using the same software, white, black, and red ternary images were displayed as a histogram with luminance (black, white) on the horizontal axis and frequency on the vertical axis.

[0294] In the phase image of the adhesive property modified layer B shown in Fig. 12, the black part means the polyester phase and particles, and the white part means the polyurethane phase. The adhesion force modification layer B and the hard coat layer C have an interfacial force with a depth of 20 nm. The area ratio of the tan phase (white part) is calculated by the following formula. The “measurement area” on the right side of the following equation means the range surrounded by the line 20 (interface BZC) and the line 21 in the phase image of FIG. Area ratio of polyurethane phase (%) = (white area Z measurement area) X 100

[0295] (2) Presence / absence of locations where the width of the polyester phase exceeds 1 μm at the minimum

In the above-mentioned phase mode image, the presence or absence of a polyester phase mainly composed of a copolymerized polyester having a width of the minor axis exceeding 1 μm was examined at 10 different measurement locations.

[0296] (3) Fractal dimension of phase separation structure

Using the scanning probe microscope (SII NanoTechnology, SPI3800N system ZSPA300), phase-mode images (bitmap format, 512 X 512 pixels) obtained in phase measurement mode (phase mode) are processed. The software (Ad obe, Photoshop ver7.0) was loaded and displayed on the display so that the image size would be 205mm x 205mm (see Figure 1). Next, using the lead brush tool (master diameter: 3px) of the software, a black line was drawn at the boundary between the light and dark hues to clarify the boundary between the two phases (see Figure 2). At this time, the dark portion with a diameter of 2 mm or less in the light hue with the size on the screen is judged to be a particle that is unevenly distributed in the light hue, and the operation of drawing the boundary line is not performed on this portion. I got it. For example, when silica particles are used, it can be confirmed that they are unevenly distributed in a light hue.

[0297] An image with a clear boundary line is saved as a bitmap format image, and then the fractal dimension analysis is performed by the box counting method, and the obtained fractal dimension value is used to determine the complexity of the boundary line of phase separation. The index is shown. Image analysis software (AT— Image ver. 3.2) was used for analysis by the box counting method. Specifically, the saved bitmap image was opened on the image analysis software (AT- Image ver3.2), and binary image processing was performed using the luminance histogram from image extraction on the menu (see Fig. 6). The threshold for binarization was 8. For the binarized image, the fractal dimension was selected by selecting the fractal dimension from the image measurement cursor on the menu. At this time, for the calculation of the fractal dimension by the method of least squares, the counting result of a box having a side length of 6 to 63 pixels was used.

[0298] The analysis of the fractal dimension by the box counting method is a known method. The use of other image analysis software or programs for the original analysis may use other software having the same function as long as the reproducibility of the analysis results is sufficiently obtained. Other software includes, for example, “Agricultural Technology Research Organization, National Institute of Livestock and Grassland Research, Fractal Analysis System Version 3.33”, “Digital 'Being'Kids'

Image analysis software such as “Poplmaging Ver. 3.40”.

[0299] (4) Average particle size of inorganic fine particles in hard coat phase C

A hard coat film sample is embedded in a visible light curable resin (eg, epoxy resin).

And allowed to cure at room temperature. Next, an ultrathin section was prepared using an ultramicrotome equipped with a diamond knife and stained with ruthenium tetroxide. The stained ultrathin section was observed with a transmission electron microscope (manufactured by JEOL Ltd., TEM2010) for observing the cross section of the hard coat layer C and taking a photograph. Note that the magnification of the photograph is appropriately set in the range of 10,000 to 100000 times according to the observed particle size of the inorganic particles. In Example 1 of the present invention, the magnification was set to 80,000 (acceleration voltage 200 kv). From this photograph, the average particle diameter based on the number of inorganic fine particles in the hard coat layer C was determined.

[0300] (5) Haze

In accordance with JIS K7136, using a haze meter (Nippon Denshoku, NDH2000), haze was measured at three different locations on the film sample, and the average value was used.

[0301] (6) Blocking resistance

The adhesion modified layers of the two adhesive modified substrate films were superposed on each other. Next, they were subjected to a pressure of lkgfZcm ² and adhered in an atmosphere of 50 ° C. and 60% RH for 24 hours. After that, peeling was performed at the interface between the adhesive modified layer and the adhesive modified layer of the two adhesive modified base films adhered, and the peeled state was judged according to the following criteria.

◯: Lightly peelable with no change in adhesion modified layer

△: Peeling sound is generated and the adhesive modified layer is partially transferred to the other side X: Two films are stuck and cannot be peeled or the base polyester film is cleaved even if peelable Stuff

[0302] (7) Hardness index of the adhesion modified layer

A surface property measuring instrument (Shintoa Chemical Co., Ltd.) Made by HEIDON14) and scratched. At this time, a genuine needle with a 75 μm diameter sapphire at the tip was used as a scratching needle. The traveling speed of the needle was 150 mmZ, and the weight was 5 gf.

[0303] The surface shape of the scratches attached to the adhesion modified layer was measured using a three-dimensional non-contact surface shape measuring device (Micromap, Micromap550) under the following conditions, and the profile mode data was displayed. . Figure 5 shows a typical example. From the obtained shape data of the scratch, the height difference between the adjacent convex and concave was measured at 30 locations, and the average value thereof was obtained and used as the hardness index of the adhesive modified layer. At this time, protrusions having a height of 30 nm or more were judged to be protrusions caused by particles contained in the adhesive modified layer or the thermoplastic resin film, and the measurement data power was excluded. In addition, protrusions with a height of 1 nm or less were also excluded from measurement data because they are affected by noise.

[0304] (Measurement conditions)

.Profile mode: Wave mode

• Objective lens: 10x

• Resolution: 160 x 160 pixels

• Measurement length: 207. lnm

[8305] (8) Adhesion with hard coat layer

(8-1) Adhesion between adhesion modified layer B and hard coat layer C

A surface opposite to the hard coat layer C of the hard coat film or optical functional film obtained in Examples and Comparative Examples was attached to a glass plate having a thickness of 5 mm to which a double-sided tape was attached. Next, 100 grid-like cuts that penetrated through the hard coat layer C and the adhesive modified layer B and reached the thermoplastic resin film A were made using a cutter guide with a gap interval of 2 mm. Next, an adhesive tape (manufactured by Nichiban Co., Ltd., No. 405; width of 24 mm) was attached to the grid-shaped cut surface. The air remaining at the interface at the time of pasting was pushed with an eraser to bring it into close contact, and then the adhesive tape was peeled off vertically. In addition, a new adhesive tape was applied in the same way and peeled off in a vertical direction. This adhesive tape peeling operation was repeated a total of 10 times, and the following formula force was also visually determined for adhesion. In addition, what is partly peeled within one grid is also included in the number of peeled. Adhesion (%) = (1—Number of peeled Zioo pieces) X 100

[0306] (8 2) Evaluation with adhesive modified substrate film

It consists of two types of photo-curing acrylic resin, solvent-diluted type and solvent-free type, and does not contain particles. Evaluation was made according to the above method. A sample for evaluating the adhesion of the adhesion-modified base film to the hard coat layer was prepared according to the following method.

[0307] (a) Adhesiveness to a hard coat layer composed of a solvent-diluted photocurable acrylic resin

Mix 50 parts by weight of hard coat agent (Daiichi Seika, Seika Beam EXFOl (B)), 25 parts by weight of toluene, and 25 parts by weight of methyl ethyl ketone on the surface of the adhesion modified layer B of the film sample. After applying the stirred coating agent with a wire bar and drying at 70 ° C for 1 minute to remove the solvent, it was hardened with a thickness of 3 m under the conditions of 200 mjZcm ² , irradiation distance 15 cm, traveling speed 5 mZ with a high-pressure mercury lamp. A hard coat film having a coat layer was obtained.

[0308] (b) Adhesiveness with a no-coat layer composed of a solvent-free photo-curing acrylic resin. A hard coat agent (manufactured by Dainichi Seika Co., Ltd.) on a 5 mm thick glass plate kept clean. , Seika Beam EXFOl (B)) About 5 g is placed on top of the film sample so that the surface of the adhesion modified layer and the hard coat agent are in contact with each other, and a manual load rubber with a width of 10 cm and a diameter of 4 cm from the top of the film sample. Crimping was performed so as to extend the coating agent with a roller. Next, from the film surface side, the hard coat layer was cured by irradiating with ultraviolet rays under conditions of 500 mjZcm ² , irradiation distance 15 cm, and traveling speed 5 mZ with a high-pressure mercury lamp. Next, the film sample having the hard coat layer was peeled off from the glass plate to obtain a hard coat film.

[0309] (9) Pencil hardness

In accordance with JIS—K5400, the surface of hard coat layer C is measured by a pencil hardness test. In the pencil hardness test, the test was repeated 5 times.If all the tests showed that the surface of the hard coat layer C did not show any abnormal appearance such as scratches, the hardness of the pencil used in the test was determined. Use pencil hardness. For example, if a 3H pencil is used and 5 tests are performed, and no abnormal appearance occurs in all tests, the material has a pencil hardness of at least 3H. In this evaluation, 3H or higher was given as ◯, and 2H or lower was taken as X. [0310] (Example 1)

(1) Preparation of coating solution

The coating solution used in the present invention was prepared according to the following method.

Dimethyl terephthalate (95 parts by mass), dimethyl isophthalate (95 parts by mass), ethylene glycol (35 parts by mass), neopentyl dallicol (145 parts by mass), zinc acetate (0.1 mass part) and antimony trioxide ( (0.1 part by mass) was charged into a reaction vessel and subjected to a transesterification reaction at 180 ° C for 3 hours. Next, 5-sodium sulfoisophthalic acid (6.0 parts by mass) was added, and the esterification reaction was carried out at 240 ° C for 1 hour, and then at 250 ° C under reduced pressure (10-0.2mmHg) A polycondensation reaction was carried out over 2 hours to obtain a copolyester having a number average molecular weight of 19,500 and a soft spot of 60 ° C.

[0311] 7.5 parts by mass of an aqueous dispersion of 30% by mass of the obtained copolyester (A), 20% by mass of self-crosslinking polyurethane (B) containing isocyanate groups blocked with sodium bisulfite 11.3 parts by mass of an aqueous solution (Daiichi Kogyo Seiyaku Co., Ltd., Elastron H-3), 0.3 parts by mass of Elastolone Catalyst (Daiichi Kogyo Seiyaku Co., Ltd., Cat64), 39.8 parts by mass of water and isopropyl Alcohol was mixed in 37.4 parts by mass. Sarasuko, colloidal silica (manufactured by NISSAN CHEMICAL INDUSTRY CO., LTD.), 0.6 parts by mass of 10% by weight aqueous solution of fluoro-based surfactant (Dainippon Ink and Chemicals, MegaFuck F142D) OL: 2.3 parts by weight of a 20% by weight aqueous dispersion with an average particle size of 40 nm), 3 parts of dry process silica (Nippon Aerosil, Aerosil OX50; average particle size 200 nm, average primary particle size 40 nm) as particles B 0.5 mass part of 5 mass% aqueous dispersion was added. Next, the pH of the coating solution is adjusted to 6.2 with 5% by weight aqueous sodium bicarbonate solution, and the solution is microfiltered with a felt-type polypropylene filter with a filtration particle size (initial filtration efficiency: 95%) of 10 μm. A was adjusted. The surfactant used was pretreated by the following method.

[0312] To the above surfactant, isopropyl alcohol (IPA) was added and dissolved by heating in a 30 ° C hot bath to prepare a 15 mass% surfactant IPA solution. This solution was filtered through a quantitative filter paper (Advantech Toyo, No. 5C) to remove insolubles and dust in the solution. After filtering the solution, the solution was put in a sealed glass container and allowed to stand in a freezer at 0 ° C. for 24 hours. After the elapse of 24 hours, the solution containing the precipitated solid is removed using the above quantitative filter paper. And suction filtered. The solid on the filter paper was vacuum-dried to obtain a solid, diluted with water to a 10% by weight aqueous solution, and used as a pretreated surfactant.

[0313] The surfactant obtained in the pretreatment was analyzed with a TLC-coated plastic sheet (manufactured by Merck, silica gel 60) using methanol as a developing solution. As a result of coloring the sample spot with iodine vapor, it was confirmed that no spot equivalent to polyethylene glycol was detected.

[0314] (2) Production of adhesive modified substrate film

Polyethylene terephthalate (PET) resin pellets containing no particles and having an intrinsic viscosity of 0.62 dlZg as a raw material polymer were dried under reduced pressure (lTorr) at 135 ° C. for 6 hours. Next, the dried PET resin pellets are supplied to an extruder, melted and extruded into a sheet at about 285 ° C, rapidly cooled and solidified on a metal roll maintained at a surface temperature of 20 ° C, and cast film Got. At this time, a stainless sintered filter medium having a filtration particle size (initial filtration efficiency: 95%) force of 15 m was used as a filter medium for removing foreign substances in the molten resin.

[0315] The obtained cast film was heated to 95 ° C with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a difference in peripheral speed, and a uniaxially oriented PET film. Got. Next, the coating liquid A was finely filtered with a felt type polypropylene filter medium having a filtration particle size (initial filtration efficiency: 95%) of 10 μm, and applied to one side of a uniaxially oriented PET film by a reverse roll method. At this time, the application roll and metering roll of the coater were rolls with an ultra-hard chrome finish surface of 0.2S or less and roundness and cylindricity of 3Zl000mm.

[0316] After that, in a drying furnace divided into four zones located just above the coater, the first zone (135 ° C for 1.0 second), the second zone (65 ° C for 2.2 seconds), the first The coated surface was dried in 3 zones (1.8 ° C at 40 ° C) and 4th zone (1.8 seconds at 30 ° C). The coating amount was set to 0.08 gZm ² as the final solid content. The film transit time from application to the film to the entrance of the drying oven was 0.8 seconds. At this time, the wind speed of the drying air in the first zone is 3 OmZ seconds, the supply air flow of the drying air is 130 m ³ Z seconds, the exhaust air flow is 170 m ³ Z seconds, and the air supply from the second zone to the fourth zone The air volume was set to 100m ³ Z seconds and the exhaust air volume was set to 150m ³ Z seconds so that dry air did not flow to one side of the coater. The film tension is 7000 NZ The coating force was held between both ends of the film with a pinch roll until the entrance to the drying furnace.

[0317] Further, in the coating at this time, a coating apparatus in which the ratio of the volume of the coating liquid receiving tray to the capacity of the circulation tank and the volume of the blending tank had the following relationship was used.

(a) Capacitance ratio of coating liquid pan to circulation tank capacity = 1Z50

(b) Capacity ratio of circulation tank to mixing tank = 1Z40

[0318] Subsequently, while holding the edge of the film with a clip, the film was guided to a hot air zone at a temperature of 120 ° C and a wind speed of 15 mZ seconds, and stretched 4.3 times in the width direction. Next, the first heat setting zone (temperature: 200 ° C), the second heat setting zone (temperature: 225 ° C), and the third heat setting zone (temperature: 230 ° C) while maintaining the width stretched in the width direction. ° C), 4th heat fixation zone (temperature: 230 ° C), 5th heat fixation zone (temperature: 210 ° C), 6th heat fixation zone (temperature: 170 ° C), 7th heat fixation zone (temperature: 120 ° C) was successively passed. In addition, 3% relaxation treatment was performed in the width direction in the sixth heat setting zone. Next, the uncoated portions of both ends of the film are trimmed, wound up by a winder, further divided into four equal parts in the width direction, slitted, and the width is 1000 mm, the film length is 1000 m, and the film thickness is 125. A roll of adhesive modified polyester film of μm was obtained. The hot air velocity in the heat setting zone was 15 mZ seconds, the passage time was 4.5 seconds in each zone, the nozzle spacing for blowing hot air was 350 mm, and the number of nozzles per zone was 8.

[0319] Table 4 shows the physical properties and properties of the adhesion-modified base film. In addition, in the longitudinal direction and the width direction of the roll of the obtained adhesive-modified polyester film, the maximum, minimum, haze maximum, minimum, Table 5 shows the maximum and minimum adhesion to the coated layer. In addition, all the measurement points were anti-blocking.

[0320] (3) Manufacture of hard coat film

Next, a hard coat film was obtained by laminating a hard coat layer C containing inorganic fine particles on one surface of the adhesive modified layer B of the above-mentioned adhesive modified base film by the following method.

[0321] As a coating liquid for forming a hard coat layer, an ultraviolet curable acrylate monomer Mono-, Sani匕zirconium ultrafine particles, mainly composed of methyl E chill ketone, organic Z inorganic Ha Iburitsudo based hard coating agent CFSR Co., DeSolite Z7410B; solid concentration: 50 mass ^_0/0) were prepared. This hard coat agent was applied to the surface of the adhesion modified layer B of the adhesion modified substrate film so as to have a dry thickness of 8 m, and dried at 40 ° C. for 1 minute. Subsequently, ultraviolet rays were irradiated with a high-pressure mercury lamp under the condition of lOOOmiZcm ² to cure the resin and form a hard coat layer c.

The obtained hard coat layer contained 31 parts by mass of ultrafine zirconium oxide particles having an average particle diameter of 10 nm with respect to 100 parts by mass of attalylate resin.

[0322] (Example 2)

In Example 1, as the surfactant used in the coating solution, a 10% by mass aqueous solution of a fluorine-based cationic surfactant (manufactured by Neos Co., Ltd., Footgent 310) pretreated by the same method as in Example 1 was used. An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the coating solution B was changed.

Next, a hard coat film in which a hard coat layer C containing inorganic fine particles was laminated on one side was obtained in the same manner as in Example 1 on the surface of the adhesive modified layer B of the above adhesive modified base film. .

[Example 3]

In the heat setting process of Example 1, the temperature of each heat setting zone is 190 ° C in the first heat setting zone, 205 ° C in the second heat setting zone, 220 ° C in the third heat setting zone, 4 An adhesion-modified polyester film was obtained in the same manner as in Example 1 except that the heat setting zone was set to 220 ° C.

[0324] (Example 4)

In Example 1, the adhesive modified polyester was prepared in the same manner as in Example 1 except that the mass ratio of the copolyester and polyurethane in the coating solution was changed to the following coating solution C, which was changed to 60 Z40. A film was obtained. (Preparation of coating solution c)

9.0 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (A) used in Example 1 and 9.0 parts by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1; The catalyst (Daiichi Kogyo Seiyaku Co., Ltd., Cat64) 0.3 parts by mass, water 40.6 parts by mass, and isopropyl alcohol 37.3 parts by mass were mixed. Further, 0.6 part by mass of the surfactant aqueous solution used in Example 1 and a 20% by mass aqueous dispersion of colloidal silica (manufactured by Nissan Chemical Industries, Snowtex OL; average particle size 40 nm) as particle A 2. 3 parts by mass, particles B as a dry process silica (manufactured by Nippon Aerosil Co., Ltd., Aerosil OX50; average particle size 200 nm, average primary particle size 4 Onm) The pH was adjusted with a 5% by weight aqueous sodium bicarbonate solution, and a filter with a filtration performance of 5 m and 1 m was passed in this order to obtain coating solution C.

[0325] Next, a hard coat film in which a hard coat layer C containing inorganic fine particles is laminated on one surface on the surface of the adhesive modified layer B of the above-mentioned adhesive modified base film in the same manner as in Example 1. Got.

[Example 5]

In Example 1, the adhesive modified polyester was prepared in the same manner as in Example 1 except that the coating solution D was changed to the following coating solution D in which the mass ratio of the copolyester and polyurethane in the coating solution was changed to 40 Z60. A film was obtained.

(Preparation of coating solution D)

6.0 parts by mass of a 30% by mass aqueous dispersion of the copolyester (A) used in Example 1 and 13.5 parts by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1 The catalyst for use (Daiichi Kogyo Seiyaku, Cat64) 0.3 parts by mass, water 38.9 parts by mass, and isopropyl alcohol 37.5 parts by mass were mixed. Further, 0.6% by mass of a 10% by mass aqueous solution of the surfactant used in Example 1 and 20% by mass aqueous dispersion of colloidal silica (Nissan Chemical Industries, Snowtex OL; average particle size 40 nm) as particles A 2.3 parts by weight, 0.5 parts by weight of a 3.5% by weight aqueous dispersion of dry-process silica (manufactured by Nippon Aerosil Co., Ltd., Aerosil OX50; average particle diameter 200 nm, average primary particle diameter 40 nm) Then, the pH was adjusted to 6.2 with a 5% by weight aqueous sodium bicarbonate solution, and a filter with a filtration performance of 5 μm and 1 μm was passed in this order to obtain coating solution D. [0327] Next, in the same manner as in Example 1, a hard coat film in which a hard coat layer C containing inorganic fine particles is laminated on one surface is formed on the surface of the adhesive modified layer B of the adhesive modified substrate film. Got.

[Example 6]

In Example 1, an adhesive modified polyester film was obtained in the same manner as in Example 1 except that the coating amount was 0.12 gZm ² as the final solid content. Next, a hard coat film in which a hard coat layer C containing inorganic fine particles was laminated on one side was obtained in the same manner as in Example 1 on the surface of the adhesive modified layer B of the above adhesive modified base film. .

[0329] (Example 7)

The adhesive modified polyester film was prepared in the same manner as in Example 1 except that the following coating solution E was used, in which the amount of the surfactant in the coating solution was changed to 0.03% by mass in Example 1. Got.

(Preparation of coating solution E)

In preparation of the coating liquid of Example 1, 0.3 parts by mass of a 10% by mass aqueous solution of a fluorine-based nonionic surfactant (manufactured by Dainippon Ink and Chemicals, MegaFuck F142D) and 38 parts of water was added. 2 Mass parts and isopropyl alcohol were changed to 39.3 parts by mass.

[0330] Next, in the same manner as in Example 1, a hard coat film in which a hard coat layer C containing inorganic fine particles is laminated on one surface is formed on the surface of the adhesive modified layer B of the adhesive modified substrate film. Got.

[0331] (Example 8)

In Example 1, the amount of the surfactant in the coating solution was changed to 0.10% by mass, except that the following coating solution F was used. Le film was obtained.

(Formulation of coating solution F)

In preparation of the coating liquid of Example 1, 1.0 part by mass of 10 mass% aqueous solution of fluorine-based surfactant (Dainippon Ink & Chemicals, MegaFac F142D) and 37 parts of water were added. Changed 5 parts by mass and 39.3 parts by mass of isopropyl alcohol. [0332] Next, in the same manner as in Example 1, a hard coat film in which a hard coat layer C containing inorganic fine particles is laminated on one surface is formed on the surface of the adhesive modified layer B of the adhesive modified substrate film. Got.

[Example 9]

In Example 1, the passage time of the film from the coating to the entrance of the drying oven was 0.7 seconds, the drying time was 0.8 seconds, and the passage time of each zone in the heat setting treatment process was 3.5 seconds. An adhesion-modified polyester film was obtained in the same manner as in Example 1, except that the thickness was changed to 100 m.

[Example 10]

In Example 1, the passage time of the film from coating to the entrance of the drying furnace is 1.0 second, the drying time is 1.9 seconds, and the passage time of each zone in the heat setting process is 6.6 seconds. An adhesion-modified polyester film was obtained in the same manner as in Example 1 except that the thickness was changed to 188 m.

[0335] (Example 11)

In the same manner as in Example 1 except that the pH of the coating solution was changed to the coating solution G adjusted to 7.9 using a 5% by weight sodium carbonate aqueous solution, the adhesive modified polyester A film was obtained.

[Example 12]

In Example 1, adhesive modified layer B was applied to both sides of a uniaxially oriented polyester film. Except that, an adhesive modified polyester film was obtained in the same manner as in Example 1. The film transit time from the film application to the drying furnace inlet was 0.8 seconds on one side and 1.0 seconds on the other side.

[0337] A hard coat film was obtained in which the hard coat layer C was laminated on both sides of the above-mentioned adhesive modified base film via the adhesive modified layer B. The method for forming the hard coat layer C is as follows.

[0338] The hard coating agent containing inorganic particles used in Example 1 is applied to one surface of the adhesive modified layer B of the above-mentioned adhesive modified base film to a film thickness after curing of 3 m. As described above, it was applied with a Meyer bar and dried at 40 ° C for 60 seconds. In addition, irradiate 300mjZcm ² of ultraviolet rays.

The resin was cured to form a hard coat layer C on one side.

Next, the same hard coat agent as above is also applied to the surface of the adhesive modification layer B on the opposite side.

Then, it was applied with a Meyer bar so that the film thickness after curing was 3 m, and dried at 40 ° C for 60 seconds. Furthermore, 500 mjZcm ² ultraviolet rays were irradiated to cure the resin, and a hard coat layer C was formed on the other surface.

[Example 13]

In Example 1, an adhesion-modified polyester film was obtained in the same manner as in Example 1 except that the coating liquid H that had not been pretreated with the surfactant was used.

The phase separation structure of the polyester phase and the polyurethane phase by the scanning probe microscope (SPM) on the surface of the adhesive modified layer of the obtained adhesive modified polyester film can be distinguished but is somewhat unclear.

[0340] Next, in the same manner as in Example 1, a hard coat film in which a hard coat layer C containing inorganic fine particles is laminated on one surface is formed on the surface of the adhesive modified layer B of the above-mentioned adhesive modified substrate film. Got.

The phase separation structure of the polyester phase and the polyurethane phase in the adhesion modified layer B on the cutting surface of the obtained node coat film was also somewhat unclear, as described above.

[Example 14]

In Example 1, the adhesive-modified polyester was prepared in the same manner as in Example 1 except that the following coating liquid I was used in which the mass ratio of the dispersion medium (water ZIPA) in the coating liquid was changed to 50Z50. Obtained Finolem.

(Formulation of coating liquid I)

In preparation of the coating liquid of Example 1, 7.5 parts by weight of 30% by weight aqueous dispersion of the copolymerized polyester used in Example 1 and 20% by weight aqueous solution of polyurethane used in Example 1 13.3 parts by mass, elastron catalyst (Daiichi Kogyo Seiyaku Co., Ltd., Cat64) 0.3 parts by mass, water 30.4 parts by mass, and isopropyl alcohol 46.8 parts by mass. Further, 6 parts by weight 0.5 to 10% by weight aqueous solution of the surfactant used in Example 1, rollers Idarushirika as particles A (manufactured by Nissan Chemical Industries, Snowtex OL; average particle size 40 nm) 20 parts by mass ^_0/0 Water 2.3 parts by weight of the dispersion, 0.5 parts by weight of a 3.5% by weight aqueous dispersion of dry-process silica as particles B (manufactured by Nippon Aerosil Co., Ltd., Aerosil OX 50; average particle size 200 nm, average primary particle size 40 nm) The pH was adjusted to 6.2 with a 5% by weight aqueous sodium bicarbonate solution, and a filtration performance of 5 μm and a 1 μm filter were sequentially passed through to make coating solution I.

[0342] Next, in the same manner as in Example 1, a hard coat film in which a hard coat layer C containing inorganic fine particles is laminated on one surface is formed on the surface of the adhesive modified layer B of the adhesive modified substrate film. Got.

[0343] (Example 15)

In Example 1, the pH of the coating solution was changed to 4.6 with acetic acid. The adhesive modified polyester film having a thickness of 125 m was prepared in the same manner as in Example 1 except that coating! Got.

[Example 16]

In Example 1, an adhesive modified polyester film was obtained in the same manner as in Example 1 except that the coating liquid K was used in which the polyurethane (B) was changed to the following polyurethane. Polyurethane was obtained by the following method.

(Preparation of polyurethane)

Adipic acid ZZ 1.6-hexanediol Z Neopentyl glycol (molar ratio: 4Z Z3Z2) is mixed with 93 parts by mass of polyester diol (OHV: lll. 8eqZton, AV: 1. le qZton) and 22 parts by mass of xylylene diisocyanate. By reacting for a time, a urethane prepolymer (NCOZOH ratio: 1.50, free isocyanate group: theoretical value 3.29% by mass, actually measured value 3.16% by mass) was obtained.

[0345] The obtained urethane prepolymer was cooled to 60 ° C, added with 4.5 parts by mass of methyl ethyl ketoxime, reacted at 60 ° C for 50 minutes, and contained 1.3 mass% of free isocyanate. And a partially blocked urethane prepolymer was obtained. Subsequently, the urea prepolymer was cooled to 55 ° C., and a mixed solvent consisting of 9 parts by mass of isopropyl alcohol and 140 parts by mass of methanol was added and uniformly mixed. Subsequently, 9.3 parts by mass of a 50% by mass aqueous sodium bisulfite solution and 5.4 parts by mass of a 30% by mass aqueous solution of N-methyltaurine were added and vigorously stirred. Water solubility began to appear after about 30 minutes, and free sodium bisulfite became almost zero after 2 hours, and the reaction was completed. Water was added to this to obtain a 20% by mass aqueous solution that was cloudy and viscous.

[0346] Next, a hard coat film in which a hard coat layer C containing inorganic fine particles is laminated on one surface on the surface of the adhesive modified layer B of the above-mentioned adhesive modified base film in the same manner as in Example 1. Got.

[0347] (Comparative Example 1)

(1) Preparation of coating solution L

13.7 parts by weight of dimethyl terephthalate, 20.0 parts by weight of dimethyl isophthalate, 9.1 parts by weight of 5-Na sulfodimethylisophthalate, 40.0 parts by weight of ethylene glycol, 10.0 parts by weight of ethylene glycol, Calcium acetate monohydrate 0.049 parts by mass was mixed, and transesterification was performed at 200 to 230 ° C. until the theoretical amount of methanol was distilled off. Next, 0.09 part by mass of orthophosphoric acid was added and polymerized at 280 ° C. under reduced pressure to obtain a copolyester.

[0348] polyethers containing sulfonate groups the polyether Echirenokishido that starting sulfonated metabisulfite sodium from § Lil alcohol (SO content: 8.3 mass ^_0/0

Three

, Polyethylene O dimethylsulfoxide content: 83 mass ^_0/0) 192 parts by weight, polytetramethylene adipate base over preparative (number average molecular weight: 2, 250) 1013 parts by weight, polypropylene No sulfoxide polyether initiated by bisphenol A ( Number average molecular weight: 550) 248 parts by mass are mixed and 100 ° C under vacuum And dehydrated.

[0349] The mixture was brought to 70 ° C, and a mixture of 178 parts by mass of isophorone diisocyanate and 244 parts of hexamethylene-1,6-diisocyanate was added thereto, and then the resulting mixture was mixed with an isocyanate content of 5 It stirred in the range of 80 to 90 degreeC until it became 6 mass%. The prepolymer was cooled to 60 ° C., and 56 parts by mass of biuret polyisocyanate obtained from 3 mol of hexamethylene diisocyanate and 1 mol of water, and 175 parts by mass of bischemitin capable of obtaining isophorodiamine and acetone power were added. A polyurethane aqueous dispersion was obtained in this order.

[0350] The above-mentioned copolymerized polyester and polyurethane aqueous dispersion were blended so that the solid content would be 20 parts by mass and 80 parts by mass, respectively, and an aqueous dispersion having a solid content concentration of 10% by mass was prepared and coated. Liquid. In the coating solution, particles and a surfactant were not blended.

[0351] (2) Production of adhesive modified substrate film

Polyethylene terephthalate resin pellets containing no particles and having an inherent viscosity of 0.66 dlZg as a raw material polymer were dried under reduced pressure (lTorr) at 135 ° C for 6 hours, and then supplied to an extruder at about 285 ° C. It was melt extruded into a sheet and rapidly cooled and solidified on a metal roll maintained at a surface temperature of 60 ° C to obtain a cast film. At this time, a stainless-steel sintered filter medium having a filtration particle size (initial filtration efficiency: 95%) force of 15 m was used as a filter medium for removing foreign substances in the molten resin as in Example 1.

[0352] Next, the cast film was heated to 95 ° C with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a difference in peripheral speed, to obtain a uniaxially oriented PET film. I got an Irum. Next, the coating liquid L was finely filtered with a felt type polypropylene filter medium having a filtration particle size (initial filtration efficiency 95%) of 10 μm, and applied to one side of a uniaxially oriented PET film by a reverse roll method. Subsequently, the edge of the film was gripped with a clip and guided to a hot air zone heated to 110 ° C. After drying, the film was stretched 3.5 times in the width direction. The wind speed in the tenter at this time was 15 mZ seconds and the drying time was 20 seconds. The time from application to the film to the tenter entrance was 10.0 seconds. The coating amount was 0.15 g / m ² as the final solid content.

[0353] Next, while maintaining the width of the film stretched in the width direction, the first heat setting zone (200 ° C), the second heat setting zone (205 ° C), the third heat setting zone, and the fourth heat setting zone Heat setting zone (210 ° C), no. 5th heat setting zone (215 ° C), 6th heat setting zone (220 ° C), 7th heat setting zone (170 ° C) were sequentially passed. Furthermore, after 3% relaxation treatment in the width direction in the seventh heat setting zone, the uncoated portions at both ends of the film were trimmed to obtain an adhesiveness-modified polyester film having a thickness of 125 m. The hot air velocity in the heat setting zone was 15 mZ seconds, the passage time was 4.5 seconds in each zone, the nozzle spacing for blowing hot air was 700 mm, and the number of nozzles per zone was four.

The phase separation structure between the copolyester and the polyurethane was unclear over the surface of the adhesion modified layer of the obtained adhesion modified polyester film.

[0354] (3) Manufacture of hard coat film

[0355] (Comparative Example 2)

(1) Preparation of coating solution M

3.0 parts by mass of a 30% by mass aqueous dispersion of the copolyester (A) used in Example 1 and 18.0 parts by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1; The catalyst for use (Daiichi Kogyo Seiyaku, Cat64) 0.3 parts by mass, water 70.7 parts by mass, and isopropyl alcohol 4.7 parts by mass were mixed. Furthermore, 0.6% by mass of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid as a surfactant and 20% by mass aqueous dispersion of colloidal silica (Nissan Chemical Industries, Snowtex OL; average particle size 40 nm) as particle A 2.3 parts by weight of dry silica as particle B (manufactured by Nippon Aerosil Co., Ltd., Aerosil OX50; average particle size 200 nm, average primary particle size 40 nm) The coating liquid was M. The pH of coating solution M was 4.8 because pH was not adjusted.

[0356] (2) Production of adhesive modified substrate film

Polyethylene terephthalate resin pellets containing no particles used in Example 1 and having an intrinsic viscosity of 0.62 dl / g as a raw material polymer were dried at 135 ° C for 6 hours under reduced pressure (lTorr), and then supplied to an extruder. A cast film was obtained by melting and extruding into a sheet at about 285 ° C and rapidly solidifying on a metal roll maintained at a surface temperature of 20 ° C. At this time, the molten resin As a filter medium to be removed, a sintered sintered filter medium made of stainless steel having a filter particle size (initial filtration efficiency: 95%) of 15 m was used.

[0357] The obtained cast film was heated to 95 ° C with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a difference in peripheral speed to obtain a uniaxially oriented PET film. I got an Irum. Next, the coating liquid M was microfiltered with a felt type polypropylene filter medium having a filtration particle size (initial filtration efficiency: 95%) of 10 μm, and applied to one side of a uniaxially oriented PET film by a reverse roll method.

[0358] Subsequently, while holding the edge of the film with a clip, the film was guided to a hot air zone heated to 80 ° C, dried, and then stretched 4.0 times in the width direction. The wind speed in the tenter at this time was 15 mZ seconds, and the drying time was 20 seconds. As for the coating force, the time to the tenter entrance was 10.0 seconds. The coating amount was set to 0.1 lOgZm ² as the final solid content. Furthermore, the temperature in each heat setting process is 200 ° C in the first heat setting zone, 210 ° C in the second heat setting zone, 220 ° C in the third heat setting zone, and 225 ° C in the fourth heat setting zone. Comparative example, except that 230 ° C in the 5th heat setting zone, 235 ° C in the 6th heat setting zone, and 240 ° C in the 7th heat setting zone In the same manner as in 1, an adhesion-modified polyester film having a film thickness of 125 μm was obtained.

A phase separation structure between the polyester phase and the polyurethane phase was not observable on the surface of the adhesion modified layer of the obtained adhesion modified polyester film.

[0359] (3) Production of hard coat film

The phase separation structure of the polyester phase and the polyurethane phase in the adhesion modified layer B on the cut surface of the obtained node coat film also had an unobservable force as described above.

[0360] (Comparative Example 3)

(1) Preparation of coating solution N

7.5 parts by mass of a 30% by mass aqueous dispersion of the copolyester (A) used in Example 1 and 11.3 parts by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1 Touch 0.3 parts by mass of medium (Daiichi Kogyo Seiyaku Co., Ltd., Cat64), 40.5 parts by mass of water, and 39.5 parts by mass of isopropyl alcohol were mixed. Furthermore, 0.6% by mass of 10% by weight aqueous solution of non-pretreated fluoro-based surfactant (Dainippon Ink Chemical Co., Ltd., MegaFac F142D), without using particle B, particle A As a coating solution N, 0.03 parts by mass of a 3.5 mass% aqueous dispersion of aggregate silica (manufactured by Fuji Silicon Chemical Co., Ltd., Silica 310; average particle size of 1.4 / zm) was added. The pH of coating solution N was not adjusted. The pH of the coating liquid N was 4.6.

[0361] (2) Production of adhesive modified base film

Polyethylene terephthalate resin pellets containing no particles used in Example 1 and having an intrinsic viscosity of 0.62 dl / g were fed to the extruder as a raw material polymer, melted and extruded into a sheet at about 285 ° C, and the surface temperature was The film was rapidly cooled and solidified on a metal roll kept at 20 ° C to obtain a cast film. At this time, a stainless sintered filter medium having a filtration particle size (initial filtration efficiency: 95%) force of 15 m was used as a filter medium for removing foreign substances from the molten resin.

[0362] The obtained cast film was heated to 95 ° C with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a difference in peripheral speed to obtain a uniaxially oriented PET film. I got an Irum. Next, the coating liquid L was finely filtered with a felt type polypropylene filter medium having a filtration particle size (initial filtration efficiency: 95%) of 10 μm, and applied to one side of a uniaxially oriented PET film by a reverse roll method.

[0363] After coating, the solution was introduced into a drying oven and dried at 120 ° C for 3.2 seconds. The coating amount was set to 0.08 gZm ² as the final solid content. The coating time was 3.2 seconds for the film to pass to the drying oven. In addition, the wind speed of the first zone of the drying furnace is 15 mZ seconds, the second zone force is the same as the fourth zone, and the air velocity of the fourth zone is the same as in Example 1. Both were 70m ³ Z seconds, and the exhaust air was naturally exhausted from the front and back of the drying furnace.

[0364] Subsequently, the film was stretched in the same manner as in Example 1 except that the transverse draw ratio was 4.0 times, and subjected to heat fixing and relaxation treatment in the width direction in the same manner as in Comparative Example 1. An adhesive modified polyester film having a thickness of 125 m was obtained. The phase separation structure of the polyester phase and the polyurethane phase on the surface of the adhesion modified layer of the obtained adhesion modified polyester film is I couldn't observe it.

[0365] (3) Manufacture of hard coat film

Similarly to the above, the phase separation structure of the polyester phase and the polyurethane phase in the adhesion modified layer B on the cutting surface of the obtained node coat film also had an unobservable force.

[0366] (Comparative Example 4)

In Example 1, the film thickness was 125 in the same manner as in Example 1 except that the passage time of the film from application of coating solution A to the drying furnace was 3.2 seconds. m adhesive modified polyester film was obtained.

[0367] (Comparative Example 5)

3.0 parts by mass of a 30% by mass aqueous dispersion of the copolyester (A) used in Example 1 and 18.0 parts by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1; The catalyst (Daiichi Kogyo Seiyaku Co., Ltd., Cat64) 0.3 parts by mass, water 37.3 parts by mass, and isopropyl alcohol 37.8 parts by mass were mixed. Further, 0.6% by mass of a 10% by mass aqueous solution of the surfactant used in Example 1 and 20% by mass aqueous dispersion of colloidal silica (Nissan Chemical Industries, Snowtex OL; average particle size 40 nm) as particles A 2.3 parts by weight, 0.5 parts by weight of a 3.5% by weight aqueous dispersion of dry-process silica (manufactured by Nippon Aerosil Co., Ltd., Aerosil OX50; average particle diameter 200 nm, average primary particle diameter 40 nm) Then, the pH was adjusted to 6.2 with a 5% by mass aqueous sodium bicarbonate solution to obtain coating solution O. As a coating solution, an adhesive modified polyester Finolem having a film thickness of 125 m was obtained in the same manner as in Example 1 except that the coating solution O was used.

[0368] Next, in the same manner as in Example 1, a hard coat layer C containing inorganic fine particles is laminated on one surface on the surface of the adhesion modified layer B of the above adhesive modified substrate film. I got a film.

[0369] (Comparative Example 6)

12.0 parts by mass of a 30% by mass aqueous dispersion of the copolyester (A) used in Example 1 and 4.5 parts by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1 for elastron A catalyst (Daiichi Kogyo Seiyaku Co., Ltd., Cat64) 0.3 parts by mass, water 42.3 parts by mass and isopropyl alcohol 37.2 parts by mass were mixed, and the surfactant used in Example 1 was further mixed. 0.6 parts by weight of 10% by weight aqueous solution, 2.3 parts by weight of 20% aqueous dispersion of colloidal silica (Nissan Chemical Industries, Snowtex OL; average particle size 40 nm) as particles A, dry as particles B 0.5% by weight of a 3.5% by weight aqueous dispersion of silica (manufactured by Nippon Aerosil Co., Ltd., Aerosil OX50; average particle size 200nm, average primary particle size 40nm) is added with 5% by weight aqueous sodium bicarbonate solution to pH 6. It adjusted to 2 and it was set as the coating liquid P. An adhesive modified polyester film having a film thickness of 125 m was obtained in the same manner as in Example 1 except that the coating liquid P was used as the coating liquid.

[0370] Next, a hard coat film in which a hard coat layer C containing inorganic fine particles is laminated on one surface on the surface of the adhesive modified layer B of the above-mentioned adhesive modified base film in the same manner as in Example 1. Got.

[0371] (Comparative Example 7)

In Example 1, the temperature in each heat setting treatment step is 190 in the first heat setting zone. C. Adhesion modification with a film thickness of 125 m was performed in the same manner as in Example 1 except that the temperature was 195 ° C in the second heat setting zone and 200 ° C in the third heat setting zone to the fifth heat setting zone. A quality polyester film was obtained. The phase separation structure of the polyester phase and the polyurethane phase could not be observed on the surface of the adhesion modified layer of the obtained adhesion modified polyester film.

[0372] Next, a hard coat film in which a hard coat layer C containing inorganic fine particles is laminated on one surface on the surface of the adhesive modified layer B of the above-mentioned adhesive modified base film in the same manner as in Example 1. Got.

The phase separation structure of the polyester phase and the polyurethane phase in the adhesion modified layer B on the cut surface of the obtained node coat film also had an unobservable force as described above. [0373] (Comparative Example 8)

In Example 1, an adhesive modified polyester film having a film thickness of 125 μm was obtained in the same manner as in Example 1 except that the wind speed in the drying furnace was 15 mZ seconds.

[0374] (Comparative Example 9)

In Example 1, an adhesive modified polyester film having a film thickness of 125 m was obtained in the same manner as in Example 1 except that the coating amount was 0.20 gZm ² as the final solid content. It was.

[0375] (Comparative Example 10)

In Example 1, the same procedure as in Example 1 was used except that the coating solution Q was adjusted to a pH of 9.0 with 5% by weight aqueous sodium carbonate solution. A modified polyester film was obtained.

[0376] (Comparative Example 11)

In Example 1, the same procedure as in Example 1 was used except that coating solution R prepared without adding a surfactant to the coating solution was used. Polyester Steno Reinolem was obtained.

[0377] (Example 17) 7.5 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (A) used in Example 1 and 11.3 parts by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1 The catalyst (Daiichi Kogyo Seiyaku Co., Ltd., Cat64) 0.3 parts by mass, water 40.5 parts by mass and isopropyl alcohol 39.5 parts by mass were mixed. Further, 0.6 parts by mass of a 10% by mass aqueous solution of the surfactant used in Example 1 and particles A as aggregate silica (manufactured by Fuji Silicon Chemical Co., Ltd., Silicia 310; average particle size 1.4 / zm ), And 3.3 parts by weight of an aqueous dispersion of 3.5% by weight, adjust the pH to 6.2 with a 5% by weight aqueous sodium bicarbonate solution, and pass through a 5 m and 1 m filter in order. The coating solution S was obtained. Particle B was not mixed with the coating solution. An adhesive modified polyester film having a film thickness of 125 m was obtained in the same manner as in Example 1 except that the coating solution S was used.

[0378] Next, a hard coat film in which a hard coat layer C containing inorganic fine particles is laminated on one surface on the surface of the adhesive modified layer B of the above-mentioned adhesive modified base film in the same manner as in Example 1. Got.

[0379] (Comparative Example 12)

In Example 1, the film thickness was determined in the same manner as in Example 1 except that the coating liquid T prepared so that only the amount of the surfactant in the coating liquid was 0.60% by mass in solid content was used. A 125 m adhesive modified polyester film was obtained.

[0380] (Example 18)

In Example 1, the temperature in each heat setting treatment step is 200 in the first heat setting zone. C, 210 ° C in the 2nd heat setting zone, 215 ° C in the 3rd heat setting zone, 220 ° C in the 4th heat setting zone, 225 ° C in the 5th heat setting zone, 230 in the 6th heat setting zone The film was coated on both ends in the same manner as in Example 1 except that the temperature was 170 ° C in the seventh heat setting zone, and 3% relaxation treatment was performed in the width direction in the seventh heat setting zone. An adhesive modified polyester film having a film thickness of 125 μm was obtained by trimming the unexposed portion.

Next, on the surface of the adhesion modified layer B of the above-mentioned adhesion modified substrate film, Example 1 and Similarly, a hard coat film in which a hard coat layer c containing inorganic fine particles was laminated on one side was obtained.

[0381] (Comparative Example 13)

In Example 1, 7.5 parts by mass of a 30% by mass aqueous dispersion of the copolyester (A) used in Example 1 and a 20% by mass aqueous solution of the polyurethane (B) used in Example 1 11.3 parts by mass, elastron catalyst (Daiichi Kogyo Seiyaku Co., Ltd., Cat64) 0.3 parts by mass, water 51.0 parts by mass and isopropyl alcohol 26.2 parts by mass were mixed. Sarasako, 0.6% by weight of 10% by weight aqueous solution of the surfactant used in Example 1, 20% by weight of colloidal Siri force (Nissan Chemical Industries, Snowtex OL; average particle size 40nm) as particles A 2.3 parts by mass of an aqueous dispersion and 0.5 parts by mass of a 3.5% by mass aqueous dispersion of dry-process silica (Nippon Aerosil, Aerosil OX50; average particle size 200 nm, average primary particle size 40 nm) as particles B An adhesion-modified polyester film was obtained in the same manner as in Example 1 except that the pH was adjusted to 6.2 with a 5% by weight aqueous sodium bicarbonate solution and the coating solution U was used.

[0382] (Comparative Example 14)

In Example 1, as a hard coat agent, a hard coat layer (Seika Beam EXF-01B, manufactured by Dainichi Seika Co., Ltd.), which does not contain inorganic fine particles and is composed of a solvent-diluted photo-curing acrylated resin. A hard coat film in which a hard coat layer not containing inorganic fine particles was laminated on one side was obtained in the same manner as in Example 1 except that it was used.

The obtained node coat film was excellent in adhesion between the hard coat layer and the adhesion modified layer, but the hardness decreased and the curl increased.

[0383] (Example 19)

In preparation of the coating solution of Example 1, a fluorine-based non-on type surfactant (Dainippon Ink & Chemicals, MegaFac F142D) in place of a 10% by mass aqueous solution was used. Adhesive modified polyester film in the same manner as in Example 1 except that 5% by weight aqueous solution of an activator (Dainippon Ink & Chemicals, MegaFuck F444) was used and coating liquid V was used. Got. Next, a hard coat film in which a hard coat layer C containing inorganic fine particles is laminated on one surface is formed on the surface of the adhesive modified layer B of the above-mentioned adhesive modified base film in the same manner as in Example 1. Obtained.

[0384] (Example 20)

In Example 1, an adhesive modified polyester film was obtained in the same manner as in Example 1 except that the adhesive modified layer B was applied to both sides of the uniaxially oriented polyester film. The film transit time from the film application to the drying furnace inlet was 0.8 seconds on one side and 1.0 seconds on the other side.

[0385] A prism lens film is obtained in which a hard coat layer C is laminated on one side and a prism lens sheet layer D is laminated on the other side of the above-mentioned adhesive modified base film via an adhesive modified layer B. The

First, a method for forming the hard coat layer C will be described.

The hard coating agent containing inorganic particles used in Example 1 is applied to one surface of the adhesive modified layer B of the above adhesive modified base film so that the film thickness after curing is 3 m. It was applied with a Meyer bar and dried at 40 ° C for 60 seconds. Furthermore, 300 mjZcm ² of ultraviolet rays were irradiated and cured to form a hard coat layer C on one side.

Next, a method for forming the prism lens layer D will be described.

After injecting an ultraviolet ray curing type resin solution CFSR Corporation Desolite Z9590) into a molding die cut with a prismatic reverse mold with a pitch of 0.05 mm and a vertex angle of 90 °, the above hard coat layer On the surface of the adhesive modification layer B opposite to C, the above mold was overlaid. Next, from the hard coat layer C side, ultraviolet rays of 80 wZcm were irradiated by an ultraviolet lamp (output: 6.4 kw) to cure the resin, and then peeled to form a prism lens layer.

[0388] (Example 21)

In Example 1, an adhesive modified polyester film was obtained in the same manner as in Example 1 except that the adhesive modified layer was applied to both sides of the uniaxially oriented polyester film. The film transit time from the film application to the drying furnace inlet was 0.8 seconds on one side and 1.0 seconds on the other side.

[0389] A hard coat on one side of the above-mentioned adhesive modified base film via an adhesive modified layer B A light diffusing film in which the layer c was laminated with the light diffusing layer i on the other surface was obtained.

First, a method for forming the hard coat layer C will be described.

[0391] Next, a method of forming the light diffusion layer D 'will be described.

The coating solution for light diffusion layer shown below was applied to the surface of the adhesion modifying layer B opposite to the hard coat layer C and dried at 130 ° C. for 3 minutes.

[0392] (Composition of coating solution for light diffusion layer)

(a) Particle [26.3 parts by mass]

Spherical acrylic resin particles (Eposta MA1010, manufactured by Nippon Shokubai Co., Ltd .; average particle size 10 / z m)

(b) Resin [19.5 parts by mass]

Acrylic binder resin solution (Made by Mitsubishi Rayon Co., Ltd., Dianar LR-10 65; solid content concentration: 45% by mass)

(c) Solvent [54. 2 parts by mass]

• Methyl ethyl ketone [24.2 parts by mass]

• Propylene glycol monomethyl ether [15.0 parts by mass]

'Propylene glycol monomethyl ether acetate [15.0 parts by mass]

[0393] (Example 22)

In Example 1, an adhesive modified polyester film was obtained in the same manner as in Example 1 except that the coating amount was 0.02 gZm ² as the final solid content.

[0394] (Example 23)

In Example 1, as a coating device, the capacity of the receiving tray of the coating liquid, the capacity of the circulation tank And the ratio of the mixing tank capacity is the same as in Example 1 except that a coating apparatus having the following conditions is used. The film has a length force of S2000 m, a width of 1000 mm, and a thickness of 125 μm. A roll of adhesive modified polyester film was obtained.

(a) Capacity of coating solution tray Capacity of Z circulation tank = 1/5

(b) Capacity of circulation tank Capacity of Z preparation tank = 1Z50

(c) Roundness and cylindricity of application roll and metering roll: 6Zl000mm

(d) No pinch roll installed between coater and drying oven

[0395] Next, a hard coat film in which a hard coat layer C containing inorganic fine particles is laminated on one surface on the surface of the adhesive modified layer B of the above-mentioned adhesive modified base film in the same manner as in Example 1. Got.

[0396] In Examples 1 to 23 and Comparative Examples 1 to 14, the composition and characteristics of the coating solution are shown in Table 1, the coating-drying conditions are shown in Table 2, the heat setting conditions are shown in Table 3, and the adhesive modification group Table 4 shows the physical properties and characteristics of the material film. In addition, the maximum and minimum PEs surface fraction, maximum and minimum haze values, and maximum adhesion to the hard coat layer in the longitudinal and width directions of the resulting adhesive-modified polyester film roll. Table 5 shows the minimum values. The blocking resistance was ◯ at all measurement points.

[0397] [Table 1]

Coating liquid composition Coating liquid Resin particles P1 particles P2 Solvent Surfactant

Copolymerization average addition average addition average addition pre-formulation

Water / IPA PH ί J PEs / PU Particle size Particle size Type

Mass ratio

Mass ratio of

jum mass% jum mass% mass ¾ mass% Example 1 50/50 0.04 0.45 0.20 0.02 60/40 Nonion Exist 0.06 6.2 5.30 Example 2 50/50 0.04 0.45 0.20 0.02 60/40 Power control Yes 0.06 6.2 5.30 Example 3 50/50 0.04 0.45 0.20 0.02 60/40 Noni talent Yes 0.06 6.2 5.30 Example 4 60/40 0.04 0.45 0.20 0.02 60/40 Noni talent Yes 0.06 6.2 5.30 Example 5 40/60 0.04 0.45 0.20 0.02 60 / 40 Noni talent Yes 0.06 6.2 5.30 Example 6 50/50 0.04 0.45 0.20 0.02 60/40 Noni talent Yes 0.06 6.2 5.30 Example F 50/50 0.04 0.45 0.20 0.02 60/40 Nonion Yes 0.03 6.2 5.30 Example 8 50/50 0.04 0.45 0.20 0.02 60/40 Nonion Yes 0.10 6.2 5.30 Example 9 50/50 0.04 0.45 0.20 0.02 60/40 Noni Yes Yes 0.06 6.2 5.30 Example 10 50/50 0.04 0.45 0.20 0.02 60/40 Noni Yes 0.06 6.2 5.30 Example 11 50/50 0.04 0.45 0.20 0.02 60/40 Non-unique Yes 0.06 7.9 5.30 Example 12 50/50 0.04 0.45 0.20 0.02 60/40 Non-unique Yes 0.06 6.2 5.30 Example 13 50 / 50 0.04 0.45 0.20 0.02 60/40 0.06 6.2 5.30 Example 14 50/50 0.04 0.45 0.20 0.02 50/50 Nonion Yes 0.06 6.2 5.30 Example 15 50/50 0.04 0.45 0.20 0.02 60/40 Nonion Yes 0.06 4.6 5.30 Example 16 50/50 0.04 0.45 0.20 0.02 60/40 Nonion Yes 0.06 6.2 5.30 Example 17 50/50 1.4 3.0 0.20 0.02 60/40 Nonion Yes 0.06 6.2 5.30 Example 18 50/50 0.04 0.45 0.20 0.02 60/40 Nonion Yes 0.06 6.2 5.30 Example 19 50/50 0.04 0.45 0.20 0.02 60/40 Noni talented 0.03 6.2 5.30 Example 20 50/50 0.04 0.45 0.20 0.02 60/40 Noni talented 0.06 6.2 5.30 Example 21 50/50 0.04 0.45 0.20 0.02 60 / 40 Nonion Yes 0.06 6.2 5.30 Example 22 50/50 0.04 0.45 0.20 0.02 60/40 Noni Gen Yes Yes 0.06 6.2 5.30 Example 23 50/50 0.04 0.45 0.20 0.02 60/40 Nonion Yes 0.06 6.2 5.30 Comparative Example 1 20/80 100/0 Nonion-10.00 Comparative Example 2 20/80 0.04 0.36 0.20 0.04 95/5 Fans to 0.06 4.8 10.93 Comparative Example 3 50/50 1.4 0.02 60/40 Noni 0.06 4.6 4.87 Comparative Example 4 50/50 0.04 0.45 0.20 0.02 6 0/40 Noni talent Yes 0.06 6.2 5.30 Comparative example 5 20/80 0.04 0.45 0.20 0.02 60/40 Noni talent Yes 0.06 6.2 5.30 Comparative example 6 80/20 0.04 0.45 0.20 0.02 60/40 Noni talent Yes 0.06 6.2 5.30 Comparative Example 7 50/50 0.04 0.45 0.20 0.02 60/40 Nonni Presence 0.06 6.2 5.30 Comparative Example 8 50/50 0.04 0.45 0.20 0.02 60/40 Noni Presence 0.06 6.2 5.30 Comparative Example 9 50/50 0.04 0.45 0.20 0.02 60/40 Nonion Yes 0.06 6.2 5.30 Comparative Example 10 50/50 0.04 0.45 0.20 0.02 60/40 Nonion Yes 0.06 9.0 5.30 Comparative Example 11 50/50 0.04 0.45 0.20 0.02 60/40--to 6.2 5.30 Comparative Example 12 50/50 0.04 0.45 0.20 0.02 60/40 Nonion Yes 0.60 6.2 5.30 Comparative Example 13 50/50 0.04 0.45 0.20 0.02 72/28 Noni Genius Yes 0.06 6.2 5.30 Comparative Example 14 50/50 0.04 0.45 0.20 0.02 60/40 Nonion Yes 0.06 6.2 5.30 2] Application Drying conditions

Immediately after application

Final drying process inlet Drying temperature Drying time Wind speed Passing time to coating amount (° C) (sec) (m / s)

(g / m ² )

(Seconds)

Example 1 0.8 135 1.0 30 0.08 Example 2 0.8 135 1.0 30 0.08 Example 3 0.8 135 1.0 30 0.08 Example 4 0.8 135 1.0 30 0.08 Example 5 0.8 135 1.0 30 0.08 Example 6 0.8 135 1.0 30 0.12 Example 7 0.8 135 1.0 30 0.08 Example 8 0.8 135 1.0 30 0.08 Example 9 0.7 135 0.8 30 0.08 Example 10 1.0 135 1.9 30 0.08 Example 11 0.8 135 1.0 30 0.08 Example 12 0.8 / 1.0 135 1.0 30 0.08 Example 13 0.8 135 1.0 30 0.08 Example 14 0.8 135 1.0 30 0.08 Example 15 0.8 135 1.0 30 0.08 Example 16 0.8 135 1.0 30 0.08 Example Π 0.8 135 1.0 30 0.08 Example 18 0.8 135 1.0 30 0.08 Example 19 0.8 135 1.0 30 0.08 Example 20 0.8 135 1.0 30 0.08 Example 21 0.8 135 1.0 30 0.08 Example 22 0.8 135 1.0 30 0.02 Example 23 0.8 135 1.0 30 0.08 Comparative Example 1 10 110 20 15 0.15 Comparative Example 2 10 80 20 20 0.10 Comparative Example 3 3.2 120 1.0 15 0.08 Comparative Example 4 3.2 135 1.0 30 0.08 Comparative Example 5 0.8 135 1.0 30 0.08 Comparative Example 6 0.8 135 1.0 30 0.08 Comparative Example 7 0.8 135 1.0 30 0.08 Comparative Example 8 0.8 135 1.0 15 0.08 Comparative Example 9 0.8 135 1.0 30 0.20 Comparative Example 10 0.8 135 1.0 30 0.08 Comparative Example 11 0.8 135 1.0 30 0.08 Comparative Example 12 0.8 135 1.0 30 0.08 Comparative Example 13 0.8 135 1.0 30 0.08 Comparative Example 14 0.8 135 1.0 30 0.08 3 ] Heat setting conditions

Heat setting temperature (° c)

# 1 # 2 # 3 # 4 # 5 # 6 # 7

V "-''-'',-'N''-'''-'',-''--(seconds) Example 1 200 225 230 230 210 170 120 4.5 Example 2 200 225 230 230 210 170 120 4.5 Example 3 190 205 220 220 210 170 120 4.5 Example 4 200 225 230 230 210 170 120 4.5 Example 5 200 225 230 230 210 170 120 4.5 Example 6 200 225 230 230 210 170 120 4.5 Example 7 200 225 230 230 210 170 120 4.5 Example 8 200 225 230 230 210 170 120 4.5 Example 9 200 225 230 230 210 170 120 3.5 Example 10 200 225 230 230 210 170 120 6.6 Example 11 200 225 230 230 210 170 120 4.5 Example 12 200 225 230 230 210 170 120 4.5 Example 13 200 225 230 230 210 170 120 4.5 Example 14 200 225 230 230 210 170 120 4.5 Example 15 200 225 230 230 210 170 120 4.5 Example 16 200 225 230 230 210 170 120 4.5 Example 17 200 225 230 230 210 170 120 4.5 Example 18 200 210 215 220 225 230 170 4.5 Example 19 200 225 230 230 210 170 120 4.5 Example 20 200 225 230 230 210 170 120 4.5 Example 21 200 225 230 230 210 170 120 4.5 Example 22 200 225 230 230 210 170 120 4.5 Example 23 200 225 230 230 210 170 120 4.5 Comparative Example 1 200 205 210 213 215 220 170 4.5 Comparative Example 2 200 210 220 225 230 235 240 4.5 Comparative Example 3 200 205 210 213 215 220 170 4.5 Comparative Example 4 200 225 230 230 210 170 120 4.5 Comparative Example 5 200 225 230 230 210 170 120 4.5 Comparative Example 6 200 225 230 230 210 210 170 120 4.5 Comparative Example 7 190 195 200 200 200 170 120 4.5 Comparative Example 8 200 225 230 230 210 170 120 4.5 Comparative Example 9 200 225 230 230 210 170 120 4.5 Comparative Example 10 200 225 230 230 210 170 120 4.5 Comparative Example 11 200 225 230 230 210 170 120 4.5 Comparative Example 12 200 225 230 230 210 170 120 4.5 Comparative Example 13 200 225 230 230 210 170 120 4.5 Comparative Example 14 200 225 230 230 210 170 120 4.5 4] Adhesive modified base film

Table 5] Adhesion of the modified adhesive layer with the HC layer ()

PEs Hayes (»

Phase area ratio Solvent-free HC layer Solvent dilution HC layer

(%) / Adhesive modified layer Adhesive modified layer Maximum value Minimum value Maximum value Minimum value Maximum value Minimum value Maximum value Minimum value Longitudinal direction 73 63 0. 59 0. 56 100 94 100 96 Example 1

Width direction 72 64 0. 59 0. 56 100 96 100 97 Longitudinal direction Ή 60 0. 6 0. 56 100 93 100 95 Example 23

Width direction 75 61 0. 6 0. 56 100 91 100 94 [0402] [Table 6]

Industrial applicability

[0403] The hard coat film of the present invention has excellent adhesion to the hard coat layer containing inorganic fine particles while maintaining high hardness, so that it is a prism lens sheet, a light diffusion film, an antireflection (AR ) Suitable as a base material for optical functional films for displays such as films, transparent conductive films, infrared absorbing films, electromagnetic wave absorbing films. In addition to the optical functional film for display, the hard coat film of the present invention can be used for applications requiring concealability. In that case, it is preferable to use a white film containing white pigments or cavities as the thermoplastic resin film of the substrate.

Claims

The scope of the claims

[1] An adhesive modified base film in which an adhesive modified layer B containing a copolymerized polyester and polyurethane is formed on one or both sides of a thermoplastic resin film A, and either one of the films A hard coat film having a layer structure of AZBZC or BZAZBZC, in which a hard coat layer C containing inorganic fine particles is laminated on the surface of the adhesion modified layer B of

Adhesive modified layer B has a micro phase separation structure or a nano phase separation structure of polyester (PEs) phase and polyurethane (PU) phase, and the cutting surface of the hard coat film is formed using a scanning probe microscope. When observed in phase measurement mode, the interfacial force between the adhesive modified layer B and the hard coat layer C is within the range of a depth of 20 nm. The polyurethane phase of the adhesive modified layer B is defined by the following formula (1). A hard coat film characterized by having an area ratio of 30% or more and 60% or less (showing a bright hue in a phase image).

PU phase area ratio (%) = (PU phase area Z measurement area) X 100 · · · (1)

[2] An adhesive modified substrate film in which an adhesive modified layer B containing a copolymerized polyester and polyurethane is formed on one side or both sides of a thermoplastic resin film A, and one or both sides of the film A hard coat film having a layer structure of AZBZC or BZAZBZC, in which a hard coat layer C containing inorganic fine particles is laminated on the surface of the adhesion modified layer B of

Adhesive modified layer B has a micro phase separation structure or a nano phase separation structure of polyester (PEs) phase and polyurethane (PU) phase, and the surface of adhesive modified layer B using a scanning probe microscope. Is observed in the phase measurement mode, the area ratio of the polyester phase (showing a dark hue in the phase image) on the surface of the adhesive reforming layer B defined by the following formula (2) is 5 m x 5 m Hard coat film characterized by being in the range of 35% or more and less than 90%.

[3] The hard coat film according to claim 1 or 2, wherein the content of the inorganic fine particles in the hard coat layer C is 20 to 80% by mass.

[4] The thermoplastic resin film does not contain particles, or contains 50 ppm or less, and the adhesion modified layer contains 0.1 to 20% by mass of particles. Described in Node coat of Finolem.

5. The hard coat film according to claim 4, wherein the particles are silica particles.

[6] The hard coat film according to claim 1 or 2 has a hard coat layer, a light diffusing layer, a prismatic lens layer, an electromagnetic wave absorbing layer, a near-infrared blocking layer, a transparent conductive film on the opposite side of the hard coat layer C. An optical functional final layer in which at least one optical functional layer selected from the layers is laminated.

[7] An optical functional film in which an antireflection layer or an antifouling layer is laminated on the hard coat layer C of the hard coat film according to claim 1 or 2.