JP2015067690A - Hard coat film for retardation film, and retardation film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat film for a retardation film, which is free of influences of offset of a leveling agent while including the leveling agent in a hard coat layer, and which can suppress retardation unevenness of a retardation film, and a retardation film with reduced retardation unevenness, which is free of influences of offset of a leveling agent while including the leveling agent in a hard coat layer.SOLUTION: The hard coat film includes a hard coat layer disposed on one surface side of a transparent substrate film. The hard coat layer comprises a cured product of a curable resin composition for a hard coat layer, which comprises a polyfunctional monomer having at least two ethylenically unsaturated bond-containing groups, and a fluorine compound having a perfluoroalkenyl group and a polyethylene oxide group. The fluorine compound has an average addition molar number of the ethylene oxide of 7 to 24, and has a weight average molecular weight of 700 to 1500.

Description

  The present invention relates to a hard coat film for a retardation film and a retardation film.

Conventionally, in a liquid crystal display device, various techniques have been developed in order to improve the problem of viewing angle dependency. As one of them, a retardation film having a retardation layer showing birefringence is used as a liquid crystal cell. Liquid crystal display devices disposed between polarizing plates are known (for example, Patent Documents 1 and 2).
As the retardation film having the retardation layer, an alignment layer having an alignment regulating force for aligning liquid crystal compounds in a certain direction on the transparent substrate film, and formed on the alignment layer and arranged in a certain direction. Those having a retardation layer containing a liquid crystal compound are used.

  Conventionally, as a flat panel display, a two-dimensional display has been mainstream, but in recent years, a flat panel display capable of three-dimensional display has begun to attract attention. Further, in future flat panel displays, it is a natural tendency to be capable of three-dimensional display, and flat panel displays capable of three-dimensional display are being studied in a wide range of fields.

In order to perform three-dimensional display on a flat panel display, it is usually necessary to display a right-eye video and a left-eye video separately to the viewer in some manner. As a method for separately displaying the right-eye video and the left-eye video, for example, a passive method is known. Such a passive three-dimensional display method will be described with reference to the drawings. FIG. 3 is a schematic diagram illustrating an example of a passive three-dimensional display. As shown in FIG. 3, in this method, first, the pixels constituting the flat panel display are classified into two types of pixels, a right-eye video display pixel and a left-eye video display pixel, and the right-eye pixel is displayed in the display display area. The pixels are arranged in a pattern so that the left-eye pixels are adjacent to each other. One group of pixels displays a right-eye image, and the other group of pixels displays a left-eye image. Also, using a linear polarizing plate and a pattern phase difference film (hereinafter simply referred to as a pattern phase difference film) in which a pattern phase difference layer corresponding to the arrangement pattern of the pixel is formed, an image for the right eye is used. And the image for the left eye are each converted into circularly polarized light. In addition, the viewer wears circularly polarized glasses that employ a right-eye lens and a left-eye lens, and the right-eye image passes only through the right-eye lens, and the left-eye image passes only through the left-eye lens. Like that.
In this way, the right-eye video reaches only the right eye, and the left-eye video reaches only the left eye, thereby enabling three-dimensional display.
Such a passive method has an advantage that three-dimensional display can be easily performed by using the pattern retardation film and the corresponding circular polarizing glasses.

  As the above-mentioned pattern retardation film, for example, in Patent Document 3, an alignment layer in which the alignment regulating force is controlled in a pattern shape on a transparent resin film, and the alignment of the liquid crystalline material formed on the alignment layer is the alignment described above. A patterned retardation film having a retardation layer (liquid crystal layer) patterned so as to correspond to the pattern of the layer is disclosed.

  As described above, in each of the retardation film and the pattern retardation film, the liquid crystal material is arranged in a certain direction by the alignment layer, and the optical axis is constant in the whole film or in each pattern in the film. It is required to be.

  On the other hand, the image display surface of the retardation film is required to have hardness so as not to be damaged during handling. Therefore, conventionally, providing a hard coat layer on the surface opposite to the surface on which the alignment layer and the retardation layer of the transparent base film used for the retardation film has been imparted has been performed. Yes. The heart coat layer often functions as an optical functional layer such as an antiglare layer by adding other components such as particles and an antistatic agent. Since such a hard coat layer needs to be uniformly formed on the surface of the transparent substrate film, as a material for forming the hard coat layer, a material to which a leveling agent such as a fluorine leveling agent is added may be used. It is used (for example, Patent Document 4).

JP-A-3-67219 JP-A-4-322223 JP 2012-73516 A JP 2003-326649 A

  However, when a transparent substrate film provided with a hard coat layer containing a leveling agent is continuously wound up in a roll shape, the leveling agent in the hard coat layer is wound up and in contact It moves to the surface of the transparent substrate film where the hard coat layer is not provided (hereinafter, it may be referred to as “leveling agent is set off” or “leveling agent is set off”). When the alignment layer is formed on the surface of the transparent substrate film on which the labeling agent is offset, there is a problem that uneven coating occurs, and as a result, uneven retardation occurs in the retardation film.

  The present invention has been made in view of the above problems, and includes a leveling agent in a hard coat layer, and has no influence of a settling of the leveling agent, and can suppress retardation unevenness of the retardation film. An object of the present invention is to provide a hard coat film and a retardation film in which the leveling agent is not influenced and the retardation unevenness is reduced while the hard coat layer contains the leveling agent.

The hard coat film for retardation film according to the present invention is a hard coat film in which a hard coat layer is provided on one side of a transparent substrate film,
The hard coat layer is a curable resin composition for a hard coat layer containing a polyfunctional monomer having at least two ethylenically unsaturated bond-containing groups and a fluorine compound having a perfluoroalkenyl group and a polyethylene oxide group. Made of hardened material,
The fluorine compound has an average added mole number of the ethylene oxide of 7 to 24 and a weight average molecular weight of 700 to 1500.

The retardation film according to the present invention is a retardation film in which a hard coat layer is provided on one surface side of a transparent substrate film, and an alignment layer and a retardation layer are provided in this order on the other surface side,
The hard coat layer is a curable resin composition for a hard coat layer containing a polyfunctional monomer having at least two ethylenically unsaturated bond-containing groups and a fluorine compound having a perfluoroalkenyl group and a polyethylene oxide group. Made of hardened material,
The fluorine compound has an average added mole number of the ethylene oxide of 7 to 24 and a weight average molecular weight of 700 to 1500.

  According to the present invention, a hard coat film for a retardation film that has no leveling agent inversion while containing a leveling agent in a hard coat layer and can suppress retardation unevenness of the retardation film, and a hard coat It is possible to provide a phase difference film in which the leveling agent is not affected while the leveling agent is included in the layer and the retardation unevenness is reduced.

It is sectional drawing which shows typically an example of the hard coat film for retardation films which concerns on this invention. It is sectional drawing which shows typically an example of the phase difference film which concerns on this invention. It is the schematic which shows an example of the liquid crystal display device which can display a three-dimensional image | video with a passive system.

Hereinafter, the hard coat film for retardation film and the retardation film according to the present invention will be described in order.
In the present invention, the optical axis means a slow axis.
In the present invention, the retardation film includes a pattern retardation film unless otherwise specified.
In the present invention, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.

<< Hardcoat film for retardation film >>
The hard coat film for retardation film according to the present invention is a hard coat film in which a hard coat layer is provided on one side of a transparent substrate film,
The hard coat layer is a curable resin composition for a hard coat layer containing a polyfunctional monomer having at least two ethylenically unsaturated bond-containing groups and a fluorine compound having a perfluoroalkenyl group and a polyethylene oxide group. Made of hardened material,
The fluorine compound has an average added mole number of the ethylene oxide of 7 to 24 and a weight average molecular weight of 700 to 1500.

The hard coat film for retardation film according to the present invention has a hard coat layer, is imparted with hardness, and is excellent in scratch resistance. Moreover, since the fluorine compound contained in the hard coat layer functions as a leveling agent, the hard coat layer of the present invention is uniformly formed without unevenness.
In order to form a hard coat layer uniformly, a leveling agent such as a fluorine compound has been conventionally added. However, when a conventional hard coat film is rolled up, The inside of the leveling agent sometimes occurred. Therefore, when a retardation film is produced using a conventional hard coat film, the offset leveling agent repels the coating film of the composition for forming the alignment layer, resulting in coating unevenness, and the alignment layer has a film thickness. It will have unevenness, and as a result, poor alignment due to the influence of the uneven film thickness of the alignment layer, uneven film thickness of the entire retardation film due to the uneven film thickness of the alignment layer, etc., which cause the uneven retardation. There was a problem.
On the other hand, when a retardation film is produced using the hard coat film according to the present invention, the hard coat layer contains a fluorine compound as a leveling agent, and there is no influence of the settling of the leveling agent, and the retardation film Phase difference unevenness is suppressed. Although its action is not clear, it is thought to be due to the properties of the specific fluorine compound contained as a leveling agent in the hard coat layer provided in the hard coat film of the present invention. The fluorine compound used in the present invention is a fluorine compound having a perfluoroalkenyl group and a polyethylene oxide group, and since the average added mole number and weight average molecular weight of ethylene oxide are within the above specific range, it has excellent hydrophilicity, and Low molecular weight. Due to the particular influence of such properties, the fluorine compound is less likely to cause set-off itself, or even if it is set off, if a coating film is formed on the fluorine compound, it is difficult to cause repelling, or these It is considered that the film thickness unevenness of the alignment layer can be suppressed and the retardation unevenness of the retardation film can also be suppressed by performing both actions.

In FIG. 1, sectional drawing of an example of the hard coat film for retardation films which concerns on this invention is shown typically. In the retardation film hard coat film 10 of FIG. 1, a hard coat layer 12 is provided on one side of the transparent base film 11.
Hereinafter, each structure of the hard coat film for retardation films which concerns on this invention is demonstrated.

<Transparent substrate film>
As the transparent substrate film, a known transparent substrate film used for a retardation film can be appropriately selected and used, and a transparent resin substrate having a predetermined transparency is usually used. Examples of the transparent resin base material include acetyl cellulose resins such as triacetyl cellulose, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, olefin resins such as polyethylene and polymethylpentene, acrylic resins, polyurethane resins, Examples thereof include polyether sulfone, polycarbonate, polysulfone, polyether, polyether ketone, acrylonitrile, methacrylonitrile, cycloolefin polymer, and cycloolefin copolymer.

  The transparent substrate film preferably has a transmittance in the visible light region of 80% or more, and more preferably 90% or more. Here, the transmittance | permeability of a transparent base film can be measured by JISK7361-1 (the test method of the total light transmittance of a plastic-transparent material).

Among transparent resin base materials, it is preferable that the retardation is low. More specifically, the in-plane retardation value (Re value) of the transparent substrate film is preferably in the range of 0 nm to 10 nm, more preferably in the range of 0 nm to 5 nm, and 0 nm to 3 nm. More preferably, it is in the range. If retardation value is below the said upper limit, it will be easy to manufacture the retardation film which has desired retardation.
From the viewpoint that the in-plane retardation tends to approach zero, among the transparent resin base materials, those formed using a resin such as an acetyl cellulose resin, a cycloolefin polymer, a cycloolefin copolymer, or an acrylic resin are preferable.

Moreover, it is preferable that a transparent base film is a flexible material which has the flexibility which can be wound up in roll shape from the point by which the effect by this invention is exhibited more notably.
Such flexible materials include cellulose derivatives, norbornene polymers, cycloolefin polymers, polymethyl methacrylate, polyvinyl alcohol, polyimide, polyarylate, polyethylene terephthalate, polysulfone, polyethersulfone, amorphous polyolefin, modified acrylic polymer, polystyrene. And epoxy resins, polycarbonates, polyesters, and the like. Of these, cellulose derivatives are preferably used in the present invention. This is because the cellulose derivative is particularly excellent in optical isotropy, and therefore can be excellent in optical characteristics.

  In the present invention, among the cellulose derivatives, it is preferable to use a cellulose ester, and among the cellulose esters, it is preferable to use a cellulose acylate. This is because cellulose acylates are advantageous in terms of availability because they are widely used industrially.

  As the cellulose acylates, lower fatty acid esters having 2 to 4 carbon atoms are preferable. The lower fatty acid ester may include only a single lower fatty acid ester such as cellulose acetate, and may include a plurality of fatty acid esters such as cellulose acetate butyrate and cellulose acetate propionate. There may be.

  In the present invention, cellulose acetate can be particularly preferably used among the lower fatty acid esters. As the cellulose acetate, it is most preferable to use triacetyl cellulose having an average acetylation degree of 57.5% to 62.5% (substitution degree: 2.6 to 3.0). Here, the degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation can be determined by measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like). In addition, the acetylation degree of the triacetyl cellulose which comprises a triacetyl cellulose film can be calculated | required by said method, after removing impurities, such as a plasticizer contained in a film.

  The thickness of the transparent substrate film used in the present invention is not particularly limited as long as it is within a range in which necessary self-supporting properties can be imparted, depending on the use of the hard coat film for retardation film of the present invention, etc. A range of 25 μm to 125 μm is preferable, a range of 40 μm to 100 μm is particularly preferable, and a range of 60 μm to 80 μm is particularly preferable. It is because sufficient self-supporting property may not be provided when the thickness of the transparent substrate film is thinner than the above range. Further, when the thickness is thicker than the above range, for example, when a long retardation film is formed and then cut to form a single-wafer retardation film, processing waste increases or a cutting blade This is because there is a case where the wear of the metal becomes faster.

The structure of the transparent substrate film used in the present invention is not limited to a structure composed of a single layer, and may have a structure in which a plurality of layers are laminated. When it has the structure by which the several layer was laminated | stacked, the layer of the same composition may be laminated | stacked, and the several layer which has a different composition may be laminated | stacked.
For example, a primer layer for improving the adhesion between the transparent substrate film and the hard coat layer may be formed on the transparent substrate film. This primer layer has only adhesiveness to both the transparent substrate film and the hard coat layer, is visible optically transparent, and can pass ultraviolet light. For example, vinyl chloride / vinyl acetate copolymer A system, a urethane type, or the like can be appropriately selected and used.

<Hard coat layer>
The hard coat layer of the present invention comprises a cured product of the curable resin composition for the hard coat layer, imparts hardness to the hard coat film for retardation film according to the present invention, and realizes excellent scratch resistance.
In the present invention, the “hard coat layer” means a layer having a hardness of “H” or higher in a pencil hardness test specified by JIS 5600-5-4 (1999).
The curable resin composition for a hard coat layer contains a polyfunctional monomer having at least two ethylenically unsaturated bond-containing groups, and a fluorine compound having the specific perfluoroalkenyl group and a polyethylene oxide group, As long as the effects of the present invention are not impaired, other components such as a polymerization initiator, a thermosetting resin, an antiglare agent, an antistatic agent, functional fine particles, and a solvent can be contained as necessary.
The hard coat layer of the present invention is selected from the group consisting of an antiglare layer, a low refractive index layer, a medium refractive index layer and a high refractive index layer, an antistatic layer and an antifouling layer by further adding other components. It may function as one or more functional layers.

The polyfunctional monomer having two or more ethylenically unsaturated bond-containing groups is a radical polymerizable monomer, and a photopolymerization initiator is combined as necessary.
Examples of the ethylenically unsaturated bond-containing group include a (meth) acryloyl group, a vinyl group, and an allyl group. Among them, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is more preferable.

  Examples of the polyfunctional monomer having two or more ethylenically unsaturated bond-containing groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, and propylene glycol di (meth). Acrylate, glycerol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol Trimethylolpropane di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, acrylated isocyanurate, bis (acryloxyneopentyl glycol) adipate, bisphenol A di (meth) acrylate , Tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, butanediol di (meth) acrylate, hexanediol (meth) acrylate, phthalic acid di (meth) acrylate, phosphoric acid di (meth) acrylate, Bifunctional monomers such as zinc di (meth) acrylate;

  Trimethylolpropane tri (meth) acrylate, polymethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Alkyl-modified dipentaerythritol tri (meth) acrylate, succinic anhydride-modified pentaerythritol tetra (meth) acrylate, phosphoric acid tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, di Pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, alkyl-modified dipentaerythritol tetra (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, succinic anhydride-modified dipentaerythritol penta (meth) acrylate, urethane tri (meth) acrylate , Tri- or higher functional monomers such as ester tri (meth) acrylate, urethane hexa (meth) acrylate, and ester hexa (meth) acrylate.

Among these polyfunctional monomers, those having three (meth) acrylate groups (trifunctional) or more are preferable. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Succinic acid modification of erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate Dipentaerythritol hexa (meth) acrylate is preferable, trimethylolpropane tri (meth) acrylate (TMPTA), pentaerythritol tri (meth) acrylate (PETA), pen Pentaerythritol tetra (meth) acrylate (PETTA) is more preferable.
These polyfunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Although content of a polyfunctional monomer is not specifically limited, It is preferable that it is 40-99.5 mass% with respect to the total solid of the curable resin composition for hard-coat layers.

The curable resin composition for a hard coat layer contains a fluorine compound having a perfluoroalkenyl group and a polyethylene oxide group, and the fluorine compound has an average added mole number of the ethylene oxide of 7 to 24, and has a weight. The average molecular weight is 700-1500.
Here, the said weight average molecular weight can be measured by gel permeation chromatography (GPC), for example, and can be specified as a weight molecular weight of polystyrene conversion.

  Since the fluorine compound used in the present invention has a perfluoroalkenyl group and is the above-mentioned specific low molecular weight compound, and the average added mole number of ethylene oxide is in the above-specified range, the unevenness of the hard coat layer is reduced. It functions as a fluorine-based leveling agent that is excellent in reducing effect, and among the fluorine compounds that function as a fluorine-based leveling agent, it is excellent in hydrophilicity and has a low molecular weight. Due to the particular influence of such properties, the fluorine compound is less likely to cause set-off itself, or even if it is set off, if a coating film is formed on the fluorine compound, it is difficult to cause repelling, or these It is considered that the film thickness unevenness of the alignment layer can be suppressed and the retardation unevenness of the retardation film can also be suppressed by performing both actions.

In the fluorine compound, examples of the perfluoroalkenyl group include residues obtained by removing one fluorine atom from tetrafluoroethylene, hexafluoropropene, and oligomers thereof. Among them, the residue of an oligomer of hexafluoropropene is preferable, and a 2-tetramer of hexafluoropropene, particularly a 2-trimer residue of hexafluoropropene is preferably used.
Among them, the fluorine compound used in the present invention is represented by the following chemical formula (1), chemical formula (2), and chemical formula (3) because it has a high effect of suppressing the influence of setback while suppressing unevenness of the hard coat layer. It has at least one perfluoroalkenyl group selected from the group consisting of perfluoroalkenyl groups represented by the following formula (1) and perfluoroalkenyl groups represented by formula (2). It preferably has one or more perfluoroalkenyl groups selected from the group.

  In addition, the fluorine compound has a high effect of further reducing the retardation unevenness of the retardation film, so that the ratio (MMW / EOn) of the weight average molecular weight (MMW) to the average added mole number (EOn) of ethylene oxide is 100 or less. It is preferable that it is 60 or more.

  Specific examples of the fluorine compound include an addition reaction product of perfluoroalkene and polyethylene oxide, and an addition reaction product of hexafluoropropene dimer and trimer with polyethylene oxide is preferably used. .

  As a commercial item of the said fluorine compound, the Neos Co., Ltd. product, 250,251,215M, 212M etc. are mentioned, for example.

  Although content of the said fluorine compound is not specifically limited, It is preferable that it is 0.3-10 mass% with respect to the total solid of the curable resin composition for hard-coat layers. When the content of the fluorine compound is equal to or higher than the lower limit value, the effect of reducing the unevenness of the hard coat layer is excellent, and when the content is equal to or lower than the upper limit value, the retardation unevenness of the retardation film is sufficiently suppressed. it can.

A photopolymerization initiator may be used in combination with the polyfunctional monomer. Examples of the photopolymerization initiator include acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, and the like. These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.
Although content of the said photoinitiator is not specifically limited, It is preferable that it is 0.1-10 mass% with respect to the total solid of the curable resin composition for hard-coat layers.

  The curable resin composition for a hard coat layer may further contain a thermosetting resin. Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin, Examples thereof include polysiloxane resins.

The curable resin composition for a hard coat layer may further contain an antiglare agent in order to impart an antiglare property to the hard coat layer and to function as an antiglare layer. As the antiglare agent, known ones can be used, and inorganic or organic fine particles can be used. Among them, transparent plastic beads are preferable, and specifically, for example, styrene beads, melamine beads, acrylics. Examples thereof include beads, acrylic-styrene beads, polycarbonate beads, and polyethylene beads.
Although content of the said glare-proof agent is not specifically limited, It is preferable that it is 1-30 mass% with respect to the total solid of the curable resin composition for hard-coat layers.

The hard coat layer curable resin composition may further contain an antistatic agent. As the antistatic agent, a conventionally known antistatic agent can be used. For example, a cationic antistatic agent such as a quaternary ammonium salt described in JP-A-2007-264221, or tin-doped indium oxide (ITO). Fine particles such as these can be used.
Although content of the said antistatic agent is not specifically limited, It is preferable that it is 10-50 mass% with respect to the total solid of the curable resin composition for hard-coat layers.

The curable resin composition for a hard coat layer may further contain functional fine particles. The functional fine particles are components for imparting functionality such as hardness and refractive index control capability to the hard coat layer, and fine particles used in conventionally known hard coat layers can be used.
For example, silica fine particles having excellent hardness can be used to impart hardness. The silica fine particles may be reactive silica fine particles having an organic component capable of undergoing a crosslinking reaction with the binder component on the particle surface described in JP-A-2008-165041. By using the reactive silica fine particles, it is possible to form a crosslink with the binder component and further increase the hardness of the hard coat layer.
Low refractive index fine particles such as fluoride fine particles such as sodium fluoride and hollow silica fine particles are used to control the refractive index of the hard coat layer, antimony doped tin oxide (ATO), phosphorus doped tin oxide (PTO), zirconia High refractive index fine particles such as (ZrO ₂ ) and antimony oxide (Sb ₂ O ₅ ) may be used.
Although content of the said functional fine particle is not specifically limited, It is preferable that it is 1-10 mass% with respect to the total solid of the curable resin composition for hard-coat layers.

  The curable resin composition for a hard coat layer may contain a solvent for improving coatability. Solvents include alcohols such as isopropyl alcohol, methanol and ethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as methyl acetate, ethyl acetate and butyl acetate; halogenated hydrocarbons; toluene, xylene and the like Aromatic hydrocarbons; or mixtures thereof.

  The film thickness (at the time of curing) of the hard coat layer may be appropriately adjusted according to the use of the hard coat film for retardation film, and is not particularly limited, but is preferably 1 to 10 μm.

The hard coat layer can be formed by applying, drying and curing the curable resin composition for hard coat layer on one side of the transparent substrate film. The method of application | coating, drying, and hardening can be suitably selected from a well-known method according to the component in the said resin composition.
Examples of the coating method of the resin composition include an air knife coating method, a curtain coating method, a roll coating method, a wire bar coating method, a gravure coating method, a die coating method, a blade coating method, a micro gravure coating method, a spray coating method, A known method such as a spin coating method is used. Examples of the ultraviolet light source used for curing the resin composition include a light source of an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp lamp. As the wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm can be used.

In addition, the hard coat film for retardation films according to the present invention solves the problem due to the back-off of the leveling agent contained in the hard coat layer, and has a remarkable effect when wound into a roll after forming the hard coat layer. However, it does not prevent other functional layers from being provided on the surface of the hard coat layer for the purpose of imparting further functionality during use.
Examples of other functional layers include a low refractive index layer, a medium refractive index layer, a high refractive index layer, an antistatic layer, and an antifouling layer.

(Low refractive index layer)
The low refractive index layer is a layer having a lower refractive index than the layer adjacent to the transparent base film side of the layer, and is made of a cured product of the composition for low refractive index layer. In the composition for low refractive index layer, fine particles such as low refractive index curable resins such as known fluororesins and hollow silica fine particles are appropriately used so that the refractive index is lower than the layer adjacent to the transparent substrate film side. Can be used.

(Medium refractive index layer and high refractive index layer)
The medium refractive index layer and the high refractive index layer are layers that can be provided to adjust the reflectance of the hard coat film, for example, by providing the low refractive index layer on the transparent base film side.
The film thicknesses of the medium refractive index layer and the high refractive index layer may be appropriately adjusted according to the required performance, and can be set to 1 to 5 μm, for example.
The medium refractive index layer and the high refractive index layer usually mainly contain a binder component and refractive index adjusting particles. As the binder component, those similar to the hard coat layer can be used.
As the refractive index adjusting particles, functional fine particles having a high refractive index mentioned in the hard coat layer may be used.

(Antistatic layer)
The antistatic layer is a layer that can be provided as necessary to prevent the generation of static electricity and prevent the adhesion of dust, or to prevent external static electricity damage when incorporated in a liquid crystal display or the like. is there.
The antistatic layer comprises a cured product of a composition containing an antistatic agent and a binder component. What is necessary is just to adjust the film thickness of an antistatic layer suitably, and it is preferable that it is 10-300 nm.
As the performance of the antistatic layer, it is preferable that the surface resistance after forming the hard coat film is 1012 Ω / □ or less.
As the antistatic agent and the binder component, the same materials as those described for the hard coat layer can be used.

(Anti-fouling layer)
For the purpose of preventing dirt on the outermost surface of the hard coat film, an antifouling layer can be provided on the outermost surface on the hard coat layer side. The antifouling layer makes it possible to impart antifouling properties and scratch resistance to the hard coat film. An antifouling layer consists of hardened | cured material of the resin composition for antifouling layers containing antifouling agent and curable resin, for example.
The antifouling agent and the curable resin contained in the antifouling layer composition can be appropriately selected from known antifouling agents and curable resins, and one or more can be used.

<< retardation film >>
The retardation film according to the present invention is a retardation film in which a hard coat layer is provided on one surface side of a transparent substrate film, and an alignment layer and a retardation layer are provided in this order on the other surface side,
The hard coat layer is a curable resin composition for a hard coat layer containing a polyfunctional monomer having at least two ethylenically unsaturated bond-containing groups and a fluorine compound having a perfluoroalkenyl group and a polyethylene oxide group. Made of hardened material,
The fluorine compound has an average added mole number of the ethylene oxide of 7 to 24 and a weight average molecular weight of 700 to 1500.

The retardation film according to the present invention is provided with an alignment layer and a retardation layer in this order on the surface of the transparent base film on the side where the hard coat layer of the hard coat film for retardation film according to the present invention is not present. Can be obtained. Therefore, the retardation film according to the present invention is a retardation film in which the unevenness of the retardation is reduced without the influence of the settling of the leveling agent while including the leveling agent in the hard coat layer.
The hard coat layer in the retardation film according to the present invention is added with other components in the same manner as the hard coat layer in the retardation film hard coat film according to the present invention. It may function as one or more functional layers selected from the group consisting of a layer, a medium refractive index layer, a high refractive index layer, an antistatic layer and an antifouling layer. In the retardation film according to the present invention, a low refractive index layer, a medium refractive index layer, and a high refractive index layer are provided on the side of the transparent base film provided with the hard coat layer for the purpose of imparting further functionality It does not prevent the provision of other functional layers such as an antistatic layer and an antifouling layer.

  FIG. 2 schematically shows a cross-sectional view of an example of the retardation film according to the present invention. In the retardation film 20 of FIG. 2, the hard coat layer 12 is provided on one surface side of the transparent substrate film 11, and the alignment layer 21 and the retardation layer 22 are provided in this order on the other surface side.

  In the retardation film according to the present invention, as the transparent substrate film and the hard coat layer, the same materials as those used in the above-described hard coat film for a retardation film according to the present invention can be used. Is omitted.

<Alignment layer>
The alignment layer is a layer having an alignment regulating force capable of aligning the liquid crystal compound having refractive index anisotropy contained in the retardation layer in a certain direction. For example, the photo-alignment compound or a reaction product thereof is It can be made into the layer which exhibits orientation regulation power by containing and irradiation of polarized ultraviolet rays.
Here, the photo-alignment compound refers to a compound that can exhibit an alignment regulating force by irradiation with polarized ultraviolet rays. Further, “alignment regulating force” means an interaction for aligning liquid crystal compounds described later.

  Such a photo-alignment compound is not particularly limited as long as it exhibits the above-mentioned alignment regulating force by irradiating polarized light. Such photo-alignment compounds include a photoisomerization material that reversibly changes the alignment regulation force by changing only the molecular shape by cis-trans change, and a photoreaction material that changes the molecule itself by irradiating polarized light. Can be broadly classified. In the present invention, any of the photoisomerizable material and the photoreactive material can be suitably used, but it is more preferable to use a photoreactive material. As described above, the photoreactive material is a material that reacts with polarized light to develop an alignment regulating force by irradiating polarized light. Therefore, the photoreactive material can irreversibly develop an alignment regulating force. Therefore, the photoreactive material is superior in the temporal stability of the orientation regulating force.

  The photoreactive material can be further classified according to the type of reaction caused by irradiation with polarized light. Specifically, a photodimerization type material that develops an alignment regulation force by causing a photodimerization reaction, a photodegradable material that produces an orientation regulation force by producing a photodecomposition reaction, an orientation regulation by producing a photobinding reaction It can be divided into a photocoupled material that expresses force, and a photolytic-coupled material that develops alignment regulation force by causing a photodecomposition reaction and a photocoupled reaction. In the present invention, any of the above-mentioned photoreactive materials can be suitably used, but among them, it is more preferable to use a photodimerization type material from the viewpoint of stability and reactivity (sensitivity).

  The photodimerization-type material used for this invention will not be specifically limited if it is a material which can express an orientation control force by producing photodimerization reaction. Especially, it is preferable that the wavelength of the light which produces a photodimerization reaction is 280 nm or more, It is preferable to exist in the range of 280 nm-400 nm especially, Furthermore, it is preferable to exist in the range of 300 nm-380 nm.

  Examples of such a photodimerization type material include cinnamate, coumarin, benzylidenephthalimidine, benzylideneacetophenone, diphenylacetylene, stilbazole, uracil, quinolinone, maleinimide, cinnamylideneacetic acid, and polymers having these derivatives. . In particular, in the process, a polymer having at least one of cinnamate or coumarin, a polymer having cinnamate and coumarin, and derivatives thereof are preferably used. Specific examples of such a photodimerization type material include, for example, JP-A-9-118717, JP-A-10-506420, JP-A-2003-505561, WO2010 / 150748, WO2011 / 126019. And the compounds described in Japanese Laid-Open Patent Publication No. WO2011 / 126021 and WO2011 / 126022.

  As the cinnamate and coumarin, those represented by the following formulas Ia and Ib are preferably used.

In the above formula, A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furylene, 1,4- or 2,6-naphthylene, Unsubstituted, fluorine, chlorine or a cyclic, linear or branched alkyl residue of 1 to 18 carbon atoms (unsubstituted or mono- or polysubstituted by fluorine, chlorine, 1 Represents phenylene that is mono- or polysubstituted by more than one non-adjacent —CH ₂ — group, which may be independently substituted by Z ₁ ).
Z ₁ represents —O—, —CO—, —CO—O—, —O—CO—, —NR ₁ —, —NR ₁ —CO—, —CO—NR ₁ —, —NR ₁ —CO—. O—, —O—CO—NR ₁ —, —NR ₁ —CO—NR ₁ —, —CH═CH—, —C≡C—, —O—CO—O— and —Si (CH ₃ ) ₂ — It represents a group selected from O—Si (CH ₃ ) ₂ — (R ₁ represents a hydrogen atom or lower alkyl).
In the above formula, B represents a hydrogen atom or a group capable of reacting or interacting with a second substance such as a polymer, oligomer, monomer, photoactive polymer, photoactive oligomer, photoactive monomer, or surface. Represent.
In the above formula, S ₁ and S ₂ are independently of each other a single bond or a spacer unit, for example a linear or branched alkylene group having 1 to 40 carbon atoms (unsubstituted, fluorine or chlorine Mono- or poly-substituted, and one or more non-adjacent —CH ₂ — groups may be independently substituted by Z ₂ , but the oxygen atoms are not directly bonded to each other).
Z ₂ represents —O—, —CO—, —CO—O—, —O—CO—, —NR ₁ —, —NR ₁ —CO—, —CO—NR ₁ —, —NR ₁ —CO—. O—, —O—CO—NR ₁ —, —NR ₁ —CO—NR ₁ —, —CH═CH—, —C≡C—, —O—CO—O— and —Si (CH ₃ ) ₂ — A group selected from O—Si (CH ₃ ) ₂ — (R ₁ represents a hydrogen atom or lower alkyl), an aromatic group or an alicyclic group.
In the above formula, Q represents an oxygen atom or —NR ₁ — (R ₁ represents a hydrogen atom or lower alkyl).
In the above formula, X and Y are independently of each other hydrogen, fluorine, chlorine, cyano, alkyl having 1 to 12 carbon atoms (optionally substituted by fluorine and optionally not one or more adjacent). alkyl -CH ₂ - groups are -O -, - CO-O - , - O-CO- and / or an) are replaced by -CH = CH-.
In addition, as such a photodimerization-type material, specifically, what is commercially available as ROP-103 (trade name) from Rollic Corporation in WO08 / 031243 and WO08 / 130555 can be used. .

  Moreover, as a photo-alignment compound used for this invention, you may have refractive index anisotropy. As the photo-alignment compound having such refractive index anisotropy, specifically, those described in JP-A-2002-82224 can be used.

  In addition, the photo-alignment compound used for this invention may be only one type, or may use 2 or more types.

The composition for forming an alignment layer contains at least a photo-alignment compound, but may contain other compounds as necessary.
Such other compounds are not particularly limited as long as they do not impair the alignment regulating force of the alignment layer, but monomers or oligomers having one or more functional groups are preferably used. By including such a monomer or oligomer, when a retardation layer containing a liquid crystal compound having refractive index anisotropy is formed on the alignment layer, it can be excellent in adhesion to the retardation layer.

  Examples of the monomer or oligomer include a monofunctional monomer having an acrylate functional group (for example, reactive ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone), and a polyfunctional monomer. (For example, polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, triethylene (polypropylene) glycol diacrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate Isocyanuric acid poly (meth) acrylate (for example, isocyanuric acid EO diacrylate)), bisphenol fluorene derivatives (for example, bisphenoxyethanol fluorenedi (meth) acrylate, bisphenol fluorenedin epoxy (meth) acrylate), etc. alone or mixed It can be used as a thing.

  Furthermore, it is preferable to use the monomer or oligomer that is solid at normal temperature (20 to 25 ° C.). Thereby, even when the retardation film is stored in a rolled state, blocking due to the alignment layer sticking to the back surface of the substrate can be prevented.

  The content of the monomer or oligomer is not particularly limited as long as it does not impair the alignment regulating force of the alignment layer formed in this step and can exhibit desired adhesion and the like. The range of 0.01 to 3 times the mass of the orientation compound is preferable, and the range of 0.05 to 1.5 times is particularly preferable.

Moreover, the said composition for alignment layer formation can contain a solvent for a coating property improvement etc. The solvent can be appropriately selected according to the material included in the composition for forming an alignment layer, and is not particularly limited. For example, methanol, ethanol, ethylene glycol, 2-propanol (IPA), propylene glycol, Alcohol solvents such as ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol (PGME); methyl acetate, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol 1-monomethyl ether Ester solvents such as 2-acetate (PGMEA) and ethyl lactate; acetone, cyclopentanone, cyclohexanone, 2-heptanone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) Ketone solvents; chlorinated aliphatic hydrocarbon solvents such as pentane, hexane and heptane; non-chlorine aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ethers such as tetrahydrofuran and dimethoxyethane Examples of the solvent include chlorine-containing solvents such as chloroform and chlorobenzene.
These solvents may be used alone or in combination of two or more.
The content of the solvent in the composition for forming an alignment layer may be appropriately adjusted and is not particularly limited, but from the viewpoint of coating properties, it is 50 to 98 mass with respect to the entire composition for forming an alignment layer containing a solvent. % Is preferred.

  The alignment layer is formed by applying the composition for forming an alignment layer on the side of the transparent base film where the hard coat layer is not present, drying it, and irradiating it with light. The method for coating, drying, and light irradiation may be appropriately selected from conventionally known methods.

  Moreover, the coating amount of the composition for forming an alignment layer on the transparent substrate film may be any as long as the obtained alignment layer expresses a desired alignment regulating force, and may be appropriately adjusted. Especially, it is preferable that the thickness of the alignment layer obtained will be 50-300 nm, and it is more preferable that it will be 100-200 nm. When the thickness of the alignment layer is within the above range, the alignment layer is excellent in the alignment regulating force.

As a drying method, drying may be performed immediately after application while blowing air with a blower or the like. As specific drying temperature, 30 degreeC-120 degreeC is mentioned, for example, 40-110 degreeC is preferable. Further, the drying wind speed is preferably 0.2 m / s to 50 m / s, and the drying time is suitably adjusted within a range of 20 seconds to 3 minutes, preferably 30 seconds to 2 minutes.
Here, the solid content concentration of the composition for forming the alignment layer, the temperature of the composition for forming the alignment layer, the drying temperature, the wind speed of the drying air, the drying time, the solvent atmosphere concentration in the drying zone, and the like will be described later. The thickness of the osmotic layer can be adjusted. In particular, a method of adjusting the thickness of the osmotic layer by selecting drying conditions is preferable.
The drying may be naturally dried at 20 to 30 ° C. without blowing air in order to increase the thickness of the permeation layer.

As light irradiation, light irradiation may be performed from the side on which the alignment layer forming composition is applied, or light irradiation is performed from the transparent substrate film side opposite to the surface on which the alignment layer forming composition is applied. May be.
What is necessary is just to adjust an irradiation amount suitably so that it may become the exposure amount which can orient the photoalignment compound contained in the composition for alignment layer formation.

In the present invention, by irradiating with light, the dried coating film is photo-aligned and cured at the same time to form an alignment layer, and the permeation layer in which the photo-alignment compound has penetrated into the transparent substrate film. May be formed. Here, the permeation layer refers to a layer in which at least the components of the transparent substrate film and the photoalignment compound are mixed.
In this invention, it is preferable to have a osmosis | permeation layer from the point which can improve the adhesiveness of a transparent base film and an orientation layer.
The presence of the permeation layer can be confirmed by, for example, an electron micrograph of a cross section of the retardation film, mapping by a microscopic IR of the cross section, or a TOF-SIMS method.

In addition, in the present invention, the alignment layer may have an alignment regulating force by forming fine irregularities on the surface without using the photoalignment compound, in addition to the embodiment using the photoalignment compound. In the case of using such an alignment layer, for example, a rod-like liquid crystal compound is used as a liquid crystal compound to be contained in the retardation layer formed on the alignment layer, and the rod-like shape is formed by fine irregularities formed on the alignment layer surface. By aligning the liquid crystal compound in a certain direction, the alignment regulating force can be exhibited.
The fine concavo-convex shape is not particularly limited as long as the rod-shaped liquid crystal compound can be arranged in a certain direction. For example, a mode in which minute line-shaped concavo-convex structures are randomly formed in a substantially constant direction, a line shape Examples include an embodiment in which the concavo-convex structure is formed in a stripe shape.
Such an alignment layer is formed by, for example, applying and drying a curable resin composition for an alignment layer containing an ultraviolet curable resin, and forming and curing a fine uneven shape on the surface of the coating film by a method such as shaping. Can be formed. Specific examples include an alignment layer described in JP 2012-73516 A.

<Phase difference layer>
In the retardation layer, a desired retardation is imparted by regularly arranging liquid crystal compounds along the alignment regulating force of the alignment layer.
In addition, the composition for forming a retardation layer contains at least a liquid crystal compound and a solvent, and may contain other components as necessary.

  Examples of the liquid crystal compound include a liquid crystalline molecular material exhibiting a liquid crystal phase such as a nematic phase or a smectic phase. Among these, a nematic liquid crystalline molecular material is preferable because it can be regularly arranged. Furthermore, among the nematic liquid crystalline molecular materials, those having spacers at both mesogenic ends are more preferable because a retardation film having excellent flexibility and excellent transparency can be produced.

The liquid crystal compound is preferably a polymerizable liquid crystal compound having a polymerizable functional group in the molecule, and more preferably a polymerizable liquid crystal compound having a polymerizable functional group capable of three-dimensional crosslinking.
The polymerizable liquid crystal compound has a polymerizable functional group in the liquid crystal molecule, and can be cross-linked between the liquid crystal molecules by the action of a radical generated from the photopolymerization initiator by irradiation of light or an electron beam. Stability of the retardation film is improved. Examples of the polymerizable liquid crystal compound include a nematic liquid crystalline molecular material, a cholesteric liquid crystalline molecular material, a chiral nematic liquid crystalline molecular material, a smectic liquid crystalline molecular material, and a discotic liquid crystalline molecular material having a polymerizable group. Can do.

  The method for forming the retardation layer is not particularly limited as long as it can accurately coat a retardation layer having a desired thickness. About the method of application | coating, drying, and hardening, the method similar to the formation method of the said orientation layer can be used.

  Although the thickness of a phase difference layer is not specifically limited, For example, it can set within the range of 1 nm-2000 nm, Preferably, it is 500 nm-1500 nm.

  Moreover, in the case of a pattern phase difference film, it can manufacture with reference to the method etc. of Unexamined-Japanese-Patent No. 2012-14064, for example.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
[Example 1]
1. Preparation of Hard Coat Film for Retardation Film First, components having the following composition were blended to prepare a curable resin composition for a hard coat layer.
Polyfunctional monomer (PET-30, manufactured by Nippon Kayaku Co., Ltd., pentaerythritol triacrylate, mixture of pentaerythritol tetraacrylate): 40 parts by mass Fluorine compound (Factent 251, manufactured by Neos Co., Ltd., weight average molecular weight) 800, average addition mole number of ethylene oxide 8, addition reaction product of trimer of hexafluoropropene and polyethylene oxide): 0.2 part by mass / solvent (methyl isobutyl ketone (MIBK)): 60 parts by mass

On one side of a 60 μm thick triacetylcellulose (TAC) film (Fujitack TD60UL, manufactured by Fuji Film Co., Ltd.), the hard coat layer curable resin composition obtained above was applied. The film was dried at 30 ° C. for 30 seconds, and then irradiated with ultraviolet rays at a dose of 200 mJ / m ^{2 in} a nitrogen atmosphere to form a hard coat layer having a thickness of 4.5 μm. A coated film was obtained.

2. Production of retardation film (crimping hard coat film)
Prepare two hard coat films obtained by separating the hard coat film for retardation film obtained above, and the TAC film surface of the other hard coat film is in contact with the hard coat layer side of one hard coat film After overlapping and pressing with a rubber roller 40 times, it was left at 100 ° C. for 30 minutes.

(Formation of alignment layer)
For forming an alignment layer, 100 parts by mass of a photo-alignment material (trade name: ROP-103, manufactured by Rorick) having both a photodimerization site and a thermal crosslinking site is dissolved in 900 parts by mass of propylene glycol monomethyl ether (PGME). A composition was obtained.
The two hard coat films for retardation film that have been pressure-bonded as described above are peeled off, and obtained on the TAC film surface of the other hard coat film that has been in contact with the hard coat layer side surface of one hard coat film. The alignment layer forming composition was applied by a gravure coating method so that the film thickness after curing was 200 nm, and the coating film was allowed to flow in a dryer adjusted to 100 ° C. for 1 minute to evaporate the solvent, and polarized ultraviolet rays Was irradiated at an exposure amount of 18 mJ / m ² . Thereby, an alignment layer having a thickness of 200 nm was formed.

(Formation of retardation layer)
By adding 20 parts by mass of a liquid crystal compound represented by the following chemical formula and 5 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by BASF Corporation) to 80 parts by mass of cyclohexanone, a composition for forming a retardation layer is obtained. Obtained.
On the alignment layer, the retardation layer-forming composition obtained above is applied, the coating film is dried at 80 ° C. for 75 seconds, and then irradiated with ultraviolet rays at an exposure amount of 111 mJ / m ^2. A retardation layer having a thickness of 1000 nm was formed to obtain a retardation film.

[Example 2]
As a fluorine compound to be contained in the hard coat layer, instead of FT 251, FT 212M (manufactured by Neos Co., Ltd., weight average molecular weight 1000, average addition mole number of ethylene oxide 12, hexafluoropropene trimer and polyethylene oxide The hard coat film and retardation film for retardation films of Example 2 were obtained in the same manner as in Example 1 except that the addition reaction product was used.

[Example 3]
As a fluorine compound to be contained in the hard coat layer, instead of FT 251, FT 215M (manufactured by Neos Co., Ltd., weight average molecular weight 1,100, average addition mole number 15 of ethylene oxide, hexafluoropropene trimer and polyethylene oxide The hard coat film and retardation film for retardation film of Example 3 were obtained in the same manner as in Example 1 except that the addition reaction product was used.

[Example 4]
As a fluorine compound to be contained in the hard coat layer, instead of FT 251, FT 250 (Neos Co., Ltd., weight average molecular weight 1,400, average addition mole number of ethylene oxide 22, hexafluoropropene trimer and polyethylene oxide The hard coat film and retardation film for retardation film of Example 4 were obtained in the same manner as in Example 1 except that the addition reaction product was used.

[Comparative Example 1]
Example 1 except that Fluorent 212P (manufactured by Neos Co., Ltd., weight average molecular weight 2300, average number of added moles of ethylene oxide 12) was used instead of Fluorent 251 as the fluorine compound to be contained in the hard coat layer. In the same manner, a hard coat film for a retardation film and a retardation film of Comparative Example 1 were obtained.

[Comparative Example 2]
Example 1 except that Fluorent 208G (manufactured by Neos Co., Ltd., weight average molecular weight 1600, average number of added moles of ethylene oxide 8) was used instead of Fluorent 251 as the fluorine compound to be contained in the hard coat layer. In the same manner as described above, a hard coat film for a retardation film and a retardation film of Comparative Example 2 were obtained.

[Evaluation]
(Uneven phase difference)
The retardation layer side surface of the retardation film obtained in each Example and each Comparative Example was visually observed to confirm the occurrence of film thickness unevenness, and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1. In the present invention, unevenness refers to local phase difference unevenness, and the form of unevenness is not particularly limited. For example, the unevenness is generated in the form of dots, lines, strips, and the like.
[Criteria]
A: No unevenness B: Unevenness occurs in an area of less than 50% of the coated surface C: Unevenness occurs in an area of 50% or more of the coated surface

In Table 1, “EOn” represents the average number of moles of ethylene oxide added, and “MMW” represents the weight average molecular weight.

(Summary of results)
In the hard coat films for retardation films obtained in Examples 1 to 4, the average addition mole number of ethylene oxide of the fluorine compound contained in the curable resin composition for the hard coat layer is 7 to 24, and the weight average molecular weight is Since it was 700-1500, in the phase difference film obtained using the said hard coat film for phase difference films, the spot unevenness did not generate | occur | produce or hardly generate | occur | produced.
On the other hand, the hard coat film for retardation film obtained in Comparative Examples 1 and 2 has a too high weight average molecular weight of the fluorine compound contained in the curable resin composition for hard coat layer. In the retardation film obtained using the film, unevenness occurred in an area of 50% or more with respect to the coated surface, resulting in retardation unevenness.

DESCRIPTION OF SYMBOLS 10 Hard coat film 11 for phase difference films Transparent substrate film 12 Hard coat layer 20 Phase difference film 21 Orientation layer 22 Phase difference layer

Claims (2)

A hard coat film provided with a hard coat layer on one side of the transparent substrate film,
The hard coat layer is a curable resin composition for a hard coat layer containing a polyfunctional monomer having at least two ethylenically unsaturated bond-containing groups and a fluorine compound having a perfluoroalkenyl group and a polyethylene oxide group. Made of hardened material,
The said fluorine compound has the average addition mole number of the said ethylene oxide of 7-24, and the weight average molecular weight is 700-1500, The hard coat film for retardation films characterized by the above-mentioned. A phase difference film in which a hard coat layer is provided on one side of a transparent substrate film, an orientation layer and a phase difference layer are provided in this order on the other side,
The hard coat layer is a curable resin composition for a hard coat layer containing a polyfunctional monomer having at least two ethylenically unsaturated bond-containing groups and a fluorine compound having a perfluoroalkenyl group and a polyethylene oxide group. Made of hardened material,
The retardation film, wherein the fluorine compound has an average added mole number of ethylene oxide of 7 to 24 and a weight average molecular weight of 700 to 1500.