KR100898255B1 - Hard coat film and optically functional film - Google Patents

Abstract

The present invention provides an adhesive modified base film having an adhesive modified layer B comprising copolymerized PEs and PU formed on one or both surfaces of the thermoplastic resin film A, and an adhesive modified layer B on any one of the films. A hard coat film in which the hard coat layer C containing inorganic fine particles is laminated on the surface of the adhesive coat layer, wherein the adhesive modifying layer B has a micro phase separation structure or a nano phase separation structure on the PEs phase and the PU phase, and also uses a scanning probe microscope. When the cutting surface of the hard coat film was observed in the phase measurement mode, the area ratio of the PU phase of the adhesive modified layer B in the range up to 20 nm at the interface between the adhesive modified layer B and the hard coat layer C was 30. It is related with the hard coat film characterized by the above-mentioned.

Description

Hard coat film and optically functional film {Hard coat film and optically functional film}

This invention is an optical function, such as a hard-coat film mainly used for a member for a display, an antireflection film, a light-diffusion sheet, a prism-like lens sheet, a near-infrared cut off film, a transparent conductive film, an anti-glare film, etc. using this film. It is about a film. In detail, it is excellent in adhesiveness with the hard-coat layer containing a base film and inorganic fine particles, and also another optical function layer (hard coat layer, light-diffusion layer, prism layer, infrared absorption layer, transparent conductive layer, anti-glare layer, etc.), Moreover, it is related with the hard-coat film excellent in scratch resistance, and the optical functional film using the same.

Generally, in the hard coat film used for display members, such as a liquid crystal display (LCD) and a plasma display panel (PDP), a thermoplastic resin film and a hard coat (HC) layer are laminated | stacked via the adhesive modified resin layer. . In addition, the optical function film for displays is bonded together using the optical function film from which a function differs generally through an adhesive layer, and is used. However, the demand for a large flat display from the market of the recent low price is increasing. For this reason, also in the member for display, development of the composite film which laminated | stacked the other optical function layer on one piece of hard-coat film is performed. For example, in a liquid crystal display (LCD), an optical film such as an antireflection layer (AR layer) that prevents reflection of external light, a prism-like lens layer used for condensing or diffusing light, and a light diffusion layer that improves luminance in a hard coat film. The optical composite functional film which laminated | stacked the functional layer is mentioned.

As the thermoplastic resin film serving as the base material of the hard coat film, a transparent film made of polyethylene terephthalate (PET), polyamide, acrylic, polycarbonate (PC), triacetyl cellulose (TAC), cyclic polyolefin, or the like is used. have. Among these base films, in particular, biaxially oriented polyester films are widely used as thermoplastic resin films of various optical functional films in terms of excellent transparency, dimensional stability, and chemical resistance.

In general, in the case of a biaxially oriented thermoplastic film such as a biaxially oriented polyester film or a biaxially oriented polyamide film, since the film surface is highly crystallized, there is a drawback that the adhesion to various paints, adhesives, inks and the like is insufficient. For this reason, the method of providing the easily adhesive property to the biaxially-oriented thermoplastic resin film surface by various methods conventionally has been proposed.

In addition, in a film having no polar group such as a polyolefin film, adhesion to various paints, adhesives, inks, etc. is very insufficient, and therefore, after physical treatment or chemical treatment such as corona discharge treatment or flame treatment is performed in advance. The method of providing easy adhesiveness to the film surface by various methods has been proposed.

For example, by providing an adhesive modified layer containing an adhesive modified resin such as a film, polyester, acrylic, polyurethane, acrylic graft polyester, etc. on the surface of the thermoplastic resin film by a coating method, Methods for imparting easy adhesion are generally known. Among these coating methods, an aqueous coating containing a dispersion in which the solution or resin of the resin is dispersed in a dispersion medium after performing corona discharge treatment directly or as necessary on the thermoplastic resin film before the crystal orientation is completed. The film is applied to a substrate film, and after drying, is stretched in at least one axial direction, and then subjected to heat treatment to complete the crystal orientation of the thermoplastic resin film (so-called inline coating method), or after production of the thermoplastic resin film, the film The method of drying after apply | coating the coating liquid of an aqueous system or a solvent system (so-called offline coating method) is industrially widely implemented.

Displays, such as LCDs and PDPs, have been enlarged and reduced in cost every year, and in the manufacturing process of the optical functional film used as the member, the production speed is made high. With the speed of such a manufacturing process, the stress accompanying hardening shrinkage became easy to generate | occur | produce in the interface of a functional film, such as a hard-coat layer, a diffusion layer, and a prism layer, and a base film. For this reason, when cutting an optical functional film to a specific size for manufacturing a display, when the adhesiveness in the said interface is inadequate, the problem that the edge part becomes easy to peel especially has arisen. The tendency is that the larger the size of the film wound in roll shape and the higher the production speed in the manufacturing process, the more noticeable the effect of interfacial peeling due to the impact during cutting becomes. It became insufficient.

Moreover, the processing agent used in order to form functional layers, such as a said prism layer and a diffusion layer, in many cases, apply | coats a processing agent directly to a base film, without diluting with an organic solvent from a viewpoint of reducing environmental load. For this reason, the wettability improvement effect of the adhesive modifying layer by the organic solvent may not be fully acquired, and higher adhesiveness is calculated | required. On the other hand, in the use which places importance on smoothness like a hard coat, in order to lower | hang the viscosity of a processing agent and to obtain a favorable leveling effect, the processing agent is often diluted with the organic solvent. In this case, appropriate solvent resistance is required for the adhesive modified layer of the adhesive modified base film.

In order to improve the adhesiveness between a functional layer and a base film, the method of using resin with low glass transition temperature is common for resin which comprises an adhesive modified layer. However, when resin with a low glass transition temperature is used, blocking resistance tends to fall when an adhesive modified base film is continuously wound up to roll shape, and the film is unwound from a roll shape film.

Moreover, in order to reduce cost recently, the enlargement of the processing machine for laminating | stacking functional layers, such as a hard-coat layer and a diffusion layer, to a base film advances, and the roll diameter of the easily adhesive film used as a base film is also enlarged. As a result, in the case where the roll is wound with a high tension force in order to prevent the roll from being skewed, the blocking is more likely to occur since the pressing is carried out at a high pressure, particularly at the core portion of the roll.

In order to improve blocking resistance, the method of giving unevenness | corrugation to the surface of an adhesive modified base film and making a contact area small is generally employ | adopted. In order to provide an unevenness | corrugation to a film surface, the method of increasing content of an inorganic particle or organic particle | grains contained in an adhesive modification layer or a base film, or the method of using particle | grains with a large particle size are common. However, since the refractive index of the particle | grains generally available among the things commercially available differs from the refractive index of resin used for an adhesive modification layer, and these voids are formed around a particle with extending | stretching process of a film, these methods In this case, a decrease in the light transmittance of the film, an increase in haze, and the like occur. In particular, transparency required for the base film of the optical functional film is lowered. That is, in the conventional method, it was very difficult to improve the adhesiveness and blocking resistance with a functional layer, maintaining transparency, by the new problem accompanying speeding up a process and increasing the roll diameter of a film.

In recent years, optically functional films have been provided with hard coat layers on both sides of a base film for the purpose of preventing adhesion to a light guide plate, increasing transmittance, or reducing curl, or a prism lens layer or light. In many cases, the hard coat layer is laminated on the surface opposite to the optical functional layer such as the diffusion layer. In particular, the hard coat film is usually formed of a thin cured coating film (hard coat layer) 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.

By the way, since the thickness of a hard-coat layer is thin compared with a base film, the hardness of a hard coat film itself does not become high enough under the influence of a base film. For this reason, in order to further improve the scratch resistance of a hard coat, including an inorganic particle in a hard coat layer is examined.

On the other hand, when an inorganic particle is contained in a hard coat layer, since the ratio of curable resin in a hard coat layer falls, the adhesiveness in the interface of the adhesive modified layer of an adhesive modified base film and a hard coat layer falls.

In particular, it is known that a biaxially oriented polyester film is inferior in adhesiveness with the coating agent mainly containing acrylic resin used for a prism lens, a hard coat, etc. For this reason, the thing which provided the adhesive modified layer which consists of polyurethane etc. on the surface of a polyester film is proposed variously (for example, refer patent document 1). However, in the case where the adhesive modified layer made of polyurethane is formed, the adhesion to functional layers such as the hard coat layer is improved, but the adhesion to the polyester film as the substrate is not sufficient, and as a result, the adhesive modified layer and The adhesiveness is insufficient at the interface of the functional layer. In particular, the adhesion of the interface between the adhesive modifying layer and the hard coat layer containing the inorganic particles is remarkably inferior.

Patent Document 1: Japanese Patent Application Laid-Open No. 6-340049

Moreover, the resin composition layer which has copolyester and a polyurethane as a main component is provided on the base film which becomes biaxially-oriented polyethylene terephthalate by the inline coat method, and is made with the functional layers, such as a base polyester film, and ink. The method of improving adhesiveness is proposed (for example, refer patent document 2). Specifically, after applying a water-dispersible coating liquid containing a copolyester and a polyurethane (= 20/80; mass%) to a polyester film uniaxially stretched in the longitudinal direction, it is led to a tenter and dried and transversely stretched. It heat-sets at and 220 degreeC, and the easily adhesive biaxially-oriented polyester film is obtained.

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

However, although the adhesiveness improves with the method of patent document 2, in recent years, the functional film, such as an adhesive modified layer and an inorganic particle, such as a base film, a hard-coat layer, and a diffusion layer, which are requested | required as a base film used for an optical functional film, are mentioned. The adhesiveness of the interface with the hard coat layer containing is inadequate.

Applicant has provided the resin composition layer which added the copolyester, polyurethane, and the inorganic particle of suitable particle diameter on the base film which consists of biaxially-oriented polyethylene terephthalates, and is transparency which is a very important characteristic as an optical base film. While maintaining this, the laminated polyester film which can fully satisfy the adhesiveness of the required level from a market | market, and had few optical defects was proposed (for example, refer patent document 3, 4). Specifically, a water dispersibility comprising a polyester film uniaxially stretched in the longitudinal direction, including copolyester, polyurethane (= 20/80; mass%), silica particles having different average particle diameters of two kinds, and anionic surfactants. After apply | coating a coating liquid, the easily adhesive biaxially-oriented polyester film obtained by carrying out by tenter, drying, and lateral stretching, and heat-setting at 240 degreeC was disclosed.

The easily-adhesive biaxially oriented polyester films obtained in Patent Literatures 3 and 4 had excellent adhesion, blocking resistance, and transparency, and optical defects such as foreign matters, scratches, and the like were greatly improved, thereby satisfying conventionally required characteristics. . However, as mentioned above, with recent cost reduction and the large screen of a display, adhesiveness of the base film requested as a base film for optical functional films, and functional layers, such as a hard-coat layer, a diffusion layer, and a prism layer, And the level of demand for blocking resistance tends to be strict every year. In particular, the adhesiveness of the interface between the adhesive modifying layer and the hard coat layer containing the inorganic particles has not been sufficiently satisfied with the current quality requirements.

Patent Document 3: Japanese Patent Application Laid-Open No. 11-323271

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

Moreover, this applicant proposed the invention regarding the easily-adhesive film roll which reduced the fluctuation | variation of application amount in order to improve the uniformity of adhesiveness (for example, refer patent document 5). The Example of patent document 5 contains the copolyester and polyurethane (= 50/50; mass%), the silica particle of 1.4 micrometers of average particle diameters, and a fluorine-type surfactant in the polyester film uniaxially stretched in the longitudinal direction. The easily-adhesive biaxially-oriented polyester film obtained by apply | coating a water-dispersible coating liquid, drying at 120 degreeC in a drying furnace, transversely stretching, and then heat-setting at 220 degreeC is described. The obtained film roll had the outstanding adhesiveness uniformly in the whole film roll, and satisfy | filled the required level from a market. However, the adhesiveness of the interface between the adhesive modifying layer and the hard coat layer containing the inorganic particles may not be sufficiently satisfied.

Patent Document 5: Japanese Patent Application Laid-Open No. 2004-10669

In addition, for the purpose of improving scratch resistance, an ionizing radiation-curable hard coat agent containing about 40 parts by mass of silica ultrafine particles having a particle size of about 50 nm or less with respect to 100 parts by mass of resin on an easily-adhesive polyethylene terephthalate film is dried at a thickness of about The hard coat film apply | coated so that it might become 15 micrometers, and hardened | cured with the electron beam is proposed (for example, refer patent document 6). However, although this hard coat film has a high hardness of the hard coat layer and is excellent in scratch resistance, the adhesiveness of the interface between the adhesive modifying layer and the hard coat layer containing inorganic particles is sufficiently sufficient for the current market demand quality. It was not enough.

Patent Document 6: Japanese Patent Application Laid-Open No. 2000-112379

On the other hand, the hard coat film which laminated | stacked the hard-coat layer which does not contain particle | grains in the easily-adhesive polyethylene terephthalate film which has an adhesive modified layer which consists of co-polyester and a melamine crosslinking agent is proposed (for example, patent document 7 Reference). However, this hard coat film cannot fully satisfy adhesiveness with a hard coat layer and the hardness of a hard coat layer.

Patent Document 7: Japanese Patent Application Laid-Open No. 2004-160774

That is, in the prior art, while maintaining a high hardness, a hard coat film excellent in adhesiveness that can withstand high-speed cutting recently demanded, in particular, adhesion with a hard coat layer containing inorganic particles, has not been obtained.

Disclosure of the Invention

Problems to be Solved by the Invention

An object of the present invention is to provide a hard coat film having a high degree of adhesiveness of an interface between an adhesive modifying layer and a hard coat layer containing inorganic particles and a high hardness and an optical functional film using the same.

Means to solve the problem

The said subject can be achieved by the following solutions.

That is, the 1st invention in this invention is the adhesive modified base film which formed the adhesive modified layer B which consists of copolyester and polyurethane in one or both surfaces of the thermoplastic resin film A, and the said film As a hard coat film containing the laminated constitution of A / B / C or B / A / B / C in which the hard-coat layer C containing inorganic microparticles | fine-particles was laminated | stacked on the surface of the adhesive modification layer B on either side, The adhesive modifying layer B has a micro phase separation structure or a nano phase separation structure on the polyester (PEs) phase and the 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 the time, the polyurethane phase of the adhesive modifying layer B, which is defined by the following formula 1 in a range up to 20 nm at the interface between the adhesive modifying layer B and the hard coat layer C, is light in phase: Color The area ratio of the produces) a hard coat film, characterized in that more than 60% to 30%.

Area ratio (PU) on PU = (area / measured area on PU) × 100... (One)

2nd invention is the adhesive modified base film which formed the adhesive modified layer B which consists of copolyester and a polyurethane on one side or both sides of the thermoplastic resin film A, and the adhesiveness of any one side of the said film. A hard coat film comprising an A / B / C or B / A / B / C layer configuration in which a hard coat layer C containing inorganic fine particles is laminated on the surface of the modified layer B, wherein the adhesive modified layer B is made of poly When the surface of the adhesive modifying layer B was observed in the phase measurement mode using a microscopic phase separation structure or nano phase separation structure on the ester (PEs) phase and the polyurethane (PU) phase, and using a scanning probe microscope, It is a hard coat film characterized by the area ratio of the polyester phase (it shows a dark color in a phase) of the surface of the adhesive modified layer B to be defined as 35% or more and less than 90% in the range of 5 micrometers x 5 micrometers.

% Area on PEs = (area on PEs / measured area) × 100... (2)

3rd invention is content of 20-80 mass% of inorganic fine particles in hard-coat layer C, It is a hard coat film as described in 1st or 2nd invention characterized by the above-mentioned.

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. Coat film.

5th invention is a hard coat film as described in 4th invention whose particle | grain is a silica particle.

6th invention selects from a hard-coat layer, a light-diffusion layer, a prism-shaped 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 of the hard-coat film of 1st or 2nd invention. It is an optical functional film in which one or more optical functional layers to be laminated are laminated.

7th invention is an optical functional film in which the antireflection layer or the antifouling layer was laminated on the hard coat layer C of the hard coat film according to the first or second invention.

Effects of the Invention

The hard coat film of the present invention is a middle layer of the thermoplastic resin film and the hard coat layer, and has a micro phase separation structure or a nano phase separation structure specific to a polyester phase and a polyurethane, and is hard at the cutting surface of the adhesive modified layer. The area ratio of the polyurethane phase in the vicinity of the interface with the coat layer is in a specific range. For this reason, even if the hard-coat layer containing inorganic fine particles is laminated, adhesiveness with a hard-coat layer can be improved, maintaining high hardness. Moreover, it is excellent in adhesiveness with optical functional layers, such as a diffusion layer and a prism layer.

Furthermore, by containing a specific amount of particles having a specific particle diameter only in the adhesive modifying layer, or localizing the particles on either the polyester phase or the polyurethane phase on the surface of the adhesive modifying layer, high transparency is maintained, Blocking resistance, handling resistance, and scratch resistance can be improved. Therefore, it is useful as a hard coat film and an optical functional film which highly require transparency. In particular, when the adhesive modifying layer contains silica particles, since the silica particles can be localized on the polyurethane, the drawback of the polyurethane having poor blocking resistance can be compensated for.

Brief description of the drawings

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing of the phase image which observed the surface of the adhesive modified layer of the adhesive modified base film used for the hard-coat film of this invention in the phase measurement mode of a scanning probe microscope.

FIG. 2 is an explanatory diagram of a phase image in which the contours of the light color and dark color interfaces are emphasized by image processing software in the phase image of FIG. 1.

FIG. 3 is an explanatory diagram of a phase image in which a dark color is seamlessly painted by image processing software in a phase phase in which the outline of the bright color and dark color interfaces of FIG. 2 is emphasized.

4 is an explanatory diagram showing a boundary line between a light color and a dark color in a phase image in which the contours of the light color and dark color interfaces of FIG. 2 are emphasized.

It is explanatory drawing which shows the height difference of the flaw at the time of measuring the surface shape of the flaw which arose on the surface of an adhesive modified layer in the wave mode using a three-dimensional non-contact surface shape measuring apparatus.

FIG. 6 shows that in Examples 1-23 and Comparative Examples 1, 4-6, and 8-14, the area ratio of the PEs on the surface of the adhesive modified layer and the PEs mass ratio in the resin component of the adhesive modified layer do not correspond. It is explanatory drawing which shows that it does not.

It is explanatory drawing which shows the arrangement | positioning of the base plate of a coating liquid, the tank for circulation, the tank for combination, and the circulation path of a coating liquid.

It is explanatory drawing of the phase image which observed the cutting surface of the adhesive modified layer at the time of cutting the hard coat film of this invention in the phase measurement mode of a scanning probe microscope, and emphasized contrast by performing color uniformity processing.

FIG. 9 is an explanatory diagram showing two red lines in a range in which a phase separation structure should be observed in a phase on which the color uniformity treatment of FIG. 8 is performed. FIG.

FIG. 10 is an explanatory diagram of a phase image binarized by image processing software with respect to the phase image of FIG. 8.

FIG. 11 is an explanatory diagram of a phase image in which two red lines of FIG. 9 are attached to the same position on the binarized phase of FIG. 10.

FIG. 12 is an explanatory diagram of a phase image in which portions not surrounded by two red lines are seamlessly painted in red with image processing software in the phase of FIG. 11.

Explanation of the sign

1: dark color (polyester phase mainly containing copolyester)

2: bright color (polyurethane phase mainly containing polyurethane)

3: projections caused by particles

4: Line highlighting the contours of the interface between the light and dark colors

5: profile curve of irregularities on the surface of the adhesive modified layer

6: bend of the scratch

7: the government of scratches

8: Example 1-23

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

10: coater

11: coating liquid saucer

12: die

13: tank for circulation

14: combination tank

15: base film

16: pinch roll

17: Hard Coat Layer C

18: adhesive modified layer B

19: thermoplastic resin film A

20: line showing the interface between the hard coat layer C and the adhesive modifying layer B

21: A line moved parallel from the interface 20 to a depth of 20 nm in the vertical direction inside the adhesive modified layer.

Implement the invention  Best form for

In this invention, the definition of the adhesiveness and hardness described in the subject is demonstrated first.

In the hard coat film of this invention, adhesiveness is the adhesion of a hard coat layer and a base film after repeating the board | substrate peeling test (100 grid | grid) with an adhesive tape 10 times to the hard-coat layer containing inorganic fine particles. It means the adhesiveness of the interface with a sex-modified layer. In the present invention, the adhesiveness defined by the following formula is 80% or more. It is preferably at least 85%, particularly preferably at least 90%.

Adhesiveness (%) = (1/100 peeled number of grid) × 100

In addition, in the adhesive modified base film used by this invention, with adhesiveness, the hard-coat layer which hardened the solvent dilution type photocurable acrylic resin by the ultraviolet-ray is formed in the adhesive modified layer of a film, and is attached to an adhesive tape. It means the adhesiveness of the interface of the acrylic hard-coat layer and the adhesive modified layer of a film after repeating the board | substrate peeling test (100 grid) by 10 times. In the present invention, the adhesiveness defined by the following formula is 80% or more. It is preferably at least 85%, particularly preferably at least 90%.

Adhesiveness (%) = (1/100 peeled number of grid) × 100

In addition, the hardness as used in this invention means "pencil hardness" evaluated by the pencil hardness test based on JIS-K5400. The pencil hardness is a pencil hardness test is repeated five times on the surface of the hard coat layer of the hard coat film, and when no abnormalities in appearance such as scratches are observed in any test, the hardness of the pencil used for the test pencil It is hardness. For example, if the test operation is performed five times using a 3H pencil and no external abnormality occurs once, the pencil hardness of the material is 3H.

In addition, the blocking resistance of the adhesive modified base film used by this invention overlaps the adhesive modified layer of two film samples so that it may oppose, and here the pressure of 1 kgf / cm <2> is 50 degreeC and 60% RH atmosphere. After contact | adhering for 24 hours under the following, it peels and the peeling state sets it as "the thing which can peel lightly without the transition of an adhesive modifying layer".

In addition, in this invention, the film highly highly transparent means the film whose haze is 1.5% or less. Preferably, haze is 1.0% or less.

In the adhesive modified base film used by this invention, in order to acquire the outstanding adhesiveness and blocking resistance, it is important to express the micro phase separation structure or nano phase separation structure specific on the surface of an adhesive modification layer. Furthermore, in the hard coat film of this invention, in order to improve the adhesiveness of the adhesive modified layer of an adhesive modified base film and the hard-coat layer containing an inorganic fine particle, it is with the surface of an adhesive modified layer, ie, a hard coat layer. At the interface, it is important to express specific micro phase separation structures or nano phase separation structures.

However, in the hard coat film of the present invention, the adhesive modifying layer B becomes an intermediate layer between the thermoplastic resin film A and the hard coat layer C. That is, from the surface of the hard coat film, the phase separation structure of the surface of the adhesive modifying layer B cannot be observed. For this reason, in this invention, the hard-coat film was cut and the phase-separated structure of the adhesive modified layer of the interface vicinity with a hard-coat layer was observed from the cutting surface.

The specific phase-separated structure of the adhesive modifying layer in the present invention includes the resin composition of the coating liquid used for forming the adhesive modifying layer, the type and concentration of the surfactant, the coating amount, the drying conditions of the adhesive modifying layer, and the heat. Fixed conditions and the like can be selectively employed to form them by controlling them.

First, the outline of the method for producing the adhesive modified base film used in the present invention will be described using a polyethylene terephthalate (hereinafter abbreviated as PET) as a representative example, but it is not limited to this representative example.

Pellets of PET substantially free of particles for imparting active activity are sufficiently dried in vacuum, then fed into an extruder, melt extruded into sheets at 280 ° C, and solidified by cooling to give an unoriented PET sheet. Unveil At this time, high precision filtration is performed in order to remove foreign substances contained in the resin at any place where the molten resin is maintained at about 280 ° C. The obtained unoriented sheet is extended | stretched 2.5-5.0 times in the longitudinal direction with the roll heated at 80-120 degreeC, and a uniaxially-oriented PET film is obtained.

Subsequently, an aqueous solution of the above-mentioned copolyester and polyurethane is applied to one side or both sides of the uniaxially oriented PET film. To apply the aqueous coating liquid, for example, a reverse roll coating method, a gravure coating method, a kiss coating method, a roll brush method, a spray coating method, an air knife coating method, a wire bar coating method, a pipe doctor method, and impregnation ) Coat method and curtain coat method, and the like, and these methods can be performed alone or in combination.

Next, the edge part of a film is gripped with a clip, it guide | induced to the hot air zone heated at 80-180 degreeC, and it extends | stretches 2.5-5.0 times in the width direction after drying. Subsequently, it guides to the heat processing zone of 220-240 degreeC, heat-processes for 1 to 20 second, and completes crystal orientation. In this heat treatment step, 1 to 12% of relaxation may be performed in the width direction or the longitudinal direction as necessary.

First, the phase separation structure of the adhesive modified layer of the adhesive modified base film used by this invention is demonstrated. Next, the raw material used for the hard coat film and the optical functional film of this invention, and manufacturing conditions are explained in full detail including the conditions factor for controlling said phase separation structure.

(1) Phase Separation Structure of Adhesive Modified Layer

In the present invention, the adhesive modifying layer is a polyester phase (hereinafter sometimes abbreviated as PEs phase) mainly composed of copolyester, and a polyurethane phase (hereinafter, PU phase) mainly composed of polyurethane. In some cases, the microphase separation structure or the nanophase separation structure may be used.

In the hard coat film of the present invention, the adhesive modifying layer B is used for the purpose of improving the adhesion between the hard coat layer containing the inorganic fine particles and the thermoplastic resin film. Moreover, when laminating | stacking the same hard-coat layer or another optical function layer on the surface on the opposite side to the said hard-coat layer, it is also used for the purpose of improving the adhesiveness of these layers and a thermoplastic resin film.

In the present invention, the adhesive modifying layer B has a structure in which micro phase separation or nano phase separation is performed on polyester (PEs) and polyurethane (PU), and the cut surface of the hard coat film is further cut using a scanning probe microscope. When observed in the phase measurement mode, the polyurethane phase of the adhesive modified layer B defined by the following formula in the range from the interface of the adhesive modified layer B to the hard coat layer C to a depth of 20 nm (in phase phase, bright color It is an important feature that the area ratio (PU area ratio) of the &quot;

% Area on PU = (area on PU / measured area) × 100

In addition, the area ratio of said PU phase is calculated | required as follows.

In the hard coat film of the present invention having the thermoplastic resin film / adhesive modified layer / hard coat layer as a structural unit, in order to calculate the area ratio of the PU phase of the adhesive modified layer of the intermediate layer, the adhesive modified layer embedded therein Need to be exposed to the surface.

As a method of exposing an adhesive modified layer to a surface, the method of cutting a film in an oblique direction using the surface interface physical property analyzer (made by Daipla Wintes Co., Ltd.) is suitable. Next, using a scanning probe microscope (SPM), the phase separation structure is observed from the phase phase 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.

The area ratio of the polyurethane phase in the vicinity of the interface with the hard coat layer in the cutting surface of the adhesive modifying layer has the following technical significance.

When the area ratio of the polyurethane phase exceeds 60%, at the time of producing the adhesive modified base film, the ratio of the polyurethane phase on the surface of the adhesive modified layer is relatively large, and the frequency of blocking resistance decreases increases. . On the other hand, when the area ratio of the polyurethane phase is less than 30%, the frequency at which the adhesion decreases increases. In particular, the fall of adhesiveness with respect to a solvent-free hard-coat agent and lens forming resin becomes remarkable.

In the adhesive modification layer near the interface with the hard coat layer, the upper limit of the area ratio of the polyurethane phase is preferably 50% in terms of blocking resistance. On the other hand, the lower limit of the area ratio of the PU phase is preferably 35% in terms of adhesiveness with other optical functional layers made of a hard coat layer or acrylic resin.

Further, on the surface of the adhesive modified layer of the adhesive modified base film before laminating the hard coat layer, a micro phase separation structure or a nano phase separation structure on the PEs phase and the PU phase is observed. When the scanning probe microscope was observed in the phase measurement mode, the area ratio of the polyester phase (showing the dark color in the phase phase) on the surface of the adhesive modified layer defined by the following formula was 5 µm x 5 µm. 35% or more and less than 90% in the range. In addition, in this invention, when providing an adhesive modified layer in both surfaces of a thermoplastic resin film, any adhesive modified layer also has the same area ratio as the polyester phase.

% Area on PEs = (area on PEs / measured area) × 100

The area ratio of PEs on the surface of this adhesive modified layer has the following technical significance. If the area ratio of the PEs phase is less than 35%, the area ratio of the polyurethane phase on the surface of the adhesive modifying layer is relatively large, and the frequency of blocking resistance decreases increases. On the other hand, when the area ratio of PEs is 90% or more, the frequency of adhesion decreases. In particular, the fall of adhesiveness with respect to a non-solvent type hard-coat agent becomes remarkable.

The lower limit of the area ratio of the PEs on the surface of the adhesive modifying layer is preferably 40%, more preferably 45%, particularly preferably 50% in terms of blocking resistance. On the other hand, the upper limit of the area ratio of the PEs phase on the surface of the adhesive modifying layer is preferably 85%, more preferably 80%, particularly preferably 75 in terms of adhesiveness with the functional layer made of acrylic resin. %to be.

In addition, in this invention, the phase measurement mode (phase mode) by a scanning probe microscope (SPM) was used for evaluation of the phase-separated structure of the adhesive modified layer surface. The phase mode generally refers to a phase delay measurement mode performed simultaneously with the surface morphology observation by the dynamic force mode (DFM mode (when SPM manufactured by SAI Nanotechnology Co., Ltd. is used).

The measuring principle of the phase separation structure of the adhesive modified layer by the phase measurement mode (phase mode) of a scanning probe microscope (SPM) is demonstrated easily.

In the phase mode, the phase delay of cantilever vibration when the DFM operation is performed is detected. In the 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 becomes constant. Here, when a signal for vibrating a bimorph (piezoelectric element) for vibrating the cantilever is called an "input signal", the phase delay of the effective cantilever vibration signal for this "input signal" in the phase measurement mode is determined. Detect simultaneously with vibration amplitude. The phase retardation is sensitive to the influence of the surface properties, so the smoother the sample surface, the larger the delay. By imaging the magnitude of this phase retardation, it becomes possible to observe the distribution of surface property (called a phase phase or a phase phase etc.). Therefore, when the resin phase in which a some physical property differs exists in the surface, evaluation of a phase separation structure is attained by this measuring method.

However, the evaluation of the phase-separated structure of the adhesive modified layer may be other modes such as a frictional force measurement mode and a viscoelasticity measurement mode in addition to the phase measurement mode as long as the surface property distribution evaluation mode by the scanning probe microscope is used. It is important to choose an observation mode that can be evaluated. In addition, in the phase measurement mode, not only the phase delay due to the difference in viscoelasticity of the adhesive modified layer can be detected, but also the phase delay due to the difference in surface properties such as the magnitude of the adsorption force can be detected.

In addition, when observing the phase separation structure of the cutting surface of the adhesive modifying layer, in order to facilitate the observation of the phase separation structure, the phase image is read by SPIP software (Version 4.1, manufactured by Image Metrology), and color equalization is performed. It is preferable to perform a process and to strengthen contrast. The reason is as follows.

When using a surface interfacial property analyzer (SAICAS) to cut the hard coat film from the base film side to the inside, it is difficult to completely avoid deformation of the cutting surface of the adhesive modification layer with respect to the cutting direction. In addition, since the inorganic particles contained in the adhesive modifying layer cannot be cut, the appearance of voids in the periphery of the inorganic particles as a result of damage during cutting cannot be avoided. By such cutting, the PU component becomes more dominant than the PEs component at the interface between the adhesive modifying layer exposed on the surface, the thermoplastic resin film or the hard coat layer, and other functional layers. This is because the PU component is more susceptible to deformation than 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 the thickness of the adhesive modified layer cut in an oblique direction is increased. It is estimated that the difference in contrast will be small in a very thin point.

The phase separation structure of the adhesive modifying layer in the present invention corresponds to a micro phase separation structure or a nano phase separation structure in terms of size. When the phase difference image of the surface (interface with a hard coat layer) of the adhesive modified layer in the adhesive modified base film used by this invention was observed, it turns out that it has the following phase separation structures.

When the PEs phase is regarded as a continuous structure having a long axis and a short axis, the main structure mainly includes a continuous structure having a width in the short axis direction of at most 1 µm and a length in the major axis direction exceeding 1 µm. That is, with respect to the total area of the PEs, the area of the portion having the continuous structure is 80% or more, preferably 85% or more, more preferably 90% or more. Moreover, even in PEs phase dispersed in island shape which does not correspond to the continuous structure described in the said definition, the terminal of the thing which has a continuous structure may be shown in the surface inside an adhesive modified layer.

It is preferable that the magnitude | size of the continuous structure on this PEs is the width | variety of a uniaxial direction at most 1 micrometer, More preferably, it is 0.8 micrometer, More preferably, it is 0.6 micrometer, Especially preferably, it is 0.4 micrometer. Although the width | variety of a short axis direction does not have a restriction | limiting in particular in the lower limit, In order to maintain a continuous structure, it is preferable that it is 0.01 micrometer in a narrowest part, Especially preferably, it is 0.05 micrometer. On the other hand, the size of the continuous structure on the PEs preferably has a length in the major axis direction of more than 1 m, more preferably 1.5 m or more, still more preferably 2.0 m or more, particularly preferably 2.5 m or more.

In the adhesive modified substrate film used in the present invention, the phase-separated structure on the surface of the adhesive-modified layer shows a complex structure that is not seen in nature, as can be seen from the representative example shown in FIG. It is difficult to define it uniquely. Said phase-separated structure can also be represented in multiple ways as follows.

For example, when the form of the phase-separated structure is expressed as a pattern, among the materials described in the literature, the "resin phase structure" ("Chemical Dictionary", page 226, June 15, 1979, Sankyo Publishing Co., Ltd.) Issuance, "Rippled structure" ("Glyph", pages 168-169, published by Novara Co., Ltd. on October 1, 2002), and "Michae-jo" .

This phase-separated structure on the surface of the adhesive modified layer is similar to that represented by the air-flow structure in the field of morphology in the polymer blend system. Moreover, it can also be represented by the mutual penetration mesh structure formed by intertwining co-polyester and self-crosslinking polyurethane.

It is also possible to formally quantitatively express the self-similarity on PEs using fractal dimensions. 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 outline of the interface between the light color (polyurethane phase) and the dark color (polyester phase) is outlined. In the highlighted phase image, as an index indicating the complexity of the boundary line (interface outline) of light and dark colors, it can be expressed quantitatively using a fractal dimension obtained from the outline of the interface using the box counting method.

In the unit area, a fractal dimension of 1 means a straight line (1 dimension), and 2 means a solid surface (2 dimension). In other words, the closer the fractal dimension is to 2, the denser the structure. On the other hand, the closer the fractal dimension is to 1, the coarse the structure.

Specifically, on the surface of the adhesive modified layer of the adhesive modified base film, in the phase in which the outline of the interface between the bright color (polyurethane phase) and the dark color (polyester phase) is emphasized, It is preferable that the fractal dimension of a dark boundary line (the outline of an interface) is 1.60-1.95 with a measuring area of 5 micrometers x 5 micrometers. 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.

For example, on the surface of the adhesive modification layer shown in FIG. 4, the fractal dimension of the boundary line (interface outline) of a light color (polyurethane phase) and a dark color (polyester phase) is 1.89 and 1.90, respectively. . 4 is a phase of FIG. 1 showing a typical phase-separated structure of the surface of the adhesive modifying layer in the present invention, highlighting the contour of the interface between the light color and the dark color, showing the boundary between the light color and the dark color. Drawing.

In this invention, in order to express the function which the copolyester and polyurethane which are raw materials of an adhesive modified layer have as much as possible, it is important that an adhesive modified layer has a micro phase separation structure or a nano phase separation structure. This is because, when both resins are completely compatible, the properties of both resins are canceled out, and as a whole, excellent properties of the copolyester or polyurethane cannot be expected. Other phase separation structures that the PEs phase and the PU phase can take in the adhesive modifying layer include a sea-island structure, which is a so-called composite form in which the PU phase is dispersed in the PEs phase and the PEs phase is dispersed in the PU phase. ) Can also be considered. Of course, this island-in-the-sea structure is inevitably reduced when the number of one resin phase is increased in the incompatible state of the resin, thereby forming a so-called island. Also in the present invention, when the manufacturing conditions are controlled, it is also possible to obtain an adhesive modified layer that becomes a separate phase having such an island-in-water structure.

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 cannot be ignored. For this reason, it is also concerned that the property of the resin which comprises a sea structure greatly affects. If so, it would be advantageous to form a phase separation structure in which every phase of the PEs phase and the PU phase phase separation structure of the present invention is entangled with each other. A phase separation structure showing the islands structure of the PEs phase and the PU phase is also mentioned as one of the representative aspects of the present invention.

Moreover, as another phase separation structure of the adhesive modification layer in this invention, it is also possible to form a core-shell structure. For example, it is a structure that a PU phase surrounds around a PEs phase and that it surrounds a PEs phase. However, in order to form such a core-shell structure, a very high level of control is required. In addition, in order to take the core-shell structure, it is thought that excellent material behavior can be expected.

Further, as an aspect of the phase separation structure, a laminated structure in which the PEs phase and the PU phase are alternately regularly arranged may also be taken. However, although it is ideal to arrange each phase in parallel at substantially equal intervals, as the width of the phase becomes larger, it becomes difficult to uniformly distribute the PEs phase and the PU phase at the interface of the adhesive modifying layer, and furthermore, the adhesive modified base film There is a concern that will affect the quality of the. Due to subtle differences in manufacturing conditions, they may be mixed in form while taking the form of an island-in-sea structure, a core-shell structure, and a laminated structure. However, in the adhesive modified layer, the PEs phase and the PU phase have a constant size, and they are evenly mixed evenly, which is important for maintaining the quality.

Further, the structure in which the PEs phase and the PU phase phase separate into two layers in the thickness direction of the adhesive modifying layer is not preferable in the present invention. The reason is that in the present invention, it is important to uniformly distribute the PEs phase and the PU phase on the surface of the adhesive modifying layer (interface with the hard coat layer) at an appropriate area ratio in view of the effect of the present invention.

In the phase-separated structure on the surface or the cutting surface of the adhesive modifying layer, the polyester phase containing copolyester as a main component and the polyurethane phase containing polyurethane as a main component have irregular shapes, respectively. In addition, these resin phases form a complicated arrangement structure that is irregularly and precisely arranged evenly on the surface and inside of the adhesive modifying layer. Moreover, the structure which the other resin phase embedded in the surface of one resin phase in incompatible state may be sufficient. In addition, in FIG. 3, a black part represents a polyester phase and a white part represents a polyurethane phase.

On the surface of the adhesive modified layer of the adhesive modified base film, when the two types of resin phases are uniformly arranged with respect to the unit area (for example, 5 × 5 μm), the dimension of one resin phase is The larger size constrains the dimensions of the other resin phase. For this reason, big bias arises in presence of resin phase. As a result, it is difficult to maintain a state where both resin phases are separated and uniformly dispersed, and variations occur in the material of the adhesive modifying layer, which is not preferable in terms of quality control.

In order to make both resin phases phase-separate and to exist in an adhesive modified layer in the state which mixed uniformly, it is preferable that the shape of PEs phase is the width | variety of the uniaxial direction at most 1 micrometer, and the length of the major axis direction is 1 micrometer or more. Of course, when there is no high demand for quality, a structure in which the width in the short axis direction is relatively large (up to about 6 m) is also possible. The phase-separated structure of the continuous phase (PEs phase) may selectively select the resin composition of the coating liquid used for forming the adhesive modified layer, the type and concentration of the surfactant, the coating amount, the drying conditions of the coating layer, and the heat setting conditions. By employing and controlling these, it can express as a micro phase separation structure or a nano phase separation structure specific for an adhesive modified layer. As a result, the aspect of the phase separation structure of the polyester phase and the polyurethane phase of the adhesive modified layer surface shown in FIG. 1 is a typical model for expressing the effect of the adhesive modified base film of this invention.

In addition, the importance of the phase separation structure will be described in detail.

The adhesive modified layer in the adhesive modified base film used for this invention has a copolyester component and a polyurethane component as a resin component, and has a PEs phase and polyurethane as a main component which have a copolyester as a main component. It is preferable that the phases are separated into PU phases so that each phase has a continuous structure. By phase-separating without mixing the said two types of resin uniformly, the co-polyester which has the outstanding adhesiveness with respect to the base film used as a thermoplastic resin film, and has comparatively favorable solvent resistance, and although solvent resistance is inferior, a hard coat layer and a diffusion layer Polyurethane which has excellent adhesiveness with respect to many resins, such as an acrylate resin, can fully utilize the characteristic of resin, without canceling each characteristic.

Although it is preferable that the copolyester is comprised independently, the polyester phase which comprises an adhesive modified layer may contain 0.01-40 mass% of polyurethane. Moreover, you may contain 0.001-20 mass% of particles in a polyester phase. In addition, in a polyester phase, surfactant may adhere to or contain the said resin. Similarly, it is preferable that a polyurethane phase consists solely of polyurethane, and can contain particle | grains, surfactant, etc. in the quantity of the grade described in said copolyester. In particular, in the case of particles having high affinity with polyurethane, it is possible to selectively localize much more on the polyurethane than on the polyester phase in the process of forming the adhesive modified layer.

Generally, in the composition which consists of a mixture of a copolyester and a polyurethane, it is usually the expression of the chemical complementary function that both become a chemically uniform material and satisfy | fill each other the property or function which they have. . On the other hand, the adhesive modified layer consisting of the polyester phase and the polyurethane phase of the present invention, as described above, the polyester phase and the polyurethane phase are physically separated from each other, so that a large bias occurs in the presence of the resin phase, and both resin phases are separated. Maintain a structure of a uniformly distributed state. The properties of each resin are mediated through the surface of each resin phase. For example, copolyesters share the function in the phase-separated state, as the blocking resistance and the polyurethanes are the adhesion. In other words, as the manifestation of the physical replenishment function, this function or principle can be said to be a novel technology that is not recognized at all in the prior art.

In the present invention, the detailed generation mechanism of the phase separation structure of the adhesive modifying layer is not clear. However, drying and heat are applied to the material composition and properties of the coating liquid, such as the composition ratio of the copolyester and polyurethane, the ratio of the dispersion medium of water and alcohol, the type of the surfactant, the impurities in the surfactant, the pH of the aqueous coating liquid, and the coating amount. It can be easily understood from the contrast of each example and the comparative example that the micro phase separation structure or the nano phase separation structure specific for the adhesive modifying layer is expressed by the balance of the delicate conditions of the time, the temperature and the wind speed of the fixing treatment.

In addition, it is thought that reaction start temperature of the isocyanate group which polyurethane has also influenced subtly. The phase-separated structure referred to herein means that the so-called PEs phase and the PU phase do not have a physical boundary but are separated from each other at a distance, but the boundaries are in contact with each other without a distance, and a lot of copolyester is gathered and biased on the PUs. Only a lot of polyurethane is biased, and the boundary between the two layers seems to be apparently separated so as to distinguish clearly. And in the case of this invention, the isocyanate group of polyurethane may react at the boundary, and has shown the complicated separation structure.

The adhesive modified base film used by this invention has the adhesive modified layer which becomes a PEs phase and a PU phase, for example, interposes between the base material which becomes a thermoplastic film, and functional layers, such as a hard-coat layer and a diffusion layer. It plays the role of the interface function which acts similarly to both surfaces of what is called a base material surface and a functional layer surface. If so, both the PEs phase and the PU phase have a structure in which both are separated, and the PEs phase has excellent properties of the copolyester inherent to both sides (the interface between the substrate and the adhesive modified layer, the interface between the adhesive modified layer, and the adhesive modified layer). The interface of functional layers, such as a hard-coat layer, is in the state exhibited to the maximum. In other words, the PU phase is in a state that exhibits the excellent properties of the polyurethane inherent to the maximum on both sides.

This is because in the adhesive modified base film having the adhesive modified layer, since the surface of the adhesive modified layer has a micro phase separation structure or a nano phase separation structure consisting of PEs phase and PU phase, the copolyester of PEs is exposed. This is because the properties or functions of the copolyester are maximized, and similarly, the polyurethane on PU is exposed to maximize the properties or functions of the polyurethane. Therefore, when each of the PEs phase and the PU phase on the surface of the adhesive modifying layer is distributed in a specific range, the properties or functions of the quantum resin can be exhibited to the maximum. This is because it is a unique structure called a laminated body, and it acts reasonably at the interface of a base material and an adhesive modified layer, and the interface of an adhesive modified layer and a functional layer.

Moreover, when this invention contains particle | grains in the resin composition which comprises a PEs phase and a PU phase, it can be localized in PU phase in silica particle, for example. This is presumably because the surface energy is closer to the silica particles in the PU phase than in the PEs phase. By localizing the silica particles on the PU, the blocking resistance, which is a disadvantage of polyurethane, can be improved, and the particle content of the entire adhesive modifying layer can be reduced, which is an advantageous structure for the function of maintaining transparency. .

Similarly, when the surface energy selects particles close to the copolyester, it suggests that the particles can be selectively localized on the PEs. The technique unprecedented from the prior art, which localizes the particles in either the phase separation structure that becomes the PEs phase or the PU phase, can highly improve the activity and blocking properties while maintaining transparency. For this reason, the present invention is also significant in terms of broadening the application range of the material design of the micro phase separation structure or the nano phase separation structure.

(2) thermoplastic resin film

As the thermoplastic resin film used in the present invention, an unoriented sheet obtained by melt extruding or solution extruding the thermoplastic resin is stretched in the uniaxial direction in the longitudinal direction or the width direction as necessary, or successively biaxially stretched or simultaneously biaxially in the biaxial direction. The biaxially stretched thermoplastic resin film which extended | stretched and performed the heat setting process is suitable.

Further, the thermoplastic resin film may be subjected to surface activation treatment such as corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, and the like within the scope of not impairing the object of the present invention. .

The thickness of the thermoplastic resin film used by this invention is 30-300 micrometers, and can be arbitrarily determined according to the specification of the use to be used. 250 micrometers is preferable and, as for the upper limit of the thickness of the said thermoplastic resin film, 200 micrometers is especially preferable. On the other hand, as for the minimum of film thickness, 50 micrometers is preferable, Especially preferably, it is 75 micrometers. If the film thickness is less than 50 µm, the stiffness and mechanical strength tend to be insufficient. On the other hand, when the film thickness exceeds 300 µm, since the absolute amount of foreign matter present in the film increases, the frequency of optical defects increases. Moreover, the slit property at the time of cut | disconnecting a film to a predetermined width | variety also worsens, and manufacturing cost becomes high. Moreover, since rigidity becomes strong, it is easy to wind up a long film in roll shape.

Examples of the thermoplastic resin include polyolefins such as polyethylene (PE), polypropylene (PP), and polymethylpentene (TPX), polyethylene terephthalate (PET), polyethylene-2,6-naphthalate (PEN), and polytetramethylene terephthalate (PTT). ), Polyester resins such as polybutylene terephthalate (PBT), polyamide (PA) resins such as nylon 6, nylon 4, nylon 66, nylon 12, polyimide (PI), polyamideimide (PAI), poly Ethersulfone (PES), polyether ether ketone (PEEK), polycarbonate (PC), polyarylate (PAR), cellulose propionate, polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl alcohol (PVA) , Polyetherimide (PEI), polyphenylene sulfide (PPS), polyphenylene oxide, polystyrene (PS), syndiotactic polystyrene, norbornene-based polymer, and the like. In addition to using these polymers independently, copolymers containing a small amount of copolymerization components may be used, or one or more other thermoplastic resins may be blended.

Among these thermoplastic resins, polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, syndiotactic polystyrene, norbornene-based polymer, polycarbonate, polyarylate and the like are suitable. Moreover, resin which has polar functional groups, such as polyester and a polyamide, is preferable at the point of adhesiveness with an adhesive modification layer.

Among them, polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, polypropylene terephthalate or a copolymer mainly composed of constituents of these resins is more suitable, and a biaxial orientation formed from polyethylene terephthalate Films are particularly suitable.

For example, when using the polyester copolymer which has a polyethylene terephthalate as a base skeleton as resin which forms a thermoplastic resin film, it is preferable to make the ratio of a copolymerization component into less than 20 mol%. If it is 20 mol% or more, film strength, transparency, and heat resistance may be inferior. As a dicarboxylic acid component which can be used as a copolymerization component, Aromatic dicarboxylic acid, such as aliphatic dicarboxylic acid, such as adipic acid and sebacic acid, isophthalic acid, phthalic acid, and 2, 6- naphthalenedicarboxylic acid, tri Polyfunctional carboxylic acid, such as a melylotic acid and a pyromelliot acid, etc. are illustrated. Moreover, as a glycol component which can be used as a copolymerization component, Fatty acid glycol, such as diethylene glycol, 1, 4- butanediol, propylene glycol, and neopentyl glycol; aromatic glycols such as p-xylene glycol; Alicyclic glycols such as 1,4-cyclohexanedimethanol; Polyethylene glycol etc. whose average molecular weights are 150-20000 are illustrated.

In addition, the thermoplastic resin may contain various additives in addition to the catalyst within a range that does not disturb the effects of the present invention. Examples of the additive include inorganic particles, heat resistant polymer particles, alkali metal compounds, alkaline earth metal compounds, phosphorus compounds, antistatic agents, ultraviolet absorbers, light agents, flame retardants, heat stabilizers, antioxidants, antigelling agents, surfactants, and the like. Can be.

The particles are suitable for the film surface in terms of handling properties (active, running property, blocking property, air entrainment of accompanying air during winding, etc.) during the production of the thermoplastic resin film, the winding in the roll shape or the unwinding. It is used to give surface irregularities.

As inorganic particles, calcium carbonate, calcium phosphate, amorphous silica, crystalline glass filler, kaolin, talc, titanium dioxide, alumina, silica-alumina composite oxide particles, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, mica, etc. Can be mentioned. Examples of 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, and the like. Can be.

When using a polyester film as a thermoplastic resin film, since a silica particle is comparatively close to a polyester resin and refractive index is easy to obtain high transparency among the said particle | grains, it is the most suitable for the use where strong transparency is calculated | required. On the other hand, white pigments, such as titanium oxide, are suitable for the use which requires hiding property. In addition, the particle | grains to be contained in a thermoplastic resin film may be used together, or may use multiple types together.

What is necessary is just to determine the kind, average particle diameter, and addition amount of the said particle | grains according to the use of a film in the range of 0.01-2 micrometers and particle content in 0.01-5.0 mass% in an average particle diameter from a balance aspect of transparency and handling property. In addition, when the adhesive modified base film used by this invention is used for the use which highly requires transparency, a thermoplastic resin film does not contain particle | grains which cause a fall in transparency, but a particle | grain is contained in an adhesive modified layer. It is preferable to set it as the structure which contains.

The term "without substantially containing particles" means, for example, in the case of inorganic particles, 50 ppm or less, preferably 10 ppm or less, most preferably below the detection limit when the inorganic element is quantified by fluorescence X-ray analysis. It means content which becomes. This is because, even if the particles are not actively added to the base film, the contaminants derived from foreign foreign matter, the contaminants adhering to the line or the device in the manufacturing process of the raw material resin or the film may peel off and be mixed in the film. .

In addition, a single layer may be sufficient as the laminated constitution of the thermoplastic resin film used by this invention, and it can also be set as the laminated structure which provided the function which cannot be obtained by a single layer. In the case of a laminated structure, a coextrusion method is suitable.

The case where polyester is used as a raw material of a thermoplastic resin film is demonstrated in detail below about the manufacturing method of a base film.

As for the intrinsic viscosity of the polyester pellet used as a film raw material, the range of 0.45-0.70 dl / g is preferable. When the intrinsic viscosity is less than 0.45 dl / g, breakage tends to occur at the time of film production. On the other hand, when the intrinsic viscosity exceeds 0.70 dl / g, the increase in the pressurization pressure becomes large, high accuracy filtration becomes difficult, and the productivity tends to decrease.

Moreover, in the hard coat film of this invention or the optical functional film using the said film, it is preferable to remove the foreign material contained in the polyester of a raw material which causes an optical defect. To remove foreign matter in the polyester, high-precision filtration is performed at any place where the molten resin is maintained at about 280 ° C at the time of melt extrusion. The filter medium used for high-precision filtration of the molten resin is not particularly limited, but the filter medium of the stainless sintered compact has excellent removal performance of aggregates and high-melting-point organic materials containing Si, Ti, Sb, Ge, and Cu as main components. Suitable.

As for the filter particle size (95% of initial stage filtration efficiency) of the media used for high precision filtration of molten resin, 15 micrometers or less are preferable. If the filter particle size of the media exceeds 15 µm, foreign matter removal of 20 µm or more is likely to be insufficient. Although the productivity may fall by performing highly accurate filtration of a molten resin using the filter medium of 15 micrometers or less of filter particle size (initial filtration efficiency 95%), it is very important for obtaining a film with few optical defects.

In the extrusion process of the molten resin, even in the case of fine foreign matter passing through the filter medium, crystallization proceeds around the foreign matter in the cooling process of the sheet-like melt, which causes nonuniformity of orientation in the alignment process, resulting in a slight difference in thickness. To generate a lens state. Here, the light is refracted or scattered as if there is a lens, and when viewed with the naked eye, it appears larger than the actual foreign matter. This small thickness difference can be observed as the difference between the height of the convex portion and the depth of the concave portion, and if the height of the convex portion is 1 μm or more, and the depth of the concave portion adjacent to the convex portion is 0.5 μm or more, the size is determined by the lens effect. Is a material having a shape of 20 μm, it is visually recognized as a size of 50 μm or more, and may also be recognized as an optical defect of size of 100 μm or more.

In order to obtain a highly transparent film, it is preferable not to contain particles in the thermoplastic resin film. However, the smaller the particle content and the higher the transparency, the more the optical defects due to minute unevenness tend to be more clear. In addition, since the surface of the thick film is less likely to be quenched than the thin film and crystallization tends to proceed, it is necessary to quench the entire film at the time of producing the unoriented sheet. As a method for cooling the unoriented sheet, a molten resin is extruded from a slit portion of a die onto a sheet on a rotary cooling drum, and a method of rapidly cooling the sheet-like melt to a rotary cooling drum while making it into a sheet is suitable. As a method of cooling the air surface (the surface opposite to the surface which contacts a cooling drum) of this unoriented sheet | seat, the method of spraying and cooling with high speed airflow is effective.

(3) adhesive modified layer

The adhesive modified base film used by this invention is a thermoplastic resin film which runs the resin containing copolyester and polyurethane, the dispersion medium containing water and alcohol, and the aqueous coating liquid which uses surfactant as a main component. A coating step of applying one or both surfaces continuously, a drying step of drying the coating layer (adhesive modifying layer), followed by a drawing step of stretching in at least one axial direction, and a heat setting step of heat-setting the coated film further. The adhesive modified base film provided with the adhesive modification layer which has the micro phase separation structure or the nano phase separation structure obtained by continuously forming through a process process is manufactured. Moreover, you may form a crosslinked structure in co-polyester by mixing at least 1 type of crosslinking agent chosen from an epoxy type crosslinking agent, a melamine type crosslinking agent, and an oxazoline type crosslinking agent to a coating liquid, and heat-processing.

In the manufacturing method of the adhesive modified base film which provided the adhesive modification layer which has this micro phase separation structure or a nano phase separation structure, the mass ratio (PEs / PU) of the said copolymerized polyester (PEs) and polyurethane (PU), It is 30/70-70/30, and it is preferable to satisfy the conditions of following (a)-(f). In addition, the case where a crosslinking agent is included in a coating liquid is also the same.

(a) The passage time of the film from immediately after application of the coating liquid to the inlet of the drying step is less than 2 seconds.

(b) 0.1 to 5 seconds at 120-150 ° C

(c) The wind speed of the drying wind is 30 m / sec or more in the drying process.

(d) The heat setting treatment process is continuously divided into a plurality of heat setting zones, and each zone is divided so that temperature control is possible independently, and the temperature of the first heat setting zone through which the film passes is 190 to 200 ° C. And the temperature of the heat setting zone set to the highest temperature is 210 to 240 ° C. and from the outlet of the first heat setting zone to the heat setting zone set to the maximum temperature (and, in the case of a plurality, the most inlet side heat setting zone). Film passing time is less than 10 seconds

(e) 0.01 to 0.18 mass% of nonionic surfactant or cationic surfactant is added to the coating liquid.

(f) The final coating amount of the adhesive modifying layer is 0.005 to 0.20 g / ㎡

Moreover, in manufacture of said adhesive modified base film, it is more preferable to satisfy the conditions of following (g)-(i).

(g) The passing time of the film from immediately after application of the coating liquid to the inlet of the drying step is less than 1.5 seconds.

(h) 0.5 to 3 seconds at 130 ~ 150 ℃

(i) In the heat setting process, the temperature of the heat setting zone set to the highest temperature is 225 to 235 ° C. and the heat setting zone set to the highest temperature from the outlet of the first heat setting zone (moreover, in the case where there are a plurality, Passing time of film to side heat setting zone) is 5 seconds or less

In addition, active, winding resistance and scratch resistance can be imparted by containing fine particles having an appropriate particle diameter in the adhesive modified layer laminated by the above-described inline coating method and forming appropriate irregularities on the surface of the adhesive modified layer. . For this reason, it is not necessary to contain microparticles | fine-particles in a thermoplastic resin film, and high transparency can be maintained.

It is preferable that the adhesive modified base film used by this invention smooths the 3-dimensional center surface average surface roughness SRa of the adhesive modified layer surface to 0.002-0.010 micrometer. As for the upper limit of SRa, 0.0080 micrometers is more preferable at the point of transparency, Especially preferably, it is 0.0060 micrometers. On the other hand, the lower limit of SRa is more preferably 0.0025 µm, particularly preferably 0.0030 µm in view of handling properties such as activity, winding properties, and scratch resistance.

On the smooth surface whose SRa of the adhesive modified layer surface is less than 0.002 micrometer, the blocking resistance at the time of winding up an adhesive modified base film in roll shape, or handling property, such as activity or winding property at the time of film manufacture or processing, and scratch resistance This lowers and is not preferable. On the other hand, when SRa of the adhesive modified layer surface exceeds 0.010 micrometer, haze rises and transparency worsens, and it is not preferable as a base film of a hard coat film or the optical functional film using the same.

In the adhesive modified base film used by this invention, an adhesive modified layer has the following four morphological and structural characteristics, and can be obtained by the following means.

(a) micro phase separation or nano phase 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) In the case where the adhesive modified layer contains particles, the particles are unevenly distributed on polyester or polyurethane.

Moreover, it is preferable that the polyester phase which has co-polyester observed on the surface of an adhesive modifying layer as a main component has a continuous structure whose width is a maximum of 1 micrometer and a length exceeds 1 micrometer, More preferably, a copolymer poly The ester phase and the polyurethane phase are structures having a high velocity structure. Within the range of the area ratio of the PEs phase on the surface of the adhesive modified layer, the polyester phase composed mainly of the copolyester has a microscopic uniform structure having a fine continuous structure having a width of at most 1 μm and a length of more than 1 μm. Adhesiveness is obtained.

In a phase-separated structure in which a portion having a width exceeding a maximum of 1 μm is interspersed on a polyester mainly composed of copolyester, it is locally applied to functional layers such as a hard coat layer, a diffusion layer, and a prism layer. The inferior adhesiveness generate | occur | produces. When a location with low adhesiveness exists on the surface of an adhesive modified layer, it may lead to macro peeling from the part as a starting point. In order to make the width | variety of the said polyester phase into the fine continuous structure of 1 micrometer at most, it is important to select suitably the time required to reach the maximum temperature in a heat setting zone from a lateral stretch zone, and heat setting conditions. In particular, when the time taken from the transverse stretching zone to the heat-setting zone in the zone reaching the highest temperature is too long, the phase separation of the adhesive modifying layer proceeds too much, and as a result, the width of the polyester phase containing copolyester as a main component is increased. In the narrowest part, the location exceeding 1 micrometer will be dotted. Specific heat setting conditions at the time of manufacturing an adhesive modified base film are mentioned later.

In order to control the phase-separated structure of the final adhesive modified layer surface, the solvent evaporation rate in the drying step described later and subsequent heat treatment are very important. By controlling the solvent evaporation rate in the drying step, the composition ratio of the polyester component and the polyurethane component on the surface of the adhesive modifying layer can be changed.

For example, in the case of using a mixed solvent of water / isopropyl alcohol, the solvent remaining on the surface during the late drying process in a weak drying condition increases the proportion of water. For this reason, the ratio in which a relatively high hydrophilic polyurethane exists in the surface of an adhesive modified layer becomes high compared with when drying an adhesive modified layer on strong conditions. In addition, changing the coating amount also has the same effect as controlling the solvent evaporation rate. That is, when the application amount is increased, drying takes time, and the residual solvent present on the application surface immediately before drying increases the proportion of water. That is, the ratio of the polyurethane component in the surface of an adhesive modified layer can be made high compared with the case where a coating amount is small.

In the stretching step and the heat setting treatment step, phase separation of the polyester component and the polyurethane component proceeds. However, when the thermal crosslinking of either resin starts, 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 step and the heat setting treatment step.

As mentioned above, adhesiveness is controlled by the control of the ratio which exists near the surface of the adhesive modified layer of polyester / polyurethane in a drying process, and the phase separation progress in an extending process and a heat setting treatment process. It becomes possible to strictly control the surface phase separation structure of the modified layer, and the rate at which each phase is present near the surface of the adhesive modified layer. In addition, by controlling the surface energy of the particles contained in the adhesive modifying layer, the particles can be selectively localized to either a polyester phase containing copolyester as a main component or a polyurethane phase containing polyurethane as a main component. .

The adhesive modified layer contains copolyester and polyurethane as main resin components. In co-polyester alone, although adhesiveness with a polyester base film is sufficient, adhesiveness with the hard-coat layer containing inorganic fine particles is inferior. Moreover, since it is a relatively soft resin, it is easy to produce cohesive failure with respect to the impact at the time of cutting.

On the other hand, in polyurethane alone, adhesiveness with the hard coat layer containing inorganic fine particles is relatively excellent. However, adhesiveness with a polyester base film is inferior. Moreover, the blocking resistance at the time of winding up an adhesive modified base film in roll shape is inferior. For this reason, the quality of a hard coat film and an optical functional film manufactured using the adhesive modified base film which has an adhesive modification layer of polyurethane sole system falls remarkably. In order to avoid such a problem, it is necessary to contain a large amount of particles in the adhesive modifying layer, to include particles having a large particle diameter, or to increase the content of the particles. As a result, since the haze of a film rises, it is not especially preferable as a base film of a hard-coat film and an optical functional film with strong transparency requirements.

(3-1) Coating liquid combination process used to form an adhesive modified layer

In the present invention, the adhesive modified layer is formed using an application method. The material used for a coating liquid is resin, a dispersion medium, or a solvent. In this invention, it is preferable that the coating liquid used in order to form an adhesive modified layer is aqueous. Moreover, in this invention, it is preferable embodiment to use together a particle | grain and surfactant other than a resin component. Moreover, additives, such as an antistatic agent, a ultraviolet absorber, an organic lubricant, an antimicrobial agent, a photocatalyst, can be used as needed. In addition, a catalyst may be added to the coating liquid in order to promote the thermal crosslinking reaction of the resin, and various chemical substances such as inorganic substances, salts, organic substances, alkaline substances, acidic substances and organic metal-containing compounds may be used. Can be. Moreover, in order to adjust pH of aqueous solution, you may add an alkaline substance or an acidic substance. The coating liquid is dispersed or dissolved in a dispersion medium or a solvent under stirring, and then, in addition to the particles and the surfactant, various additives are used in combination, if necessary, to be diluted and adjusted to the desired solid content concentration.

Moreover, in order to disperse | distribute the resin component and particle | grains of a coating liquid uniformly, it is preferable to filter finely the coating liquid in order to remove foreign substances, such as a coarse particle aggregate and in-process dust.

The type of the media for fine filtration of the coating liquid is not particularly limited as long as it has the above performance, and examples thereof include filament type, felt type, and mesh type. The material of the media for finely filtration of the coating liquid is not particularly limited as long as it has the above-mentioned performance and does not adversely affect the coating liquid, and examples thereof include stainless steel, polyethylene, polypropylene, nylon and the like.

The filter medium for fine filtration of the coating liquid is preferably a filter medium having a filter 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 a filter performance of 1 μm or less It is the media of. Most preferably, the method uses a combination of filters having different filtration performances. When a filter medium having a filter particle size of more than 25 µm is used, removal of coarse aggregates tends to be insufficient. For this reason, the coarse aggregate which could not be removed by filtration spread | dispersed by the orientation stress in the uniaxial orientation or biaxial orientation process after application | coating drying, and is recognized as an aggregate of 100 micrometers or more, and it becomes easy to cause an optical defect.

The raw material used for a coating liquid is demonstrated in detail below.

(a) resin

In the present invention, copolyester (PEs) and polyurethane (PU) are used as the resin constituting the adhesive modifying layer. (PEs) / (PU) = 70 / 30-30 / 70 is preferable, and, as for the mass ratio on the solid content basis of copolymer polyester (PEs) and polyurethane (PU) in a coating liquid, Especially preferably, 60 / 40-40 / 60. Moreover, resin which comprises an adhesive modified layer can also use together the said copolyester and 3rd resin other than a polyurethane. Moreover, you may use together a crosslinking agent.

In addition, in this invention, the area ratio of the polyester phase of the adhesive modified layer surface, and the mass ratio of the copolyester with respect to the resin component of an adhesive modified layer do not correspond, as shown in FIG. In FIG. 6, even if the mass ratio of the copolyester with respect to the resin component of an adhesive modified layer is 50%, it shows clearly that the PEs surface fraction of the surface of an adhesive modified layer changes to 30 to 91%. This fact suggests that the composition ratio of copolyester and polyurethane is different in the surface and the inside of an adhesive modification layer. That is, this suggestion means that the composition ratio of the copolyester and polyurethane can be arbitrarily controlled in the thickness direction of the adhesive modifying layer.

Moreover, the hardness index of the surface of an adhesive modified layer can be 3.0-15.0 nm by making ratio of the copolyester and polyurethane in an adhesive modified layer in the said range. If the hardness index of the surface of the adhesive modified layer is less than 3.0 nm, the adhesive modified layer is withdrawn. For this reason, after forming functional layers, such as a hard-coat layer, a diffusion layer, and a prism layer which make an acrylic resin a component, and performing a high speed cutting to a predetermined size, sufficient adhesiveness with respect to the shear force at the time of high speed cutting is carried out. It is difficult to obtain. Moreover, when the hardness index of the surface of an adhesive modified layer exceeds 15.0 nm, blocking resistance will fall easily. Moreover, there exists a tendency for the coating property, adhesiveness, and solvent resistance to a base film to become inadequate.

In the present invention, it is assumed that the phase separation structure of the water dispersion type copolyester component and the hydrophilic polyurethane component is formed as follows. Both resin components mixed with a common solvent are uniformly dispersed or dissolved in the coating liquid. The coated surface which is subjected to the drying process after coating on the PET film is in a uniform state without a clear phase separation structure. Thereafter, the phase separation structure is expressed by the heat treatment in the stretching step and the heat setting treatment step. That is, it separates into the phase which has a copolyester as a main component, and the phase which has a polyurethane as a main component. It is also believed that with the progress of phase separation, the proportion of copolyester components with lower surface energy present near the surface of the adhesive modifying layer increases.

(Copolymer polyester)

It is preferable that the copolyester used for the adhesive modifying layer used by this invention uses an aromatic dicarboxylic acid component and the glycol branched from ethylene glycol as a glycol component as a component. The branched glycol component is, for example, 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-hexyl-1,3- Propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-n-butyl-1,3-propanediol, 2-ethyl-2-n-hexyl-1,3-propanediol , 2,2-di-n-butyl-1,3-propanediol, 2-n-butyl-2-propyl-1,3-propanediol, and 2,2-di-n-hexyl-1,3- And propanediol.

The molar ratio of the branched glycol component is preferably 10 mol%, particularly preferably 20 mol%, based on the total glycol component. On the other hand, it is preferable that an upper limit is 80 mol%, More preferably, it is 70 mol%, Especially preferably, it is 60 mol%. Moreover, you may use together diethylene glycol, propylene glycol, butanediol, hexanediol, 1, 4- cyclohexane dimethanol, as needed.

As the aromatic dicarboxylic acid component, terephthalic acid and isophthalic acid are most preferred. With respect to all the dicarboxylic acid components, in the range of 10 mol% or less, other aromatic dicarboxylic acids, especially diphenylcarboxylic acid and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, are added You may copolymerize.

It is preferable to use resin which is water-soluble or water-dispersible as the copolyester used as a resin component of an adhesive modified layer in this invention. For this reason, it is preferable to use 5-sulfoisophthalic acid or its alkali metal salt in 1-10 mol% range other than the said dicarboxylic acid component, in order to provide water dispersibility to polyester, For example, Terephthalic acid, 5-sulfoisophthalic acid, 4-sulfonaphthalene isophthalic acid-2,7-dicarboxylic acid and 5- (4-sulfophenoxy) isophthalic acid or an alkali metal salt thereof.

(Polyurethane)

As the polyurethane used for the adhesive modifying layer, it is preferable to use a resin which is water-soluble or water-dispersible. For example, as resin containing a block type isocyanate group, the heat-reactive type water-soluble urethane etc. which sealed the terminal isocyanate group by the hydrophilic group (henceforth abbreviate block) are mentioned.

Examples of the blocking agent for the isocyanate group include phenols, alcohols, lactams, oximes, or active methylene compounds containing bisulfite and sulfonic acid groups. Blocked isocyanate groups hydrophilize or solvate urethane prepolymers. When the thermal energy is applied to the resin in the drying step or the heat setting treatment step in manufacturing the film, the blocking agent is released from the isocyanate group, so that the resin immobilizes the water-dispersible copolyester mixed in the self-crosslinked crevice. At the same time, it also reacts with the end groups of the resin. Since resin in coating liquid adjustment is hydrophilic, water resistance is bad, but when a thermal reaction is completed by apply | coating, drying, and heat setting, the hydrophilic group of a urethane resin, ie, a blocking agent, falls, and the coating film with favorable water resistance is obtained.

Among the above-mentioned blocking agents, bisulfite is most preferable from the viewpoint of the blocking agent falling from the isocyanate group at the heat treatment temperature and the heat treatment time in the film production process and from the viewpoint of industrial availability. As a chemical composition of the urethane prepolymer used in the said resin, (1) The organic polyisocyanate which has 2 or more active hydrogen atoms in a molecule, or the compound whose molecular weight which has at least 2 active hydrogen atoms in a molecule is 200-20,000, ( 2) A compound having a terminal isocyanate group obtained by reacting an organic polyisocyanate having two or more isocyanate groups in a molecule or (3) a chain extender having at least two active hydrogen atoms in a molecule.

Generally known as the compound of (1) include two or more hydroxyl groups, carboxyl groups, amino groups or mercapto groups in the terminal or molecule, and particularly preferred compounds include polyether polyols and polyether ester polyols. Can be mentioned. Moreover, as polyether polyol, For example, the compound which superposed | polymerized alkylene oxides, such as ethylene oxide and a propylene oxide, or styrene oxide, epichlorohydrin, etc., or their random polymerization, block polymerization, or a polyhydric alcohol The compound obtained by carrying out addition polymerization is mentioned.

As polyester polyol and polyether ester polyol, a linear or branched compound is mainly mentioned. Polyvalent saturated or unsaturated carboxylic acids such as succinic acid, adipic acid, phthalic acid and maleic anhydride, or the carboxylic acid anhydride and the like, and ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6- It can obtain by condensing polyhydric saturated and unsaturated alcohols, such as hexanediol and a trimethylol propane, polyalkylene ether glycols, such as relatively low molecular weight polyethyleneglycol and polypropylene glycol, or a mixture of these alcohols.

Moreover, as polyester polyol, polyesters obtained from lactone and hydroxy acid are mentioned. As the polyether ester polyol, polyether esters in which ethylene oxide or propylene oxide is added to polyesters prepared in advance can be used.

As organic polyisocyanate of said (2), isomers of toluylene diisocyanate, aromatic diisocyanates, such as 4, 4- diphenylmethane diisocyanate, aromatic aliphatic diisocyanates, such as xylylene diisocyanate, isophorone di Alicyclic diisocyanates such as isocyanate and 4,4-dicyclohexylmethane diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate, or compounds thereof The polyisocyanate added previously with trimethylol propane etc. in plurality is mentioned.

Examples of the chain extender having at least two active hydrogens of the above (3) include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, glycerin, trimethylolpropane, and penta Polyhydric alcohols such as erythritol, diamines such as ethylenediamine, hexamethylenediamine, and piperazine, amino alcohols such as monoethanolamine and diethanolamine, thiodiglycols such as thiodiethylene glycol, or water Can be.

In order to synthesize | combine a urethane prepolymer, it is 5 minutes at 150 degrees C or less, Preferably it is 70-120 degreeC by the single-type or multistage isocyanate polyaddition method using the said chain extending agent normally. To several hours. The ratio of isocyanate groups to active hydrogen atoms is freely selected if it is 1 or more, but it is necessary that free isocyanate groups remain in the urethane prepolymer obtained. Moreover, content of the free isocyanate group should just be 10 mass% or less, but considering the stability of the urethane polymer aqueous solution after blocking, it is preferable that it is 7 mass% or less.

The urethane prepolymer obtained is preferably blocked using bisulfite. The mixture is mixed with an aqueous bisulfite solution and the reaction is allowed to proceed with stirring for about 5 minutes to 1 hour. It is preferable that reaction temperature shall be 60 degrees C or less. Thereafter, the mixture is diluted with water to an appropriate concentration to obtain a heat-reactive water-soluble urethane composition. The composition is prepared at an appropriate concentration and viscosity when used. Usually, heating to around 80 to 200 ° C. dissociates the bisulfite of the blocking agent and regenerates an active isocyanate group. This produces a polyurethane polymer or has the property of causing addition to other functional groups.

As an example of resin (B) containing the block-type isocyanate group demonstrated above, the brand name Elastron by Dai-ichi Kogyo Pharmaceutical Co., Ltd. is typically illustrated. Elastron is an isocyanate group blocked by sodium bisulfite, and it is water-soluble because a carbamoylsulfonate group having strong hydrophilicity exists at the terminal of the molecule.

(b) solvent

In the present invention, the solvent broadly includes not only the liquid for dissolving the resin but also the dispersion medium used to disperse the resin in the form of particles. In order to practice this invention, various solvents, such as an organic solvent and an aqueous solvent, can be used.

As for the solvent used for a coating liquid, the liquid mixture which mixed water and alcohols, such as ethanol, isopropyl alcohol, benzyl alcohol, in the whole coating liquid in the range of 30-50 mass% is preferable. Moreover, if it is less than 10 mass%, you may mix organic solvents other than alcohol in the range which can melt | dissolve. However, the sum total of alcohols and other organic solvents in a coating liquid shall be less than 50 mass%.

When the amount of the organic solvent added is less than 50 mass% with respect to the total solvent, there is an advantage that the drying property is improved at the time of coating drying and the appearance of the coating layer is improved compared with the case of water alone. When the amount of the organic solvent added is 50% by mass or more with respect to all the solvents, the solvent evaporation rate is increased, and the concentration of the coating liquid tends to occur during coating. As a result, since the viscosity of a coating liquid rises and applicability | paintability falls, the external appearance of a coating film may be caused. In addition, the volatilization of the organic solvent also increases the risk of fire and the like. In addition, when the addition amount of the organic solvent is less than 30% by mass relative to the total solvent, the proportion of water is relatively increased, and the polyurethane component having high hydrophilicity is segregated near the surface of the adhesive modified layer. As a result, it becomes difficult to make the area ratio on the PEs 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 within an appropriate range.

(c) pH adjustment of the coating liquid

It is preferable that the coating liquid used for forming an adhesive modified layer in this invention has a pH of 5-5 or less. When the pH of the coating liquid is less than 5, the area ratio of the PEs on the surface of the adhesive modified layer is increased, or the area ratio of the PU phase near the interface with the hard coat layer at the cutting surface of the adhesive modified layer is decreased, resulting in an adhesive property. This tends to fall. On the other hand, when pH of a coating liquid is 8 or more, remarkable aggregation arises according to the kind of particle | grains, haze rises, and transparency is unpreferable. The pH adjuster is not particularly limited as long as it does not adversely affect adhesion, blocking resistance, or coating property or can be ignored. For example, sodium bicarbonate or sodium carbonate may be used to increase the pH, and acetic acid or the like may be used to lower the pH.

(d) use with surfactants

When apply | coating the said aqueous coating liquid to the surface of a thermoplastic resin film, surfactant is generally used in order to improve the wettability to the said film, and to apply | coat a coating liquid uniformly. In addition, in this invention, surfactant can be used as one of means for controlling the phase-separation structure of the surface of an adhesive modified layer or an inside.

The type of surfactant is not particularly limited as long as good coatability is obtained and an appropriate phase separation structure is obtained from the surface or inside of the adhesive modifying layer. Among the surfactants, fluorine-based surfactants are suitable for obtaining good applicability by addition of a small amount. Moreover, in order to make the area ratio on the PEs of the surface of an adhesive modified layer, or the area of PU phase near an interface with the hard-coat layer in the cutting surface of an adhesive modified layer into an appropriate range, cationic surfactant or nonionic It is preferable to mix | blend 0.01-0.18 mass% of system type surfactant with respect to coating liquid.

When anionic surfactant is used, compatibility with the copolyester and polyurethane shown above may be improved, and the phase separation structure prescribed | regulated by this invention is hard to be obtained. The addition amount of surfactant can be suitably selected if it is a range which can obtain favorable applicability | paintability, without impairing adhesiveness with functional layers, such as a hard-coat layer and a diffusion layer. For example, in the case of a fluorine-based surfactant, 30 times or less thereof is suitable from the critical micelle concentration with respect to pure water. At 30 times or more of the critical micelle concentration, since the particles contained in the coating liquid tend to aggregate, the haze of the obtained laminated film rises, which is not particularly preferable as the base film of the light diffusing functional film. In addition, the surfactant component may bleed out to the surface of the adhesive modifying layer, which may adversely affect the adhesion. On the other hand, favorable application property is not obtained below the critical micelle concentration. In addition, it becomes difficult to control the area ratio on the PEs on the surface of the adhesive modified layer or the area ratio on the PU near the interface with the hard coat layer on the cutting surface of the adhesive modified layer in an appropriate range.

(Purification of surfactant)

It is preferable to use the refined thing for surfactant used for this invention. Commercially available surfactants generally contain trace amounts of impurities. In particular, polyethylene glycol as an impurity may inhibit the obtaining of a good phase separation structure depending on the content. In order to prevent this, it is preferable to perform pretreatment which removes an impurity from surfactant, and to use the refined surfactant.

As a pretreatment process of removing an impurity, if an impurity can be removed without altering surfactant, a method is not specifically limited. For example, the following method is mentioned.

The method of melt | dissolving surfactant and polyethyleneglycol at least in the soluble organic solvent, leaving it to stand at low temperature, saturating and settling the surfactant which is a main component, and then filtering out the surfactant which improved the purity is carried out. In the case of a perfluoroalkyl ethylene oxide adduct-based surfactant, after heating and dissolving it in isopropyl alcohol in a 30 degreeC warm bath, it is left to stand at 0 degreeC for about 24 hours, and the precipitate is filtered out and the surfactant is obtained by improving purity. Can be.

(e) particles

It is preferable that the haze of the adhesive modified base film is 1.5% or less when using a hard coat film or an optical functional film using this film for the purpose of highly required transparency. It is further more preferable that said haze is 1.0% or less. When the haze exceeds 1.5%, when the film is used for a lens film for LCD, a base film for backlight, or the like, the sharpness of the screen is lowered, which is not preferable.

In order to make the haze of an adhesive modified base film 1.5% or less, it is preferable not to contain particle | grains in a thermoplastic resin film. In the case where the particles are not contained in the thermoplastic resin film, in order to improve scratch resistance, handling properties when winding up or unwinding (active, running property, blocking property, air releasing property of accompanying air at the time of winding up), It is preferable to contain a specific amount of particles of a suitable size in the adhesive modifying layer to form appropriate irregularities on the surface of the adhesive modifying layer.

As particle | grains, the particle | grains which have high affinity with copolyester or polyurethane are preferable, and it is preferable that there exists a difference of the degree to which the affinity for both is unevenly distributed on either side. By localizing the particles on one side of the resin in which the particles are phase separated, the particles are appropriately gathered, and excellent blocking resistance can be obtained by adding relatively few particles, that is, without significantly increasing the haze.

The particles to be contained in the adhesive modification layer include calcium carbonate, calcium phosphate, amorphous silica, crystalline glass filler, kaolin, talc, titanium dioxide, alumina, silica-alumina composite oxide particles, barium sulfate, calcium fluoride, lithium fluoride, Inorganic particles such as zeolite, molybdenum sulfide, mica, crosslinked polystyrene particles, crosslinked acrylic resin particles, crosslinked methyl methacrylate particles, benzoguanamine formaldehyde condensate particles, melamine formaldehyde condensate particles, polytetrafluoro And heat resistant polymer particles such as ethylene particles.

Among these particles, silica particles are suitable in the following aspects.

The 1st advantage is that since the resin component and refractive index of an adhesive modified layer are comparatively close, it is easy to obtain a high transparency film. The second advantage is that the silica particles tend to be ubiquitous on the phase-separated polyurethane, thereby compromising the inherent properties of the polyurethane-type resin, which is inferior in blocking resistance on the polyurethane present on the adhesive modified layer surface. That can be. This is considered to be because surface energy of a silica particle and a polyurethane is closer than co-polyester, and affinity is high.

Moreover, although the shape of particle | grains is not specifically limited, The particle | grains close to a spherical form are preferable from the aspect which gives a diactivation.

It is preferable to make content of particle | grains in an adhesive modified layer into 20 mass% or less with respect to an adhesive modified layer, More preferably, it is 15 mass% or less, Especially preferably, it is 10 mass% or less. When content of particle | grains in an adhesive modifying layer exceeds 20 mass%, transparency will deteriorate and adhesiveness of a film will also become inadequate easily. On the other hand, the lower limit of the particle content is preferably 0.1 mass%, more preferably 1 mass%, particularly preferably 3 mass% with respect to the adhesive modifying layer.

Moreover, you may contain two or more types of particle | grains from which an average particle diameter differs in an adhesive modified layer. Moreover, you may contain what differs in average particle diameter from the same kind of particle | grains. In any case, what is necessary is just to make the average particle diameter and total content of particle | grains into the said range. When apply | coating the said coating liquid, in order to remove the coarse aggregate of particle | grains in a coating liquid, it is preferable to arrange | position a filter medium so that a coating liquid may be filtered fine immediately before application | coating.

Moreover, 20-150 nm is preferable and, as for the average particle diameter of particle | grains, More preferably, it is 40-60 nm. If the average particle diameter is less than 20 nm, not only it is difficult to obtain sufficient blocking resistance, but also scratch resistance tends to deteriorate. On the other hand, when the average particle diameter of particle | grains exceeds 150 nm, since a haze rises and a particle falls easily, it is unpreferable.

In the present invention, sufficient blocking resistance and scratch resistance may not be obtained with only particle A having an average particle diameter of 20 to 150 nm. For this reason, in order to further improve blocking resistance and scratch resistance, it is preferable to use together a small amount of particle | grains B with a large average particle diameter further. 160-1000 nm is preferable and, as for the average particle diameter of the particle | grain B with a large average particle diameter, Especially preferably, it is 200-800 nm. When the average particle diameter of the particle B is less than 160 nm, scratch resistance, activity, and winding property may deteriorate. On the other hand, when the average particle diameter of the particle B exceeds 1000 nm, there exists a tendency for a haze to become high. In addition, it is preferable that particle | grain B is the aggregate particle which the primary particle aggregated, and it is preferable from the viewpoint of scratch resistance that the particle | grain which has ratio of 4 times or more of the average particle diameter in agglomerated state and the average particle diameter of a primary particle is used.

When two kinds of particles are used, for example, the content ratio (P1 / P2) of particle A (average particle diameter: 20 to 150 nm) and particle B (average particle diameter: 160 to 1000 nm) in the adhesive modifying layer is 5 It is set to -30, and content of particle | grain B is made into 0.1-1 mass% with respect to solid content of an adhesive modified layer. Controlling the particle content of two kinds of specific particle diameters in the above range is suitable for optimizing the three-dimensional center plane average surface roughness of the surface of the adhesive modifying layer to achieve both transparency and handling resistance and blocking resistance. When content of particle | grains B exceeds 1 mass% with respect to an adhesive modified layer, there exists a tendency for the rise of a haze to become remarkable.

The measurement of the average primary particle diameter and average particle diameter of the said particle | grains is performed by the following method.

The particle | grain is photographed with an electron microscope, the largest diameter of 300-500 particle | grains is measured at the magnification which the size of one smallest particle becomes 2-5 mm, and makes the average value into an average primary particle diameter or an average particle diameter. In addition, when obtaining the average particle diameter of the particle | grains in the adhesive modified layer of a laminated | multilayer film, the cross section of a laminated | multilayer film is image | photographed at 120,000 times magnification using a transmission electron microscope (TEM), and the particle which exists in the cross section of an adhesive modified layer is used. The maximum diameter of can be found. The average particle diameter of the particle | grains B which become an aggregate makes the cross section of the adhesive modified layer of a laminated | multilayer film photograph 300-500 pieces at 200 times magnification using an optical microscope, and measures the maximum diameter.

(f) crosslinking agent

As mobile phones, PDAs, and mobile computers, opportunities for using information terminals outdoors are increasing. In addition, as used in touch panels used in automobile navigation and the like, materials used in cars that become hot in summer are increasing. Therefore, a hard coat film with a small change in quality even under such high temperature and harsh environment, that is, a film excellent in moisture heat adhesiveness, is desired in such a use.

When using the hard coat film of this invention for such a use, in order to improve the heat-and-moisture resistance of an adhesive modifying layer, the adhesive containing resin which has a crosslinked structure by adding a crosslinking agent to a coating liquid, and then heat-processing is performed. Form a modifying layer. As a crosslinking agent, 1 or more types chosen from an epoxy crosslinking agent, a melamine type crosslinking agent, and an oxazoline type crosslinking agent are used. A crosslinking agent can be selected in consideration of affinity with the copolyester resin used for a coating liquid, and the moisture heat adhesiveness required for an adhesive modified layer.

In particular, when high moisture heat adhesiveness is required, an epoxy crosslinking agent or a melamine crosslinking agent is preferable among the crosslinking agents. Although it does not specifically limit as an epoxy type crosslinking agent, For example, Water-soluble epoxy crosslinking agent made from Nagase Chemical Industries, Ltd. (Deconal series; EX-521, EX-512, EX-421, EX-810, EX-811, EX-851, etc.) ) Is available as a commercial item. As a melamine type crosslinking agent, Sumitomo Chemical Co., Ltd. Sumitex resin series (M-3, MK, M-6, MC etc.) and the methylated melamine resin (MW-22, MX-706 etc.) by Sanwa Chemical Co., Ltd. are commercial items, for example. It is available as. As the oxazoline-based crosslinking agent, Epocross series (WS-700) made by Nippon Shokubai Co., Ltd., NX Linker FX made by Shin-Nakamura Chemical Co., Ltd., and the like can be obtained as commercial products.

The crosslinking agent is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total amount (100 mass%) of the copolyester resin and the crosslinking agent in the adhesive modifying layer. It is preferable to make it contain in the coating liquid for solvents. When the content of the crosslinking agent exceeds 40% by mass, the adhesive modifying layer is submerged, so as to withstand high-speed cutting in the processing step after forming a functional layer such as a hard coat layer or a diffusion layer made of an acrylate resin. May not be sufficiently obtained. On the other hand, when content of a crosslinking agent is less than 5 mass%, the durability currently calculated | required may be hard to be acquired recently. In addition, in a coating liquid, you may add a catalyst as needed in order to accelerate crosslinking.

(3-2) Coating process

As for the process of apply | coating the said aqueous coating liquid, the in-line coat method apply | coated during the manufacturing process of the said film is preferable. More preferably, it applies to the base film before crystal orientation is completed. It is preferable that solid content concentration in an aqueous coating liquid is 30 mass% or less, Especially preferably, it is 10 mass% or less. As for the minimum of solid content concentration, 1 mass% is preferable, More preferably, it is 3 mass%, Especially preferably, it is 5 mass%. The film coated with the aqueous coating liquid is guided to a tenter for orientation and heat setting, and is heated there, to form a stable film by thermal crosslinking reaction to form a polyester-based laminated film.

(Amount of application)

It is preferable to make the coating amount at the time of undrying (it abbreviates as a wet coating amount hereafter) 2 g / m <2> or more and less than 10 g / m <2>. In order to obtain the dry coating amount (coating amount of the final adhesive modified layer) of the design at less than 2 g / m 2 of the wet coating amount, it is necessary to increase the solid content concentration of the coating liquid. When the solid content concentration of a coating liquid is made high, since the viscosity of a coating liquid becomes high, a striped coating unevenness tends to occur. On the other hand, when wet application amount is 10 g / m <2> or more, it is easy to be influenced by the drying wind in a drying furnace, and application | coating unevenness tends to generate | occur | produce. Moreover, in order to prevent the fault by adhesion of dust, it is preferable to apply | coat a coating liquid in the clean environment whose cleanness is class 5000 or less.

In addition, it is preferable to manage the application amount (solid content mass per film unit area) of a final adhesive modified layer at 0.005-0.20 g / m <2>. In the prior art, when the coating amount is less than 0.05 g / m 2, sufficient adhesiveness is hardly obtained. However, when the adhesive modifying layer has a specific phase separation structure, a laminated film having excellent adhesion to the functional layer and the substrate is obtained even when the coating amount is less than 0.05 g / m 2. Adhesiveness will become inadequate when coating amount is less than 0.005 g / m <2>. In addition, when application amount is less than 0.05 g / m <2>, it is preferable that the particle | grains to be used use the particle | grains whose average particle diameter is 60 nm or less. When the average particle diameter of particle | grains exceeds 60 nm, particle | grains will fall easily from an adhesive modified layer at the time of manufacture or processing of an adhesive base film. In the case where the particles are unevenly distributed on the polyurethane, the particles are unlikely to fall off when the coating amount is 0.005 g / m 2 or more. On the other hand, when application amount exceeds 0.20 g / m <2>, the polyurethane component which segregates on the adhesive modified layer surface increases, and blocking resistance falls.

In addition, although the thickness of an adhesive modified layer can be measured by cutting the cross section of an adhesive modified layer with a microtome, and observing with an electron microscope, when an adhesive modified layer is soft, it may deform | transform at the time of cutting. For simplicity, if the coating amount is already known, the thickness can be converted from the density of the adhesive modifying layer. For example, in the case where the density of the adhesive modifying layer is 1 g / cm 3, if the coating amount is 1 g / m 2, the thickness corresponds to 1 μm. The density of the adhesive modifying layer is obtained by obtaining the density of each material from the types of resins and particles constituting the adhesive modifying layer, multiplying the density of each material by the mass ratio of the material, and obtaining the sum of the thicknesses of the adhesive modifying layers. Can be estimated.

(3-3) Drying process

In the manufacturing method of an adhesive modified base film, after apply | coating a coating liquid to a thermoplastic resin film, the coating film apply | coated thinly is dried. Generally, after apply | coating a coating liquid, when drying a coating film, it often makes it dry using the preheating zone of a tenter. In this case, depending on the size of the film forming equipment and the traveling speed of the film, generally, the time from application to start of drying takes at least about 5 seconds. In the meantime, the balance of water and alcohol which are solvents of the coating liquid is disturbed, and the polyurethane component having high hydrophilicity tends to segregate on the adhesive modified layer surface. For this reason, in the finally obtained adhesive modified base film, the area ratio on the PEs of the surface of an adhesive modified layer, or the area ratio of the PU phase near the interface with the hard-coat layer in the cutting surface of an adhesive modified layer is suitable. It becomes difficult to control to the range. In this invention, it is an important point to arrange the drying furnace (free dryer) dedicated to drying a coating film as close as possible to the exit of the film advancing direction of a coating device, and to apply | coat a coating liquid to a polyester film, and to dry immediately. .

In a drying furnace, it is preferable that the temperature of the drying wind which contacts a coating surface is 120 degreeC or more and less than 150 degreeC. In addition, the wind speed is preferably 30 m / sec or more. More preferable drying temperature is 130 degreeC or more and less than 150 degreeC. When this drying temperature is less than 120 degreeC or less than 30 m / sec of wind speed, a drying speed will become slow, the balance of water and alcohol which are solvents of a coating liquid will be disturbed, and the ratio of water will become easy to increase relatively. For this reason, a highly hydrophilic polyurethane component segregates on the adhesive modified layer surface. For this reason, in the finally obtained adhesive modified base film, the area ratio on the PEs of the surface of an adhesive modified layer, or the area ratio of the PU phase near the interface with the hard-coat layer in the cutting surface of an adhesive modified layer is suitable. It becomes difficult to control to the range. On the other hand, when a drying temperature is 150 degreeC or more, crystallization of a thermoplastic resin film tends to occur and the frequency which a fracture generate | occur | produces at the time of lateral stretch increases.

Moreover, in said drying furnace, it is preferable to dry for 0.1 to 5 second, maintaining temperature at 120 degreeC or more and less than 150 degreeC. The drying time is more preferably 0.5 to 3 seconds. When the drying time is less than 0.1 second, drying of the coating film becomes insufficient, and when passing through the roll disposed between the drying step and the transverse stretching step, the roll is easily contaminated on the application surface where the drying is insufficient. On the other hand, when the drying time exceeds 5 seconds, crystallization of the thermoplastic resin film is likely to occur, and the frequency at which fracture occurs during lateral stretching increases.

After drying a coating film at the temperature of 120 degreeC or more and less than 150 degreeC in the said drying furnace, it is preferable to immediately cool the adhesive modified base film which has an adhesive modified layer to near room temperature. When the adhesive modified base film contacts a roll near room temperature as the surface temperature of the said adhesive modified base film is 100 degreeC or more, a flaw will be easy to generate | occur | produce by shrinkage of a film.

When the wind speed in a drying furnace is set to 30 m / sec or more normally, since strong drying wind will contact the undried surface in a drying furnace, dry staining will be easy to generate | occur | produce. However, in the present invention, it is possible to carry out at a wind speed of 30 m / sec or more by exhausting the air volume to be injected and the same or more air volume to the outside of the drying furnace. In addition, it is also important that the exhaust wind flows to the opposite side to the coater, and to prevent staining of the coated surface by the exhaust wind from the coater.

It is important that the passing time of the film from immediately after application to entering the drying furnace is less than 2 seconds, preferably less than 1.5 seconds. If the time from the coating to the drying furnace is 2 seconds or more, the balance between the water and the alcohol, which is the solvent of the coating liquid, is disturbed during this period, whereby a highly hydrophilic polyurethane component tends to segregate on the adhesive modified layer surface. Lose. For this reason, the finally obtained adhesive modified base film has the area ratio on the PEs of the surface of an adhesive modified layer, or the area ratio of the PU phase near the interface with the hard-coat layer in the cutting surface of an adhesive modified layer to an appropriate range. It becomes difficult to do it.

In order to maintain the passage time of the film from immediately after the application until entering the drying furnace, it is necessary to select the running speed of the film appropriately, but it is preferable to bring the coater and the inlet furnace as close as possible. In addition, in order to prevent the mixing of the dust from the drying wind in a drying furnace, it is preferable to use the air cleaned by the HEPA filter. It is preferable that the HEPA filter used at this time uses the filter which has the ability to cut 95% or more of dust of 0.5 micrometers or more of nominal filtration accuracy.

It is preferable that a drying process consists of a drying zone divided into what is called 2-8 zones which changed the conditions of a drying temperature and a drying time sequentially. Especially preferably, the multistage drying apparatus divided into 3-6 zones is employ | adopted. For example, when a coating liquid is apply | coated to one side or both sides of a uniaxially-oriented thermoplastic resin film, and it is dried in the multistage drying furnace arrange | positioned directly on a coater, the following method is suitable.

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

The numerical ranges of the drying conditions vary slightly depending on the solid content concentration of the coating liquid, and are not limited to the representative conditions. In addition, when performing hot air drying, it is important to make the air volume change at each stage, too.

For example, the following method is suitable.

In the first drying zone, the wind speed of the drying wind is set to 20 to 50 m / sec, the air supply air volume of the drying wind is set to 100 to 150 m 3 / sec, and the exhaust air volume is set to 150 to 200 m 3 / sec. From the second drying zone to the fourth drying zone, the air supply air volume is set to 60 to 140 m 3 / sec and the exhaust air volume is set to 100 to 180 m 3 / sec. In any drying zone, it is set so that dry wind does not flow to a coater side, and the edge part of a film is gripped with a clip, it guides to the hot wind zone of 10-20 m / sec wind speed at the temperature of 100-140 degreeC, and it is 2-6 times in the width direction Stretch

Moreover, what is necessary is just to adjust a drying temperature and total drying time suitably in time for 0.1 to 5 second, Preferably it is 0.5 second to less than 3 second, maintaining temperature from 120 degreeC to 150 degreeC. Determination of each stage (zone) in this drying process takes appropriate conditions at the manufacturing site in consideration of all conditions such as the concentration of the dispersion, the application amount, the traveling speed of the applied traveling film, the temperature of the hot air, the wind speed, and the air volume. You can decide.

(3-4) Heat setting treatment process

In the method for producing an adhesive modified base film, the lateral stretching step, the heat setting treatment step, and the cooling step are continuously divided into 10 to 30 zones, and each zone is independently divided to enable temperature control, and each zone It is designed so that a sudden temperature change does not occur in between. In particular, in the heat setting maximum temperature setting zone from the second half of the transverse stretching zone, the temperature is gradually raised to suppress a sudden temperature change between adjacent zones. In the present invention, when producing an adhesive modified base film having a phase-separated structure specific to the surface or inside of the adhesive modified layer, temperature control is particularly important in a drying step or a heat setting treatment step. In addition, in order to form a crosslinked structure in resin which comprises an adhesive modified layer, the temperature in a heat setting treatment process is very important, and this temperature has a big influence on a crosslinking reaction rate.

Hereinafter, the embodiment is explained in full detail.

As described above, the heat treatment conditions in the heat setting treatment process determine the phase separation state of the adhesive modified layer. That is, from the maximum temperature in the heat setting treatment process, the time required to reach the maximum temperature, and the temperature at which phase separation of the adhesive reforming layer starts to proceed remarkably, from the maximum temperature in the heat setting treatment process. It is important to properly set the time it takes to reach.

Although the temperature in each heat setting zone in a heat setting treatment process differs slightly according to the kind of resin which comprises a thermoplastic resin film, what is necessary is just to set suitably within the temperature range of 100-260 degreeC. Hereinafter, the case where the polyethylene terephthalate which is typical thermoplastic resin is made into a thermoplastic resin film is demonstrated as an example.

It is preferable to control the maximum temperature in a heat setting treatment process to 210-240 degreeC, More preferably, a minimum is 225 degreeC and an upper limit is 235 degreeC. Generally, in the initial stage of heat setting treatment, heat setting is performed at a relatively high temperature of 210 to 240 ° C., and the temperature is gradually lowered to 100 to 200 ° C. as it becomes a later step.

If the maximum temperature in a heat setting treatment process is less than 210 degreeC, it is difficult to form a micro phase separation structure or a nano phase separation structure in an adhesive modified layer. Therefore, the adhesiveness of a base material and a functional layer which can endure peeling of the interface by the impact at the time of high speed cutting currently requested | required becomes difficult to be obtained sufficiently. Moreover, the thermal contraction rate of the obtained adhesive modified base film becomes large and it is unpreferable.

In addition, when the maximum temperature in a heat setting treatment process exceeds 240 degreeC, the PEs surface fraction of the surface of an adhesive modified layer becomes large, and a hard coat layer, a diffusion layer, a prism layer, the printing layer printed with ultraviolet curable ink, etc. The adhesiveness to the functional layer of the tends to be lowered. In addition, since the time taken to reach the maximum temperature of the heat setting treatment is increased from the temperature at which the phase separation of the adhesive reforming layer starts to proceed remarkably, the thinnest portion of the polyester phase containing the copolyester as a main component The point where the width | variety of more than 1 micrometer exists is dotted. As a result, locations with poor adhesion to functional layers such as a hard coat layer, a diffusion layer, a prism layer, and a printing layer printed with an ultraviolet curable ink may be generated locally, which may lead to macroscopic peeling from the portion. .

It is preferable to specifically set 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.

In the present invention, the passing time of the film from the temperature setting zone where the phase separation of the adhesive reforming layer starts to proceed remarkably to the entrance of the maximum temperature setting zone of the heat setting treatment step is preferably 3 seconds or more and less than 20 seconds. Especially preferably, they are 4 second or more and less than 15 second.

When the said transit time is less than 3 second, the time for expressing the phase separation structure prescribed | regulated by this invention may be insufficient. On the other hand, when said passage time is 20 seconds or more, phase separation advances excessively, and it becomes easy to be in the state where the location where the width | variety of the thinnest part of a phase which has co-polyester as a main component exceeds 1 micrometer is dotted. As a result, a location inferior to adhesiveness with respect to functional layers, such as a hard-coat layer, a diffusion layer, a prism layer, and the printing layer printed with UV ink locally, may generate | occur | produce a macro peeling from the part as a starting point.

In the present invention, the temperature at which the phase separation of the adhesive modifying layer starts to proceed remarkably is estimated to be about 200 ° C in the range of the coating liquid composition shown in Examples of the present invention. However, since the temperature is naturally different depending on the resin component of the adhesive modifying layer, it is not limited to this temperature.

The heat setting treatment process will be described in more detail.

In general, the transverse stretching step, the heat setting treatment step, and the cooling step are divided into 10 to 30 zones in the tenter to suppress sudden temperature changes in adjacent zones, and temperature control is independently performed in each zone. Particularly, in the zone set to the highest temperature of the heat setting treatment process from the second half of the lateral stretching zone, it is preferable to raise the temperature of each zone step by step in the film advancing direction so that a sudden temperature change between each heat setting zone does not occur. Do.

In the present invention, it is important to rapidly and uniformly increase the passing time of the film from the temperature setting zone where the phase separation starts to proceed remarkably to the entrance of the maximum temperature setting zone of the heat setting treatment step. In order to raise a temperature rapidly, the method of improving heat transfer efficiency in each heat setting zone, for example, the method of making the wind speed of the hot air injected into a film high, is effective. However, this method is generally susceptible to temperature staining, so that when staining occurs in the phase-separated state of the adhesive modifying layer, foreign matters such as oligomers that slightly adhere to the device in the heat-setting zone are blown up, It may adhere to the film and lead to optical defects.

On the other hand, if the wind speed is too low, a sufficient temperature increase rate cannot be obtained. Therefore, in the present invention, the wind speed is preferably 10 m / sec or more and less than 20 m / sec. In order to raise the laminated film rapidly and uniformly, a means for arranging the intervals of the nozzles for injecting the hot air at relatively short intervals of 500 mm or less is effective. When arranging the nozzle spacing for spraying hot air at 500 mm or less, for example, when the nozzle spacing is arranged at 300 mm, 350 mm, and 400 mm, the equipment maintenance phase becomes disadvantageous, but it is important to complete the present invention. Do. The number of nozzles per zone corresponding to one stage is about 6-12, and the number is determined in consideration of the state of nozzle spacing, ventilation volume, and ventilation time. In addition, the wind speed described in this invention means the wind speed in the film surface which faces the hot air injection nozzle exit, and is measured using the thermal anemometer (made by Nippon Kanomex, Anemone model 6161).

One preferable embodiment of the heat setting treatment process at the time of manufacturing an adhesive modified base film is shown.

The heat setting treatment step is divided into a plurality of heat setting zones in succession, and each zone is divided so that temperature control can be performed independently. The heat setting zone is divided into a process in which 2 to 10 steps of heat setting zones are continuously arranged, preferably a process of 4 to 8 steps, and the temperature control management of the adhesive-modified base film in the heat setting zone divided into these steps It is preferable to

For example, in the case of a polyester film having an adhesive modification layer, the heat setting zone divided into six stages is successively passed through as follows, and the heat setting treatment is performed by giving a subtle temperature difference in each step, and the film The method of trimming the uncoated part of both ends is mentioned. 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 and 210 in the fifth heat setting zone. 170 degreeC in a 6th heat setting zone and 120 degreeC in a 7th heat setting zone. In the sixth heat-setting zone, a 3% relaxation treatment is performed in the width direction.

The above stage corresponds to one heat setting zone. Thus, it is suitable to have a subtle temperature difference to the temperature of the heat setting zone of each stage, ie, to have a temperature difference of about 5-40 degreeC. The setting of this temperature difference is arbitrarily determined in consideration of all factors such as the traveling speed, the air volume and the thickness of the adhesive modified layer of the thermoplastic resin film having the adhesive modified layer.

When using it as a base film of optical functional films, such as a lens film and a diffusion plate, even if it is a comparatively thick film whose film thickness is 100 micrometers or more, a film length is a form wound up in roll shape at least 1000 m or more and sometimes 2000 m or more normally, a prism It is provided to the process of laminating | stacking a layer or a diffusion layer.

In the present invention, the area ratio of the PEs phase (showing a dark color in the 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 (in phase) It is preferable to make the difference of the maximum value and minimum value of the area ratio of the longitudinal direction into 15% or less, when measuring light color) by 100 m space in the longitudinal direction of a film, More preferably, it is 10% or less . By making the difference of the maximum value and minimum value of the area ratio in the longitudinal direction into 15% or less, the adhesive modified base film roll which has stable adhesiveness and blocking resistance is obtained.

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 are used in the present invention. It is important to keep it constant at the time of manufacturing continuously the adhesive modified base material film roll of a. However, especially the ratio of the mixed solvent used for a coating liquid changes easily, and the study which keeps the ratio of this mixed solvent constant is the area ratio of PEs of the surface in the longitudinal direction of a film roll, and the PU phase of the cutting surface. It is important to reduce the variation of the area ratio. For example, the fluctuation range of the area ratio on the PEs on the surface of the adhesive modified layer and the area ratio on the PU on the cutting surface can be controlled to 15% or less by the means shown below. In addition, the means for keeping the ratio of the mixed solvent constant is not limited to the following method.

It is effective to stabilize the concentration ratio of the mixed solvent by increasing the capacity of the circulation tank (13 in FIG. 7) with respect to the capacity of the support dish (11 in FIG. 7) of the coating liquid. Specifically, as shown in FIG. 7, when the capacity of the base plate of the coating liquid is 1, the volume ratio of the circulation tank is preferably 10 or more, particularly preferably 50 or more. When the capacity ratio (volume of the circulation tank / capacity of the support dish of the coating liquid) is less than 10, that is, the capacity of the circulation tank is too small, the variation in the concentration ratio of the mixed solvent tends to be large.

In addition, when the capacity of the circulation tank is set to 1, the capacity ratio of the combination tank (14 in FIG. 7) is preferably 10 or more, particularly preferably 20 or more. Thereby, the capacity | capacitance of a circulation tank can always be made constant at the time of supply, when supplying a coating liquid from a combination tank to a circulation tank.

In addition, increasing the precision (roundness and cylindricality) of the applicator roll in the coating device is also effective in reducing the coating thickness of the adhesive modified layer in the longitudinal direction of the film roll. Moreover, it is also effective in the aspect which makes small the fluctuation | variation of the characteristic accompanying the fluctuation of the area ratio on PEs of the surface of an adhesive modified layer in the longitudinal direction of a film roll, or the area on PU of a cutting surface.

As shown by JIS B 0621, the roundness of said applicator roll is an index represented by the difference of each radius of two concentric circles by the minimum area method determined using the recording type roundness measuring instrument. In addition, the unit of roundness of a roll is mm. In addition, the cylinder degree of an applicator roll moves a stand with a micrometer which placed the said roll on the surface plate in the axial direction, and measures it in various measurement planes over the whole length in the state which put the measuring instrument on the cylindrical upper surface. This is an index expressed by 1/2 of the maximum difference read at that time. In addition, the unit of cylindricality is mm.

In this invention, the thickness variation of the coating layer of a longitudinal direction can be reduced by improving roll precision (roundness and cylinder degree). Specifically, the roll accuracy (roundness and cylindricality) is preferably less than 5/1000 mm.

In addition, at the time of application | coating of a coating liquid, the surface finish of each roll of a reverse coater shall be 0.3 S or less, and the precision (roundness and cylindricality) of an applicator roll and a metaring roll shall be less than 5/1000 mm and 2/1000 mm. By making it into the above, the fluctuation | variation of the amount of wet application can be suppressed, and also the thickness fluctuation of a coating film can be suppressed. It is preferable to use an application roll whose precision (roundness and cylindricality) of an applicator roll and a metaring roll is 3/1000 mm.

In addition, when the tension of the film is set to 4000 to 10,000 N / disk width (disk 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 is uniform. In addition, the tension of the film is different depending on the thickness of the film, so that a relatively thin film maintains flatness by releasing a lower tension.

When the tension of the film exceeds 10000 N / disk width, the film may be deformed or broken. On the other hand, when the tension of a film is less than 4000 N / disk width, the planarity of the film at the time of application | coating may become inadequate, and meandering of a film may generate | occur | produce. As a result, the transfer amount of the coating liquid becomes nonuniform in the longitudinal direction of the film, and the wet coating amount of the film greatly fluctuates so that the thickness variation of the coating layer becomes larger.

Moreover, in order to control the fluctuation | variation (difference of the maximum value and the minimum value) of the area ratio on the PEs of the surface or PU phase of a cutting surface in an adhesive modified layer to 10% or less in the width direction of a film roll, a film roll It is important to reduce the fluctuations in the thickness of the coating layer in the width direction. For this purpose, it is effective to improve the planarity of the width direction at the time of application | coating. Specifically, immediately after application with a reverse roll, only the both end surfaces of a film are gripped using a pinch roll (16 of FIG. 7). By holding both ends of a film on a pinch roll, the flatness of the width direction of a film is improved on an industrial scale, and the wet coating amount of the width direction of a film is stabilized. Thereby, thickness fluctuation of the application layer in the width direction of a film roll can be reduced. When the both ends of the film are not gripped by the pinch rolls, the wet coating amount in the width direction and the longitudinal direction of the film is greatly varied, and the thickness variation of the coating layer is also greater.

(4) hard coat layer and other optical functional layers

The hard coat film of this invention is the adhesive modified base film which formed the adhesive modified layer B which consists of copolyester and a polyurethane on one side or both sides of the thermoplastic resin film A, and the adhesive modification of this film It is a hard coat film containing the laminated constitution of A / B / C or B / A / B / C in which the hard-coat layer C containing inorganic fine particles was laminated | stacked on one side of layer B. As curable resin which comprises a hard-coat layer, ionizing radiation curable resin is preferable. As ionizing radiation curable resin, the following resin is mentioned, for example.

The ionizing radiation curable resin is preferably a resin having an acrylate functional group, particularly preferably polyester acrylate or urethane acrylate. Polyester acrylate consists of acrylate or methacrylate (Hereinafter, acrylate and / or methacrylate may be described as (meth) acrylate) of oligomer of polyester type polyol, or its mixture. do. Moreover, urethane (meth) acrylate is comprised by the thing which (meth) acrylated the oligomer which becomes a polyol compound and a diisocyanate compound.

As a monomer which comprises (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and methoxyethyl (meth) acrylate , Butoxyethyl (meth) acrylate, and phenyl (meth) acrylate are mentioned.

In addition, when it is necessary to further increase the hardness of the hard coat layer, it is preferable to use a polyfunctional monomer together. For example, as a polyfunctional monomer, trimethylol propane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tree ( Meta) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neopentylglycoldi (meth) acrylate are exemplified.

As oligomers of polyester polyols, adipic acid and glycols (ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, etc.), triols (glycerine, trimethylolpropane, etc.), sebacic acid And polyadipate polyols, which are condensation products with glycols and triols, and polysebate polyols. In addition, some or all of the aliphatic dicarboxylic acids may be substituted with other organic acids. For example, isophthalic acid, terephthalic acid, or phthalic anhydride can be used as a component for increasing the hardness of the hard coat layer.

When apply | coating a hard coat agent to the surface of the adhesive modification layer of a base film, you may dilute using a diluent as needed in order to improve leveling property. Examples of the diluent include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane, nonane and decane, ketones such as methyl ethyl ketone, diethyl ketone and diisopropyl ketone. What is necessary is just to select the compounding quantity of a diluent suitably so that it may become an appropriate viscosity.

As the inorganic fine particles to be contained in the hard coat layer C, for example, inorganic oxides such as amorphous silica, crystalline glass filler, silica, zirconium oxide, titanium dioxide, alumina, 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 sulfide and mica.

In the case where an antireflection layer composed of a high refractive index layer / low refractive index layer or a high refractive index layer / medium refractive index layer / low refractive index layer is laminated on the surface of the hard coat layer C, the antireflection layer is formed by high refractive index of the hard coat layer C. The high refractive index layer can be omitted. As a result, cost can be reduced. In order to make the refractive index of the hard-coat layer C high, it is effective to contain an inorganic fine particle with a high refractive index in a hard-coat layer. Examples of the inorganic fine particles having a high refractive index include zirconium oxide and titanium oxide.

It is important that content of the inorganic fine particle in a hard-coat layer is 20 mass% or more and 80 mass% or less. If the content of the inorganic fine particles is less than 20% by mass, scratch resistance is insufficient. On the other hand, when content of an inorganic fine particle exceeds 80 mass%, there exists a tendency for transparency to fall. Moreover, as for the average particle diameter of an inorganic fine particle, 5-100 nm is preferable from a transparency viewpoint. However, such inorganic fine particles having a small average particle diameter tend to aggregate and are unstable. Therefore, in order to improve the dispersion stability of an inorganic fine particle, it is preferable to provide a photosensitive group to the surface of an inorganic fine particle, and to improve affinity with curable resin.

A hard coat agent containing such inorganic fine particles can obtain a commercial item. For example, the ultraviolet curable resin (Desorite; Z7400A, Z7410A, Z7400B, Z7410B, Z7400C, Z7410C, Z7410D, Z7410E, Z7501, Z7503, Z7521, Z7527) by JSR Corporation is mentioned.

The ionizing radiation curable resin is cured by irradiating ultraviolet rays or electron beams. When irradiated with ultraviolet rays, energy of 100 to 3000 mJ / m2 is used in a wavelength range of 100 to 400 nm, preferably 200 to 400 nm, using an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, and a metal halide lamp. Irradiate UV rays with In the case of irradiating an electron beam, a scanning or curtain type electron beam accelerator is used to irradiate an electron beam in a wavelength region of 100 nm or less with an energy of an acceleration voltage of 1000 keV or less, preferably 100 to 300 keV. .

What is necessary is just to determine the thickness of a hard-coat layer according to a use in the range of 0.1-30 micrometers. More preferably, it is 1-15 micrometers. When the thickness of the hard coat layer is in the above range, the hardness of the surface of the hard coat layer is high and it is difficult to be scratched. In addition, the hard coat layer is hard to fall off, and cracks hardly enter the hard coat layer when the hard coat film is bent.

Next, the optical functional film described in this invention is a film which laminated | stacked the optical functional layer on the opposite surface or the hard coat layer C of the hard coat film of this invention, and has two following embodiments.

(a) The optical functional film which laminated | stacked one or more optical functional layers chosen from a hard-coat layer, a light-diffusion layer, a prism-shaped 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. .

(b) The optical functional film which laminated | stacked the anti-reflection layer or the antifouling layer on the hard-coat layer C.

The lens film using a lens layer as an optical function layer and the light-diffusion film using a light-diffusion layer are demonstrated below as a representative example.

(Lens film)

The prism lens film or Fresnel lens film has an ionizing radiation curable hard coat layer containing inorganic fine particles on one side of an adhesive modified base film having an adhesive modified layer composed mainly of copolyester and polyurethane. It is laminated | stacked and the structure which laminated | stacked the prism lens layer or the Fresnel lens layer on the opposite surface. Although a lens film may be called a lens sheet, in this invention, a sheet is also included in a film.

Next, the active energy ray hardening resin component which comprises a prism lens layer is demonstrated.

As an active energy ray hardening resin component, 1 or more types of radically polymerizable monomers or oligomers determine the performance of the manufactured lens sheet, and are suitably selected according to the performance of the target lens film.

A resin component uses the monomer or oligomer which can be radically polymerized individually or in combination of 2 or more types. In particular, when two or more resins are used, mechanical strength, impact resistance, heat resistance, surface hardness, and chemical resistance required for the lens film can be imparted. Moreover, when using 60 mass parts or more of compounds which have an acryloyl group or a methacryloyl group as a radically polymerizable functional group with respect to a composition, when irradiating an active energy ray, it partially copolymerizes and it disinfects in an instant. For this reason, when forming a lens layer, optical deformation by convection becomes small.

As a resin component, ester type (meth) acrylate obtained by condensation reaction of aliphatic, alicyclic, aromatic mono, or polyalcohol with acrylic acid, or methacrylic acid, an isocyanate compound which has two or more isocyanate groups in a molecule | numerator, and a hydroxyl Ring opening of the glycidyl group of the urethane poly (meth) acrylate obtained by the urethanation reaction with the (meth) acrylate containing a real group or a thiol group, the compound which has two or more epoxy groups in a molecule, and acrylic acid or methacrylic acid (Meth) acryloyl functionalities, such as polyester (meth) acrylate obtained by condensation reaction with the epoxy poly (meth) acrylate obtained by reaction, saturated or unsaturated polyhydric carboxylic acid, a polyhydric alcohol, and (meth) acrylic acid Monomer, oligomer, styrene, chlorostyrene, bromostyrene, dibromostyrene And vinyl compounds such as divinylbenzene, and (meth) allyl compounds such as diethylene glycol bisallylcarbonate, diallyl phthalate, and diallyl biphenylate.

Preferred specific examples are shown below. The following various resin components may be used alone or in combination of two or more thereof. In addition, the resin for prism lenses or Fresnel lenses can obtain a commercial item. For example, UV hardening resin (Desorite; Z9590, Z9502) by JSR Corporation is mentioned.

(a) aliphatic mono (meth) acrylates

Methyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate

(b) alicyclic mono (meth) acrylate

Cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate

(c) aromatic mono (meth) acrylates

Phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylic 2-phenylphenyl (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 2-phenylphenyl-2-methyloxyethyl (meth) acrylic 2-naphthyl (meth) acrylate, 2-bromophenyl (meth) acrylate, 4-bromophenyl (meth) acrylate, 2,4-dibromophenyl (meth) acrylate, 2, 4,6-tribromophenyl (meth) acrylate, phenylthioethyl (meth) acrylate, phenylthioethoxyethyl (meth) acrylate

(d) ester di (meth) acrylate of aromatic skeleton

Bis (4- (meth) acryloxyethoxyphenyl) methane, bis (4- (meth) acryloxydiethoxyphenyl) methane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2 , 2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acrylic Oxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxydipropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxy-3,5-dibromo Phenyl) propane, 2,2-bis (4- (meth) acryloxydiethoxy-3,5-dibromophenyl) propane, 2,2-bis (4- (meth) acryloxypentaethoxy-3, 5-dibromophenyl) propane, bis (4- (meth) acryloxyethoxyphenyl) sulfone, bis (4- (meth) acryloxydiethoxyphenyl) sulfone, bis (4- (meth) acryloylthio Phenyl) sulfide, bis (4- (meth) acryloxyethylthiophenyl) sulfide

(e) ester di (meth) acrylate of alicyclic skeleton

Bis (4- (meth) acryloxycyclohexyl) methane, bis (4- (meth) acryloxyethoxycyclohexyl) methane, bis (4- (meth) acryloxydiethoxycyclohexyl) methane, bis (4- (Meth) acryloxycyclohexyl) propane, bis (4- (meth) acryloxyethoxycyclohexyl) propane, bis (4- (meth) acryloxydiethoxycyclohexyl) propane, dicyclopentanedi (meth) acrylic Rate

(f) ester di (meth) acrylate of aliphatic skeleton

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol (n = 4-15) di (meth) acrylate, propylene glycol di (meth) ) Acrylate, 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, neopentyl glycol di (meth) acrylate, di (meth) acrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate

(g) polyfunctional (meth) acrylates

Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate

(h) urethane poly (meth) acrylate

Tris (isocyanate hexyl) isocyanurate, isophorone diisocyanate, bis (4,4'- isocyanate cyclohexyl) methane, 1, 3-bis (isocyanate methyl) cyclohexane, metha xylylene diisocyanate, 2,4- Polyisocyanate compounds such as tolylene diisocyanate and 2,6-tolylene diisocyanate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Reaction products with (meth) acrylates containing hydroxyl groups, such as 4-hydroxybutyl (meth) acrylate

(i) epoxy poly (meth) acrylates

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

(j) polyester poly (meth) acrylate

A reaction product of at least one 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

As an active energy ray sensitive catalyst, it is more preferable to generate a radical source mainly by responding to the active energy ray of wavelength 200-400 nm. As a specific example, benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxy benzophenone, diethoxy acetophenone, benzyl dimethyl ketal, 2, 2- diethoxy acetophenone , Carbonyl compounds such as 1-hydroxycyclohexylphenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and tetramethylthiuram monosul Sulfur compounds, such as a feed and tetramethyl thiuram disulfide, and acyl phosphine oxides, such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, are mentioned. These are used in 1 type, or 2 or more types of mixing systems. Among these, benzophenone, benzoin isopropyl ether, methylphenylglyoxylate, 1-hydroxycyclohexylphenyl ketone, benzyl dimethyl ketal and 2,4,6-trimethylbenzoyl diphenyl phosphine oxide are more preferable.

Content of an active energy ray sensitive catalyst is 0.005-5 mass parts with respect to 100 mass parts of total amounts of a resin component, More preferably, it is 0.02-2 mass parts.

In addition, in the lens layer, various additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, yellowing inhibitors, organic releasing agents, pigments, dyes, bluing agents, organic or inorganic, within the range that the function as a lens is not impaired Fine particles, fillers, antistatic agents, surfactants, leveling agents, nucleating agents, diffusion agents and the like may be blended.

The method of laminating said active-line curable resin as a component of a lens layer on the surface of the adhesive modified layer of an adhesive modified base film selects various methods according to a required characteristic or a use. For example, the method of apply | coating the said resin to the bar cut | disconnected in the prism shape, or the said resin was poured in the shape of the lens layer, such as a prism shape, and the adhesive modified layer of an adhesive modified base film Use the method of overlapping the surface of the.

In addition, an active ray means the electromagnetic wave which polymerizes an acryl-type vinyl group, such as an ultraviolet-ray, an electron beam, and radiation ((alpha) ray, (beta) ray, (gamma) ray etc.). In practice, ultraviolet rays are simple. As an ultraviolet source, an ultraviolet fluorescent lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp is used, for example. In addition, the electron beam method is advantageous in that the apparatus is expensive and requires operation under an inert gas, but does not need to contain a photopolymerization initiator, a photosensitizer, or the like.

The thickness of a lens layer is arbitrarily selected according to the objective of a lens film, and the shape of a lens unit. Generally, 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, the effect as the lens layer tends not to be obtained. On the other hand, when the thickness of the lens layer is thicker than 5 mm, it tends to be insufficient in terms of luminance.

In addition, the pitch of a lens unit is also selected arbitrarily according to the objective of a lens film, or the shape of a lens unit. In general, the distance between the centers of the lens layers is preferably 0.03 to 0.5 mm, more preferably 0.05 to 0.3 mm.

In particular, a prism-like lens film in which a prism-like lens layer is laminated is preferable in view of brightness and ease of formation. Moreover, 80-150 degrees of the right angle of a prism is preferable, More preferably, it is 85-130 degree.

(Light diffusion film)

In the present invention, the light-diffusion film laminates an ionizing radiation curable hard coat layer containing inorganic fine particles on one side of an adhesive modified base film having an adhesive modified layer containing copolyester and polyurethane as a main component. The light diffusing layer is laminated on the opposite surface. Although a light-diffusion film may be called a light-diffusion sheet, in this invention, a sheet is also included in a film.

The light diffusing layer is composed of a composition containing a binder resin and a light diffusing agent. As said resin, resin which has optical transparency is suitable. For example, acrylic resin, polyester resin, polyvinyl chloride, polyurethane, a silicone resin is mentioned. This resin is commercially available from Mitsubishi Rayon Co., Ltd. under the brand name of "Dialal Series."

Moreover, as particle | grains used as a light-diffusion agent, transparent particle | grains are suitable, For example, silicone resin particle, acrylic resin particle, nylon resin particle, urethane resin particle, styrene resin particle, polyethylene resin particle, silica particle, polyester resin And particles. These particles may be used alone or in combination of two or more thereof. In addition, the surface or the whole of the said microparticles | fine-particles may be bridge | crosslinked. It is preferable to set it as 5-150 mass parts with respect to 100 mass parts of resin from a viewpoint that the mixing ratio of particle | grains with respect to resin is obtaining sufficient light diffusivity, ensuring a light transmittance.

Moreover, the average particle diameter of the said particle | grains is 1-70 micrometers normally, Preferably it is 5-50 micrometers. That is, when the average particle diameter of particle | grains falls out of the said range, there exists a possibility that the balance of light transmittance and light diffusivity may be disturbed and a front brightness may not become high. In addition, when spherical particle is used as particle | grains, each spherical particle acts as one kind of lens, and can provide a more effective light-diffusion effect. In particular, the spherical particles are effective. As for the spherical particle | grains, a spherical silica particle is marketed by Nippon Shokubai Co., Ltd. under the brand name of Eposuta, for example.

The typical manufacturing method of a light-diffusion film is shown below.

The coating liquid which mixed and dispersed binder resin, a solvent, and particle | grains in a specific ratio is the well-known coating method on the surface of the adhesive modified layer (the surface opposite to the surface which laminate | stacks a hard coat layer) of an adhesive modified base film. Apply with 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.

Suitable combination methods of the coating liquid are as follows.

First, binder resin is melt | dissolved in a solvent in a specific ratio. Particles and other subcomponents are dispersed in this dissolving liquid at a specific ratio as necessary to prepare a mixed dispersion liquid. At this time, the viscosity of the mixed dispersion is adjusted to be in the range of 1 to 500 poise. In addition, the viscosity of a liquid can be measured using a Brookfield viscometer (type B viscometer).

Next, the said coating liquid is apply | coated to the surface of the adhesive modified layer of an adhesive modified base film, and it is dried. The coating method of a coating liquid is selected according to the viscosity of a solution or the thickness of the coating layer made into the objective. For example, as a coating method, the comma direct method, the roll coating method, the dipping method, the knife coat method, the curtain flow method, the spray coating method, the spin coating method, and the laminating method are mentioned.

Moreover, as for the thickness of an adhesive modified base film, 50-200 micrometers is preferable from a use surface and workability | operativity. Moreover, 2-30 micrometers of the thickness of a light-diffusion layer are preferable. Examples of the solvent include toluene, methyl ethyl ketone, xylene, cyclohexane, and ethyl acetate.

Moreover, although the mixing ratio of a solvent with respect to binder resin is set suitably according to a coating method, workability, a kind of solvent, etc., 50-500 mass parts of solvents are preferable with respect to 100 mass parts of binder resins.

In addition, the mixing ratio of a solvent with respect to particle | grains is suitably set in the range of 20-500 mass parts of solvents with respect to 100 mass parts of particle | grains according to a coating method, workability, a kind of solvent, etc. More preferably, it is 50-300 mass parts of solvents with respect to 100 mass parts of particle | grains. That is, when the mixing ratio of the solvent to the particles is in the above range, the amount of the solvent to the particles is an amount suitable for softening the resin.

Moreover, as an auxiliary component of the light-diffusion layer, for example, an isocyanate compound, an epoxy resin, a methylolated melamine resin, a methylolated urea resin, a metal salt, a crosslinking agent such as a metal hydroxide, a guanidine derivative, a phosphoric acid-containing anionic activator, sulfonic acids, and a fourth ammonium salt And antistatic agents such as pyridinium salts, imidazoline derivatives, morpholine derivatives, polyoxyethylene-alkylphenols, alkylamide ethers and sorbitan fatty acid esters, and silane coupling agents may be contained alone or in combination of two or more.

Next, although the hard coat film of this invention and the optical functional film using the same are demonstrated using an Example and a comparative example, this invention is not limited to these Examples naturally. In addition, the physical property and the characteristic of the adhesive modified base film, hard coat film, and optical functional film which were described in the Example were evaluated using the following method.

(1) Phase Separation Structure of Adhesive Modified Layer

(1-1) Surface of adhesive modified layer of adhesive modified base film

(1-1-1) Phase Phase Observation

Evaluation of the phase-separated structure of the adhesive modified layer on the surface of the adhesive modified layer was carried out using a scanning probe microscope (manufactured by SAI Nanotechnology, SPI 3800N System / SPA 300) in phase measurement mode (phase mode). It was done by. In phase, the larger the phase delay is, the darker the phase delay is. The small phase retardation means that the phase retardation is harder or relatively smaller than the other phases. In the adhesive modified layer of the adhesive modified base film used by this invention, a dark color is a polyester phase and a bright color is a polyurethane phase.

The measuring principle of the phase measurement mode in a scanning probe microscope is described in "1-2. Application (http://www.siint.com/technology/probe_applications.html)" of SIA Nanotechnology Co., Ltd. website. "1. Mode" in "Phase Mode". Phase measurement by SPM ”.

The cantilever used for the measurement was mainly DF3 (elastic constant: about 1.6 N / m), and new products were always used to prevent degradation of sensitivity and resolution due to probe contamination. The scanner used FS-20A. In addition, the phase image observation was performed at the resolution of 512x512 pixel or more, and the observation visual field was 5 micrometers x 5 micrometers. Measurement parameters such as the amplitude decay rate, the scanning speed, and the scanning frequency of the cantilever during measurement were set to conditions under which line scanning was carried out, the sensitivity was high, and resolution was observed with good resolution.

(1-1-2) Measurement of Area Ratio of Polyester Phase

(a) Image analysis

The obtained phase mode image (bitmap format, 512 x 512 pixels) was read with image processing software (Adobe Photoshop ver7.0) and displayed on the display so that the size of the image was 205 mm x 205 mm (Fig. 1). Reference). Subsequently, a black line was drawn at the boundary between the light and dark colors with the pencil tool (master diameter: 3px) of the software to clarify the boundary between the two phases (see FIG. 2). In addition, the color fill tool of the software was used to binarize the dark color to black and the light color to white and binarize (see FIG. 3). At this time, the dark part of diameter 2mm or less which is in a light color by the size on a screen was judged to be particle | grains unevenly distributed in the light color, and it was painted white perfectly. For example, when silica particles were used, it was confirmed that they were unevenly distributed in bright colors.

In this binary image, the histogram with the luminance (black and white) as the horizontal axis, the frequency as the vertical axis is displayed by the same software, the area ratio of the black portion (polyester phase) is obtained, and in the adhesive modified base film It was set as the area ratio of the polyester phase in the surface of the adhesive modified layer of the.

(b) paper weight method

The measurement of the area ratio of the polyester phase on the surface of the adhesive modifying layer can be performed using a paper weight method in addition to the image analysis method. The measurement procedure is as follows.

The obtained phase mode image was saved as a digital image in bitmap format. Subsequently, this image was printed out on A4 sized high-quality paper by a printer (manufactured by Xerox, DocuPrintC830). About the output image (200 mm x 200 mm) in the bright room under 500 lux illumination, the boundary between the light color and the dark color in the image was made clear by 4B pencil by visual confirmation. Under the present circumstances, it was confirmed that the dark part of diameter 0.1 micrometer or less which exists in a bright color is particle | grains contained in the adhesive modification layer which is unevenly distributed on bright color. For this reason, this dark part was included in the light color, without drawing a line between the boundary of the light color and the dark part inside it. Then, the boundary line which cleared the light color and dark color was divided | segmented by dividing | segmenting with a cutter knife. Subsequently, the mass of the paper of the light color (polyurethane phase) and the dark color (polyester phase) was measured, and the mass ratio of the dark color (polyester phase) to the total mass of the paper of the light color and the dark color was%. It calculated | required in units and made it the area ratio of the polyester phase in the surface of an adhesive modified layer.

(c) Variation of area ratio of polyester phase (difference between maximum value and minimum value)

(c-1) Longitudinal direction of film roll

The roll which becomes an adhesive modified base film more than length 1000m and width 50mm or more was unwound. About the longitudinal direction (MD) of the said film, the area ratio of the polyester phase (it shows a dark color on a phase) on the adhesive modified layer surface was measured at the following location. Next, the area ratio of the polyester phase in the adhesive modified layer surface was calculated | required in each location. Moreover, the difference between the maximum value and the minimum value was calculated | required from those area ratios.

The measurement of the area ratio of the polyester phase on the surface of the adhesive modified layer is performed when the first end and the other end of the stationary region where the film properties are stable are set to the first end. The first measurement is performed at the inner side 2 m or less of the end portion, and the final measurement is performed at the inner side 2 m or less of the second end portion, and every 100 m from the first measurement point.

(c-2) Width direction of film roll

An adhesive-modified base film roll of 1000 m or more in length and 50 mm or more in width was uncoiled, and the film was divided into quarters in the width direction with respect to the width direction (TD) of the film. Next, in each center part, the area ratio of the polyester phase (it shows a dark color in a phase phase) of the adhesive modified layer surface was measured. 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. You may perform this measurement by the jumbo roll before slitting the width direction of a film to a narrow size.

(1-2) Cutting surface of the inclination of the adhesive modification layer in a hard coat film

In the hard coat film of the present invention, the adhesive modifying layer B is an intermediate layer between the thermoplastic resin film A and the hard coat layer C. For this reason, it is difficult to directly observe the phase-separated structure of resin in the interface (surface of the adhesive modified layer in an adhesive modified base film) of adhesive modified layer B and hard-coat layer C. Thus, the present inventors have found that the 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 modifying layer is generally thin, it is difficult to observe the phase separation structure of the resin from the cutting surface of the adhesive modifying layer. Therefore, the hard coat film was cut at an oblique and shallow angle with respect to the thickness direction. As a result, the observation area in the thickness direction of the adhesive modified layer could be extended. By this technique, the phase-separated structure of the resin which comprises the adhesive modified layer in the interface vicinity of the adhesive modified layer B and the hard-coat layer C was observed.

Below, the manufacturing method of the evaluation sample and the evaluation method of the area ratio of the polyurethane phase in the cutting surface of the adhesive modified layer of the interface vicinity with hard-coat layer C are demonstrated in detail.

(1-2-1) Preparation of Cutting Sample

The hard coat film of this invention contains the laminated constitution of A / B / C or B / A / B / C when A is a thermoplastic resin film, B is an adhesive modified layer, and C is a hard coat layer. It is a laminated body. In addition, the optical functional film using this hard-coat film is a laminated body containing the laminated constitution of D (including C) / B / A / B / C, when another optical function layer is set to D.

In a hard coat film or an optical functional film, it cuts in the oblique direction on the conditions shown below using the cutting device 1 (SAICAS DN20-S type) from the surface of the thermoplastic resin film A or the optical functional layer D. When the knife blade reaches the predetermined depth, the button "cutting depth limit" is pressed to cut at a constant depth. In addition, when the thermoplastic resin film to be cut is thick, it is preferable to perform a plurality of cutting in the same place.

(a) Cutting means: diamond knife (face angle: 40 degrees)

(b) Moving speed of horizontal blade: 3000 ㎚ / s

(c) Movement speed of vertical blade: 200 ㎚ / s

In addition, said "predetermined depth" means the depth in which the majority of the thermoplastic resin film is cut | disconnected and it does not reach the adhesive modified layer. In addition, "cutting depth limitation" means cutting only in the horizontal direction, with the moving speed of the vertical blade being zero.

Subsequently, using the cutting device 2 (SAICAS NN-04 type) in the same place, cutting with high precision was carried out in the oblique direction on condition shown below, and the cutting sample was produced.

(d) Cutting means: diamond knife (face angle: 40 degrees)

(e) Moving speed of horizontal blade: 500 ㎚ / s

(f) Movement speed of vertical blade: 20 ㎚ / s

In addition, said cutting conditions are typical conditions for cutting the hard-coat film obtained by the Example and comparative example which were described in this invention. Depending on the sample, the method of three-dimensional cutting using a three-dimensional cutting jig may be effective. In addition, although the width | variety of the blade of a diamond knife is 1 mm normally, 0.3 mm may be effective. In Examples and Comparative Examples described in the present invention, a diamond knife having a blade width of 1 mm was used.

Therefore, when the kind of material of each layer of a hard coat film differs from the material used by the Example and comparative example which were described in this invention, it is preferable to perform a preliminary test and to determine appropriate cutting conditions.

When cutting from the surface of the optical functional layer D (including the hard coat layer C), heating or cooling may be necessary at the time of cutting depending on the physical properties of the optical functional layer. For heating or cooling, a low or high temperature gas injector (TTFC-L type, manufactured by Dipla Wintes Co., Ltd.) may be used. The temperature or the flow rate of the gas at the time of heating or cooling is appropriately adjusted according to the state of the cutting surface.

(1-2-2) Observation of phase

In the cutting surface of the obtained cutting sample, the phase-separated structure of the resin of the adhesive modifying layer B is observed by the phase image obtained in the phase measurement mode (phase mode) using said scanning probe microscope (SPM). The phase mode generally refers to a phase delay measurement mode performed simultaneously with the shape observation by the dynamic force mode (DFM mode (when SPM manufactured by SAI Nanotechnology Co., Ltd.) is used). On the phase of the cutting surface of the adhesive modifying layer B, a dark color is a polyester phase and a light color is a polyurethane phase.

The cantilever used for the measurement was mainly DF3 (elastic constant: about 1.6 N / m), and new products were always used to prevent degradation of sensitivity and resolution due to probe contamination. The scanner used FS-100A. In addition, the observation visual field of a phase was 3 micrometers x 3 micrometers. Measurement parameters such as the amplitude decay rate, the scanning speed, and the scanning frequency of the cantilever during measurement were set to conditions under which line scanning was carried out, the sensitivity was high, and resolution was observed with good resolution.

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

The drawings attached to the application documents also include drawings displayed as color images. However, in the case of electronic filing, the color images are stored in a JPEG file format and displayed in gray scale. In addition, black and white images are also stored in a JPEG file format and displayed in gray scale to prevent deterioration of image quality.

(a) Phase read

The obtained phase image is read out in color using SPIP software (Version 4.2.5, manufactured by Image Metrology).

(b) emphasis of contrast of the phase separation structure (see FIG. 8);

This software is then subjected to Color Equalization to emphasize the contrast so that the phase separation structure is easily visible.

(c) Confirmation of the observation range of the phase separation structure (see FIG. 9).

The phase image on which the color uniformization process is performed is copied, and the screen of the presentation software (Microsoft PowerPoint 2002) is affixed. Next, the red line 20 is drawn on the interface (B / C) of the adhesive modifying layer B and the hard coat layer C. FIG. At this time, when the interface is not clear, the contrast is adjusted.

Moreover, the red line which shows said interface is copied in parallel and affixed on the position of 20 nm in the vertical direction from this interface B / C toward the adhesive modified layer B (line 21 of FIG. 9). ). In addition, when producing a cutting sample, the laminated body is cut in an oblique direction. For this reason, in the cutting conditions shown above, the position of 20 nm in depth toward the adhesive modified layer B from said interface is corresponded to the position of 500 nm from an interface in FIG.

Thus, phase separation of resin in the cutting surface of adhesive modified layer B is carried out in the range enclosed by these two red lines, ie, the range from the interface (B / C) to the depth of 20 nm of adhesive modified layer B. It is set as the range which observes a structure.

(d) Image processing of phase separation structure

The image of FIG. 8 is stored in a JPEG file format, affixed to a screen of image processing software (Adobe Photoshop ver6.0.1), and displayed in two gray scales of 128 with a threshold value (see FIG. 10). ).

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

This image of FIG. 11 is displayed on the screen of image processing software (manufactured by Adobe, Photoshop ver6.0.1). In addition, portions other than the adhesive modifying layer B are painted seamlessly in red using a brush tool (see FIG. 12). Trinized images of white, black, and red were displayed in histograms using the same software, with the luminance (black, white) being the horizontal axis and the frequency being the vertical axis.

In addition, in the phase image of the adhesive modifying layer B shown in FIG. 12, a black part means a polyester phase and a particle | grain, and a white part means a polyurethane phase. The area ratio of the polyurethane phase (white part) of the adhesive modified layer B in the cutting surface of the range from the interface of the adhesive modified layer B to the hard coat layer C to a depth of 20 nm is calculated by the following formula. In addition, the "measurement area" of the right side of the following formula means the range enclosed by the line 20 (interface B / C) and the line 21 on the phase of FIG.

Area ratio (%) of polyurethane phase = (area of white part / measurement area) × 100

(2) the presence or absence of a location where the width of the polyester phase exceeds at least 1 μm

In the said phase mode image, about 10 different measurement places, on the polyester which has a co-polyester as a main component, the presence or absence of what exceeded 1 micrometer was the narrowest width | variety of a uniaxial direction.

(3) the fractal dimension of the phase-separated structure

Image processing of a phase mode image (bitmap format, 512 x 512 pixels) obtained by the phase measurement mode (phase mode) using the scanning probe microscope (S-I Nano Technology, SPI3800N system / SPA300) described above. The image was read by software (Adobe, Photoshop ver7.0) and displayed on the display such that the size of the image was 205 mm x 205 mm (see Fig. 1). Subsequently, a black line was drawn at the boundary between the light and dark colors with the pencil tool (master diameter: 3px) of the software to clarify the boundary between the two phases (see FIG. 2). At this time, the dark part of 2 mm or less in diameter in the clear color was judged to be the particle unevenly distributed in the clear color, and the operation which draws a boundary line was not performed about this part. For example, when silica particles were used, it was confirmed that they were unevenly distributed in bright colors.

After the image with the clear borderline was stored as a bitmap format image, the fractal dimension analysis was performed by the box counting method, and the obtained fractal dimension was taken as an index indicating the complexity of the phase separation borderline. The image analysis software (AT-Image ver3.2) was used for the analysis by the box counting method. Specifically, the stored bitmap image was opened on image analysis software (AT-Image ver3.2), and binarization processing by luminance histogram was performed from image extraction on a menu (see Fig. 6). In addition, the threshold at the time of binarization was set to 8. For the binarized image, the fractal dimension was selected from the image measurement on the menu, and the fractal dimension was obtained. At this time, the calculation of the fractal dimension by the least-squares method used a box count result of 6 pixels to 63 pixels on one side.

In addition, the analysis of the fractal dimension by the box counting method is a well-known method, and using other image analysis software or a program for the dimensional analysis may use software having other dynamic functions as long as sufficient reproducibility of the analysis result is obtained. As other software, image analysis software, such as "Fractal analysis system version 3.33 made by the Agricultural Technology Research Institute Livestock Grassland Research Institute" and "Digital Being Kids Co., Ltd. PopImaging Ver. 3.40", is mentioned, for example.

(4) Average particle diameter of inorganic fine particles in hard coat phase C

The sample of the hard-coat film was embedded in visible-light curable resin (for example, epoxy resin), and was left to harden at room temperature. Subsequently, ultra-thin sections were made using ultramicrotoms equipped with diamond knives and stained with ruthenium tetraoxide. This dyed ultrathin section was observed using the transmission electron microscope (TEM2010, Nippen Denshi Co., Ltd.), the cross section of the hard-coat layer C, and the photograph was taken. In addition, the enlargement magnification of a photograph is suitably set in the range of 10,000-100,000 times according to the particle size of the observed inorganic particle. In Example 1 of the present invention, the magnification was 80,000 times (acceleration voltage 200 kv). The average particle diameter of the number reference of the inorganic fine particles in the hard-coat layer C was calculated | required from this photograph.

(5) haze

Based on JIS K7136, haze was measured about three different places of a film sample using the haze meter (made by Nippon Denshoku, NDH2000), and the average value was used.

(6) blocking resistance

The adhesive modified layers of the two adhesive modified base films were respectively laminated. Subsequently, 1 kgf / cm <2> pressure was added to these, and it contact | adhered for 24 hours in 50 degreeC and 60% RH atmosphere. Then, peeling was carried out at the interface between the adhesive modified layer and the adhesive modified layer of the two adhesively modified substrate films in close contact, and the peeling state thereof was determined based on the following criteria.

(Circle): thing which can peel lightly without the transition of an adhesive modified layer

(Triangle | delta): Peeling sound generate | occur | produces and the adhesive modified layer is partially transferred to the counter surface.

X: Two films adhere | attached and cannot peel off, or the base polyester film cleaves even if it peels

(7) Hardness Index of Adhesive Modified Layer

The surface of the adhesive modified layer of the adhesive modified base film was scratched using a surface measuring instrument (manufactured by Shintoa Chemical Co., Ltd., HEIDON14). At this time, a genuine needle having a sapphire of 75 µm in radius was used as the needle to scratch the tip. The running speed of the needle was 150 mm / min and the weight was 5 gf.

The surface shape of the scratches formed on the adhesive modified layer was measured under the following conditions by using a three-dimensional non-contact surface shape measuring device (Micromap550, manufactured by Micromap), and the profile mode data was displayed. A representative example is shown in FIG. From the obtained flaw shape data, the height difference of the concave and convex which adjoins was measured in 30 places, the average value was calculated | required, and it was set as the hardness index of an adhesive modified layer. At this time, projections having a height of 30 nm or more were judged to be projections resulting from particles contained in the adhesive modified layer or the thermoplastic resin film and were excluded from the measurement data. In addition, protrusions having a height of 1 nm or less were similarly excluded from the measurement data because of the influence of noise.

(Measuring conditions)

Profile mode: Wave mode

Objective lens: 10 times

Resolution: 160 × 160 pixels

Measurement length: 207.1 nm

(8) Adhesion with Hard Coat Layer

(8-1) Adhesion between Adhesive Modified Layer B and Hard Coat Layer C

On the glass plate of thickness 5mm which affixed the double-sided tape, the surface opposite to the hard-coat layer C of the hard-coat film or optical functional film obtained by the Example and the comparative example was stuck. Subsequently, 100 grid-shaped wounds penetrating the hard coat layer C and the adhesive modifying layer B to reach the thermoplastic resin film A were made using cutter guides having a gap gap of 2 mm. Subsequently, an adhesive tape (Nits. No. 405, 24 mm width) was affixed on the wound surface of a grid. The air remaining at the interface at the time of sticking was completely pressed by an eraser, and then the adhesive tape was peeled off vertically. In addition, the new adhesive tape was replaced in the same manner, and similarly peeled off vertically. The peeling operation of this adhesive tape was repeated 10 times in total, and the adhesiveness was visually calculated | required from the following formula. In addition, the number peeled partially in one grid also includes the number peeled.

Adhesiveness (%) = (1/100 peeled number of grid) × 100

(8-2) Evaluation on Adhesive Modified Substrate Film

The hard coat layer which consists of two types of photocurable acrylic resins of a solvent dilution type and a non-solvent type, and does not contain particle | grains was formed, and the adhesiveness of a hard coat layer and the adhesive modifying layer B was evaluated in accordance with the said method. The sample for evaluating adhesiveness with the hard-coat layer of an adhesive modified base film was produced according to the following method.

(a) Adhesion with the hard coat layer composed of solvent dilution type photocurable acrylic resin

The coating agent which mixed 50 mass parts of hard-coat agents (made by Dainichi Seika, Seikabeam EXF01 (B)), 25 mass parts of toluene, and 25 mass parts of methyl ethyl ketones by mixing on the surface of the adhesive modified layer B of a film sample, and stirring well. Was applied to the wire bar and dried at 70 ° C. for 1 minute to remove the solvent, and then, having a hard coat layer having a thickness of 3 μm under conditions of 200 mJ / cm 2, irradiation distance of 15 cm, and traveling speed of 5 m / min with a high pressure mercury lamp. A hard coat film was obtained.

(b) Adhesion with a hard coat layer composed of a solvent-free photocurable acrylic resin

On the glass plate of thickness 5mm kept clean, about 5 g of a hard coat agent (made by Dainichi Seika, Seika Beam EXF01 (B)) is raised, and the surface of the adhesive modification layer of a film sample is overlapped so that a hard coat agent may contact. It crimped as if a hard coat agent was extended with the manual load rubber roller of width 10cm and diameter 4cm from the top of the film sample. Subsequently, ultraviolet-ray was irradiated on the film surface side with the high pressure mercury lamp on the conditions of 500 mJ / cm <2>, irradiation distance 15cm, and traveling speed 5m / min, and the hard-coat layer was hardened. Next, the film sample having a hard coat layer was peeled from the glass plate to obtain a hard coat film.

(9) pencil hardness

In accordance with JIS-K5400, the surface of the hard coat layer C is measured by the pencil hardness test. In the pencil hardness test, the test is repeated five times. When the external abnormalities such as scratches are not found on the surface of the hard coat layer C in the entire test, the hardness of the pencil used in the test is taken as the pencil hardness. For example, if 5 tests are performed using a 3H pencil and no external abnormality occurs in all the tests, the pencil hardness of the material is 3H or more. In this evaluation, 3H or more and (circle) and 2H or less were made into x.

(Example 1)

(1) Combination of Coating Liquid

The coating liquid used for this 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 glycol (145 parts by mass), zinc acetate (0.1 parts by mass) and antimony trioxide (0.1 parts by mass) ) Was placed in a reaction vessel, and transesterification was carried out at 180 ° C. over 3 hours. Next, 5-sodium sulfoisophthalic acid (6.0 parts by mass) is added, and the esterification reaction is carried out at 240 ° C. over 1 hour, and then at 250 ° C. under reduced pressure (10 to 0.2 mmHg) for 2 hours. The polycondensation reaction was performed and the copolymer average polyester whose number average molecular weight is 19,500 and a softening point of 60 degreeC was obtained.

20 mass% aqueous solution of the self-crosslinking polyurethane (B) containing the isocyanate group which blocked 7.5 mass parts and 30 mass% aqueous dispersions of the obtained copolymerized polyester (A) with sodium bisulfite (Daiichi Kogyo Pharmaceutical Co., Ltd. Tron H-3) was mixed with 11.3 parts by mass, 0.3 parts by mass of the catalyst for elastron (Daiichi Kogyo Pharmaceutical Co., Cat64), 39.8 parts by mass of water, and 37.4 parts by mass of isopropyl alcohol. 0.6 mass parts of 10 mass% aqueous solution of a fluorine-type nonionic surfactant (Dainippon Ink Chemicals Co., Ltd., Megapack F142D) and colloidal silica (Nissan Chemicals, Snortex OL; average particle diameter 40nm) as particle A 2.3 parts by mass of a 20 mass% aqueous dispersion of water) and 0.5 parts by mass of a 3.5 mass% aqueous dispersion of dry silica (Nippon Aero Real, Aerosil OX50; average particle diameter 200 nm, average primary particle size 40 nm) were added as particles B. . Subsequently, the pH of the coating liquid was adjusted to 6.2 with a 5% by weight aqueous solution of sodium bicarbonate, fine filtering was performed with a filter made of a felt polypropylene having a filter particle size (initial filtration efficiency: 95%) of 10 µm to prepare a coating liquid A. . In addition, the said surfactant used what was pretreated by the following method.

Isopropyl alcohol (IPA) was added to the surfactant, and the solution was heated and dissolved in a hot bath at 30 ° C to prepare an IPA solution of 15% by mass of the surfactant. The solution was filtered by quantitative filtering (Advantech Co., No. 5C) to remove insoluble matter and dust in the solution. After filtering the above solution, the solution was placed in a sealed glass container and allowed to stand for 24 hours in a freezer at 0 ° C. After 24 hours, the solution containing the precipitated solid was suction filtered using the above quantitative filter. The solid on the filtrate was dried in vacuo to give a solid, diluted with 10 mass% aqueous solution with water and used as a pretreated surfactant.

In addition, the surfactant obtained by the said pretreatment was analyzed with the plastic sheet (melt-made, silica gel 60) apply | coated TLC with methanol as a developing solution. As a result of coloring the sample spot by iodine vapor, it was confirmed that the spot equivalent to polyethylene glycol was not detected.

(2) Preparation of Adhesive Modified Substrate Film

Polyethylene terephthalate (PET) resin pellets having an intrinsic viscosity of 0.62 dl / g containing no particles as a starting polymer were dried under reduced pressure (1 Torr) at 135 ° C for 6 hours. Subsequently, the PET resin pellet after drying was supplied to the extruder, and it melt-extruded into the sheet form at about 285 degreeC, and it quench-solidified on the metal roll maintained at the surface temperature of 20 degreeC, and obtained the cast film. At this time, a stainless sintered filter medium having a filter particle size (initial filtration efficiency: 95%) of 15 µm was used as a filter medium for removing foreign substances in the molten resin.

The cast film thus obtained 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 circumferential speed difference to obtain a uniaxially oriented PET film. Subsequently, the coating solution A was precisely filtered with a felt-like polypropylene filter medium having a filter particle size (initial filtration efficiency: 95%) of 10 μm, and applied to one side of the uniaxially oriented PET film by a reverse roll method. In addition, at this time, the application roll of the coater and the metaling roll used the roll whose surface by ultra hard chrome plating finish is 0.2 S or less, and roundness and cylindricality were 3/1000 mm.

The first zone (1.0 seconds at 135 ° C.), the second zone (2.2 seconds at 65 ° C.), the third zone (1.8 seconds at 40 ° C.), and the fourth zone in a drying furnace divided into four zones placed directly above the coater. The coated surface was dried at (1.8 ° C. at 30 ° C.). In addition, the application amount was made into 0.08 g / m <2> as a final solid amount. The passing time of the film from the coating to the film to the inlet of the drying furnace was 0.8 seconds. At this time, the wind speed of the dry wind of the first zone is 30 m / sec, the air supply air volume of the dry wind is 130 m3 / sec, the exhaust air volume is 170 m3 / sec, and the air supply air volume from the second zone to the fourth zone is 100 m3. / Second, the exhaust air volume was set to 150 m 3 / second to prevent the drying air flow to the coater side. In addition, the tension of the film was 7000 N / disk, and both ends of the film were gripped with a pinch roll between application | coating and the drying furnace entrance.

In addition, in the application | coating at this time, the coating apparatus which has the relationship of the capacity ratio of the base plate of a coating liquid, the capacity of the circulation tank, and the capacity of the combination tank was used.

(a) Capacity ratio of base plate of coating liquid and capacity of circulation tank = 1/50

(b) Capacity ratio of the circulation tank to the combined tank = 1/40

Subsequently, the edge part of the film was gripped with a clip, led to a hot air zone having a temperature of 120 ° C. and a wind speed of 15 m / sec, and stretched 4.3 times in the width direction. Next, while maintaining the width stretched in the width direction, the first heat setting zone (temperature: 200 ℃), the second heat setting zone (temperature: 225 ℃), the third heat setting zone (temperature: 230 ℃), 4 Continuously setting the heat setting zone (temperature: 230 ℃), the fifth heat setting zone (temperature: 210 ℃), the sixth heat setting zone (temperature: 170 ℃), and the seventh heat setting zone (temperature: 120 ℃) Passed through. Further, in the sixth heat setting zone, a 3% relaxation treatment was performed in the width direction. Subsequently, the uncoated portions of both ends of the film are trimmed and wound up by a winding device, and further divided into four in the width direction to slit, and the adhesive modified poly having a width of 1000 mm, a film length of 1000 m, and a film thickness of 125 μm. An ester film roll was obtained. In addition, the wind speeds of the hot air in the heat setting zone were all 15 m / sec, the passing time was 4.5 seconds in each zone, the nozzle spacing for spraying the hot air was 350 mm, and the number of nozzles per zone was eight.

Table 4 shows the physical properties and properties of the adhesive modified base film. Moreover, the maximum value, minimum value, maximum value of haze, minimum value, adhesiveness with respect to a hard-coat layer in the longitudinal direction and the width direction of the obtained adhesive modified polyester film roll. Table 5 shows the maximum and minimum values of. In addition, all the measurement points were (circle) about blocking resistance.

(3) Production of hard coat film

Next, the hard coat film which laminated | stacked the hard coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of said adhesive modified base film on one side by the following method was obtained.

As a coating liquid for forming a hard-coat layer, the organic / inorganic hybrid hard coat agent (made by JSR Corporation, Desolite Z7410B; solid content concentration: 50) which has an ultraviolet curing acrylate monomer, a zirconium-oxide ultrafine particle, and methyl ethyl ketone as a main component. Mass%) was prepared. This hard coat agent was apply | coated to the surface of the adhesive modified layer B of an adhesive modified base film so that it might become 8 micrometers in dry thickness, and it dried at 40 degreeC for 1 minute. Subsequently, ultraviolet rays were irradiated with a high pressure mercury lamp under conditions of 1000 mJ / cm 2, and the resin was cured to form a hard coat layer C.

In the obtained hard coat layer, 31 mass parts of zirconium oxide ultrafine particles of 10 nm of average particle diameters were contained with respect to 100 mass parts of acrylate resins.

(Example 2)

Coating liquid B using Example 10 WHEREIN: The 10 mass% aqueous solution of the fluorine-type cationic surfactant (Neos Co., Ltd. product made by Neos Co., Ltd.) pretreated by the method similar to Example 1 was used as surfactant. An adhesive modified polyester film was obtained in the same manner as in Example 1 except for changing to.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on one surface was carried out similarly to Example 1 on the surface of the adhesive modified layer B of the said adhesive modified base film.

(Example 3)

In the heat setting treatment step 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, and the fourth heat setting zone. An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the temperature was set at 220 ° C.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on one surface was carried out similarly to Example 1 on the surface of the adhesive modified layer B of the said adhesive modified base film.

(Example 4)

In Example 1, the adhesive modified polyester film was obtained by the same method as Example 1 except having changed the mass ratio of co-polyester and polyurethane in a coating liquid to the following coating liquid C which changed to 60/40. .

(Combination of coating solution C)

9.0 mass parts of the 30 mass% aqueous dispersion of the copolymerized polyester (A) used in Example 1, 9.0 mass parts of the 20 mass% aqueous solution of the polyurethane (B) used in Example 1, and the catalyst for elastron (Daiichi 0.3 parts by mass of Industrial Pharmaceutical Agent, Cat64), 40.6 parts by mass of water, and 37.3 parts by mass of isopropyl alcohol were respectively mixed. 0.6 parts by mass of the aqueous surfactant solution used in Example 1 and 20 parts by mass of an aqueous dispersion of colloidal silica (Nissan Chemical Co., Snotex OL; average particle diameter of 40 nm) as 2.3 parts by mass and Particle B were used as particles A. 0.5 mass part of 3.5 mass% aqueous dispersions of dry silica (Nippon Aero Real, Aerosil OX50; average particle diameter 200 nm, average primary particle diameter 40 nm) were added, pH was adjusted with a 5 mass% sodium bicarbonate aqueous solution, and the filtration performance was 5 micrometers. And 1 micrometer filter were passed through in order to make coating liquid C. FIG.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Example 5)

In Example 1, the adhesive modified polyester film was obtained by the method similar to Example 1 except having changed to the following coating liquid D which changed the mass ratio of co-polyester and polyurethane in a coating liquid to 40/60.

(Combination of Coating Liquid D)

6.0 mass parts of 30 mass% aqueous dispersions of the copolymerized polyester (A) used in Example 1, 13.5 mass parts of 20 mass% aqueous solution of the polyurethane (B) used in Example 1, and catalyst for elastron (Daiichi 0.3 parts by mass of Industrial Pharmaceutical Agent, Cat64), 38.9 parts by mass of water and 37.5 parts by mass of isopropyl alcohol, respectively. 0.6 parts by mass of a 10% by mass aqueous solution of the surfactant used in Example 1 and 2.3 parts by mass of a 20% by mass aqueous dispersion of colloidal silica (Nissan Chemical Industries Co., Ltd., Snortex OL; average particle diameter: 40 nm) as particles A As the particle B, 0.5 parts by mass of a 3.5 mass% aqueous dispersion of dry silica (Nippon Aero Real, Aerosil OX 50; average particle diameter: 200 nm, average primary particle size: 40 nm) was added, and pH was adjusted to 6.2 with a 5 mass% aqueous solution of sodium bicarbonate. It adjusted to and, it passed through the filter of 5 micrometers and 1 micrometer of filtration performances, and set it as the coating liquid D.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(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 set to 0.12 g / m 2 as the final solid amount.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Example 7)

In Example 1, the adhesive modified polyester film was obtained by the same method as Example 1 except using the following coating liquid E which changed the compounding quantity of surfactant in a coating liquid to 0.03 mass%.

(Combination of Coating Fluid E)

In the combination of the coating solution of Example 1, 0.3 parts by mass of a 10% by mass aqueous solution of a fluorine-based nonionic surfactant (Dainippon Ink and Chemicals, Megapack F142D), 38.2 parts by mass of water, and 39.3 by isopropyl alcohol were used. Change to mass parts.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Example 8)

In Example 1, the adhesive modified polyester film was obtained by the same method as Example 1 except having used the following coating liquid F which changed the compounding quantity of surfactant in a coating liquid to 0.10 mass%.

(Combination of Coating Fluid F)

In the combination of the coating solution of Example 1, 1.0 parts by mass of a 10% by mass aqueous solution of a fluorine-based nonionic surfactant (Dainippon Ink and Chemicals Co., Ltd., Megapack F142D), 37.5 parts by mass of water, and 39.3 by mass of isopropyl alcohol Change to mass parts.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on one surface was carried out similarly to Example 1 on the surface of the adhesive modified layer B of the said adhesive modified base film.

(Example 9)

In Example 1, the film passing time from the coating to the inlet of the drying furnace was 0.7 seconds, the drying time was 0.8 seconds, the passage time of each zone in the heat setting treatment process was 3.5 seconds, and the film thickness was 100 μm. An adhesive modified polyester film was obtained by the same method as Example 1 except having changed.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Example 10)

In Example 1, the passage time of the film from the coating to the inlet of the drying furnace was 1.0 second, the drying time was 1.9 seconds, the passage time of each zone in the heat setting treatment process was 6.6 seconds, and the film thickness was 188 μm. An adhesive modified polyester film was obtained by the same method as Example 1 except having changed.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Example 11)

In Example 1, the adhesive modified polyester film was obtained by the method similar to Example 1 except having changed the pH of coating liquid into coating liquid G adjusted to 7.9 using 5 mass% sodium carbonate aqueous solution.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Example 12)

In Example 1, the adhesive modified polyester film was obtained by the method similar to Example 1 except having apply | coated the adhesive modification layer B to both surfaces of the uniaxially-oriented polyester film. In addition, the pass time of the film from the application to the film to the drying furnace entrance was 0.8 second on one side, and 1.0 second on the opposite side.

The hard coat film which laminated | stacks the hard-coat layer C on both surfaces to the said adhesive modified base film through the adhesive modified layer B was obtained. In addition, the formation method of the hard-coat layer C is as follows.

The hard coat agent containing the inorganic particle used in Example 1 was apply | coated to one surface of the adhesive modified layer B of said adhesive modified base film so that the Mayer bar may apply | coat so that the film thickness after hardening may be 3 micrometers, and it is 40 degreeC, 60 Dried for seconds. Additionally, 300 mJ / cm 2 of ultraviolet light was irradiated to cure the resin and to form a hard coat layer C on one side.

Subsequently, the same hard coat agent was apply | coated also to the surface of the adhesive modifying layer B of the opposite side so that the film thickness after hardening may be set to 3 micrometers, and it dried for 40 degreeC and 60 second. Additionally, 500 mJ / cm 2 of ultraviolet light was irradiated to cure the resin and to form a hard coat layer C on the other side.

(Example 13)

In Example 1, the adhesive modified polyester film was obtained by the same method as Example 1 except having used coating liquid H which did not pretreat surfactant.

Although the phase separation structure of the polyester phase and the polyurethane phase by a scanning probe microscope (SPM) in the surface of the adhesive modified layer of the obtained adhesive modified polyester film was distinguishable, it was somewhat unclear.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

The phase-separated structure of the polyester phase and the polyurethane phase in the adhesive modification layer B of the cut surface of the obtained hard coat film was also somewhat unclear as mentioned above.

(Example 14)

In Example 1, the adhesive modified polyester film was obtained by the same method as Example 1 except having used the following coating liquid I which changed the mass ratio of the dispersion medium (water / IPA) of coating liquid to 50/50.

(Combination of Coating Liquid I)

In the combination of the coating liquid of Example 1, 7.5 mass parts of 30 mass% aqueous dispersions of the copolyester used in Example 1, 11.3 mass parts of 20 mass% aqueous solution of the polyurethane used in Example 1, and Elas 0.3 mass part of Tron catalyst (Daiichi Kogyo Pharmaceutical Co., Cat64), 30.4 mass part of water, and 46.8 mass part of isopropyl alcohol were mixed, respectively. 0.6 parts by mass of a 10% by mass aqueous solution of the surfactant used in Example 1 and 2.3 parts by mass of a 20% by mass aqueous dispersion of colloidal silica (Nissan Chemical Industries Co., Ltd., Snortex OL; average particle diameter: 40 nm) as particles A As the particle B, 0.5 parts by mass of a 3.5 mass% aqueous dispersion of dry silica (Nippon Aero Real, Aerosil OX 50; average particle diameter: 200 nm, average primary particle size: 40 nm) was added, and pH was adjusted to 6.2 with a 5 mass% aqueous solution of sodium bicarbonate. It adjusted to and, it passed through the filter of 5 micrometers and 1 micrometer of filtration performances, and set it as coating liquid I.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Example 15)

In Example 1, the adhesive modified polyester film which is 125 micrometers in thickness was obtained by the same method as Example 1 except having used coating liquid J which changed the pH of coating liquid to 4.6 with acetic acid.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Example 16)

In Example 1, the adhesive modified polyester film was obtained like Example 1 except having used the coating liquid K which changed the polyurethane (B) to the following polyurethane. Polyurethane was obtained by the following method.

(Preparation of polyurethane)

93 parts by mass of polyester diol (OHV: 111.8 eq / ton, AV: 1.1 eq / ton) having a composition of adipic acid // 1.6-hexanediol / neopentyl glycol (molar ratio: 4/3/2) 22 mass parts of rendiisocyanate was mixed and reacted for 1 hour at 95-100 degreeC under nitrogen stream, and a urethane prepolymer (NCO / OH ratio: 1.50, free isocyanate group: theoretical value 3.29 mass%, actual value 3.16 mass%) Got.

The obtained urethane prepolymer was cooled to 60 degreeC, 4.5 mass parts of methyl ethyl ketone oximes were added, it was made to react at 60 degreeC for 50 minutes, and the urethane prepolymer containing 1.3 mass% of free isocyanate and also partially blocked was obtained. Subsequently, the said urethane prepolymer was cooled to 55 degreeC, the mixed solvent used as 9 mass parts of isopropyl alcohol and 140 mass parts of methanol was added, and it mixed uniformly. 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, followed by vigorous stirring. After about 30 minutes, water soluble began to appear, and after 2 hours, the free sodium bisulfite became almost zero, and the reaction was terminated. Water was added to this to give a cloudy and more viscous 20 mass% aqueous solution.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Comparative Example 1)

(1) Combination of Coating Liquid L

33.7 parts by mass of dimethyl terephthalate, 20.0 parts by mass of dimethyl isophthalate, 9.1 parts by mass of 5-Na sulfodimethylisophthalate, 40.0 parts by mass of ethylene glycol, 10.0 parts by mass of diethylene glycol, and 0.049 parts by mass of calcium acetate monohydrate, 200 The transesterification was carried out until the theoretical amount of methanol distilled out at -230 degreeC. Next, 0.09 mass part of orthophosphoric acid was added, and it superposed | polymerized at 280 degreeC under reduced pressure, and obtained copolyester.

192 parts by mass of polyether (SO ₃ content: 8.3% by mass, polyethylene oxide content: 83% by mass) containing a sulfonate group obtained by sulfonating polyether of ethylene oxide starting from allyl alcohol with sodium metabisulfite 1013 mass parts of methylene adipate (number average molecular weight: 2,250) and 248 mass parts of polypropylene oxide polyether (number average molecular weight: 550) disclosed by bisphenol A were mixed, and it dehydrated at 100 degreeC under vacuum.

The mixture is brought to 70 ° C, and a mixture of 178 parts by mass of isophorone diisocyanate and 244 parts of hexamethylene-1,6-diisocyanate is added thereto, and then the resulting mixture is 80 ° C until the isocyanate content is 5.6% by mass. And stirred in the range of 90 ℃. The prepolymer was cooled to 60 ° C., and polyurethane was obtained by sequentially adding 56 parts by mass of biuret polyisocyanate obtained from 3 moles of hexamethylene diisocyanate and 1 mole of water, and 175 parts by mass of bisketimine obtained from isophoronediamine and acetone. An aqueous dispersion was obtained.

Said copolymer polyester and polyurethane aqueous dispersion were respectively mix | blended so that it may be 20 mass parts and 80 mass parts by solid content, and the aqueous dispersion of 10 mass% of solid content concentration was adjusted to the coating liquid L. In addition, particle | grains and surfactant were not mix | blended in the coating liquid.

(2) Preparation of Adhesive Modified Substrate Film

Polyethylene terephthalate resin pellets having an intrinsic viscosity of 0.66 dl / g containing no particles as raw material polymers were dried under reduced pressure (1 Torr) at 135 ° C for 6 hours, fed to an extruder, and melt-extruded into sheets at about 285 ° C. The cast film was obtained by solidifying rapidly on a metal roll maintained at a surface temperature of 60 ° C. At this time, in the same manner as in Example 1, a sintered filter made of stainless steel having a filter particle size (initial filtration efficiency: 95%) of 15 µm was used as a filter medium for removing foreign substances from the molten resin.

Next, this cast film was heated at 95 degreeC by the heated roll group and the infrared heater, and it extended | stretched 3.5 times in the longitudinal direction with the roll group with a circumferential speed difference, and obtained the uniaxially-oriented PET film. Subsequently, the coating liquid L was finely filtered with a felt-like polypropylene filter medium having a filter particle size (initial filtration efficiency of 95%) of 10 µm, and applied to one surface of a uniaxially oriented PET film by a reverse roll method. Subsequently, the edge part of the film was gripped with a clip, guided to a hot air zone heated at 110 ° C, and dried, and stretched 3.5 times in the width direction. The wind speed in the tenter at this time was 15 m / sec, and the drying time was 20 seconds. The time from the application to the film to the tenter inlet was 10.0 seconds. In addition, the coating amount was made to be 0.15 g / m <2> as a final solid amount.

Next, 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 (210 ° C.) while maintaining the width of the film stretched in the width direction. ), A fifth heat setting zone (215 ° C.), a sixth heat setting zone (220 ° C.), and a seventh heat setting zone (170 ° C.) were successively passed through. After the 3% relaxation treatment in the width direction in the seventh heat-setting zone, the uncoated portion of the film both ends was trimmed to obtain an adhesive modified polyester film having a thickness of 125 µm. In addition, the wind speeds of the hot air in the heat setting zone were all 15 m / sec, the passing time was 4.5 seconds in each zone, the nozzle intervals for injecting the hot air were set at intervals of 700 mm, and the number of nozzles per zone was four.

On the adhesive modified layer surface of the obtained adhesive modified polyester film, the phase separation structure of co-polyester and polyurethane was unclear.

(3) Production of hard coat film

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Comparative Example 2)

(1) Combination of Coating Liquid M

3.0 mass parts of 30 mass% aqueous dispersions of the copolyester (A) used in Example 1, and 18.0 mass parts of 20 mass% aqueous solution of the polyurethane (B) used in Example 1, the catalyst for elastron (Daiichi 0.3 parts by mass of Industrial Pharmaceutical Agent, Cat64), 70.7 parts by mass of water and 4.7 parts by mass of isopropyl alcohol. In addition, as a surfactant, 0.6 mass parts of 10 mass% aqueous solutions of dodecylbenzenesulfonic acid, and 20 mass% aqueous dispersions of colloidal silica (Nissan Chemical Co., Snortex OL; average particle diameter 40nm) were 2.3 as particle A. As a mass part and particle | grain B, 0.5 mass part of 3.5 mass% aqueous dispersions of dry silica (Nippon Aero Real, Aerosil OX50; average particle diameter 200nm, average primary particle diameter 40nm) were added, and it was set as the coating liquid M. PH of coating liquid M was 4.8 since pH adjustment was not carried out.

(2) Preparation of Adhesive Modified Substrate Film

Polyethylene terephthalate resin pellets having an intrinsic viscosity of 0.62 dl / g containing no particles used in Example 1 as raw material polymers were dried under reduced pressure (1 Torr) at 135 ° C. for 6 hours, and then supplied to an extruder, and the sheet at about 285 ° C. The melt film was melt-extruded into a phase and rapidly solidified on a metal roll maintained at a surface temperature of 20 ° C. to obtain a cast film. At this time, a stainless sintered filter medium having a filter particle size (initial filtration efficiency: 95%) of 15 µm was used as a filter medium for removing foreign substances from the molten resin.

The cast film thus obtained 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 circumferential speed difference to obtain a uniaxially oriented PET film. Subsequently, the coating liquid M was finely filtered with a felt polypropylene medium having a filter particle size (initial filtration efficiency: 95%) of 10 µm, and applied to one surface of the uniaxially oriented PET film by a reverse roll method.

Subsequently, the end surface of the film was guided to a hot air zone heated at 80 ° C. while being gripped with a clip to dry the coated surface, and then stretched 4.0 times in the width direction. The wind speed in the tenter at this time was 15 m / sec, and the drying time was 20 seconds. The time from application to tenter inlet was 10.0 seconds. In addition, the coating amount was made to be 0.10 g / m <2> as a final solid amount. The temperature in each heat setting treatment step 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, 225 ° C. and the fifth in the fourth heat setting zone. The film thickness was 125 µm in the same manner as in Comparative Example 1, except that 230 ° C in the heat-setting zone, 235 ° C in the sixth heat-setting zone, and 240 ° C in the seventh heat-setting zone, and no relaxation treatment in the width direction were performed. Phosphorous adhesive modified polyester film was obtained.

On the adhesive modified layer surface of the obtained adhesive modified polyester film, the phase separation structure of the polyester phase and the polyurethane phase was not able to be observed.

(3) Production of hard coat film

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

The phase separation structure of the polyester phase and the polyurethane phase in the adhesive modified layer B of the cut surface of the obtained hard coat film could not be observed similarly to the above.

(Comparative Example 3)

(1) Combination of Coating Liquid N

7.5 mass parts of 30 mass% aqueous dispersions of the copolyester (A) used in Example 1, 11.3 mass parts of 20 mass% aqueous solution of the polyurethane (B) used in Example 1, and the catalyst for elastron (Daiichi 0.3 mass part of Industrial Pharmaceuticals, Cat64), 40.5 mass part of water, and 39.5 mass parts of isopropyl alcohol were respectively mixed. In addition, in a 10 mass% aqueous solution of a fluorine-based nonionic surfactant (Dainippon Ink and Chemicals Co., Megapack F142D), which had not been pretreated, 0.6 parts by mass of aggregated silica (Fuji Silysia) was used as particle A without using Part B. A chemical agent, 0.03 mass part of 3.5 mass% aqueous dispersions of the Silycia 310 (average particle diameter 1.4 micrometers) was added, and it was set as the coating liquid N. In addition, pH adjustment of the coating liquid N was not performed. PH of coating liquid N was 4.6.

(2) Preparation of Adhesive Modified Substrate Film

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

The cast film thus obtained 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 circumferential speed difference to obtain a uniaxially oriented PET film. Subsequently, the coating liquid L was precisely filtered with a filter-made polypropylene medium having a particle size of filter particles (initial filtration efficiency: 95%) of 10 µm, and applied to one surface of a uniaxially oriented PET film by a reverse roll method.

After application, the product was led to a drying furnace and dried at a temperature of 120 ° C. for 3.2 seconds. Incidentally, the coating amount was set to 0.08 g / m 2 as the final solid amount. The passing time of the film from the coating to the inlet of the drying furnace was 3.2 seconds. In addition, the wind speed of the first zone of the drying furnace is 15 m / sec, the wind speed of the second zone to the fourth zone is the same as the first embodiment, the air supply air volume of the drying wind is 70 m 3 / The exhaust air was made into natural exhaust gas from before and after a drying furnace.

Subsequently, except that the lateral stretch ratio was 4.0 times, transverse stretching was carried out in the same manner as in Example 1, heat-setting and relaxation treatment in the width direction were performed in the same manner as in Comparative Example 1, and the adhesive-modified polyester film having a film thickness of 125 µm was obtained. Got. On the adhesive modified layer surface of the obtained adhesive modified polyester film, the phase separation structure of the polyester phase and the polyurethane phase was not able to be observed.

(3) Production of hard coat film

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

The phase separation structure of the polyester phase and the polyurethane phase in the adhesive modified layer B of the cut surface of the obtained hard coat film could not be observed similarly to the above.

(Comparative Example 4)

In Example 1, the adhesive modified polyester film whose film thickness is 125 micrometers by the method similar to Example 1 except having applied the coating liquid A to the film and making the passing time of the film to the entrance to a drying furnace for 3.2 second. Got.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Comparative Example 5)

3.0 mass parts of 30 mass% aqueous dispersions of the copolyester (A) used in Example 1, and 18.0 mass parts of 20 mass% aqueous solution of the polyurethane (B) used in Example 1, the catalyst for elastron (Daiichi 0.3 parts by mass of Industrial Pharmaceutical Agent, Cat64), 37.3 parts by mass of water and 37.8 parts by mass of isopropyl alcohol were respectively mixed. 0.6 parts by mass of a 10% by mass aqueous solution of the surfactant used in Example 1 and 2.3 parts by mass of a 20% by mass aqueous dispersion of colloidal silica (Nissan Chemical Industries Co., Ltd., Snortex OL; average particle diameter: 40 nm) as particles A As particle B, 0.5 parts by mass of a 3.5 mass% aqueous dispersion of dry silica (Nippon Aero Real, Aerosil OX50; average particle diameter: 200 nm, average primary particle size: 40 nm) was added as a particle B, and the pH was changed to 6.2 with a 5 mass% aqueous solution of sodium bicarbonate. It adjusted to the coating liquid O. 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 coating liquid O was used as the coating liquid.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Comparative Example 6)

12.0 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (A) used in Example 1, 4.5 parts by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1, a catalyst for elastron (Daiichi 0.3 parts by mass of Industrial Pharmaceutical Agent, Cat64), 42.3 parts by mass of water and 37.2 parts by mass of isopropyl alcohol, respectively, and 0.6 parts by mass of a 10% by mass aqueous solution of the surfactant used in Example 1 as Particle A 2.3 mass parts of 20 mass% aqueous dispersion of colloidal silica (Nissan Chemical Co., Ltd., Snowtex OL; average particle diameter 40nm), and dry-type silica (Nippon Aero Real, Aerosil OX50; average particle diameter 200nm, average 1) as particle B 0.5 mass part of 3.5 mass% aqueous dispersions of 40 nm of particle diameters) were added, pH was adjusted to 6.2 with 5 mass% sodium bicarbonate aqueous solution, and it was set as coating liquid P. 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 coating liquid P was used as the coating liquid.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Comparative Example 7)

In Example 1, the temperature in each heat setting treatment step was set to 190 ° C. in the first heat setting zone, 195 ° C. in the second heat setting zone, and 200 ° C. in the fifth heat setting zone from the third heat setting zone. An adhesive modified polyester film having a film thickness of 125 µm was obtained in the same manner as in Example 1. On the adhesive modified layer surface of the obtained adhesive modified polyester film, the phase separation structure of the polyester phase and the polyurethane phase was not able to be observed.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

The phase separation structure of the polyester phase and the polyurethane phase in the adhesive modified layer B of the cut surface of the obtained hard coat film could not be observed similarly to the above.

(Comparative Example 8)

In Example 1, the adhesive modified polyester film which has a film thickness of 125 micrometers was obtained by the method similar to Example 1 except having set the air velocity in a drying furnace to 15 m / sec.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Comparative Example 9)

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 coating amount was set to 0.20 g / m 2 as the final solid amount.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Comparative Example 10)

In Example 1, except that the coating liquid Q which adjusted the pH of the coating liquid to 9.0 by 5 mass% sodium carbonate aqueous solution was used, the adhesive modified polyester film which is 125 micrometers in film thickness was carried out similarly to Example 1. Got it.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Comparative Example 11)

In Example 1, the adhesive modified polyester film which has a film thickness of 125 micrometers was obtained by the method similar to Example 1 except having used coating liquid R adjusted without mix | blending surfactant in a coating liquid.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Example 17)

7.5 mass parts of 30 mass% aqueous dispersions of the copolyester (A) used in Example 1, 11.3 mass parts of 20 mass% aqueous solution of the polyurethane (B) used in Example 1, and catalyst for elastron (Daiichi 0.3 mass part of Industrial Pharmaceuticals, Cat64), 40.5 mass part of water, and 39.5 mass parts of isopropyl alcohol were respectively mixed. 0.6 parts by mass of a 10% by mass aqueous solution of the surfactant used in Example 1 and 4.3 parts by mass of a 3.5% by mass aqueous dispersion of agglomerated silica (Fuji Silysia Chemicals, Silica 310; average particle diameter: 1.4 µm) as particles A The pH was adjusted to 6.2 with a 5 mass% sodium bicarbonate aqueous solution, and it passed through the filter of 5 micrometers and 1 micrometer of filtration performance in order, and set it as coating liquid S. In addition, particle | grain B was not mix | blended with the coating liquid. 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 coating solution S was used.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Comparative Example 12)

In Example 1, the adhesive modified polyester film which has a film thickness of 125 micrometers was obtained by the same method as Example 1 except having used the coating liquid T which combined only the quantity of surfactant in coating liquid so that it might become 0.60 mass% as solid content. .

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Example 18)

In Example 1, the temperature in each heat setting treatment step is 200 ° C. in the first heat setting zone, 210 ° C. in the second heat setting zone, 215 ° C. in the third heat setting zone, and 220 in the fourth heat setting zone. 225 ° C. in the fifth heat setting zone, 230 ° C. in the sixth heat setting zone, and 170 ° C. in the seventh heat setting zone, except that the 3% relaxation treatment was performed in the width direction in the seventh heat setting zone. In the same manner as in Example 1, an adhesive modified polyester film having a film thickness of 125 μm obtained by trimming the uncoated portion at both ends of the film was obtained.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Comparative Example 13)

In Example 1, 7.5 mass parts of 30 mass% aqueous dispersions of the copolyester (A) used in Example 1, and 11.3 mass parts and 20 mass% aqueous solution of the polyurethane (B) used in Example 1 0.3 mass part of Tron catalyst (Daiichi Kogyo Pharmaceutical Co., Cat64), 51.0 mass part of water, and 26.2 mass parts of isopropyl alcohol were mixed, respectively. 0.6 parts by mass of a 10% by mass aqueous solution of the surfactant used in Example 1 and 2.3 parts by mass of a 20% by mass aqueous dispersion of colloidal silica (Nissan Chemical Industries Co., Ltd., Snortex OL; average particle diameter: 40 nm) as particles A As particle B, 0.5 parts by mass of a 3.5 mass% aqueous dispersion of dry silica (Nippon Aero Real, Aerosil OX50; average particle diameter: 200 nm, average primary particle size: 40 nm) was added as a particle B, and the pH was changed to 6.2 with a 5 mass% aqueous solution of sodium bicarbonate. It adjusted and the adhesive modified polyester film was obtained by the method similar to Example 1 except having used coating liquid U.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Comparative Example 14)

In Example 1, it did not contain an inorganic fine particle as a hard-coat agent, but used the hard-coat layer (made by Daiichi Seika Co., Ltd., Seika beam EXF-01B) comprised of the solvent dilution type photocurable acrylate type resin. A hard coat film obtained by laminating a hard coat layer containing no inorganic fine particles on one side except for the same procedure as in Example 1 was obtained.

Although the obtained hard coat film was excellent in the adhesiveness of a hard coat layer and an adhesive modified layer, hardness fell and the curl also became large.

(Example 19)

In the combination of the coating liquid of Example 1, the fluorine-based nonionic surfactant (Dainippon Ink Chemical Co., Ltd.), instead of the 10 mass% aqueous solution of the fluorine-based nonionic surfactant (Dainippon Ink Chemical Co., Megapack F142D) An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the coating solution V was used using a 5% by mass aqueous solution of Megapack F444). Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Example 20)

In Example 1, the adhesive modified polyester film was obtained by the method similar to Example 1 except having apply | coated the adhesive modification layer B to both surfaces of the uniaxially-oriented polyester film. In addition, the pass time of the film from application | coating to a film to a drying furnace entrance was 0.8 second on one side, and 1.0 second on the opposite side.

The prism lens film in which the hard coat layer C was laminated | stacked on one side and the prism lens sheet layer D was laminated | stacked on the other side to the said adhesive modified base film through the adhesive modified layer B was obtained.

First, the formation method of the hard-coat layer C is demonstrated.

The hard coat agent containing the inorganic particle used in Example 1 was apply | coated to one surface of the adhesive modified layer B of said adhesive modified base film so that the Mayer bar may apply | coat so that the film thickness after hardening may be 3 micrometers, and it is 40 degreeC, 60 Dried for seconds. Additionally, 300 mJ / cm 2 of ultraviolet light was irradiated, cured and a hard coat layer C was formed on one side.

Next, the formation method of the prism lens layer D is demonstrated.

After inject | pouring an ultraviolet curable resin liquid (Desolite Z9590 by JSR Corporation) into the molding die which cut the inverted shape of the prism shape whose pitch is 0.05 mm and a right angle is 90 degrees, said hard coat layer C The above molding die was stacked on the surface of the adhesive modified layer B opposite to the above. Subsequently, 80 w / cm of ultraviolet-ray was irradiated from the hard-coat layer C side by the ultraviolet lamp (output: 6.4 kw), and after hardening resin, it peeled and formed the prism lens layer.

(Example 21)

In Example 1, the adhesive modified polyester film was obtained by the method similar to Example 1 except having apply | coated the adhesive modification layer to both surfaces of the uniaxially-oriented polyester film. In addition, the pass time of the film from application | coating to a film to a drying furnace entrance was 0.8 second on one side, and 1.0 second on the opposite side.

The light-diffusion film by which the hard-coat layer C was laminated | stacked on one side and the light-diffusion layer D 'was laminated | stacked on the other side to said adhesive modified base film via the adhesive modified layer B was obtained.

First, the formation method of the hard-coat layer C is demonstrated.

The hard coat agent containing the inorganic particle used in Example 1 was apply | coated to one surface of the adhesive modified layer B of said adhesive modified base film so that the Mayer bar may apply | coat so that the film thickness after hardening may be 3 micrometers, and it is 40 degreeC, 60 Dried for seconds. Additionally, 300 mJ / cm 2 of ultraviolet light was irradiated, cured and a hard coat layer C was formed on one side.

Next, the formation method of the light-diffusion layer D 'is demonstrated.

The coating liquid for light-diffusion layer shown below was apply | coated to the surface of the adhesive modifying layer B opposite to said hard-coat layer C, and it dried at 130 degreeC for 3 minutes.

(Composition of Coating Liquid for Light Diffusion Layer)

(a) particles [26.3 parts by mass]

Spherical Acrylic Resin Particles

(b) Resin [19.5 parts by mass]

Acrylic binder resin solution (made by Mitsubishi Rayon Corporation, diamond LR-1065; solid content concentration: 45 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]

(Example 22)

In Example 1, the adhesive modified polyester film was obtained by the same method as Example 1 except having made application amount into 0.02 g / m <2> as a final solid amount.

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

(Example 23)

In Example 1, the film was applied in the same manner as in Example 1, except that the capacity ratio of the base plate of the coating liquid, the capacity of the circulation tank, and the capacity ratio of the combination tank were used as the coating device. An adhesive modified polyester film roll having a length of 2000 m, a width of 1000 mm, and a thickness of 125 μm was obtained.

(a) Capacity of support plate of coating liquid / capacity of circulation tank = 1/5

(b) Capacity of circulation tank / capacity of combination tank = 1/50

(c) Roundness and cylindricality of application rolls and meta-ring rolls: 6/1000 mm

(d) No installation of pinch roll between coater and drying furnace

Next, the hard coat film which laminated | stacked the hard-coat layer C containing inorganic microparticles | fine-particles on the surface of the adhesive modified layer B of the said adhesive modified base film similarly to Example 1 on one side was obtained.

In Examples 1-23 and Comparative Examples 1-14, the composition and the characteristic of a coating liquid are shown in Table 1, application | coating and drying conditions are shown in Table 2, heat setting conditions in Table 3, the physical property of a adhesive modified base film, and a characteristic The properties are shown in Table 4. In addition, the maximum value, minimum value, maximum value of haze, minimum value, the maximum value of adhesiveness with respect to a hard-coat layer, and the minimum value of PEs surface fraction in the longitudinal direction and the width direction of the obtained adhesive modified polyester film roll are shown in Table 5 Shown in In addition, all the measurement points were (circle) about blocking resistance.

Since the hard coat film of this invention is excellent in adhesiveness with the hard coat layer containing inorganic fine particles, maintaining a high hardness, a prism lens sheet, a light-diffusion film, an antireflective (AR) film, a transparent conductive film, and an infrared ray It is suitable as a base material of optical functional films for displays, such as an absorption film and an electromagnetic wave absorption film.

Moreover, the hard coat film of this invention can be used also for the use which requires hiding property besides the optical functional film for displays. In that case, it is preferable to use the white film which contained the white pigment or cavity as a thermoplastic resin film of a base material.

Claims (7)

The adhesive modified base film which formed the adhesive modified layer B which consists of co-polyester and polyurethane on one or both surfaces of the thermoplastic resin film A, and the surface of the adhesive modified layer B of any one of the said films. As a hard coat film containing the laminated constitution of A / B / C or B / A / B / C in which the hard-coat layer C containing inorganic fine particles was laminated | stacked on it, The adhesive modified layer B has a micro phase separation structure or a nano phase separation structure on a polyester (PEs) phase and a polyurethane (PU) phase, and also observes the cut surface of the hard coat film in a phase measurement mode using a scanning probe microscope. When it did, the polyurethane phase of the adhesive modified layer B defined by following formula 1 in the range of the interface of adhesive modified layer B and hard-coat layer C to 20 nm in depth (it shows a bright color in a phase phase). The area ratio of is 30% or more and 60% or less, The hard coat film characterized by the above-mentioned. Area ratio (PU) on PU = (area / measured area on PU) × 100... (One) The adhesive modified base film which formed the adhesive modified layer B which consists of co-polyester and polyurethane on one or both surfaces of the thermoplastic resin film A, and the surface of the adhesive modified layer B of any one of the said films. As a hard coat film containing the laminated constitution of A / B / C or B / A / B / C in which the hard-coat layer C containing inorganic fine particles was laminated | stacked on it, The adhesive modified layer B has a micro phase separation structure or a nano phase separation structure on polyester (PEs) and polyurethane (PU), and also uses a scanning probe microscope to put the surface of the adhesive modifying layer B into a phase measuring mode. When observed, the area ratio of the polyester phase (showing the dark color in the phase phase) of the surface of the adhesive modified layer B defined by the following formula 2 was 35% or more and less than 90% in the range of 5 µm x 5 µm. Characteristic hard coat film. % Area on PEs = (area on PEs / measured area) × 100... (2) The method according to claim 1 or 2, Content of the inorganic fine particle in hard-coat layer C is 20-80 mass%, The hard coat film characterized by the above-mentioned. The method according to claim 1 or 2, The thermoplastic resin film does not contain a particle, or contains 50 ppm or less, and the adhesive modifying layer contains 0.1-20 mass% of particles, The hard coat film characterized by the above-mentioned. The method of claim 4, wherein Hard coat film, characterized in that the particles are silica particles. At least one optical layer selected from a hard coat layer, a light diffusing layer, a prism-like lens layer, an electromagnetic wave absorbing layer, a near infrared ray shielding layer, and a transparent conductive layer on a surface opposite to the hard coat layer C of the hard coat film of claim 1. Optical functional film laminated functional layer. The optical functional film in which the antireflection layer or the antifouling layer was laminated on the hard coat layer C of the hard coat film of claim 1.

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