JP2010097173A - Method for manufacturing hardcoat film, hardcoat film, polarizing plate and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a hardcoat film, which can prevent the hardcoat film from curling on a side of a hardcoat layer of the hardcoat film while maintaining the hardness of the hardcoat film. <P>SOLUTION: The method for manufacturing the hardcoat film includes forming the hardcoat layer on one side of a triacetyl cellulose base material, and thereafter applying at least a solvent on a surface side opposite to the side, wherein the hardcoat layer of the triacetyl cellulose base material is formed. The solvent is used for preventing the curl to the side of the hardcoat layer of the triacetyl cellulose base material and maintaining the hardness of the hardcoat film. The solvent includes one or more prime solvent selected from acetone, hexane, dimethyl glycol and methyl acetate in the proportion of 70 wt.% or more of the total amount of the solvent, wherein the application quantity of the solvent is 4-20 g/m<SP>2</SP>. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is used for the purpose of protecting the surface of a display, etc., a method for producing a hard coat film provided with a hard coat layer on a transparent substrate film, a hard coat film, a polarizing plate having the hard coat film, And a liquid crystal display device.

  An image display surface in an image display device such as a liquid crystal display, a CRT display, a projection display, a plasma display, or an electroluminescence display is required to be provided with scratch resistance so as not to be damaged during handling. On the other hand, by using a hard coat film in which a hard coat (HC) layer is provided on a base film, and a hard coat film (optical laminate) having optical functions such as antireflection and antiglare properties. Generally, the scratch resistance of the image display surface of the image display device is improved.

  In Patent Document 1, a hard coat layer is provided on a cellulose triacetate (TAC) film to improve the hardness.

  In the hard coat layer as described above, a curable resin such as a photocurable resin or a thermosetting resin is usually used to impart hardness to the film. However, since the components of the hard coat layer such as the curable resin are cured and contracted, the hard coat film including the TAC film and the entire optical laminate are warped (so-called curl) toward the hard coat layer. In addition, there is a problem that workability is remarkably impaired when the hard coat film or the optical laminate is attached to a polarizer or a display.

JP 2008-165040 A

  The present invention has been made to solve the above problems, and manufacturing a hard coat film that can reduce curling of the hard coat film toward the hard coat layer while maintaining the hardness of the hard coat film. It aims to provide a method.

In the method for producing a hard coat film according to the present invention, a hard coat layer is formed on one side of a triacetyl cellulose substrate, and then the surface opposite to the surface on which the hard coat layer of the triacetyl cellulose substrate is formed. And applying a solvent that reduces curling of the triacetyl cellulose base material toward the hard coat layer and at least maintains the hardness of the hard coat layer. The solvent includes acetone, hexane, dimethyl glycol, and methyl acetate. The total amount of the main solvent is 70% by weight or more of the total solvent, and the solvent coating amount is 4 to 20 g / m ^2. And

In the solvent, the total amount of one or more main solvents selected from acetone, hexane, dimethyl glycol, and methyl acetate is a ratio of 70% by weight or more of the whole solvent, and the coating amount of the solvent is 4 to 20 g / m. ^{By being 2} , curling of the triacetyl cellulose base material is reduced, and the hardness of the hard coat film is also maintained.

  In the method for producing a hard coat film according to the present invention, the solvent contains any one main solvent selected from acetone, hexane, dimethyl glycol, and methyl acetate in a proportion of 70% by weight or more of the whole solvent. It is preferable that the effect of reducing curling is high.

  In the method for producing a hard coat film according to the present invention, it is preferable that the solvent is acetone or an acetone mixed solvent containing 70% by weight or more of acetone because the curl reduction effect is high and the hardness is not easily lowered. .

The hard coat film according to the present invention is a hard coat film having at least a hard coat layer on one side of a triacetyl cellulose substrate, and the hard coat layer is formed from a cured product of a curable resin composition containing a binder component. becomes, the Raman spectroscopic measurement in the thickness direction of the triacetyl cellulose substrate, and a divided by the peak intensity of 1730 cm ^-1 to peak intensity of 1600 cm ^-1 and the peak intensity ratio, the thickness of triacetyl cellulose substrate ( μm) is T, the maximum value of the peak intensity ratio in the region from the interface opposite to the hard coat layer of the triacetyl cellulose base material to 5 μm in the film thickness direction is PB, and the hard coat of the triacetyl cellulose base material When the peak intensity ratio at the interface on the layer side is PA, the T, PA, and PB are And it satisfies the formula (I).
−0.015 ≦ (PA−PB) / T Formula (I)

  When T, PA, and PB satisfy the formula (I), curling of the triacetyl cellulose (TAC) substrate is reduced, and the hardness of the hard coat film is also maintained.

  In the present invention, the degree of curl (curl width) is measured by placing the hard coat film cut to a size of 10 cm × 10 cm on a plane with the hard coat layer facing up, and observing the lifted state at both ends. The average value (mm) of the distance between the raised corner and the corner is shown.

  In the present invention, maintaining the hardness means that the hard coat film in a state where the solvent is not applied, and the hard coat film after the solvent is applied and dried in an oven at 80 ° C. for 1 minute. Comparison of the hardness of the pencil hardness test (using a 2H pencil, 500 g load) specified in JIS K5600-5-4 (1999) on the surface of the hard coat layer, and the evaluation of the pencil hardness test when a solvent is applied It means that it is not lower than the evaluation of the state where it is not applied. That is, when the evaluation of the pencil hardness test is lower than that before application after application and drying of the solvent, the hardness is not maintained.

  In the present invention, the hard coat film produced by the above-described method for producing a hard coat film, or the above-described T, PA, and PB are charged on the hard coat layer side surface of the hard coat film satisfying the formula (I). One or more layers selected from the group consisting of a second hard coat layer that is the same as or different from the hard coat layer, and an anti-glare layer, an anti-glare layer, an anti-fouling layer, a low refractive index layer, and a hard coat layer are provided. A hard coat film is provided.

  The present invention provides a polarizing plate, characterized in that a polarizer is provided on the triacetyl cellulose substrate side of the hard coat film described above.

  The present invention provides a liquid crystal display device characterized in that a liquid crystal cell is provided on the triacetyl cellulose substrate side of the hard coat film described above.

  According to the method for producing a hard coat film of the present invention, curling of the hard coat film can be reduced while maintaining the hardness of the hard coat film.

FIG. 1 a is a cross-sectional view schematically showing an example of a hard coat film that is not curled. FIG. 1 b is a perspective view schematically showing an example of a hard coat film that is not curled. FIG. 2 a is a cross-sectional view schematically showing an example of a curled hard coat film. FIG. 2b is a perspective view schematically showing an example of a curled hard coat film. FIG. 2c is a perspective view schematically showing an example of another hard coat film in a curled state. FIG. 3 is a cross-sectional view schematically showing another example of the hard coat film in a curled state. FIG. 4 is a cross-sectional view schematically showing an example of the layer configuration of the hard coat film of the present invention. FIG. 5 is a cross-sectional view schematically showing another example of the layer configuration of the hard coat film of the present invention. FIG. 6 is a cross-sectional view schematically showing an example of the layer structure of the polarizing plate of the present invention. FIG. 7 is a cross-sectional view schematically showing an example of the layer structure of the liquid crystal display device of the present invention. FIG. 8 is a diagram showing Raman spectral intensity characteristics at the interface opposite to the side on which the hard coat layer of the triacetylcellulose base material is provided. FIG. 9 is a graph showing Raman spectral intensity characteristics in the film thickness direction of the triacetylcellulose base material before and after solvent application in Example 7.

  Hereinafter, the manufacturing method of the hard coat film of the present invention will be described first, and then the hard coat film, the transparent base film that is an essential component thereof, and the hard coat layer will be described in order.

In the present invention, (meth) acrylate represents acrylate and / or methacrylate.
In the present invention, the “hard coat layer” generally indicates a hardness of “H” or higher in a pencil hardness test under a 500 g load specified in JIS K5600-5-4 (1999).
The light of the present invention includes not only electromagnetic waves having wavelengths in the visible and non-visible regions, but also particle beams such as electron beams, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams.
Moreover, in this invention, a film thickness means the film thickness at the time of drying (dry film thickness).
In the present invention, the molecular weight means a weight average molecular weight which is a polystyrene equivalent value measured by gel permeation chromatography (GPC) when having a molecular weight distribution, and when having no molecular weight distribution, Mean molecular weight.
In the present invention, the average particle diameter of the fine particles means a 50% particle diameter (d50 median diameter) when the particles in the solution are measured by a dynamic light scattering method and the particle size distribution is represented by a cumulative distribution. . The said average particle diameter can be measured using the Nikkiso Co., Ltd. Microtrac particle size analyzer or Nanotrac particle size analyzer.
The fine particles may be agglomerated particles, and in the case of agglomerated particles, the secondary particle diameter may be within the above range.

1. Method for Producing Hard Coat Film A method for producing a hard coat film according to the present invention comprises forming a hard coat layer on one side of a triacetyl cellulose substrate, and then forming a surface on which the hard coat layer of the triacetyl cellulose substrate is formed. Is applied to the opposite side surface with a solvent that reduces curling of the triacetyl cellulose base material toward the hard coat layer and maintains at least the hardness of the hard coat layer. The solvent includes acetone, hexane, One or more main solvents selected from dimethyl glycol and methyl acetate are contained at a ratio of 70% by weight or more of the total amount of the main solvent, and the coating amount of the solvent is 4 to 20 g / characterized in that it is a m ^2.

Thus, by applying the specific solvent at a coating amount of 4 to 20 g / m ² on the surface opposite to the surface on which the hard coat layer of the triacetyl cellulose base material is formed, triacetyl as described later. The distribution of the plasticizer in the cellulose substrate can be controlled, and curling of the hard coat film can be reduced while maintaining the hardness of the hard coat film.

  The reason for this is not clear, but the following reason is presumed. That is, the above-mentioned specific solvent has an appropriate permeability to the triacetyl cellulose base material and an appropriate coating amount, so that the side opposite to the hard coat layer 20 of the triacetyl cellulose base material 10 shown in FIG. The plasticizer existing in the vicinity of the interface 30 is caused to flow out of the triacetyl cellulose base material. As a result, only the plasticizer in the vicinity of the interface 30 of the triacetylcellulose base material 10 is reduced, and the cellulose polymer of the triacetylcellulose base material 10 is densely packed in the space from which the plasticizer is removed, and the triacetylcellulose base material 10 is interfaced. A curling force is generated on the 30 side. And it is estimated that the said force antagonizes the force curled to the hard coat layer 20 side of a hard coat film, and can curl to the hard coat layer 20 side of a hard coat film.

  However, if the solvent coating amount is too large, or if a solvent having an excessively high permeability to the triacetyl cellulose substrate other than the specific solvent is used, the amount of the solvent penetrating into the triacetyl cellulose substrate increases. At that time, the solvent contains a plasticizer present in the vicinity of the interface 30 of the triacetyl cellulose substrate 10 of the hard coat film 1 shown in FIG. To penetrate. Thereby, in the vicinity of the interface 160 of the triacetyl cellulose base material 10, the amount of the plasticizer is increased due to the plasticizer contained in the solvent that has penetrated than before the solvent application to the interface 30 of the triacetyl cellulose base material 10. End up. And since the soft area | region will be formed in the interface 160 vicinity by the side of the hard-coat layer 20 of the triacetyl cellulose base material 10, it will be estimated that the hardness reduction of a hard-coat film occurs as a result.

  In the present invention, maintaining the hardness means that the hard coat film in a state where the solvent is not applied, and the hard coat film after the solvent is applied and dried in an oven at 80 ° C. for 1 minute. Comparison of the hardness of the pencil hardness test (using a 2H pencil, 500 g load) specified in JIS K5600-5-4 (1999) on the surface of the hard coat layer, and the evaluation of the pencil hardness test when a solvent is applied It means that it is not lower than the evaluation of the state where it is not applied. That is, when the evaluation of the pencil hardness test is lower than that before application after application and drying of the solvent, the hardness is not maintained.

FIG. 1a is a schematic view showing a cross section of the hard coat film 1 in an uncurled state, and FIG. 2a is a schematic view showing a cross section of the hard coat film 1 in a curled state.
In FIG. 1 a, a hard coat layer 20 is formed on one side of the triacetyl cellulose substrate 10.
FIG. 1b is a perspective view schematically showing the hard coat film 1 in an uncurled state, and FIG. 2b is a perspective view schematically showing the hard coat film 1 in a curled state. is there. FIG. 2c is a perspective view schematically showing another hard coat film 1 in a curled state.

In the present invention, the degree of curl (curl width) is measured by placing the hard coat film cut to a size of 10 cm × 10 cm on a plane with the hard coat layer facing up, and observing the lifted state at both ends. The average value (mm) of the distance between the raised corner (end point) and the corner (end point) is shown.
Specifically, for example, in FIG. 2b, among the four end points (2, 3, 4 and 5) of the hard coat layer, the average value (mm) of the distance 6 between the end points 3-4 and 5-2 is shown. .
When the curling direction is different as shown in FIG. 2c, the average value of the distance 6 between the end points 2-3 and 4-5 is obtained. That is, the distance between the end points of the curled sides (sides 3-4 and 5-2 in FIG. 2b and sides 2-3 and 4-5 in FIG. 2c).
The distance 6 is measured by placing a sample piece obtained by cutting a hard coat film into 10 cm × 10 cm on a horizontal base (plane).

  After forming the hard coat layer 20 on one surface side of the triacetyl cellulose base material 10, the solvent is applied to the surface 30 opposite to the surface on which the hard coat layer of the triacetyl cellulose base material 10 is formed. Even if the film 1 is dried, curling to the hard coat layer 20 side can be reduced while maintaining the hardness of the hard coat film 1.

  In FIG. 3, when the curled hard coat film 1 is viewed as a disk, the angle formed by the sides 2-3 and the sides 4-5 with respect to the center of the circle is a center angle 40. When the degree of curl (curl width) increases, the central angle 40 may be 360 degrees or more. A state where the central angle is 360 degrees or more is defined as a roll-shaped object. In the case of a roll-shaped object, the curl width is expressed as φx by using the diameter of the circular portion of the roll-shaped object to be formed. For example, when the diameter of the circular part of the roll-shaped object is 15 mm, it is expressed as φ15.

(solvent)
Hereinafter, the solvent will be described in detail.
The solvent contains one or more main solvents selected from acetone, hexane, dimethyl glycol, and methyl acetate in such a proportion that the total amount of the main solvents is 70% by weight or more of the entire solvent. These four kinds of main solvents are excellent in the effect of reducing the curl of the hard coat film while maintaining the hardness of the hard coat film. If the total amount of the main solvent is less than 70% by weight of the total solvent, the hardness of the hard coat layer cannot be maintained.

In the present invention, the solvent is applied in an amount of 4 to 20 g / m ^{2 with} respect to the side opposite to the side on which the hard coat layer of the triacetyl cellulose substrate having the hard coat layer formed on one side is formed. Apply with. When the application amount of the solvent is less than 4 g / m ² , curling cannot be sufficiently reduced, and when the application amount of the solvent is 20 g / m ² or more, the hardness of the hard coat film is lowered.

  The reason for this is not clear, but the following reason is presumed. That is, the above-mentioned specific solvent has an appropriate permeability to the triacetyl cellulose base material and an appropriate coating amount, so that the side opposite to the hard coat layer 20 of the triacetyl cellulose base material 10 shown in FIG. The plasticizer existing in the vicinity of the interface 30 is caused to flow out of the triacetyl cellulose base material. As a result, only the plasticizer in the vicinity of the interface 30 of the triacetylcellulose base material 10 is reduced, and the cellulose polymer of the triacetylcellulose base material 10 is densely packed in the space from which the plasticizer is removed, and the triacetylcellulose base material 10 is interfaced. A curling force is generated on the 30 side. And it is estimated that the said force antagonizes the force curled to the hard coat layer 20 side of a hard coat film, and can curl to the hard coat layer 20 side of a hard coat film.

  However, if the solvent coating amount is too large, or if a solvent having an excessively high permeability to the triacetyl cellulose substrate other than the specific solvent is used, the amount of the solvent penetrating into the triacetyl cellulose substrate increases. At that time, the solvent contains a plasticizer present in the vicinity of the interface 30 of the triacetyl cellulose substrate 10 of the hard coat film 1 shown in FIG. To penetrate. Thereby, in the vicinity of the interface 160 of the triacetyl cellulose base material 10, the amount of the plasticizer increases due to the plasticizer contained in the solvent that has penetrated before the solvent application to the interface 30 of the triacetyl cellulose base material 10. . And since the soft area | region will be formed in the interface 160 vicinity by the side of the hard-coat layer 20 of the triacetyl cellulose base material 10, it will be estimated that the hardness reduction of a hard-coat film occurs as a result.

The application amount of the solvent is 4 to 20 g / m ² , preferably 5 to 10 g / m ² .

The method for applying the solvent to the triacetyl cellulose substrate is not particularly limited as long as the application amount is 4 to 20 g / m ^2, and the composition for a hard coat layer described later is used as the triacetyl cellulose substrate. The method of applying to can be used as it is.

  In the method for producing a hard coat film according to the present invention, the solvent contains any one main solvent selected from acetone, hexane, dimethyl glycol, and methyl acetate in a proportion of 70% by weight or more of the whole solvent. It is preferable to do. Thereby, curling of the hard coat film can be further reduced while maintaining the hardness of the hard coat layer.

  In the method for producing a hard coat film according to the present invention, the solvent is preferably acetone or an acetone mixed solvent containing 70% by weight or more of acetone. Thereby, the effect of reducing curl is high and the hardness is not easily lowered.

  The hard coat film of the present invention preferably has a curl width of 20 mm or more while maintaining hardness.

(Method for forming hard coat layer)
The hard coat layer may be formed by a conventionally known method.
For example, a curable resin composition for a hard coat layer containing fine particles such as a binder component (in this specification, the binder component may be expressed as a resin) and inorganic fine particles or organic fine particles for imparting hardness is triacetyl cellulose. It is applied to one side of the substrate to form a coating film, dried as necessary, and then the coating film is cured by light and / or heat to form a hard coat layer.

The application method is not particularly limited as long as it is a method capable of uniformly applying the curable resin composition for the hard coat layer to the surface of the triacetyl cellulose substrate, and the spin coating method, the dip method, the spray method, Various methods such as a slide coating method, a bar coating method, a roll coater method, a meniscus coater method, a flexographic printing method, a screen printing method, and a speed coater method can be used.
The coating amount of the curable resin composition for the hard coat layer on the triacetyl cellulose substrate varies depending on the performance required of the obtained hard coat film, but the coating amount after drying is different. in the range of ^{1g / m 2 ~30g / m 2} , particularly preferably in the range of ^{5g / m 2 ~25g / m 2} .

  Examples of the drying method include reduced-pressure drying or heat drying, and a method combining these drying methods. For example, when a ketone solvent is used as the solvent for the curable resin composition for the hard coat layer, it is usually room temperature to 80 ° C., preferably 40 ° C. to 70 ° C., preferably 20 seconds to 3 minutes, preferably The drying process is performed in a time of about 30 seconds to 1 minute.

  Next, with respect to the coating film obtained by applying and drying the curable resin composition for the hard coat layer, depending on the binder component and the reactive functional group of the fine particles contained in the curable resin composition, light irradiation and / or By heating and curing the coating film, a hard coat layer made of a cured product of the curable resin composition for hard coat layer is formed.

For light irradiation, ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are mainly used. In the case of ultraviolet curing, ultraviolet rays or the like emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp are used. The irradiation amount of the energy ray source is about 50 to 5000 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm.
When heating, it processes at the temperature of 40 to 120 degreeC normally. Moreover, you may react by leaving it to stand for 24 hours or more at room temperature (25 degreeC).

2. Hard coat film The hard coat film according to the present invention is a hard coat film having at least a hard coat layer on one side of a triacetyl cellulose substrate,
The hard coat layer comprises a cured product of a curable resin composition containing a binder component,
In Raman spectroscopy in the thickness direction of the triacetyl cellulose substrate, and a value obtained by dividing the peak intensity of 1600 cm ^-1 peak intensity of 1730 cm ^-1 and the peak intensity ratio, the thickness of triacetyl cellulose substrate ([mu] m) T, the maximum value of the peak intensity ratio in the region from the interface opposite to the hard coat layer of the triacetyl cellulose base material to 5 μm in the film thickness direction is PB, the hard coat layer side of the triacetyl cellulose base material When the peak intensity ratio at the interface is PA, the T, PA, and PB satisfy the following formula (I).
−0.015 ≦ (PA−PB) / T Formula (I)

As described in the production method of the hard coat film, the surface opposite to the hard coat layer formed surface of the triacetyl cellulose substrate by the solvent 4~20g / m ² is applied, triacetyl In the film thickness direction of the cellulose substrate, the above T, PA, and PB satisfy the relationship of the formula (I).
By satisfying the relationship of the above formula (I), as described in the method for producing a hard coat film, a hard coat film with curling suppressed can be obtained.

FIG. 8 is a diagram showing Raman spectral intensity characteristics at the interface opposite to the side on which the hard coat layer of the triacetylcellulose base material is provided.
In FIG. 8, the peak 170 at 1600 cm ⁻¹ is derived from the benzene ring of the plasticizer contained in the triacetyl cellulose base material, and the peak 180 at 1730 cm ⁻¹ is derived from the C═O bond of the triacetyl cellulose component. Therefore, the peak intensity ratio obtained by dividing the peak intensity of 1730 cm ^-1 to peak intensity of the 1600 cm ^-1, to understand the relative abundance for a triacetyl cellulose substrate of a plasticizer, thereby, the thickness direction of the plasticizer You can see the relative distribution of.

In the conventional hard coat film, since the triacetyl cellulose base material is prepared by a solution casting method, when it is prepared on a base such as a belt conveyor, the interface on the air interface side of the triacetyl cellulose base material (hereinafter referred to as A surface). It was found that the abundance ratio of the plasticizer at the base side interface (hereinafter also referred to as B surface) was larger than the abundance ratio of the plasticizer. In addition, in order to prevent winding slip when a hard coat film provided with a hard coat layer on a triacetyl cellulose base material is wound on a roll, it is usually only on the A side when producing the triacetyl cellulose base material. A process of forming a convex part called a knurling process is performed, and then a hard coat layer is formed on the A surface. For this reason, in the conventional hard coat film, the abundance ratio of the plasticizer on the B surface side is larger than the abundance ratio of the plasticizer on the A surface side of the triacetyl cellulose substrate.
On the other hand, in the hard coat film according to the present invention, the T, PA, and PB satisfy the formula (I), that is, from the interface on the side opposite to the hard coat layer of the triacetyl cellulose base material. The hard coat layer of the hard coat film has a difference in the abundance ratio between the plasticizer in the region up to 5 μm in the film thickness direction and the plasticizer at the interface on the hard coat layer side of the triacetyl cellulose substrate. Curling to the side is reduced, and a hard coat film having excellent hardness can be obtained.

  In the present invention, a hard coat layer may be provided on either the A surface side or the B surface side of the triacetyl cellulose substrate. When a knurling treatment is performed on the A surface side, the hard coat layer is provided on the A surface side. It is preferable to provide it.

In the present invention, the peak of 1600 cm ⁻¹ is adopted as the peak of the plasticizer, but when the wave number of the peak of the plasticizer contained in the triacetylcellulose base material is other than this, the peak of the plasticizer is appropriately selected. Can be adopted.

  In the formula (I), “(PA-PB) / T” is −0.015 or more, preferably −0.013 or more. Thereby, curling of the hard coat film can be further reduced.

The hard coat film of the present invention has other functions such as an antistatic layer, an antiglare layer, a low refractive index layer, and an antifouling layer on the hard coat layer in consideration of the function or application as a hard coat film. And one or more layers selected from the group consisting of second hard coat layers that are the same as or different from the hard coat layer may be formed.
The hard coat film according to the present invention may be provided with an antistatic function or an antiglare function when the hard coat layer contains an antistatic agent and / or an antiglare agent.

FIG. 4 is a cross-sectional view schematically showing another example of the layer configuration of the hard coat film of the present invention. A low refractive index layer 50 is formed on the hard coat layer 20.
FIG. 5 is a cross-sectional view schematically showing another example of the layer configuration of the hard coat film of the present invention. An antistatic layer 60 is formed on the hard coat layer 20, and a low refractive index layer 50 is further formed on the antistatic layer 60.

  Hereinafter, the triacetyl cellulose base material, which is an essential component of the hard coat film of the present invention, and the hard coat layer, and an antistatic layer, an antiglare layer, a low refractive index layer, an antistatic layer that can be appropriately provided as necessary. The dirty layer and one or more other layers selected from the group consisting of the second hard coat layer that is the same as or different from the hard coat layer will be described in order.

2-1. Triacetyl cellulose base material The triacetyl cellulose base material used in the present invention is a plastic film or sheet having high transparency (light transmittance), and satisfies the physical properties that can be used as the transparent base material of the optical laminate. There is no particular limitation, and it can be selected and used as appropriate.
Usually, the base material used for the optical layered body is transparent, translucent, colorless, or colored, but is required to have optical transparency. In addition, the measurement of light transmittance uses the value measured in room temperature and air | atmosphere using the ultraviolet visible spectrophotometer (For example, Shimadzu Corporation UV-3100PC).

A triacetyl cellulose base material is a light-transmitting base material capable of setting an average light transmittance to 50% or more in a visible light region of 380 to 780 nm. The average light transmittance of the triacetyl cellulose base material is preferably 70% or more, and more preferably 85% or more.
Since the triacetyl cellulose base material has optical isotropy, it can be preferably used even in the case of a liquid crystal display application.

  In addition, as triacetyl cellulose in the present invention, in addition to pure triacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like are used in combination with components other than acetic acid as fatty acids forming cellulose and esters. There may be. These triacetyl celluloses may be added with other cellulose lower fatty acid esters such as diacetyl cellulose or various additives such as a plasticizer, an antistatic agent, and an ultraviolet absorber as required.

  In the present invention, the thickness of the triacetyl cellulose base material can be appropriately selected and used. It is preferable to use a 20-120 μm triacetyl cellulose base material, and it is more preferable that it is 20-80 μm.

2-2. Hard coat layer The hard coat layer of the present invention is obtained by applying, drying, and curing a curable resin composition for a hard coat layer containing at least a binder component on a triacetyl cellulose substrate as described above.
In the present invention, the “hard coat layer” indicates a hardness of “H” or more in a pencil hardness test under a 500 g load specified in JIS K5600-5-4 (1999) as described above.
The hard coat layer of the present invention is preferably 2H or more in the pencil hardness test.

  The film thickness of the hard coat layer can be appropriately selected according to the strength and required performance of the substrate, and is not particularly limited, but is preferably in the range of 1 to 100 μm, and more preferably 5 to 30 μm.

(Curable resin composition for hard coat layer)
The curable resin composition for a hard coat layer of the present invention will be described.
The curable resin composition for a hard coat layer of the present invention contains at least a binder component, and in addition, for the purpose of improving the hardness of the hard coat layer, fine particles such as inorganic fine particles and / or organic fine particles, imparting functionality. For the purpose, an antiglare agent, an antifouling agent and an antistatic agent, a leveling agent and a solvent for controlling coating suitability, and a lubricant for the purpose of preventing blocking may be contained.

(Binder component)
The binder component contained in the curable resin composition for the hard coat layer forms a matrix of the hard coat layer when cured. 1 type (s) or 2 or more types can be used for a binder component.

  The binder component is preferably a curable monomer and / or oligomer, preferably a translucent material that transmits light when formed into a coating film, and an ionizing radiation that is a resin that is cured by ionizing radiation represented by ultraviolet rays or electron beams. What is necessary is just to employ | adopt suitably a curable monomer and / or oligomer, other well-known curable monomers, and / or oligomers etc. according to a required performance. Examples of the ionizing radiation curable monomer and / or oligomer include acrylate, oxetane, and silicone.

  The binder component preferably has a reactive functional group that can undergo a crosslinking reaction between the binder components or reactive inorganic fine particles described later. A network structure is formed by cross-linking between the reactive functional groups, and the hardness is improved.

  As the reactive functional group, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include ethylenically unsaturated bonds such as (meth) acryloyl group, vinyl group and allyl group, and epoxy group.

  Moreover, it is preferable from the point of the further hardness improvement that a binder component has 2 or more of the said reactive functional groups in 1 molecule.

Specific examples are given below, but the binder component used in the present invention is not limited thereto.
As a specific example having a polymerizable unsaturated group, as a polyfunctional (meth) acrylate monomer having two or more polymerizable unsaturated groups in one molecule, for example, 1,6-hexanediol di (meth) acrylate, Bifunctional (meth) acrylate compounds such as neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate; trimethylolpropane tri (meth) acrylate, and its EO, PO, epichlorohydrin modified product, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate and its EO, PO, epichlorohydrin modified product, isocyanuric acid EO modified tri (meth) acrylate (Aronix M-31 manufactured by Toagosei Co., Ltd.) Etc.), tris (meth) acryloyloxyethyl phosphate, hydrogen phthalate- (2,2,2-tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate, and its EO, PO, epichlorohydrin modification Trifunctional (meth) acrylate compounds such as products; pentaerythritol tetra (meth) acrylate and its EO, PO, epichlorohydrin modified products, tetrafunctional (meth) acrylate compounds such as ditrimethylolpropane tetra (meth) acrylate; dipentaerythritol Penta (meth) acrylate and pentafunctional (meth) acrylate compounds such as EO, PO, epichlorohydrin, fatty acid, alkyl and urethane modified products thereof; dipentaerythritol hexa (meth) acrylate and EO and P thereof , Epichlorohydrin, fatty acids, alkyl, urethane-modified products, sorbitol hexa (meth) acrylate, and EO, PO, epichlorohydrin, fatty acids, alkyl, hexafunctional (meth) acrylate compound of the urethane modified products are exemplified.

  Examples of (meth) acrylate oligomers (or prepolymers) include epoxy (meth) acrylates obtained by addition reaction of glycidyl ether and a monomer having (meth) acrylic acid or a carboxylate group; polyols and polyisocyanates; (Meth) acrylates obtained by an addition reaction between a reaction product of (1) and a hydroxyl group-containing (meth) acrylate; polyesters obtained by esterification of a polyester polyol comprising a polyol and a polybasic acid and (meth) acrylic acid Examples of acrylates include polybutadiene (meth) acrylate, which is a (meth) acrylic compound having a polybutadiene or hydrogenated polybutadiene skeleton. When the reactive functional group which the essential component in this invention has is a polymerizable unsaturated group, especially urethane (meth) acrylate is used suitably from the point which gives hardness and a softness | flexibility to a cured film.

Examples of the glycidyl ether used in the epoxy (meth) acrylates include 1,6-hexane diglycidyl ether, polyethylene glycol glycidyl ether, bisphenol A type epoxy resin, naphthalene type epoxy resin, cardo epoxy resin, and glycerol triglycidyl ether. And phenol novolac type epoxy resins.
Examples of the polyol used in the urethane (meth) acrylates include 1,6-hexane diglycidyl ether, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone diol, polycarbonate diol, polybutadiene polyol, and polyester diol. Etc. Examples of the polyisocyanate used in the urethane (meth) acrylates include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate, hexamelletin diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and the like. Examples of the (meth) acrylate containing a hydroxyl group used in the urethane (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and pentaerythritol. (Meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate and the like.
Examples of the polyol for forming the polyester polyol used in the polyester acrylates include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, 1,4-butanediol, trimethylolpropane, and pentaerythritol. Examples of the polybasic acid include succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid.
In particular, as the binder component, pentaerythritol triacrylate (PETA), dipentaerythritol pentaacrylate (DPHA), or the like is preferably used.

  Commercially available products can be used for the above compounds. Examples of urethane acrylates having two or more polymerizable unsaturated groups include Kyoeisha Chemical Co., Ltd. trade names AH-600, AT-600, UA-306H, UA-306T, UA-306I, etc .; Nippon Synthetic Chemical Industry Co., Ltd. Product name UV-1700B, UV-3000B, UV-3200B, UV-6300B, UV-6330B, UV-7000B, etc .; Arakawa Chemical Industries, Ltd. Product name Beam Set 500 series (502H, 504H, 550B, etc.) Shin-Nakamura Chemical Co., Ltd. product name U-6HA, U-15HA, UA-32P, U-324A, etc .; Toagosei Co., Ltd. product name M-9050 etc. are mentioned.

  Moreover, as epoxy acrylates having two or more polymerizable unsaturated groups, trade name SP series (SP-4060, 1450, etc.) manufactured by Showa High Polymer Co., Ltd., VR series (VR-60, 1950; VR-90, 1100 etc.); Nippon Synthetic Chemical Industry Co., Ltd. product name UV-9100B, UV-9170B etc .; Shin-Nakamura Chemical Co., Ltd. product name EA-6320 / PGMAc, EA-6340 / PGMAc, etc. are mentioned.

  Moreover, as a reactive oligomer which has two or more polymerizable unsaturated groups, Toagosei Co., Ltd. product name macromonomer series AA-6, AS-6, AB-6, AA-714SK etc. are mentioned.

  The content of the binder component in the curable resin composition for the hard coat layer may be appropriately set according to the target hardness and the like, and is not particularly limited, but 10 to 100% by weight improves the hardness. It is preferable from the point of being easy.

(Fine particles)
The curable resin composition for a hard coat layer preferably contains fine particles from the viewpoint of improving the hardness of the hard coat layer.

  The average particle diameter of the fine particles is preferably 1 to 100 nm from the viewpoint of the transparency of the hard coat layer. The fine particles may be agglomerated particles. In the case of agglomerated particles, the secondary particle diameter may be within the above range.

  The fine particles are preferably monodispersed with a narrow particle size distribution from the viewpoint of improving hardness while maintaining the restoration rate when only the binder component is used without impairing transparency.

  There is no restriction | limiting in particular in content in the curable resin composition for hard-coat layers of the said fine particle, What is necessary is just to set suitably in consideration of hardness etc. The content of the fine particles is preferably 10 to 80% by weight with respect to the total solid content of the curable resin composition for hard coat layer from the viewpoint of improving the hardness of the hard coat layer.

  The fine particles are not limited to having a single material or a single average particle diameter, but may be a combination of two or more kinds having different materials and average particle diameters. When two or more types are used in combination, the average particle size of each particle is preferably within 1 to 100 nm.

  The fine particles may be inorganic fine particles or organic fine particles, but are preferably inorganic fine particles from the viewpoint of imparting hardness.

Examples of the inorganic fine particles include metal oxides such as silica (SiO ₂ ), aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide. Examples thereof include fine particles, fine metal fluoride particles such as magnesium fluoride and sodium fluoride. Metal fine particles, metal sulfide fine particles, metal nitride fine particles and the like may be used.

From the viewpoint of high hardness, silica and aluminum oxide are preferable. In addition, in order to form a high refractive index layer relative to other layers provided on the hard coat layer, fine particles having a high refractive index when a film such as zirconia, titania, antimony oxide, etc. is formed are appropriately selected. Can be used. Similarly, in order to obtain a relatively low refractive index layer, fine particles having a low refractive index during film formation such as fluoride fine particles such as magnesium fluoride and sodium fluoride can be appropriately selected and used. Furthermore, when it is desired to impart antistatic properties and conductivity, indium tin oxide (ITO), tin oxide, or the like can be appropriately selected and used. These can be used alone or in combination of two or more.
The surface of the inorganic fine particles usually has groups that cannot exist in this form in the inorganic fine particles. These surface groups are usually relatively reactive functional groups. For example, in the case of metal oxides, for example, hydroxyl groups and oxy groups, for example in the case of metal sulfides, thiol groups and thio groups, or in the case of nitrides, for example, amino groups, amide groups and imides. Has a group.

  Examples of the organic fine particles include plastic beads. Specific examples of the plastic beads include polystyrene beads, melamine resin beads, acrylic beads, acrylic-styrene beads, benzoguanamine beads, benzoguanamine / formaldehyde condensation beads, polycarbonate beads, and polyethylene beads. The plastic beads preferably have a hydrophobic group on the surface, and examples thereof include styrene beads.

  The inorganic fine particles are reactive inorganic fine particles having a reactive functional group capable of forming a covalent bond by cross-linking reaction between the particles or the binder component on the fine particle surface at least on a part of the particle surface. Is preferred. The hardness of the hard coat layer can be further improved by a cross-linking reaction between the reactive inorganic fine particles or between the reactive inorganic fine particles and the binder component.

The reactive inorganic fine particles include those having two or more inorganic fine particles as a core per particle. Moreover, the reactive inorganic fine particle can raise the crosslinking point in the matrix of a hard-coat layer with respect to content by making a particle size small.
The reactive inorganic fine particles may further impart a function to the hard coat layer, and are appropriately selected and used according to the purpose.

  The reactive inorganic fine particles of the present invention are improved in hardness by using solid particles having no voids or porous structure inside the particles rather than particles having voids or porous structure inside the particles such as hollow particles. From the point of view, it is preferable.

  As the reactive inorganic fine particles, conventionally known ones may be used. For example, as commercially available products, reactive silica fine particles (trade name HC-601, manufactured by ADEKA Corporation), (trade names KZ7537, manufactured by JSR Corporation) are used. Can be used.

  As the reactive inorganic fine particles, powdery fine particles that do not contain a dispersion medium may be used. However, it is preferable to use a fine particle in a solvent-dispersed sol because the dispersion step can be omitted and the productivity is high.

(Other ingredients)
In addition to the above-mentioned components, a solvent, a polymerization initiator, an antistatic agent, an antiglare agent, an antifouling agent, and an easy-to-slip agent can be added to the hard coat layer of the present invention as appropriate. Furthermore, various additives, such as a reactive or non-reactive leveling agent and various sensitizers, may be mixed. When an antistatic agent and / or an antiglare agent and / or an antifouling agent and / or a slippery agent are included, the hard coat layer according to the present invention is further antistatic and / or antiglare and / or antifouling. Sex and / or thirst can be imparted.

(Solvent of curable resin composition for hard coat layer)
Specific examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol, methyl glycol, methyl glycol acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone Ketones such as alcohol; esters such as methyl formate, methyl acetate, ethyl acetate, ethyl lactate and butyl acetate; nitrogen-containing compounds such as nitromethane, N-methylpyrrolidone and N, N-dimethylformamide; diisopropyl ether, tetrahydrofuran and dioxane Ethers such as dioxolane; halogenated hydrocarbons such as methylene chloride, chloroform, trichloroethane, and tetrachloroethane; Kishido, other objects, such as propylene carbonate; or mixtures thereof. More preferable solvents include methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like.

(Polymerization initiator)
In the present invention, in order to initiate or promote the radical polymerizable functional group or the cationic polymerizable functional group, a radical polymerization initiator, a cationic polymerization initiator, a radical and a cationic polymerization initiator are appropriately selected as necessary. May be used. These polymerization initiators are decomposed by light irradiation and / or heating to generate radicals or cations to advance radical polymerization and cationic polymerization.

Any radical polymerization initiator may be used as long as it can release a substance that initiates radical polymerization by light irradiation and / or heating. For example, examples of the photo radical polymerization initiator include imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocenes, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives, and the like. More specifically, 1,3-di (tert-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (tert-butyldioxycarbonyl) benzophenone, 3-phenyl-5- Isoxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name Irgacure 651, Ciba Japan Co., Ltd.) 1-hydroxy-cyclohexyl-phenyl- T (trade name Irgacure 184, manufactured by Ciba Japan), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trade names Irgacure 369, Ciba Japan ( Co., Ltd.), bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium) (trade name Irgacure 784, manufactured by Ciba Japan Co., Ltd.), acylphosphine oxide (trade name DAROCUR TPO, manufactured by Ciba Japan Co., Ltd.) and the like, but are not limited thereto.

Moreover, the cationic polymerization initiator should just be able to discharge | release the substance which starts cationic polymerization by light irradiation and / or a heating. Examples of the cationic polymerization initiator include sulfonic acid ester, imide sulfonate, dialkyl-4-hydroxysulfonium salt, arylsulfonic acid-p-nitrobenzyl ester, silanol-aluminum complex, (η ⁶ -benzene) (η ⁵ -cyclopentadidiene). Enyl) iron (II) and the like are exemplified, and more specifically, benzoin tosylate, 2,5-dinitrobenzyl tosylate, N-tosiphthalimide and the like are exemplified, but not limited thereto.

  Examples of radical polymerization initiators used as cationic polymerization initiators include aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, triazine compounds, iron arene complexes, and the like. More specifically, iodonium chloride such as diphenyliodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bromide, borofluoride, hexafluorophosphate salt, hexafluoro Iodonium salts such as antimonate salts, chlorides of sulfonium such as triphenylsulfonium, 4-tert-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, bromides, borofluorides, hexaf Sulfonium salts such as orophosphate salts and hexafluoroantimonate salts, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1, 2,4,6-substituted-1,3,5 triazine compounds such as 3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, etc. It is not limited to these.

(Antistatic agent)
Specific examples of the antistatic agent include quaternary ammonium salts, pyridinium salts, various cationic compounds having cationic groups such as primary to tertiary amino groups, sulfonate groups, sulfate ester bases, and phosphate ester bases. , Anionic compounds having an anionic group such as phosphonate group, amphoteric compounds such as amino acid series and aminosulfate ester series, nonionic compounds such as amino alcohol series, glycerin series and polyethylene glycol series, and alkoxides of tin and titanium And metal chelate compounds such as acetylacetonate salts thereof, and compounds obtained by increasing the molecular weight of the compounds listed above. In addition, it has a tertiary amino group, a quaternary ammonium group, or a metal chelate portion, and has a monomer or oligomer that can be polymerized by ionizing radiation, or a polymerizable functional group that can be polymerized by ionizing radiation, and Polymerizable compounds such as organometallic compounds such as coupling agents can also be used as antistatic agents.

Moreover, electroconductive fine particles are mentioned as another example of the said antistatic agent. Specific examples of the conductive fine particles include those made of a metal oxide. Examples of such metal oxides include ZnO (refractive index 1.90, the numerical value in parentheses below represents the refractive index), CeO ₂ (1.95), Sb ₂ O ₂ (1.71), SnO. ₂ (1.997), indium tin oxide (1.95) often referred to as ITO, In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), antimony-doped tin oxide (abbreviation) ATO, 2.0), aluminum-doped zinc oxide (abbreviation: AZO, 2.0), and the like. The conductive fine particles preferably have an average particle size of 0.1 nm to 0.1 μm. By being within such a range, when the conductive fine particles are dispersed in a binder, a composition capable of forming a highly transparent film having almost no haze and good total light transmittance can be obtained.

(Anti-glare agent)
Examples of the antiglare agent include fine particles, and the shape of the fine particles may be a true sphere or an ellipse, and preferably a true sphere. The fine particles may be inorganic or organic, but those formed of an organic material are preferred. The fine particles exhibit anti-glare properties and are preferably transparent. Specific examples of the fine particles include plastic beads, and more preferably those having transparency. Specific examples of plastic beads include styrene beads (refractive index 1.59), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.49), acrylic-styrene beads (refractive index 1.54), Examples thereof include polycarbonate beads and polyethylene beads. The addition amount of the fine particles is about 2 to 30 parts by weight, preferably about 10 to 25 parts by weight with respect to 100 parts by weight of the curable resin composition.

(Anti-fouling agent)
The antifouling agent is a component used for preventing or reducing contamination on the surface of the hard coat layer.
Examples of the antifouling agent include silicone-containing and fluorine-containing antifouling agents, which may be used alone or in combination. Specific examples of the antifouling agent include a fluorine-containing antifouling agent (trade name: OPTOOL DAC, manufactured by Daikin Industries, Ltd.). The content of the antifouling agent is preferably 0.01 to 1.0% by weight based on the solid content of the curable resin composition. If it is 0.1% by weight or less, the antifouling property may not be secured, and if it is 1.0% by weight or more, the hardness may be lowered.

(Lubricant)
The lubricant is a component used to improve the smoothness and / or scratch resistance of the hard coat layer surface.
Examples of the lubricant include inorganic fine particles or organic fine particles, which may be used alone or in combination. Specific examples of the lubricant include silica fine particles (trade name MIBKSIR, manufactured by Catalyst Kasei Kogyo Co., Ltd.). The particle size of the lubricant is preferably 10 to 500 nm. If it is 10 nm or less, the slipperiness may not be ensured, and if it is 500 nm or more, the haze may increase. In addition, the content of the lubricant is preferably 0.1 to 3.0% by weight with respect to the solid content of the curable resin composition. If it is 0.1% by weight or less, the slipperiness may not be ensured, and if it is 3.0% by weight or more, the hardness may decrease and the haze may increase.

2-3. Other Layers As described above, the hard coat film of the present invention is basically composed of a triacetyl cellulose base material and a hard coat layer. However, in consideration of the function or application as a hard coat film, one or more layers as described below may be further provided on the hard coat layer.

(Antistatic layer)
The antistatic layer is made of a cured product of a curable resin composition for an antistatic layer containing an antistatic agent and a curable resin. The thickness of the antistatic layer is preferably about 30 nm to 1 μm.

  As the antistatic agent, the same materials as those mentioned above for the antistatic agent for the hard coat layer can be used.

  As a curable resin contained in the curable resin composition for an antistatic layer, a known resin can be appropriately selected and used alone or in combination of two or more.

(Anti-glare layer)
The antiglare layer is made of a cured product of a curable resin composition for an antiglare layer containing an antiglare agent and a curable resin. As the curable resin, a known resin can be appropriately selected, and one kind or two or more kinds can be used.

(Anti-glare agent)
As the antiglare agent, the same antiglare agents as those described above for the hard coat layer can be used.

(Anti-fouling layer)
According to a preferred embodiment of the present invention, an antifouling layer may be provided for the purpose of preventing dirt on the outermost surface of the hard coat film. The antifouling layer can further improve the antifouling property and scratch resistance of the hard coat film. The antifouling layer comprises a cured product of a curable resin composition for an antifouling layer comprising an antifouling agent and a curable resin composition.

  The antifouling agent and curable resin contained in the curable resin composition for the antifouling layer can be appropriately selected from known antifouling agents and curable resins, and one or more can be used.

(Low refractive index layer)
A low refractive index layer is a layer whose refractive index is lower than the layer adjacent to the base film side of the said layer, and consists of hardened | cured material of the curable resin composition for low refractive index layers. In the curable resin composition for a low refractive index layer, a known low refractive index curable resin or fine particles can be appropriately used so that the refractive index is lower than that of the adjacent layer.

(Second hard coat layer)
From the viewpoint of further improving the hardness of the hard coat film, a second hard coat layer may be provided on the surface of the hard coat layer opposite to the triacetyl cellulose substrate.
The second hard coat layer may be the same as the hard coat layer, and the composition of the two hard coat layers may be the same or different.

3. Next, the polarizing plate of the present invention will be described. The polarizing plate of the present invention includes a hard coat film produced by the above-described method for producing a hard coat film, or a triacetyl cellulose substrate of a hard coat film obtained by further laminating the above other layers on the hard coat layer of the hard coat film. A polarizer is provided on the side.

  FIG. 6 is a schematic cross-sectional view showing an example of the polarizing plate of the present invention. A polarizing plate 100 shown in FIG. 6 includes a hard coat film 1 in which a triacetyl cellulose base material 10 and a hard coat layer 20 are laminated, and a polarizer 70 in which a protective film 80 and a polarizing layer 90 are laminated. The polarizer 70 is provided on the triacetyl cellulose base material 10 side of the hard coat film 1.

  Note that the polarizer is disposed on the triacetylcellulose substrate side of the hard coat film, not only when the hard coat film and the polarizer are separately formed, but also when the members constituting the hard coat film are polarized. This includes the case where it also serves as a member constituting the child.

  When using the polarizing plate of this invention for a liquid crystal display device, a liquid crystal cell is normally arrange | positioned at the polarizer side, and the hard coat film side turns into an observer side.

  In addition, about a hard coat film, since the hard coat film mentioned above should just be used, description here is abbreviate | omitted. Hereinafter, the other structure in the polarizing plate of this invention is demonstrated.

3-1. Polarizer The polarizer used in the present invention is not particularly limited as long as it has predetermined polarization characteristics, and a polarizer generally used in a liquid crystal display device can be used.

  The polarizer is not particularly limited as long as it can maintain predetermined polarization characteristics for a long period of time. For example, the polarizer may be composed of only a polarizing layer, and a protective film and a polarizing layer are bonded together. There may be. When the protective film and the polarizing layer are bonded together, the protective film may be formed only on one side of the polarizing layer, or the protective film may be formed on both sides of the polarizing layer.

  As the polarizing layer, usually, a film made of polyvinyl alcohol is impregnated with iodine and uniaxially stretched to form a complex of polyvinyl alcohol and iodine.

Moreover, as a protective film, if the said polarizing layer can be protected and it has desired transparency, it will not specifically limit.
As transparency of a protective film, it is preferable that the transmittance | permeability in visible region is 80% or more, and it is more preferable that it is 90% or more.
In addition, the transmittance | permeability of the said protective film can be measured by JISK7361-1 (The test method of the total light transmittance of a plastic-transparent material).

  As a material constituting the protective film, for example, cellulose derivative, cycloolefin resin, polymethyl methacrylate, polyvinyl alcohol, polyimide, polyarylate, polyethylene terephthalate, polysulfone, polyethersulfone, amorphous polyolefin, modified acrylic polymer, polystyrene, An epoxy resin, a polycarbonate, polyester, etc. can be mentioned. Among these, it is preferable to use a cellulose derivative or a cycloolefin resin.

  The protective film may be composed of a single layer or may be a laminate of a plurality of layers. Moreover, when the protective film is a laminate of a plurality of layers, a plurality of layers having the same composition may be laminated, or a plurality of layers having different compositions may be laminated.

  Further, the thickness of the protective film allows the flexibility of the polarizing plate of the present invention to be within a desired range, and the dimensional change of the polarizer can be within a predetermined range by bonding to the polarizing layer. Although it is not particularly limited as long as it is in the range, it is preferably in the range of 5 μm to 200 μm, particularly preferably in the range of 15 μm to 150 μm, and more preferably in the range of 30 μm to 100 μm. . When the said thickness is thinner than said range, the dimensional change of the polarizing plate of this invention may become large. Moreover, when the said thickness is thicker than said range, when cutting the polarizing plate of this invention, for example, a processing waste may increase or abrasion of a cutting blade may become quick.

  The protective film may have retardation. By using a protective film having retardation, there is an advantage that the polarizing plate of the present invention can have a viewing angle compensation function for a liquid crystal display device.

  The aspect in which the protective film has retardation is not particularly limited as long as the protective film can exhibit desired retardation. As such an aspect, for example, the protective film has a configuration composed of a single layer, and includes an aspect having retardation by containing an optical property developing agent that exhibits retardation, and the resin material described above. By having a structure in which a retardation layer containing a compound having refractive index anisotropy is laminated on a transparent substrate made of the above, an embodiment having retardation can be mentioned. In the present invention, any of these embodiments can be suitably used.

4). Next, the liquid crystal display device of the present invention will be described. The liquid crystal display device of the present invention is characterized in that a liquid crystal cell is disposed on the triacetyl cellulose substrate side of the hard coat film described above.

  FIG. 7 is a cross-sectional view schematically showing an example of the liquid crystal display device of the present invention. The liquid crystal display device 110 shown in FIG. 7 includes a liquid crystal cell 120, a first retardation plate 130 disposed on the viewer side of the liquid crystal cell 120, a polarizing plate 100 disposed on the first retardation plate, a liquid crystal It has the 2nd phase difference plate 140 arrange | positioned at the light source side of the cell 120, and the 2nd polarizer 150 arrange | positioned at the light source side of the 2nd phase difference plate 140. FIG. The polarizing plate 100 includes a polarizer 70 and a hard coat film 1 disposed on the viewer side of the polarizer 70. The hard coat film 1 is obtained by directly laminating a triacetyl cellulose base material 10 and a hard coat layer 20.

  The liquid crystal display device of the present invention has a hard coat film and a liquid crystal cell, and any liquid crystal cell may be used as long as the liquid crystal cell is disposed on the triacetyl cellulose substrate side of the hard coat film described above. Depending on the case, other constituent members may be appropriately provided. For example, the liquid crystal display device of the present invention may have a polarizer, a second polarizer, a retardation plate, a second retardation plate, etc., as illustrated in FIG.

  In addition, since it described in detail with the said hard coat film about the hard coat film, description here is abbreviate | omitted. Hereinafter, another configuration of the liquid crystal display device of the present invention will be described.

4-1. Liquid crystal cell The liquid crystal cell used for this invention is arrange | positioned at the triacetyl-cellulose base material side of the above-mentioned hard coat film.

  A conventionally well-known thing can be used as a liquid crystal cell used for this invention.

  The arrangement of the liquid crystal cell is not particularly limited as long as the liquid crystal cell is arranged on the triacetyl cellulose substrate side of the hard coat film.

4-2. Other configurations (polarizer)
In the present invention, a polarizer may be disposed between the hard coat film and the liquid crystal cell. This polarizer is disposed on the triacetylcellulose substrate side of the hard coat film.
In addition, about the polarizer, since what was described by the said polarizing plate can be used, description here is abbreviate | omitted.

(Second polarizer)
In the present invention, a second polarizer may be disposed on the light source side of the liquid crystal cell.
The second polarizer can be the same as the above polarizer.

In a TN mode, VA mode and IPS mode liquid crystal display device, the polarizer and the second polarizer are usually arranged so that the absorption axis direction of the polarizer and the absorption axis direction of the second polarizer are substantially perpendicular to each other. Is done.
The polarizer and the second polarizer may be the same or different from each other.

(First retardation plate)
In the present invention, a first retardation plate may be disposed between the hard coat film and the liquid crystal cell. The first retardation plate is disposed between the polarizer and the liquid crystal cell.
The retardation plate is not particularly limited as long as it has a predetermined retardation, and a retardation plate generally used in a liquid crystal display device can be used.

(Second retardation plate)
In the present invention, a second retardation plate may be disposed on the light source side of the liquid crystal cell. The second retardation plate is disposed between the second polarizer and the liquid crystal cell.
The second retardation plate is not particularly limited as long as it has a predetermined retardation, and a retardation plate generally used in a liquid crystal display device can be used.

Hereinafter, the present invention will be described more specifically with reference to examples. These descriptions do not limit the present invention.
As pentaerythritol triacrylate, Nippon Kayaku Co., Ltd. product, PET30 was used.
As a polymerization initiator, Irgacure 184 manufactured by Ciba Japan Co., Ltd. was used.
As the transparent substrate film, a TAC film (thickness 40 μm, triacetylcellulose resin film, trade name: KC4UY, manufactured by Konica Corporation) was used.
Abbreviations for each compound are as follows.
PETA: Pentaerythritol triacrylate Hexane: Normal hexane DMG: Dimethyl glycol MEK: Methyl ethyl ketone NMP: N-methylpyrrolidone Xylene: Paraxylene IPA: Isopropyl alcohol In the following, parts are parts by weight unless otherwise specified.

In addition, the curl degree (curl width) of the hard coat film was measured by measuring the distance between the end points of the hard coat layer by placing a sample piece obtained by cutting the hard coat film into 10 cm × 10 cm on a horizontal base (plane). It is expressed as an average value (mm) of the distance. For example, when the average value of the distance when curled to the hard coat layer side is 50 mm, it becomes H50. Moreover, when the average value of the distance when curled to the TAC substrate side is 10 mm, T10 is obtained.
Further, the curl width when the hard coat film is curled up to a roll-like object is represented by an average value of the diameters at both ends of the roll-like object. For example, when the diameter of the roll-shaped object curled to the hard coat layer side is 15 mm, Hφ15. Moreover, when the diameter of the roll-shaped object curled to the TAC substrate side is 20 mm, Tφ20.

(Raman spectroscopic evaluation)
The measurement of Raman spectroscopy for obtaining the value of (PA-PB) / T in the formula (I) was performed using the laser Raman spectrometer LabRAM HR-800 LabRAM HR-800 (manufactured by HORIBA) under the following measurement conditions. did.
・ Injection conditions: 633 nm, 11.5 mW
・ Cross-section sample preparation method: Sample is sandwiched between ultramicrotome holders and cut with a glass knife. ・ Light receiving condition: Laser is irradiated from above with a 100 × objective lens, and the stage is moved at a pitch of 1 μm. ・ Measurement condition: Exposure 10 seconds (Laser irradiation for 10 seconds)
: Accumulation 7 (7 times accumulation)
: Spectro 1350cm-1 (measured about the 1350 cm ^-1)
: Grating 600 (using 600 gratings)

(Preparation of curable resin composition)
A component having the composition shown below was blended to prepare a curable resin composition for a hard coat layer.

(Curable resin composition for hard coat layer)
PET 30: 50 parts by weight Irgacure 184: 4 parts by weight MEK: 50 parts by weight

Example 1
The curable resin composition for a hard coat layer is applied to one side of a TAC film with a Miya bar, dried in a hot oven at a temperature of 70 ° C. for 60 seconds, the solvent in the coating film is evaporated, and the accumulated light amount is 100 mJ. irradiating the so that / cm ² by curing the coating film, to form a hard coat layer having a thickness of 7 [mu] m, to prepare a hard coat film 1. The curl width one day after production was H10. A solvent mixed in a ratio of 80% by weight of DMG: 20% by weight of acetone was applied to the surface of the obtained hard coat film 1 on the TAC film side by a Miyabar coating method at a coating amount of 4 g / m ² . The hard coat film coated with the solvent was dried in an oven at 80 ° C. for 1 minute. The curl width one day after application was H20.

(Pencil hardness evaluation)
The hardness of the pencil scratch test is JIS K5600-5-4 using the test pencil (hardness 2H) defined by JIS-S-6006 for the hard coat film before application of Example 1 and one day after application. The pencil hardness test (500 g load) specified in (1999) was performed 5 times, and the number of times the scratch was not found in the 5 tests was measured. Before application, it was not scratched twice during 5 tests. The evaluation results one day after application are shown in Table 1. In Table 1, 2/5 means that 2 out of 5 tests were not scratched.

  For Examples 2 to 15 and Comparative Examples 1 to 10, a hard coat film was prepared in the same manner as in Example 1 except that the type of solvent and the coating amount were changed as shown in Table 1, and the TAC film of the hard coat film A solvent was applied to the side surface, and the curl width and pencil hardness were evaluated. The results are shown in Table 1. In addition, Comparative Example 1 is an evaluation result when no solvent is applied, and the curl width before application and after 1 day in Table 1 are the same as those of other hard coat films coated with the solvent, and the measurement conditions are the same. The curl width is shown one day after the hard coat film was prepared and heated in an oven at 80 ° C. for 1 minute. Pencil hardness evaluation was 2/5 before solvent application | coating with the hard coat film of each Example and the comparative example.

  A graph of the peak intensity ratio of the Raman spectrum in the film thickness direction of the TAC substrate of Example 7 is shown in FIG. In FIG. 9, the spectrum before solvent application is spectrum 190 (square marker), and the spectrum after solvent application is spectrum 200 (round marker). The B side of the TAC film (the side opposite to the side on which the hard coat layer is provided) is 0 μm, and the distance on the A side of the TAC film (the side on which the hard coat layer is provided) is 40 μm.

  About Example 7, Example 9, and Comparative Example 1, the hard coat film coated with the solvent before and after the solvent coating was dried in an oven at 80 ° C. for 1 minute, and the film of the TAC substrate one day after the coating. Table 2 shows the values of the formula (I) in the thickness direction.

From Table 1, Examples 1-15 are the ratios whose total amount of the said main solvent is 70 weight% or more of the said whole solvent for 1 or more types of main solvents chosen from acetone, hexane, dimethylglycol, and methyl acetate. And the coating amount is in the range of 4 to ²⁰ g / m ² , so that the curl is reduced one day after coating than before coating, and the pencil hardness is also lower than before coating. The hardness was maintained.

In Comparative Example 1 in which the solvent was not applied, the curl width was Hφ25 one day after the production, but the curl width became Hφ18 two days after the production, the diameter of the roll-like object was small, and the curl was large. It was.
In Comparative Examples 2 and 3, the main solvent contained 70% by weight or more based on the total amount of the solvent, but the amount of application was as small as 3 g / m ² , so the curl was larger than before application.
In Comparative Examples 4, 6, 7, and 8, the coating amount of the solvent is 5 g / m ² , but the curl is reduced because the main solvent does not contain 70% by weight or more based on the whole solvent, but the hardness is reduced. Could not be maintained.
In Comparative Examples 5 and 9, the coating amount of the solvent was 5 g / m ² , but the main solvent was not contained in 70% by weight or more with respect to the whole solvent, and the curl and hardness were deteriorated.
In Comparative Example 10, the amount of acetone was 100% by weight, but the coating amount was as large as 25 g / m ² , curled to the TAC film side, became a roll, and the curl was large. Furthermore, the hardness has also decreased.

From Table 2, in Examples 7 and 9, the value of (PA-PB) / T of the formula (I) was -0.02, as in Comparative Example 1, before applying the solvent. By applying a coating amount of 5 g / m ² , acetone 40 wt% methyl acetate 60 wt% at a coating amount 7 g / m ² , the value of the formula (I) one day after the solvent application is −0.0113 and -0.0150, that is, after the solvent application, the amount of plasticizer in the region of the TAC substrate in the film thickness direction from the interface opposite to the HC layer of the TAC substrate to the film thickness direction up to 5 μm is decreased. It was.

From the above, a solvent containing one or more main solvents selected from acetone, hexane, dimethyl glycol, and methyl acetate in a total amount of 70% by weight or more of the total solvent is applied. In the Raman spectroscopic measurement in the film thickness direction of the triacetyl cellulose substrate by applying the hard coat film on the side opposite to the side on which the hard coat layer of the triacetyl cellulose substrate is formed in an amount of 4 to 20 g / m ² . , (PA-PB) / T in formula (I) was -0.015 or more, curling was reduced, and hardness could be maintained.

DESCRIPTION OF SYMBOLS 1 Hard coat film 2, 3, 4, 5 End point 6 Distance 10 between end points Triacetyl cellulose base material 20 Hard coat layer 30 The surface and the interface 40 on the opposite side to the hard coat layer of a triacetyl cellulose base material Center angle 50 Low Refractive index layer 60 Antistatic layer 70 Polarizer 80 Protective film 90 Polarizing layer 100 Polarizing plate 110 Liquid crystal display device 120 Liquid crystal cell 130 First retardation plate 140 Second retardation plate 150 Second polarizer 160 Triacetyl cellulose substrate Interface 170 on hard coat layer side Peak 180 derived from plasticizer in Raman spectrum of triacetyl cellulose substrate 180 Peak derived from triacetyl cellulose component in Raman spectrum of triacetyl cellulose substrate TAC before application of solvent in Example 7 Peak strength 200 in the film thickness direction Peak strength in the film thickness direction of the TAC film after solvent application in Example 7

Claims (7)

After the hard coat layer is formed on one side of the triacetyl cellulose base, the hard coat layer of the triacetyl cellulose base is formed on the side opposite to the side on which the hard coat layer of the triacetyl cellulose base is formed. Applying a solvent that reduces curl to the side and maintains at least the hardness of the hard coat layer, the solvent includes at least one main solvent selected from acetone, hexane, dimethyl glycol, and methyl acetate, The method for producing a hard coat film, wherein the total amount of the main solvent is 70% by weight or more based on the total amount of the solvent, and the coating amount of the solvent is 4 to 20 g / m ² .   The said solvent contains any 1 type of main solvents chosen from acetone, hexane, dimethylglycol, and methyl acetate in the ratio of 70 weight% or more of the said whole solvent, The said solvent is characterized by the above-mentioned. Manufacturing method of hard coat film.   The method for producing a hard coat film according to claim 1, wherein the solvent is acetone or an acetone mixed solvent containing 70 wt% or more of acetone. A hard coat film having at least a hard coat layer on one side of a triacetyl cellulose substrate,
The hard coat layer is composed of a cured product of a curable resin composition containing a binder component,
In Raman spectroscopy in the thickness direction of the triacetyl cellulose substrate, and a value obtained by dividing the peak intensity of 1600 cm ^-1 peak intensity of 1730 cm ^-1 and the peak intensity ratio, the thickness of triacetyl cellulose substrate ([mu] m) T, the maximum value of the peak intensity ratio in the region from the interface opposite to the hard coat layer of the triacetyl cellulose base material to 5 μm in the film thickness direction is PB, the hard coat layer side of the triacetyl cellulose base material When the peak intensity ratio at the interface is PA, the T, PA, and PB satisfy the following formula (I).
−0.015 ≦ (PA−PB) / T Formula (I)   An antistatic layer, an antiglare layer, or a hard coat film produced by the production method according to any one of claims 1 to 3, or a hard coat layer side surface of the hard coat film of claim 4; A hard coat film, comprising at least one layer selected from the group consisting of an antifouling layer, a low refractive index layer and a second hard coat layer which is the same as or different from the hard coat layer.   A polarizer is provided on the triacetyl cellulose substrate side of the hard coat film produced by the production method according to any one of claims 1 to 3 or the hard coat film of claim 4 or 5. A polarizing plate, characterized by comprising:   A liquid crystal cell is provided on the hard coat film produced by the production method according to any one of claims 1 to 3 or the triacetyl cellulose substrate side of the hard coat film of claim 4 or 5. A liquid crystal display device comprising:

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