KR20190128123A - Substrate and optical film - Google Patents

Abstract

The present invention provides a substrate having high adhesion and an optical film. Provided are the substrate having a surface nitrogen present ratio of 0.1 to 1 atom%, a laminate in which an alignment film is formed on the surface of the substrate, and the optical film in which an optically anisotropic layer is formed on the alignment film of the laminate.

Description

Substrate and Optical Film {SUBSTRATE AND OPTICAL FILM}

The present invention relates to a substrate and an optical film.

As flat panel display apparatus FPD, the member containing optical films, such as a polarizing plate and a phase difference plate, is used. As such an optical film, the optical film manufactured by apply | coating the composition containing a polymeric liquid crystal compound on a base material is known. For example, Patent Document 1 describes an optical film formed by applying a composition containing a polymerizable liquid crystal compound on a substrate subjected to an alignment treatment to obtain a coating film and polymerizing the polymerizable liquid crystal compound in the coating film.

Patent Document 1: Japanese Patent Application Laid-Open No. 2007-148098

In the optical film manufactured by apply | coating the composition containing a polymeric liquid crystal compound on a base material, when adhesiveness between a base material and an optical film was inadequate, problems, such as peeling, arose at the time of processing. Therefore, development of the base material with high adhesiveness was calculated | required from the viewpoint of suppressing peeling at the time of processing.

Under these circumstances, the present inventors came to the present invention as a result of earnestly examining. That is, this invention includes the following inventions.

[1] A substrate having a surface nitrogen present ratio of 0.1 to 1 atom%.

[2] The substrate according to [1], wherein the surface carbon abundance ratio is 54.9 to 70 atom% and the surface oxygen abundance ratio is 29 to 45 atom%.

[3] The substrate according to [1] or [2], wherein the substrate is a saponified triacetyl cellulose film.

[4] The substrate according to any one of [1] to [3], wherein the substrate is a substrate on which surface treatment is performed under an atmosphere containing nitrogen and oxygen.

[5] The substrate according to [4], wherein the surface treatment is a plasma treatment.

[6] A substrate surface-treated with a plasma under an atmosphere containing nitrogen and oxygen, the substrate being surface-treated with an energy of 200 mJ / cm 2 or less.

[7] The substrate according to [6], wherein the substrate is a saponified triacetylcellulose film.

[8] A laminate in which an alignment film is formed on the surface of the base material according to any one of [1] to [7].

[9] The laminate according to [8], wherein the alignment film is an alignment film formed of a photoalignable polymer.

[10] The laminate according to [9], wherein the photo-alignment polymer is a photo-alignment polymer capable of forming a crosslinked structure by light irradiation.

[11] The laminate according to any one of [8] to [10], wherein in the adhesion test according to JIS-K5600, 36% or more of the alignment film is not peeled off on an area basis.

[12] An optical film having an optically anisotropic layer formed on the alignment film of the laminate according to any one of [8] to [11].

[13] The optical film according to [12], wherein the optically anisotropic layer is formed by polymerizing one or more polymerizable liquid crystals.

[14] The optical film according to [12] or [13], wherein in the adhesion test according to JIS-K5600, 36% or more of the optically anisotropic layer and the alignment film are not separated on an area basis.

[15] The optical film according to any one of [12] to [14], having retardation.

[16] A polarizing plate comprising the optical film according to any one of [12] to [15].

[17] A retardation plate comprising the optical film described in [15].

[18] A flat panel display device comprising the optical film according to any one of [12] to [15].

[19] A method for producing an optical film, comprising the following steps (1) to (4).

Process (1): The process of apply | coating a photo-alignment polymer on the base material in any one of [1]-[7].

Step (2): a step of forming an alignment film by crosslinking the photo-alignment polymer on the substrate

Process (3): The process of further apply | coating the composition containing a polymeric liquid crystal on an oriented film, and forming a coating film.

Step (4): A step of polymerizing the polymerizable liquid crystal in the coating film to form an optical film.

The base material of this invention is excellent in adhesiveness, and can therefore provide the optical film which does not produce peeling easily at the time of processing.

1 is a schematic cross-sectional view showing an example of a polarizing plate according to the present invention.
2 is a schematic cross-sectional view showing an example of a liquid crystal display device according to the present invention.
3 is a cross-sectional schematic diagram showing an example of an organic EL display device according to the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated, referring drawings.

<1st description of this invention>

The 1st base material of this invention is a base material whose surface nitrogen presence ratio is 0.1-1 atom%.

From the viewpoint of the adhesion of the substrate, the surface carbon abundance ratio of the first substrate is preferably 55 to 70 atom%, and the surface oxygen abundance ratio of the first substrate is preferably 30 to 45 atom%.

The base material whose surface nitrogen present ratio is 0.1-1 atom%, the surface carbon present rate is 54.9-70 atom%, and surface oxygen present rate is 29-45 atom% is more preferable. However, the sum of these surface element abundances does not exceed 100.

The surface nitrogen abundance ratio, surface carbon abundance ratio, and surface oxygen abundance ratio can be measured by analyzing the surface of a base material by X-ray photoelectron spectroscopy (XPS).

Such substrates may be treated by, for example, vacuum or under atmospheric pressure, a method of treating the surface of the substrate with plasma, a method of laser treating the substrate surface, a method of ozone treating the substrate surface, a method of saponifying the substrate surface, or a flame treatment of the substrate surface. It can prepare by the method. Furthermore, after preparing the film which consists of a material which does not have a hydroxyl group or its precursor group, and adheres to the surface of a base material the primer processing method which apply | coates a coupling agent to this film surface, or attaches the monomer which has a hydroxyl group, or the polymer which has a hydroxyl group to the surface of a base material, Or it may prepare by the graft polymerization method which irradiates and reacts with an ultraviolet-ray. Especially, the method of plasma-processing the surface of a base material under vacuum or atmospheric pressure is preferable.

As a method of surface-treating a substrate with plasma,

A method of providing a substrate between opposing electrodes under a pressure near atmospheric pressure, generating a plasma, and subjecting the substrate to surface treatment;

A method of causing a gas to flow between opposed electrodes, thereby plasmalizing the gas between the electrodes, and spraying the plasmated gas onto the substrate, and

The low discharge conditions generate | occur | produce a glow discharge plasma, and the method of surface-treating a base material is mentioned.

Among them, a method of placing a substrate between opposed electrodes under a pressure near atmospheric pressure, generating a plasma to perform surface treatment of the substrate, or allowing gas to flow between the opposed electrodes, thereby allowing gas to flow between the electrodes. And a method of injecting the plasmaized gas into the substrate is preferred. Surface treatment with such plasma is usually performed by a commercially available plasma surface treatment apparatus.

In particular, a substrate prepared by plasma-treating the surface of the substrate with an energy of 200 mJ / cm 2 or less under an atmosphere containing nitrogen and oxygen is preferable. The processing energy at the time of surface treatment of a base material can be computed from the electric power at the time of generating a plasma, the discharge width of an electrode, and the line speed of a base material. From the viewpoint of the adhesion of the substrate, it is preferable to treat the substrate with energy of 120 mJ / cm 2 or less, and more preferably to treat the energy with energy of 100 mJ / cm 2 or less. Moreover, it is preferable to process a base material with energy of 30 mJ / cm <2> or more.

As for the volume content ratio (oxygen: nitrogen) of oxygen with respect to nitrogen in the atmosphere containing nitrogen and oxygen, 0.01: 99.99-15: 85 are preferable, 0.05: 99.95-10: 90 are more preferable, 0.05: 99.95-5 : 95 is more preferable, and 0.05: 99.95-1: 99 are especially preferable.

<2nd description of this invention>

The 2nd base material of this invention is a base material surface-treated with plasma in the atmosphere containing nitrogen and oxygen, and is the surface-treated with the energy of 200 mJ / cm <2> or less.

As for the volume content ratio (oxygen: nitrogen) of oxygen with respect to nitrogen in the atmosphere containing nitrogen and oxygen, 0.01: 99.99-15: 85 are preferable, 0.05: 99.95-10: 90 are more preferable, 0.05: 99.95-5 : 95 is more preferable, and 0.05: 99.95-1: 99 are especially preferable.

As a method of performing surface treatment of a base material by plasma, the method similar to the method demonstrated in <the 1st base material of this invention> is mentioned.

The second substrate is surface treated with an energy of 200 mJ / cm 2 or less. The processing energy can be calculated from the power at the time of generating the plasma, the discharge width of the electrode, and the line speed of the substrate. From the viewpoint of the adhesion of the substrate, the substrate is preferably treated with energy of 120 mJ / cm 2 or less, and more preferably treated with energy of 100 mJ / cm 2 or less. Moreover, it is preferable to process a base material with energy of 30 mJ / cm <2> or more.

<1st description of this invention and 2nd description of this invention>

Hereinafter, the 1st base material of this invention and the 2nd base material of this invention may be collectively called "base material."

As the substrate, a transparent substrate is usually used. A transparent base material means the base material which can transmit light, especially visible light, and the light transmittance means the characteristic that the transmittance | permeability with respect to the light ray over wavelength 380-780 nm becomes 80% or more. As a specific transparent base material, glass and a translucent resin base material are mentioned, A translucent resin base material is preferable. As a base material, a film type is used normally.

As resin which comprises a translucent resin base material, Polyolefin, such as polyethylene, a polypropylene, norbornene-type polymer; Polyvinyl alcohol; Polyethylene terephthalate; Polymethacrylic acid ester; Polyacrylic acid ester; Cellulose esters; Polyethylene naphthalate; Polycarbonate; Polysulfones; Polyether sulfone; Polyether ketones; Polyphenylene sulfide; And polyphenylene oxides. Especially, triacetyl cellulose is preferable. Triacetyl cellulose includes saponified triacetyl cellulose and unsaponified triacetyl cellulose. It is preferable that a base material is a saponified triacetyl cellulose film.

<Laminated body of the present invention>

In the laminated body of this invention, the alignment film is formed in the surface of the base material of this invention. Although the oriented film is not limited, It is preferable to have solvent tolerance of the grade which does not melt | dissolve by application | coating of the composition for forming the optically anisotropic layer mentioned later, etc. Moreover, it is preferable to have heat resistance in heat processing, such as solvent removal. Examples of such an alignment film include an alignment film formed of an alignment polymer, and an alignment film formed of a photoalignable polymer is preferable.

The method by rubbing is mentioned as a method of providing an orientation regulation force to an alignment film. Moreover, in the case of the orientation film formed from the photo-alignment polymer, the method of irradiating polarization is also mentioned.

As a photo-alignment polymer, the polymer which has a photosensitive structure is mentioned. When polarized light is irradiated to the photo-alignment polymer which has a photosensitive structure, the photosensitive structure of the irradiated part will be isomerized or bridge | crosslinked, by which the photo-alignment polymer is orientated and the orientation film to which the orientation regulation force was provided can be obtained.

Examples of the photosensitive structure include an azobenzene structure, a maleimide structure, a chalcone structure, a cinnamic acid structure, a 1,2-vinylene structure, a 1,2-acetylene structure, a spiropyran structure, a spirobenzopyran structure, and a full gid structure. You may use combining the polymer which has 2 or more types of photosensitive structures. The photo-orientable polymer can be obtained by subjecting a monomer having at least one photosensitive structure to chain polymerization, coordination polymerization or ring-opening polymerization such as polycondensation, radical polymerization, anionic polymerization, cationic polymerization by dehydration, deamine, or the like.

As a photo-orientation polymer, Unexamined-Japanese-Patent No. 4450261, Unexamined-Japanese-Patent No. 4011652, Unexamined-Japanese-Patent No. 2010-49230, Unexamined-Japanese-Patent No. 4404090, Unexamined-Japanese-Patent No. 2007-156439, and Unexamined-Japanese-Patent No. 2007-232934 The photo-alignment polymer as described in a publication is mentioned.

As a photo-alignment polymer, it is preferable that it is a polymer which forms a crosslinked structure by light irradiation from a viewpoint of the durability at the time of forming the optically anisotropic layer mentioned later.

The alignment film is usually a surface containing a composition containing an orientation polymer (preferably a photo-alignment polymer) with a surface having a surface nitrogen present ratio of 0.1 to 1 atom% of the first substrate of the present invention or a plasma of the second substrate of the present invention. It is formed by apply | coating to the process surface, 0.1-30 mass% is preferable with respect to the gross mass of a composition, and, as for content of the photo-alignment polymer in the said composition, 0.2-15 mass% is more preferable.

It is preferable that the composition containing a photo-alignment polymer contains a solvent. The solvent can be appropriately selected depending on the kind of the photo-alignment polymer and the like, and water; Alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; And chlorinated hydrocarbon solvents such as chloroform and chlorobenzene. You may use combining 2 or more types of solvents.

The composition containing the photo-alignment polymer may include an additive. As an additive, it is preferable to have a carbon-carbon unsaturated bond and an active hydrogen reactive group in the molecule | numerator from a viewpoint of adhesive improvement with the optically anisotropic layer mentioned later and viscosity adjustment of the said composition. "Active hydrogen reactive group" means a group having a reactivity with a group having active hydrogen such as carboxyl group (-COOH), hydroxyl group (-OH), amino group (-NH ₂ ), and specifically, glycidyl group, oxazoline A group, a carbodiimide group, an aziridine group, an imide group, an isocyanato group, a thioisocyanato group, and a maleic anhydride group are mentioned. 1-20 are preferable and, as for the number of carbon-carbon unsaturated bonds which an additive has, 1-10 are more preferable. 1-20 are preferable and, as for the number of the active hydrogen reactive groups which an additive has, 1-10 are more preferable.

The additive preferably has at least two active hydrogen reactive groups, and the active hydrogen reactive groups may be the same or different.

Although the carbon-carbon unsaturated bond which the additive has may be a carbon-carbon double bond or a carbon-carbon triple bond, a carbon-carbon double bond is preferable. Additives containing vinyl groups and / or (meth) acryl groups are preferred. The additive whose active hydrogen reactive group is at least 1 sort (s) chosen from the group which consists of an epoxy group, a glycidyl group, and an isocyanato group is preferable, and the additive which has an acryl group and an isocyanato group is more preferable.

As a specific example of an additive, The compound which has a (meth) acryl group and epoxy groups, such as methacryloxyglycidyl ether and acryloxyglycidyl ether; Compounds having a (meth) acryl group and an oxetane group, such as oxetane acrylate and oxetane methacrylate; Compounds having a (meth) acryl group and a lactone group, such as lactone acrylate and lactone methacrylate; Compounds having a vinyl group and an oxazoline group such as vinyl oxazoline and isopropenyl oxazoline; Having a (meth) acryl group, such as isocyanatomethyl acrylate, isocyanatomethyl methacrylate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate, isocyanate group Oligomers of the compounds. Moreover, the compound which has a vinyl group, a vinylene group, and an acid anhydride structure, such as methacrylic anhydride, acrylic anhydride, maleic anhydride, and a vinyl maleic anhydride, is also mentioned. Above all, methacryloxyglycidyl ether, acryloxyglycidyl ether, isocyanatomethyl acrylate, isocyanatomethyl methacrylate, vinyl oxazoline, 2-isocyanatoethyl acrylate, 2- Isocyanatoethyl methacrylate and oligomers thereof are preferable, and isocyanatomethyl acrylate, 2-isocyanatoethyl acrylate and oligomers thereof are more preferable.

As a specific example of the additive which has an isocyanato group, the compound represented by following General formula (1) is mentioned.

[In Formula (1),

n represents the integer of 1-10, R <^1> represents a C2-C20 divalent aliphatic or alicyclic hydrocarbon group, or a C5-C20 divalent aromatic hydrocarbon group. The two R ² in each repeating unit are -NH- on one side and the other on

Is represented by. R ³ represents a group having a hydroxyl group or a carbon-carbon unsaturated bond. However, R ³ of at least one of R ³ in the general formula (1) is a carbon, a group having a carbon unsaturated bond.

Especially, the compound represented by following General formula (2) is more preferable.

[In Formula (2), n represents an integer of 1 to 10.]

The compound represented by General formula (2) may use a commercial item, such as Laromer (trademark) LR-9000 (made by BASF Corporation) as it is, and may be used after refine | purifying as needed.

As for content of the additive in the composition containing a photo-alignment polymer, the range of 0.01-10 mass% is preferable with respect to the gross mass of the composition, and the range of 0.02-5 mass% is more preferable. If it is in the said range, it will not reduce the reactivity of the photo-alignment polymer in a composition.

The laminated body of this invention can be produced by apply | coating the composition containing a photo-alignment polymer on the said base material, and irradiating polarized light before drying or after drying the obtained coating film. As a method for applying the composition on the substrate, extrusion coating, direct gravure coating, reverse gravure coating, CAP (cap) coating, die coating, inkjet, dip coating, slit coating, spin coating, and The coating method by a bar coater is mentioned. Among them, the composition can be continuously applied to the substrate in a roll to roll format, and thus, the coating is applied by the CAP coating method, the inkjet method, the dip coating method, the slit coating method, the die coating method, and the bar coater. The method is preferred.

By drying the coating film on a base material, low boiling point components, such as a solvent contained in a coating film, are removed.

As a drying method, natural drying, ventilation drying, heat drying, reduced pressure drying, and the method of combining these are mentioned. 10 to 250 degreeC is preferable and 25 to 200 degreeC of drying temperature is more preferable. Although drying time changes with kinds of solvent, 5 second-60 minutes are preferable, and 10 second-30 minutes are more preferable.

Polarized light irradiation can be performed using the apparatus of Unexamined-Japanese-Patent No. 2006-323060, for example. Moreover, a patterned alignment film can also be formed on the formed coating film by repeatedly irradiating polarized light, such as linearly polarized ultraviolet-ray, for every said area | region through the photomask corresponding to desired multiple area | region. As a photomask, what formed the light shielding pattern on films, such as quartz glass, soda-lime glass, or polyester, is used normally. The portion exposed to the light shielding pattern is blocked from being exposed to light, and the portion not covered is transmitted to the exposed light. Quartz glass is preferable at the point that the influence of thermal expansion is small. In view of the reactivity of the photo-alignment polymer, the light to be irradiated is preferably ultraviolet light.

The laminated body containing a patterned alignment film can be produced, for example by the following method.

(1) The 1st polarization which has a 1st polarization direction is irradiated to the coating film formed on the base material through the 1st photomask which has a space | gap part corresponding to a 1st pattern area | region (1st polarization irradiation). The first pattern region to which the alignment regulating force corresponding to the first polarization direction is applied is formed by the first polarization irradiation.

(2) A second polarized light having a polarization direction different from the first polarization direction (eg, a direction perpendicular to the first polarization direction) is irradiated through a second photomask having a gap portion corresponding to the second pattern region. (2nd polarization irradiation). By the second polarization irradiation, a second pattern region to which an alignment regulating force corresponding to the second polarization direction is applied is formed.

By performing the process of said (1) and (2) one or more times, the laminated body containing the patterned alignment film which has two or more pattern areas from which the direction of an orientation regulation force mutually differs can be obtained.

The film thickness of the alignment film is usually 10 nm to 10000 nm, preferably 10 nm to 1000 nm.

Since the laminated body of this invention contains the base material which has high adhesiveness, peeling from the base material of an oriented film can be suppressed. Evaluation of adhesiveness can be performed by the adhesive test according to JIS-K5600. For example, an adhesive test may be performed using commercially available apparatuses, such as Crosscut Guide I series (CCI-1, 1-mm spacing, for 25 masses) by KOTEC Corporation. For example, when the adhesion test of the laminate of the present invention is carried out using Kotec Co., Ltd. crosscut guide I series (CCI-1, 1 mm interval, for 25 masses), the mass of the alignment film is maintained without peeling from the substrate. Usually, it is 9 or more of 25 masses, and 36% or more of an oriented film is maintained in the state which does not peel from a base material on an area basis.

<Optical film of the present invention>

An "optical film" means a film which can transmit light and has an optical function such as refraction and birefringence.

The optical film of this invention is a film in which the optically anisotropic layer is formed on the orientation film of the said laminated body, and expresses phase difference.

An optically anisotropic layer can be formed, for example by orienting a liquid crystal compound. The formation of the optically anisotropic layer is preferably used for forming an optically anisotropic layer containing a liquid crystal compound. As a liquid crystal compound, a polymeric liquid crystal is preferable. The composition for optically anisotropic layer formation may contain 2 or more types of liquid crystal compounds (preferably polymeric liquid crystal).

Examples of the polymerizable liquid crystal include a compound containing a group represented by the general formula (X) (hereinafter sometimes referred to as "compound (X)").

P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ^13- (X)

[In Formula (X), P ¹¹ represents a polymerizable group.

A ¹¹ represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the bivalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, The hydrogen atom contained in the alkyl group of 6 and the said C1-C6 alkoxy group may be substituted by the fluorine atom.

B ¹¹ is -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ^16- , -NR ¹⁶ -CO-, -CO-,- CS- or a single bond is shown. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

B ¹² and B ¹³ are each independently -C≡C-, -CH = CH-, -CH ₂ -CH _2- , -O-, -S-, -C (= O)-, -C (= O ) -O-, -OC (= O)-, -OC (= O) -O-, -CH = N-, -N = CH-, -N = N-, -C (= O) -NR ^{16 -, -NR 16 -C (= O} ) -, -OCH 2 -, -OCF 2 -, -CH 2 O-, -CF 2 O-, -CH = CH-C (= O) -O-, - OC (= O) -CH = CH- or a single bond.

E <^11> represents a C1-C12 alkanediyl group, the hydrogen atom contained in this alkanediyl group may be substituted by the C1-C5 alkoxy group, and the hydrogen atom contained in the said alkoxy group may be substituted by the halogen atom. . In addition, -CH ₂ -constituting the alkanediyl group may be substituted with -O- or -CO-.]

It is preferable that carbon number of the aromatic hydrocarbon group and alicyclic hydrocarbon group of A <^11> is 3-18, It is more preferable that it is the range of 5-12, It is especially preferable that it is 5 or 6. As A ^{11, a} cyclohexane-1,4-diyl group and a 1,4-phenylene group are preferable.

E ¹¹ as is preferred alkanediyl group having 1 to 12 carbon atoms in the straight. -CH ₂ -constituting the alkanediyl group may be substituted with -O-.

Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1, 7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group and dodecane-1,12-di C1-C12 linear alkanediyl groups, such as a diary; -CH ₂ -CH ₂ -O-CH ₂ -CH _2- , -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -and the like.

As the polymerizable group represented by P ¹¹ , since the polymerization reactivity, in particular, the photopolymerization reactivity is high, a radical polymerizable group or a cationic polymerizable group is preferable, and since the handling is easy and the preparation of the liquid crystal compound is easy, the polymerizable group is It is preferable that it is group represented by the following general formula (P-11)-chemical formula (P-15).

[In the above formulas (P-11) to (P-15),

R ¹⁷ to R ²¹ each independently represent an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.]

Specific examples of the group represented by the formulas (P-11) to (P-15) include groups represented by the following formulas (P-16) to (P-20).

P ¹¹ is preferably a group represented by the formulas (P-14) to (P-20), and more preferably a vinyl group, a p-stilbene group, an epoxy group, or an oxetanyl group.

More preferably, the group represented by P ¹¹ -B ¹¹ -is an acryloyloxy group or a methacryloyloxy group.

As compound (X), the compound represented by general formula (I), general formula (II), general formula (III), general formula (IV), general formula (V), or general formula (VI) is mentioned.

P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -A ¹³ -B ¹⁵ -A ¹⁴ -B ¹⁶ -E ¹² -B ¹⁷ -P ¹² (I)

P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -A ¹³ -B ¹⁵ -A ¹⁴ -F ¹¹ (II)

P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -A ¹³ -B ¹⁵ -E ¹² -B ¹⁷ -P ¹² (III)

P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -A ¹³ -F ¹¹ (IV)

P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -B ¹⁴ -E ¹² -B ¹⁷ -P ¹² (V)

P ¹¹ -B ¹¹ -E ¹¹ -B ¹² -A ¹¹ -B ¹³ -A ¹² -F ¹¹ (VI)

(Wherein

A ^{12 to} A ¹⁴ are each independently the same as A ¹¹ , B ^{14 to} B ¹⁶ are each independently the same as B ¹² , B ¹⁷ is the same as B ^11, and E ¹² is the same as E ¹¹ .

F ¹¹ is a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxyl group, a methylol group, a formyl group, a sulfo group (-SO ₃ H ), A carboxy group, an alkoxycarbonyl group having 1 to 10 carbon atoms or a halogen atom, and -CH ₂ -constituting the alkyl group and the alkoxy group may be substituted with -O-.

As a specific example of a polymeric liquid crystal, "3.8.6 network (complete crosslinking type)" of the liquid crystal handbook (written by the Liquid Crystal Handbook Editing Committee, issued October 30, 2000), "6.5.1 liquid crystal material b. A compound having a polymerizable group among the compounds described in "Polymerizable nematic liquid crystal material", Japanese Patent Application Laid-Open No. 2010-31223, Japanese Patent Application Laid-Open No. 2010-270108, Japanese Patent Application Laid-Open No. 2011-6360, and Japanese Patent Publication The polymeric liquid crystal compound of Unexamined-Japanese-Patent No. 2011-207765 is mentioned.

Specific examples of the compound (X) include the following general formulas (I-1) to (I-4), (II-1) to (II-4), (III-1) to (III-26), The compound represented by general formula (IV-1)-general formula (IV-19), general formula (V-1)-general formula (V-2), and general formula (VI-1)-general formula (VI-6) is mentioned. In the following formulae, k1 and k2 each independently represent an integer of 2 to 12. These compounds (X) are preferable at the point of the ease of synthesis or the availability.

In addition to the said liquid crystal compound, the composition for optically anisotropic layer formation may contain a polymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, a chiral agent, a solvent, etc. When a liquid crystal compound is a polymeric liquid crystal, it is preferable that the composition for optically anisotropic layer formation contains a polymerization initiator.

[Polymerization Initiator]

As a polymerization initiator, a photoinitiator is preferable and the photoinitiator which generate | occur | produces a radical by light irradiation is preferable.

As a photoinitiator, a benzoin compound, a benzophenone compound, a benzyl ketal compound, the (alpha)-hydroxy ketone compound, the (alpha)-amino ketone compound, a triazine compound, an iodonium salt, and a sulfonium salt are mentioned. Specifically, Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (all made by Chiba Japan Co., Ltd.), Sheikh All BZ, shake all Z, shake all BEE (all are manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dausa), Adeka Optoma SP-152, Adeka Optoma SP-170 (above, all manufactured by ADEKA), TAZ-A, TAZ-PP (above, manufactured by Nihon Seibel Heg Screw Co., Ltd.) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.) ).

Content of the polymerization initiator in the composition for optically anisotropic layer formation is 0.1 mass part-30 mass parts normally with respect to 100 mass parts of polymerizable liquid crystals (preferably compound (X)) contained in the composition for optically anisotropic layer formation, Preferably Preferably it is 0.5 mass part-10 mass parts. Within this range, the polymerizable liquid crystal can be polymerized without disturbing the orientation of the polymerizable liquid crystal.

[No Polymerization System]

The composition for optically anisotropic layer formation may contain the polymerization inhibitor in order to control the polymerization reaction of a polymeric liquid crystal.

As a polymerization inhibitor, Hydroquinone which has substituents, such as hydroquinone and an alkyl ether; Catechols having substituents such as alkyl ethers such as butyl catechol; Radical supplements such as pyrogallols and 2,2,6,6-tetramethyl-1-piperidinyloxy radicals; Thiophenols; (beta) -naphthylamine and (beta) -naphthol are mentioned.

By using a polymerization inhibitor, the stability of the optically anisotropic layer formed can be improved. Content of the polymerization inhibitor in the composition for optically anisotropic layer formation is 0.1 mass part-30 mass parts normally with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably they are 0.5 mass part-10 mass parts. If it is in the said range, it can superpose | polymerize without disturbing the orientation of a polymeric liquid crystal.

[Photosensitizer]

As a photosensitizer, Xanthones, such as xanthone and thioxanthone; Anthracenes having substituents such as anthracene and alkyl ethers; Phenothiazine; Rubrene.

By using a photosensitizer, superposition | polymerization of a polymeric liquid crystal can be made highly sensitive. Content of a photosensitizer is 0.1 mass part-30 mass parts normally with respect to 100 mass parts of polymeric liquid crystals, Preferably they are 0.5 mass part-10 mass parts.

[Leveling Agent]

Examples of the leveling agent include organic modified silicone oil, polyacrylate and perfluoroalkyl leveling agents. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (above, manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341 , X22-161A, KF6001 (above, all manufactured by Shin-Etsukagaku Kogyo Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (above, all Momentary Performance Materials Japan Kogyo Co., Ltd.), fluorinert (registered trademark) FC-72, fluorine nut FC-40, fluorine nut FC-43, fluorine nut FC-3283 [above, all Sumitomo 3M Co., Ltd. Manufacture], Megapak (registered trademark) R-08, Megapak R-30, Megapak R-90, Megapak F-410, Megapak F-411, Megapak F-443, Megapak F-445, Mega Park F-470, Mega Park F-477, Mega Park F-479, Mega Park F-482, Mega Park F-483 (all manufactured by DIC Corporation), F Top (brand name) EF301, F Top EF303, F-top EF351, F-top EF352 [over all, Mitsubishi Materials Shikasei Co., Ltd.], Suplon (registered trademark) S-381, Suplon S-382, Suplon S-383, Suplon S-393, Suplon SC-101, Suplon SC-105, KH- 40, SA-100 [all, more than AGC Seiko Chemical Co., Ltd.], brand name E1830, Suflon E5844 [manufactured by Daikin Fine Chemical Co., Ltd.], BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all are brand-name: BMK Chemie make) are mentioned. You may use combining 2 or more types of leveling agents.

By using a leveling agent, a smoother optically anisotropic layer can be formed. Moreover, in the manufacturing process of an optically anisotropic layer, the fluidity | liquidity of the composition for optically anisotropic layer formation can be controlled, or the crosslinking density of an optically anisotropic layer can be adjusted. Content of a leveling agent is 0.1 mass part-30 mass parts normally with respect to 100 mass parts of polymeric liquid crystals, Preferably they are 0.1 mass part-10 mass parts.

[Chiral agent]

Examples of the chiral agent include known chiral agents (e.g., liquid crystal device handbook, Chapter 3, paragraphs 4-3, chiral agent for TN and STN, page 199, written by the Japan Academic Society Association 142 Committee, 1989). have.

Chiral agents generally contain asymmetric carbon atoms, but axial asymmetric compounds or surface asymmetric compounds that do not contain asymmetric carbon atoms can also be used as chiral agents. Examples of the layered asymmetric compound or the surface asymmetric compound include vinaphthyl, helicene, paracyclophane and derivatives thereof.

Specifically, Japanese Patent Publication No. 2007-269640, Japanese Patent Publication No. 2007-269639, Japanese Patent Publication No. 2007-176870, Japanese Patent Publication No. 2003-137887, Japanese Patent Publication No. 2000-515496 The compound as described in Unexamined-Japanese-Patent No. 2007-169178 and Unexamined-Japanese-Patent No. 9-506088 is mentioned, Preferably, paliocolor (trademark) of BASF Japan Co., Ltd. product is mentioned. LC756.

When using a chiral agent, the content is 0.1 mass part-30 mass parts normally with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably they are 1.0 mass part-25 mass parts. If it is in the said range, when superposing | polymerizing a polymeric liquid crystal compound, it can suppress more disturbing the orientation of the polymeric liquid crystal compound.

[solvent]

It is preferable that the composition for optically anisotropic layer formation contains a solvent, especially an organic solvent, in order to make operability of manufacture of an optically anisotropic layer favorable. As an organic solvent, the organic solvent which can melt | dissolve the structural component of the composition for optically anisotropic layer formation, such as a polymeric liquid crystal compound, is preferable, and the solvent which can melt | dissolve the structural component of the composition for optically anisotropic layer formation, such as a polymeric liquid crystal compound. Moreover, the solvent which is inert to the polymerization reaction of a polymeric liquid crystal compound is more preferable. Specific examples include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and phenol; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and methyl isobutyl ketone; Non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Non-chlorinated aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; And chlorinated hydrocarbon solvents such as chloroform and chlorobenzene. You may use combining 2 or more types of organic solvents. Among them, alcohol solvents, ester solvents, ketone solvents, non-chlorinated aliphatic hydrocarbon solvents and non-chlorinated aromatic hydrocarbon solvents are preferable.

When the composition for optically anisotropic layer formation contains an organic solvent, 10 mass parts-10000 mass parts are preferable with respect to 100 mass parts of solid content, More preferably, they are 100 mass parts-5000 mass parts. Solid content concentration in the composition for optically anisotropic layer formation becomes like this. Preferably it is 2 mass%-50 mass%, More preferably, it is 5-50 mass%. "Solid content" means the sum total of the component except the solvent in the composition for optically anisotropic layer formation.

An unpolymerized film is formed by apply | coating the composition for optically anisotropic layer formation on the oriented film of the laminated body of this invention. When an unpolymerized film shows liquid crystal phases, such as a nematic phase, it has birefringence by monodomain orientation.

As a method of apply | coating the composition for optically anisotropic layer forming on an oriented film, the method similar to the application | coating method of the composition containing said photo-alignment polymer is mentioned. Among them, the CAP coating method, the inkjet method, the dip coating method, the slit coating method, the die coating method and the bar coater are applied in that the composition for forming an optically anisotropic layer can be continuously applied on the alignment film in a roll-to-roll format. The method is preferred. In the case of applying the composition in a roll-to-roll form, a composition containing a photo-alignment polymer is applied on the substrate to form an alignment film on the substrate, and further, to form an optically anisotropic layer on the obtained alignment film. You may.

By superposing | polymerizing and hardening the polymeric liquid crystal compound contained in an unpolymerized film, the optical film, especially the film which has retardation property can be obtained. The optical film obtained in this way is fixed in the orientation of a polymeric liquid crystal compound, and it is hard to be influenced by the birefringence change by heat.

As a method of polymerizing a polymerizable liquid crystal compound, a photopolymerization method is preferable. According to the photopolymerization method, since polymerization can be performed at a low temperature, the selection range of the substrate to be used is widened in terms of heat resistance. The photopolymerization reaction is carried out by irradiating the unpolymerized film with visible light, ultraviolet light or laser light, and ultraviolet light is preferable.

Although light irradiation may be performed to the unpolymerized film as it is, it is preferable to irradiate light after drying a unpolymerized film and removing a solvent from the unpolymerized film. Although drying (solvent removal) may be performed in parallel with a polymerization reaction, it is preferable to remove most solvents before superposing | polymerizing. As a removal method of a solvent, the method similar to the drying method at the time of the formation of said orientation film is mentioned. Especially, natural drying or heat drying is preferable. The drying temperature is preferably in the range of 0 ° C to 250 ° C, more preferably in the range of 50 ° C to 220 ° C, and even more preferably in the range of 80 ° C to 170 ° C. The drying time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

The optical film of this invention is useful as a phase difference plate used in order to convert linearly polarized light into circularly polarized light or elliptically polarized light, to convert circularly or elliptically polarized light into linearly polarized light, or to convert the polarization direction of linearly polarized light.

The optical film of this invention is excellent in transparency in visible region, and can be used as a member for various display apparatuses. Although the thickness of the optical film of this invention may be suitably adjusted according to the use or the phase difference value, It is preferable that it is 0.1 micrometer-10 micrometers, It is more preferable that it is 0.2 micrometer-5 micrometers from the point which makes photoelasticity small. .

The optical film of this invention may be laminated | stacked several sheets, and may be used in combination with another film. When used in combination with another film, it can be used as a viewing angle compensation film, a viewing angle expansion film, an antireflection film, a polarizing film (polarizing plate), a circular polarizing film (circular polarizing plate), an elliptical polarizing film (elliptical polarizing plate), and a brightness improving film. .

The optical film of the present invention can change the optical properties according to the alignment state of the liquid crystal compound forming the optically anisotropic layer, the vertical alignment (VA) mode, in-plane switching (IPS) mode, optically compensated bend (OCB) It can be used as a phase difference plate for various liquid crystal display devices, such as a twisted nematic (TN) mode and a super twisted nematic (STN) mode.

In the optical film of the present invention, when the refractive index in the in-plane slow axis direction is n _x , the refractive index in the direction orthogonal to the in-plane slow axis (in the fast axis direction) is n _y , and the refractive index in the thickness direction is n _z , as follows. Can be classified.

Positive A plate with n _x > n _y ≒ n _z

Negative C plate of n _x ≒ n _y > n _z

Positive C plate with n _x ≒ n _y <n _z

Positive O plate and negative O plate of n _x ≠ n _y ≠ n _z

What is necessary is just to select the phase difference value of the optical film of this invention suitably in the range of 30 nm-300 nm according to the display apparatus used.

When using the optical film of this invention as a broadband (lambda) / 4 plate, Re (549) may be adjusted in the range of 113 nm-163 nm, Preferably you may adjust in the range of 130 nm-150 nm. When used as a broadband λ / 2 plate, Re (549) may be adjusted in the range of 250 nm to 300 nm, preferably in the range of 265 nm to 285 nm. If the retardation value is the above-described value, there is a tendency to be able to uniformly polarize the light of a wide range of wavelengths. The term "broadband λ / 4 plate" means a retardation film that expresses a 1/4 phase difference value with respect to light of each wavelength, and the term "wideband λ / 2 plate" means 1/2 of the light of each wavelength. The retardation film which expresses retardation value of means.

By adjusting content of the liquid crystal compound in the composition for optically anisotropic layer formation, the layer thickness of an optically anisotropic layer can be adjusted and the optical film which gives a desired phase difference can be produced. Since the retardation value [retardation value, Re ((lambda))] of the optical film obtained is determined like General formula (4), in order to acquire desired Re ((lambda)), what is necessary is just to adjust (DELTA) n ((lambda)) and film thickness d suitably.

Re (λ) = d × Δn (λ) (4)

[In the above formula, Re (λ) represents a phase difference value at a wavelength λ nm, d represents a film thickness, and Δn (λ) represents a birefringence at a wavelength λ nm.]

Since the optical film of this invention contains the base material which has high adhesiveness, it can suppress that the orientation film at the time of processing peels from a base material. Evaluation of adhesiveness can be performed by the adhesive test according to JIS-K5600. For example, an adhesive test may be performed using commercially available apparatuses, such as Crosscut Guide I series (CCI-1, 1-mm spacing, for 25 masses) by KOTEC Corporation. For example, when the adhesion test of the optical film of this invention is performed using KOTEC Corporation crosscut guide I series (CCI-1, 1-mm spacing, for 25 masses), an optically anisotropic layer and an orientation film will not peel from a base material. The mass to be maintained without is usually 9 or more out of 25 masses, and on an area basis, at least 36% of the optically anisotropic layer and the alignment film are maintained without being peeled from the substrate.

In view of the simplification and cost of the manufacturing process, the optical film of the present invention preferably comprises an alignment film composed of an alignment polymer (preferably a photo-alignment polymer) and one type of additive, and the optically anisotropic layer is polymerized with the polymerizable liquid crystal. It is preferable that it consists of an initiator and a leveling agent.

The optical film of this invention is also useful as a member which comprises a polarizing plate. The polarizing plate of this invention contains at least one optical film of this invention.

As a specific example of a polarizing plate, the polarizing plate shown to FIG. 1 (a)-FIG. 1 (e) is mentioned. The polarizing plate 4a shown in FIG. 1 (a) is a polarizing plate in which the optical film 1 and the polarizing film layer 2 of the present invention are directly laminated, and the polarizing plate 4b shown in FIG. 1 (b) is the present invention. The optical film 1 and the polarizing film layer 2 are the polarizing plates bonded together through the adhesive bond layer 3 '. The polarizing plate 4c shown to FIG. 1 (c) laminate | stacks the optical film 1 of this invention and the optical film 1 'of this invention, and also the optical film 1' and polarizing film layer of this invention. The polarizing plate 4d laminated with (2), and the polarizing plate 4d shown in FIG. 1 (d) is bonded to the optical film 1 of the present invention and the optical film 1 ′ of the present invention through the adhesive layer 3. Moreover, it is a polarizing plate which laminated | stacked the polarizing film layer 2 on the optical film 1 'of this invention. The polarizing plate 4e shown in Fig.1 (e) bonds the optical film 1 of this invention and the optical film 1 'of this invention through the adhesive bond layer 3, and also the optical film of this invention ( 1 ') and the polarizing film layer 2 are attached to each other via the adhesive layer 3'. "Adhesive" means a generic term for an adhesive and / or an adhesive.

The polarizing film layer 2 may be a film having a polarizing function, and a film obtained by adsorbing an iodine or a dichroic dye onto a polyvinyl alcohol-based film and stretching the film and a polyvinyl alcohol-based film to adsorb iodine or a dichroic dye. Can be mentioned.

The polarizing film layer 2 may be protected by the protective film as needed. As a protective film, polyolefin films, such as polyethylene, a polypropylene, and norbornene-type polymer, a polyethylene terephthalate film, a polymethacrylic acid ester film, a polyacrylic acid ester film, a cellulose ester film, a polyethylene naphthalate film, a polycarbonate film, a polysulfone film , Polyether sulfone film, polyether ketone film, polyphenylene sulfide film and polyphenylene oxide film.

It is preferable that the adhesive agent used for the adhesive bond layer 3 and the adhesive bond layer 3 'is an adhesive with high transparency and excellent heat resistance. Such adhesives include acrylic adhesives, epoxy adhesives and urethane adhesives.

The flat panel display device of the present invention includes the optical film of the present invention. As said display apparatus, the liquid crystal display device provided with the liquid crystal panel by which the optical film of this invention and the liquid crystal panel were bonded, and the organic electroluminescent panel (henceforth "EL") panel with which the optical film of this invention and the light emitting layer were bonded. An organic electroluminescence display provided with the above is mentioned. As an embodiment of the flat panel display device provided with the optical film of the present invention, a liquid crystal display device and an organic EL display device will be briefly described.

Examples of the liquid crystal display device include liquid crystal display devices 10a and 10b shown in FIGS. 2A and 2B. In the liquid crystal display device 10a illustrated in FIG. 2A, the polarizing plate 4 and the liquid crystal panel 6 of the present invention are bonded through the adhesive layer 5. In the liquid crystal display device 10b shown in FIG. 2B, the polarizing plate 4 of the present invention is on one side of the liquid crystal panel 6, and the polarizing plate 4 ′ of the present invention is different from the liquid crystal panel 6. On one side, it has the structure joined together through the contact bonding layer 5 and the contact bonding layer 5 ', respectively. In these liquid crystal display devices, the alignment of liquid crystal molecules is changed by applying a voltage to the liquid crystal panel using an electrode (not shown), thereby realizing monochrome display.

Examples of the organic EL display device include the organic EL display device 11 shown in FIG. 3. In the organic EL display device 11, the polarizing plate 4 and the organic EL panel 7 of the present invention are bonded to each other via the adhesive layer 5. The organic EL panel 7 is at least one layer made of a conductive organic compound. In such an organic EL display device, by applying a voltage to the organic EL panel using an electrode (not shown), the compound included in the light emitting layer of the organic EL panel emits light, thereby realizing monochrome display.

In the organic EL display device 11, the polarizing plate 4 is preferably a polarizing plate functioning as a broadband circular polarizing plate from the viewpoint of preventing reflection of external light on the surface of the organic EL display device 11.

Example

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by the following Example. In addition, in an example, "%" and "part" mean a mass% and a mass part, unless there is particular notice.

Synthesis Example of Photo-Oriented Polymer

Monomer represented by the formula (Z-a) is Macromol. Chem. Phys. 197, 1919-1935 (1996).

1.5 parts of monomers represented by the formula (Z-a) and 0.1 parts of methyl methacrylate were dissolved in 16 parts of tetrahydrofuran. The obtained solution was heated at 60 ° C. for 24 hours to carry out the reaction. After cooling the obtained reaction mixture to room temperature, it was dripped in the mixed solution of toluene and methanol, and the copolymer represented by general formula (Z) was precipitated, and the copolymer represented by general formula (Z) was taken out. The number average molecular weight of the copolymer represented by the formula (Z) was 33000. In the copolymer represented by the formula (Z), the content rate of the structural unit derived from the monomer represented by the formula (Z-a) was 75 mol%.

The polystyrene conversion number average molecular weight (Mn) of the copolymer represented by General formula (Z) was measured on condition of the following using GPC method.

Device; HLC-8220GPC (manufactured by Tosoh Corporation)

column; TOSOH TSKgel MultiporeH _XL -M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detectors; RI

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-5000, A-500

[Preparation of composition]

The solution obtained by mixing the following components was stirred at 80 ° C. for 1 hour, and then cooled to room temperature to prepare a composition for forming an alignment film.

After stirring the solution obtained by mixing each component shown in Table 2 for 1 hour at 80 degreeC, it cooled to room temperature and prepared the composition for optically anisotropic layer formation.

In Table 1, a mixing ratio means the content rate of each component with respect to the whole composition prepared.

LR-9000 in Table 1 is Laromer (trademark) LR-9000 by BASF Japan.

In Table 2, a mixing ratio means the content rate of each component with respect to the whole composition prepared.

In Table 2, Irg369 is Irgacure 369 by BASF Japan, BYK361N is a leveling agent by Big Chemical Japan, and LC242 is a liquid crystal compound by BASF represented by the following chemical formula.

[Measurement of Surface Element Ratio]

Using a Sekisui Chemical Co., Ltd. atmospheric pressure plasma surface treatment apparatus (roll direct head type AP-T04S-R890), plasma is generated on the conditions of the output 60W (equivalent to 100 mJ / cm <2> energy), and saponification is carried out. Triacetylcellulose film surface was treated. XPS analysis of the surface which carried out the plasma process was performed on condition of the following using S-Probe ESCA Model2803 by Surface Science Instruments. XPS analysis was similarly performed on the saponified triacetylcellulose film which was not subjected to plasma treatment, and the saponified triacetylcellulose film surface-treated on the conditions of 300 W of output (equivalent to energy of 500 mJ / cm <2>). The results are shown in Table 3.

[Measuring conditions]

Irradiation X-ray: AlKα

X-ray spot diameter: 250 × 1000 μm (oval)

Use of neutral gun

Example 1 [Production Example 1 of Optical Film of the Present Invention]

Output 60W under the atmosphere (volume ratio nitrogen: oxygen = 99.9: 0.1) containing nitrogen and oxygen using the atmospheric pressure plasma surface treatment apparatus (roll direct head type AP-T04S-R890) made by Sekisui Chemical Co., Ltd. A plasma was generated under the conditions (equivalent to energy of 100 mJ / cm 2) to treat the saponified triacetylcellulose film surface. The composition for alignment film formation prepared above was apply | coated to the surface which performed the plasma processing, it dried, and the film of thickness 300nm was formed. Subsequently, using a spotcure (SP-7, manufactured by Ushio Denki Co., Ltd.) with polarized ultraviolet light (polarization UV) irradiation jig in the vertical direction with respect to the surface of the formed film, linearly polarized light at 15 mW / cm 2 for 5 minutes. UV was irradiated to form an alignment film. The composition for optically anisotropic layer formation prepared above was apply | coated to the surface which irradiated the polarization UV using the bar coater, it heated at 120 degreeC, and the unpolymerized film was formed on the orientation film. After cooling to room temperature, polymerization was carried out by irradiating ultraviolet light at a wavelength of 365 nm at 40 mW / cm 2 for 1 minute using UniCure (VB-15201BY-A, manufactured by Ushio Denki Co., Ltd.) to obtain an optical film ( X) was produced.

Comparative Example 1 [Manufacture Example 1 of Comparative Optical Film]

In the said Example 1, it carried out on the same conditions as the said Example 1 except not having performed a plasma surface treatment, and produced the comparative optical film 1.

Comparative Example 2 [Manufacture Example 2 of Comparative Optical Film]

In the said Example 1, the comparative optical film 2 was produced on the same conditions as the said Example 1 except having made the plasma surface treatment conditions into 300 W (equivalent to 500 mJ / cm <2> energy). .

Example 2 [Manufacture example 2 of the optical film of this invention]

440 V, using an atmospheric pressure plasma surface treatment apparatus (roll direct head type AP-T04S-R890) manufactured by Sekisui Chemical Co., Ltd. (roll direct head type AP-T04S-R890) in an atmosphere containing nitrogen and oxygen (volume ratio nitrogen: oxygen = 99.9: 0.1) Plasma was generated under the conditions of 0.1 A (equivalent to 74 mJ / cm 2 of energy) to treat the saponified triacetylcellulose film surface. The composition for alignment film formation prepared above was apply | coated to the surface which performed the plasma processing, it dried, and the film of thickness 300nm was formed. Subsequently, using a spot cure (SP-7, manufactured by Ushio Denki Co., Ltd.) with polarized ultraviolet light (polarization UV) irradiation jig in the vertical direction with respect to the surface of the formed film, it is a straight line for 5 minutes at an illuminance of 15 mW / cm 2. Polarized UV was irradiated to form an alignment film. The composition for optically anisotropic layer formation prepared above was apply | coated to the surface which irradiated the polarization UV using the bar coater, it heated at 120 degreeC, and the unpolymerized film was formed on the orientation film. After cooling to room temperature, polymerization was carried out by irradiating the ultraviolet light with a roughness of 40 mW / cm 2 at a wavelength of 365 nm using Unicure (VB-15201BY-A, manufactured by Ushio Denki Co., Ltd.) for 1 minute to obtain an optical film. (X2) was produced.

Comparative Example 3 [Manufacture Example 3 of Comparative Optical Film]

In the said Example 2, it carried out on the conditions similar to the said Example 2 except having not performed the plasma surface treatment, and produced the comparative optical film 3.

Comparative Example 4 [Manufacture Example 4 of Comparative Optical Film]

In the said Example 2, the comparative optical film 4 was produced on the same conditions as the said Example 2 except having made the plasma surface treatment conditions into 300 W (equivalent to 500 mJ / cm <2> energy). .

[Adhesive evaluation]

According to JIS-K5600, peeling resistance of the above-mentioned optical film and the comparative optical film was evaluated using the Crosscut guide I series (CCI-1, 1 mm interval, for 25 masses) by KOTEC Corporation. . Table 4 shows the results of counting the remaining number of the alignment film held without peeling after the peeling test.

[Measurement of Optical Properties]

The retardation value of the above-mentioned optical film (X), the comparative optical film (1), and the comparative optical film (2) was measured by a measuring instrument (KOBRA-WR, manufactured by Ouji-Igekiki Co., Ltd.). The retardation value Re (λ) was measured at a wavelength λ of 549 nm. The results are shown in Table 4.

The optical film produced in the Example was able to confirm the tendency which was excellent in adhesiveness.

Since the base material of this invention is excellent in adhesiveness, the optical film in which peeling at the time of processing was suppressed can be produced.

1, 1 ': optical film of the present invention
2: polarizing film layer
3, 3 ': adhesive layer
4a, 4b, 4c, 4d, 4e, 4, 4 ': polarizing plate of the present invention
5, 5 ': adhesive layer
6: liquid crystal panel
7: organic EL panel
10a, 10b: liquid crystal display device
11: organic EL display device

Claims (19)

A substrate having a surface nitrogen present ratio of 0.1 to 1 atom%. The substrate according to claim 1, wherein the surface carbon abundance ratio is 54.9 to 70 atom% and the surface oxygen abundance ratio is 29 to 45 atom%. The substrate according to claim 1 or 2, wherein the substrate is a saponified triacetylcellulose film. The substrate according to any one of claims 1 to 3, wherein the substrate is a substrate subjected to surface treatment in an atmosphere containing nitrogen and oxygen. The substrate of claim 4, wherein the surface treatment is a plasma treatment. A substrate surface-treated with a plasma under an atmosphere containing nitrogen and oxygen, the substrate being surface-treated with an energy of 200 mJ / cm 2 or less. The substrate of claim 6, wherein the substrate is a saponified triacetylcellulose film. The laminated body with which the oriented film was formed in the base material surface in any one of Claims 1-7. The laminate according to claim 8, wherein the alignment film is an alignment film formed of a photoalignable polymer. The laminate according to claim 9, wherein the photo-alignment polymer is a photo-alignment polymer capable of forming a crosslinked structure by light irradiation. The laminate according to any one of claims 8 to 10, wherein in the adhesion test according to JIS-K5600, 36% or more of the alignment film is not peeled off on an area basis.  The optical film in which the optically anisotropic layer was formed on the orientation film of the laminated body in any one of Claims 8-11. The optical film according to claim 12, wherein the optically anisotropic layer is formed by polymerizing one or more polymerizable liquid crystals. The optical film according to claim 12 or 13, wherein in the adhesion test according to JIS-K5600, 36% or more of the optically anisotropic layer and the alignment film are not separated on an area basis. The optical film of any one of Claims 12-14 which has retardation. The polarizing plate containing the optical film of any one of Claims 12-15. Retardation plate containing the optical film of Claim 15. The flat panel display provided with the optical film as described in any one of Claims 12-15. The manufacturing method of the optical film containing following process (1)-(4):
Process (1): process of apply | coating photo-alignment polymer on the base material in any one of Claims 1-7.
Step (2): a step of forming an alignment film by crosslinking the photo-alignment polymer on the substrate
Process (3): The process of further apply | coating the composition containing a polymeric liquid crystal on an oriented film, and forming a coating film.
Step (4): A step of polymerizing the polymerizable liquid crystal in the coating film to form an optical film.

Images