TWI750311B - Polarizing film, circularly polarizing plate and display device - Google Patents

Abstract

It is an object of the present invention to provide a thin polarizing film, which is capable of suppressing deterioration with time of polarization performance. Another object of the present invention is to provide a circularly polarizing plate including the polarizing film and a display device.

To solve the problems, a polarizing film laminated with a polarizer containing a compound exhibiting dichroism and a protective layer is provided, wherein the protective layer is a cured film of a composition containing a polymerizable compound, The content of the monofunctional polymerizable compound in the composition is 60% by mass or more based on the total polymerizable compound contained in the composition.

Description

Polarizing film, circular polarizing plate and display device

The present invention relates to a polarizing film, more specifically, a polarizing film formed by laminating a polarizer and a protective layer containing a compound exhibiting dichroism, a circular polarizing plate and a display device provided with the polarizing film.

Conventionally, in various video display panels such as liquid crystal display panels and electro-luminescence (EL) display panels, polarizing films are used by being bonded to video display elements such as liquid crystal cells and EL display elements.

Such a polarizing film is known to have one side or both sides of a polarizer formed by adsorbing and aligning a compound exhibiting dichroism, such as iodine and a dichroic dye, on a polyvinyl alcohol-based resin film. A polarizing film composed of a protective layer such as a cellulose film laminated. In addition, in recent years, with the demand for thinner displays, further thinning of the polarizing film, which is one of the components of the display, has also been demanded. For such a demand, for example, Patent Document 1 and Patent Document 2 propose to disclose a thin main A host-guest polarizer is composed of a polymerizable liquid crystal compound and a compound exhibiting dichroism.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2007-510946

[Patent Document 2] Japanese Patent Application Laid-Open No. 2013-37353

By using the polarizing films described in Patent Document 1 and Patent Document 2, further thinning can be expected compared to the iodine polyvinyl alcohol type polarizing film. However, when the host-guest polarizer described in Patent Document 1 is attached to the polymer film (protective layer) and the display device, dyes may be generated from the polarizer to the polymer film and the polymer film depending on the external environmental conditions to which the polarizer is exposed. The problem of the loss of anisotropy due to diffusion in the adhesive and the decrease in polarization performance over time.

In order to solve this problem, the polarizing film described in Patent Document 2 disposes a polarizing film in which an alignment layer, a polarizing layer, and a protective layer are formed on a transparent substrate in an inline manner on a front panel (glass substrate). However, since the protective layer requires a solvent drying step, depending on the type of solvent contained in the composition for producing the protective layer and the kind of the protective layer to be constructed, a compound showing dichroism may diffuse into the protective layer during the drying step and A situation in which polarization performance decreases over time.

Therefore, an object of the present invention is to provide a thin polarizing film which solves the above-mentioned problems that may occur uniquely in a polarizing film, and which can suppress the decrease in polarization performance with time. Furthermore, the objective of the present invention is to provide a circularly polarizing plate and a display device including the polarizing film.

The present invention provides the following better aspects.

[1] A polarizing film formed by laminating a polarizer containing a compound exhibiting dichroism and a protective layer, the protective layer being a cured film of a composition containing a polymerizable compound, and relative to the composition As for the total polymerizable compounds contained, the content of the monofunctional polymerizable compound in the composition is 60% by mass or more.

[2] The polarizing film according to the above [1], wherein the viscosity of the composition is 120 cps or less at 27°C.

[3] The polarizing film according to the above [1] or [2], wherein the monofunctional polymerizable compound contains a compound having a (meth)acryloyl group.

[4] The polarizing film according to any one of the above [1] to [3], wherein the monofunctional polymerizable compound contains a compound having a (meth)acryloyl group and a hydroxyl group.

[式中，n表示1至12的整數，A¹表示O或NH，X¹表示亦可具有取代基之亞甲基，n為2以上的整數時，該亞甲基的至少一個亦可被氧原子取代且上述取代基可相同或不同。 [5] The polarizing film according to the above [4], wherein the compound having a (meth)acryloyl group and a hydroxyl group is represented by the following formula (1):

[In the formula, n represents an integer of 1 to 12, A ¹ represents O or NH, X ¹ represents a methylene group which may have a substituent, and when n is an integer of 2 or more, at least one of the methylene groups may also be replaced by Oxygen atoms are substituted and the aforementioned substituents may be the same or different.

[6] The polarizing film according to any one of the above items [1] to [5], wherein the polarizer further contains a polymer of a non-colorable polymerizable liquid crystal compound.

[7] The polarizing film according to the above [6], wherein the polarizer is a polymer containing 80% by mass or more of a non-colorable polymerizable liquid crystal compound relative to the total mass of the polarizer, and the non-colorable polymerizable The polymer of the polymerizable liquid crystal compound exhibits a smectic liquid crystal phase, and the compound exhibiting dichroism is aligned with the polymer of the non-colorable polymerizable liquid crystal compound and contained therein.

[8] The polarizing film according to any one of the above items [1] to [7], wherein the compound exhibiting dichroism is an azo dye.

[9] A circularly polarizing plate comprising the polarizing film and retardation film according to any one of the above items [1] to [8].

[10] The circular polarizing plate according to the aforementioned [9], wherein the retardation film system satisfies the following formula (X): Re(450nm)/Re(550nm)<1 (X) In the formula, Re(λ ) represents the frontal retardation value for light of wavelength λnm].

[11] A display device comprising the polarizing film according to any one of the above items [1] to [8], or the circular polarizing plate according to the above [9] or [10].

According to the present invention, it is possible to provide a thin polarizing film that can suppress the decrease in polarization performance over time. In addition, a circular polarizing plate and a display device including the polarizing film can also be provided.

1‧‧‧Polarizer

2‧‧‧Protective layer

3‧‧‧Protective layer

10‧‧‧Polarizing film

FIG. 1 shows the structure of one embodiment of the polarizing film of the present invention.

[Form for carrying out the invention]

The polarizing film which concerns on one Embodiment of this invention is the polarizing film which laminated|stacked the polarizer containing the compound which shows dichroism, and a protective layer.

Hereinafter, embodiments of the present invention will be described in detail. In addition, the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made within the scope of not impairing the spirit of the present invention.

The structure of one embodiment of the polarizing film of the present invention will be described based on FIG. 1 .

The polarizing film (10) has a structure in which a protective layer (2) is laminated on one side of the polarizer (1). Another protective layer (3) can also be laminated on the other side of the polarizer (1). In addition, an alignment film (not shown) may be laminated between the polarizer (1) and the protective layer (2) and/or between the polarizer (1) and the protective layer (3). The above-mentioned polarizing film may also have an adhesive layer (not shown) on the opposite side of the protective layer and the side adjacent to the polarizing film as needed. From the viewpoint of improving the heat resistance of the polarizing film, it is preferable not to have an adhesive layer. . The adhesive layer has the function of bonding the polarizing film to other components such as the front panel.

Hereinafter, each component of the polarizing film which concerns on one Embodiment of this invention is demonstrated in detail.

<Polarizer>

The polarizer of the present invention is a film containing a compound exhibiting dichroism, and is more preferably a film further containing a polymer of a non-colorable polymerizable liquid crystal compound from the viewpoint of easy alignment control. When the polarizer further contains a polymer of a non-colorable polymerizable liquid crystal compound, from the viewpoint of alignment, the polarizer is more preferably a compound system exhibiting dichroism whose alignment is formed by the polymer of the non-colorable polymerizable liquid crystal compound. It is a film formed in the formed film, and a film formed by curing the non-colorable polymerizable liquid crystal compound in the state of alignment in the horizontal direction with respect to the protective layer.

From the viewpoint of the orientation of the non-colorable polymerizable liquid crystal compound, the thickness of the polarizer is preferably 0.5 μm to 5 μm, more preferably 1 μm to 3.5 μm. When the thickness of the polarizer is greater than or equal to the above lower limit value, the alignment order tends to be improved because it is not easy to align in the vertical alignment direction. When the thickness of the polarizer is below the above-mentioned upper limit value, the alignment order tends to improve because it is not easy to align in a random alignment direction. The thickness of the polarizer can be measured using, for example, an interferometric thickness meter, a laser microscope, or a stylus type thickness meter.

The manufacturing method of the polarizer is not particularly limited, for example, the polarizer can be obtained by a method comprising the following steps: a composition containing a non-colored polymerizable liquid crystal compound and a compound exhibiting dichroism (hereinafter, also referred to as "polarized light") can be obtained. The composition for forming a mirror") is applied to the surface of a substrate, an alignment film or a protective layer to form a coating film, and a step of polymerizing the above-mentioned non-colorable polymerizable liquid crystal compound. Here, the non-colorable polymerizable liquid crystal compound is preferably polymerized in an aligned state, particularly in a state aligned in the horizontal direction in the protective layer. In addition, when the above-mentioned composition for forming a polarizer contains a solvent, a step of drying the coating film may be included if necessary. As a drying method, a natural drying method, a ventilation drying method, a heating drying method, a vacuum drying method, etc. are mentioned.

[Non-coloring polymerizable liquid crystal compound]

The term "non-colorable polymerizable liquid crystal compound" refers to a compound that is not colored, has a polymerizable group, and has liquid crystallinity. The polymerizable group means a group that participates in the polymerization reaction, and a photopolymerizable group is preferred. Here, the photopolymerizable group refers to a group that can participate in a polymerization reaction by an active radical, an acid, or the like generated from a photopolymerization initiator described later. Examples of the polymerizable group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloyloxy, oxiranyl, and oxetanyl. Wait. In particular, acryloxy, methacryloyloxy, vinyloxy, oxiranyl and oxetanyl groups are preferred, and acryloxy is more preferred. The liquid crystallinity may be a thermotropic liquid crystal or a readily soluble liquid crystal.

The non-colorable polymerizable liquid crystal compound may be a thermotropic liquid crystal compound exhibiting a nematic liquid crystal phase or a thermotropic liquid crystal compound exhibiting a smectic liquid crystal phase. The non-colorable polymerizable liquid crystal compound of the present invention is preferably a thermotropic liquid crystal compound exhibiting a smectic liquid crystal phase from the viewpoint of having excellent alignment properties and obtaining high polarization characteristics, more preferably Thermotropic liquid crystal compounds exhibiting an advanced smectic liquid crystal phase. Especially smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J The thermotropic liquid crystal compound of smectic phase, smectic K phase or smectic L phase is more preferable to show the heat of smectic B phase, smectic F phase, smectic H phase or smectic I phase The isotropic liquid crystal compound is more preferable. When the liquid crystal phase formed by the non-colorable polymerizable liquid crystal compound is such an advanced smectic liquid crystal phase, a polarizer with high polarization performance can be produced. In addition, such a polarizer with high polarizing performance is preferable to obtain a Bragg peak in X-ray diffraction measurement, and such a polarizer can obtain a high-level structure derived from a hexagonal phase and a crystal phase. Prague Spikers. The Bragg peaks are sharp peaks derived from the periodic structure of molecular alignment, and films with periodic intervals of 3 to 6 Å can be obtained. Furthermore, from the viewpoint of obtaining higher polarization characteristics, in the polarizer according to an embodiment of the present invention, the polymer of the non-colorable polymerizable liquid crystal compound exhibits a smectic liquid crystal phase, especially an advanced smectic phase. The liquid crystal phase is preferred.

Specifically, as such a non-colorable polymerizable liquid crystal compound, the compound represented by following formula (A) (Hereinafter, it may be called compound (A)) etc. are mentioned. The non-colorable polymerizable liquid crystal compound may be used alone or in combination of two or more.

U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (A) [in formula (A), X ¹ , X ² and X ³ They represent independently of each other a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. However, ^{at least one of X 1} , X ² and X ³ may be a 1,4-phenylene group having a substituent. _{-CH 2} constituting the cyclohexane-1,4-diyl group may also be replaced by -O-, -S- or -NR-. R represents an alkyl group or a phenyl group having 1 to 6 carbon atoms.

Y ¹ and Y ² independently represent -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, a single bond, -N=N-, -CR ^a =CR ^b -, -C ≡C- or -CR ^a =N-. R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

U ¹ represents a hydrogen atom or a polymerizable group.

U ² represents a polymerizable group.

W ¹ and W ² independently represent a single bond, -O-, -S-, -COO- or -OCOO-.

V ¹ and V ² independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the alkanediyl group may also be replaced by -O-, -S- or -NH- replacement].

In the compound (A) ^{, at least one of X 1} , X ² and X ³ is more preferably a 1,4-phenylene group which may have a substituent.

The 1,4-phenylene group which may have a substituent is preferably unsubstituted. Cyclohexane-1,4-diyl which may also have substituents is preferably trans-cyclohexane-1,4-diyl which may also have substituents, and trans-cyclohexane which may also have substituents The hexane-1,4-diyl system is preferably unsubstituted.

The optionally substituted 1,4-phenylene group or the optionally substituted cyclohexane-1,4-diyl group includes a methyl group, an ethyl group, and a butyl group with carbon numbers such as a methyl group, an ethyl group, and a butyl group. 1 to 4 alkyl groups, cyano groups and halogen atoms, etc.

Y ¹ is preferably -CH ₂ CH ₂ -, -COO- or a single bond, and Y ² is preferably -CH ₂ CH ₂ - or -CH ₂ O-.

U ² is a polymerizable group. U ¹ is a hydrogen atom or a polymerizable group, more preferably a polymerizable group. U ¹ and U ² are preferably polymerizable groups at the same time, and more preferably photopolymerizable groups at the same time. A polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that it can be polymerized under relatively low temperature conditions.

The polymerizable groups represented by U ¹ and U ² may also be different from each other, but are preferably the same. Examples of the polymerizable group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloyloxy, oxiranyl, and oxetanyl. Wait. In particular, acryloxy, methacryloyloxy, vinyloxy, oxiranyl and oxetanyl groups are preferred, and acryloxy is more preferred.

Examples of the alkanediyl group represented by V ¹ and V ² include methylene group, ethylidene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,4-diyl group. Alkane-1,5-diyl, Hexane-1,6-diyl, Heptane-1,7-diyl, Octane-1,8-diyl, Decane-1,10-diyl, Decane Tetraoxane-1,14-diyl and eicosane-1,20-diyl and the like. V ¹ and V ² are preferably alkanediyl groups having 2 to 12 carbon atoms, more preferably alkanediyl groups having 6 to 12 carbon atoms.

The alkanediyl group having 1 to 20 carbon atoms which may also have a substituent may optionally have a cyano group and a halogen atom. The alkanediyl group is preferably unsubstituted, and an unsubstituted and linear alkanediyl group is preferred. base is better.

W ¹ and W ^{2 are} , independently of each other, more preferably a single bond or -O-.

Specific examples of the compound (A) include compounds represented by formula (1-1) to formula (1-23), and the like. When the compound (A) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans form.

Among the exemplified compounds (A), the formula (1-2), the formula (1-3), the formula (1-4), the formula (1-6), the formula (1-7), the formula ( 1-8), formula (1-13), formula (1-14), and formula (1-15) are preferably at least one of the group consisting of compounds represented by each of them.

The exemplified compound (A) can be used alone or in combination for a polarizer. Moreover, when combining 2 or more types of non-colorable polymerizable liquid crystal compounds, it is preferable that at least 1 type is a compound (A), and it is more preferable that 2 or more types are a compound (A).

By combining two or more types of non-colorable polymerizable liquid crystal compounds, the liquid crystallinity may be temporarily maintained even at a temperature equal to or lower than the liquid crystal-crystal phase transition temperature. The mixing ratio when combining the two types of polymerizable liquid crystal compounds is usually 1:99 to 50:50, preferably 5:95 to 40:60, more preferably 10:90 to 30:70.

Compound (A) can be produced by, for example, the known methods described in Lub et al., Recl. TRav. Chim. Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156.

The content of the non-colorable polymerizable liquid crystal compound in the polarizer-forming composition is preferably 80% by mass or more, more preferably 82% by mass or more, and 99.5% by mass relative to the solid content of the polarizer-forming composition. It is preferably not more than 99% by mass, more preferably not more than 94% by mass, and particularly preferably not more than 90% by mass. When the content of the non-colorable polymerizable liquid crystal compound is within the above range, the orientation tends to be high. Here, the term "solid content" means the total amount of the components after removing the solvent from the composition for forming a polarizer. Therefore, the obtained polarizer preferably contains 80% by mass or more, more preferably 82% by mass or more, and 99.5% by mass of the polymer of the non-colorable polymerizable liquid crystal compound relative to the total mass of the polarizer. % or less is preferable, more preferably 99 mass % or less, still more preferably 94 mass % or less, particularly preferably 90 mass % or less.

The composition for forming a polarizer may also contain a solvent, a polymerization initiator, a sensitizer, a polymerization inhibitor, a leveling agent, and a reactive additive as components other than the non-colorable polymerizable liquid crystal compound and the compound exhibiting dichroism .

[Compounds exhibiting dichroism]

The compound showing dichroism contained in the composition for forming a polarizer refers to a compound showing different properties (dichroism) in the absorbance in the long axis direction of the molecule and the absorbance in the short axis direction. In a more preferred embodiment of the present invention, the compound exhibiting dichroism is contained in the polymer of the non-colorable polymerizable liquid crystal compound in alignment with the polymer of the non-colorable polymerizable liquid crystal compound, from the viewpoint that the alignment can be easily controlled. Furthermore, in a more preferred embodiment of the present invention, the polarizer contains a polymer of a non-colorable polymerizable liquid crystal compound in the above-mentioned range or more (eg, 80% by mass or more), and the polymer of the non-colorable polymerizable liquid crystal compound shows a smectic pattern When the compound exhibiting dichroism is oriented to the polymer of the non-colorable polymerizable liquid crystal compound and contained therein, the orientation is further improved and higher polarization characteristics are obtained.

色素、花青色素、萘色素、偶氮色素及蒽醌色素等、尤其是以偶氮色素為佳。偶氮色素可列舉單偶氮色素、雙偶氮色素、參偶氮色素、肆偶氮色素及茋偶氮色素等，更佳為雙偶氮色素及參偶氮色素。顯示二色性的化合物可為單獨，亦可組合2種以上，以組合3種以上為佳。特別是組合3種以上的偶氮化合物為更佳。 The compound exhibiting dichroism preferably _{has an absorption maximum wavelength (λ max} ) in the range of 300 to 700 nm. Examples of such dichroic compounds include acridine dyes,

Pigments, cyanine pigments, naphthalene pigments, azo pigments and anthraquinone pigments, etc., especially azo pigments are preferred. Examples of the azo dyes include monoazo dyes, disazo dyes, ginseno dyes, stilbene dyes, and stilbene azo dyes, and more preferred are disazo dyes and sazo dyes. The compound which exhibits dichroism may be independent, and may combine 2 or more types, and it is preferable to combine 3 or more types. In particular, it is more preferable to combine three or more azo compounds.

Examples of the azo dye include compounds represented by formula (B) (hereinafter, referred to as "compound (B)" in some cases).

A ¹ (-N=NA ² ) _p -N=NA ³ (B) [in formula (B), A ¹ and A ³ independently represent a phenyl group which may have a substituent and a naphthalene which may have a substituent group or a valent heterocyclic group which may also have a substituent. A ² represents a 1,4-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocyclic group which may have a substituent. p represents an integer of 1 to 4. When p is an integer of 2 or more, a plurality of A ² may be the same or different from each other]

唑及苯并

唑等的雜環化合物除去1個氫原子後之基。二價雜環基可列舉從上述雜環化合物除去2個氫原子後之基。 The monovalent heterocyclic group includes quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole,

azoles and benzos

A base obtained by removing one hydrogen atom from a heterocyclic compound such as azole. The divalent heterocyclic group includes a group obtained by removing two hydrogen atoms from the above-mentioned heterocyclic compound.

The phenyl group, naphthyl group and monovalent heterocyclic group in A ¹ and A ³ , and the p-phenylene group, naphthalene-1,4-diyl group and divalent heterocyclic group in ^{A 2 optionally have substituents,} Examples include alkyl groups having 1 to 4 carbon atoms; alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, and butoxy; and fluorinated alkyl groups having 1 to 4 carbon atoms such as trifluoromethyl. ; cyano group; nitro group; halogen atom; substituted or unsubstituted amino group such as amino group, diethylamino group and pyrrolidinyl group (the so-called substituted amino group refers to one or two alkanes having 1 to 6 carbon atoms The amine group of the alkanediyl group, or the amine group of the alkanediyl group with the carbon number of 2 to 8 is formed by bonding two substituted alkyl groups to each other. The unsubstituted amine group is -NH ₂ ). Moreover, a methyl group, an ethyl group, a butyl group, a hexyl group, etc. are mentioned as a specific example of the C1-C6 alkyl group.

Among the compounds (B), compounds represented by the following formulae (2-1) to (2-6) are preferred.

[式(2-1)至(2-6)中，B¹至B²⁰係互相獨立地表示氫原子、碳數1至6的烷基、碳數1至4的烷氧基、氰基、硝基、取代或未取代的胺基(取代胺基及未取代胺基的定義係如上述)、氯原子或 三氟甲基。

[In formulae (2-1) to (2-6), B ¹ to B ²⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, A nitro group, a substituted or unsubstituted amine group (the definitions of substituted amine group and unsubstituted amine group are as above), a chlorine atom or a trifluoromethyl group.

n1 to n4 represent integers of 0 to 3 independently of each other.

When n1 is 2 or more, a plurality of B ² may be identical or different from each other, n2 is 2 or more, plural B ⁶ may be identical or different from each other, n3 is 2 or more, plural B ⁹ may be the same or different from each other , when n4 is 2 or more, a plurality of B ¹⁴ may be the same or different from each other]

The above-mentioned anthraquinone dye is preferably a compound represented by the formula (2-7).

[式(2-7)中，R¹至R⁸係互相獨立地表示氫原子、-R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^x或鹵素原子。

[In formula (2-7), R ¹ to R ⁸ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms].

色素係以式(2-8)表示之化合物為佳。 the above

The pigment is preferably a compound represented by the formula (2-8).

[式(2-8)中，R⁹至R¹⁵係互相獨立地表示氫原子、-R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^x或鹵素原子。

[In formula (2-8), R ⁹ to R ¹⁵ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms].

The above-mentioned acridine dye is preferably a compound represented by the formula (2-9).

[式(2-9)中，R¹⁶至R²³係互相獨立地表示氫原子、-R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^x或鹵素原子。

[In formula (2-9), R ¹⁶ to R ²³ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms].

^{The alkyl group having 1 to 4 carbon atoms represented by R x} in the formula (2-7), the formula (2-8) and the formula (2-9) includes methyl, ethyl, propyl, butyl and the like, Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group, and a naphthyl group.

The aforementioned anthocyanin pigment is preferably the compound represented by the formula (2-10) and the compound represented by the formula (2-11).

[式(2-10)中，D1及D2係互相獨立地表示式(2-10a)至式(2-10d)的任一者表示之基。

[In the formula (2-10), D1 and D2 represent the bases represented by any one of the formulae (2-10a) to (2-10d) independently of each other.

n5表示1至3的整數]。

n5 represents an integer from 1 to 3].

[式(2-11)中，D³及D⁴係互相獨立地表示式(2-11a)至式(2-11h)的任一者表示之基。

[In the formula (2-11), D ³ and D ⁴ independently represent a group represented by any one of the formulae (2-11a) to (2-11h).

n6表示1至3的整數]。

n6 represents an integer from 1 to 3].

The content of the compound showing dichroism in the polarizer-forming composition is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the non-colorable polymerizable liquid crystal compound content Preferably, it is more preferably 0.1 to 12 parts by mass. When the content of the compound exhibiting dichroism is within the above range, the non-colorable polymerizable liquid crystal compound can be polymerized without disturbing the alignment of the non-colorable polymerizable liquid crystal compound. When the content of the compound exhibiting dichroism is too large, the alignment of the non-colorable polymerizable liquid crystal compound may be inhibited. Therefore, the content of the compound exhibiting dichroism can also be determined within the range in which the non-colorable polymerizable liquid crystal compound can maintain the liquid crystal state. In addition, from the same viewpoint as above, in the polarizer obtained, the content of the compound showing dichroism is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the polymer of the non-colorable polymerizable liquid crystal compound , more preferably 0.1 to 20 parts by mass, still more preferably 0.1 to 12 parts by mass.

The compound exhibiting dichroism may be a polymer having a polymerizable group and having the dyes listed above as a monomer as a backbone. When the compound exhibiting dichroism is a polymer having a polymerizable group and a monomer having the above-mentioned dye as a backbone, the transfer of the compound exhibiting dichroism to the protective layer can be further suppressed. However, when the compound showing dichroism is a polymer, since the orientation tends to be lowered, the polarization performance tends to be lowered. Therefore, in a more preferred aspect of the present invention, the compound exhibiting dichroism does not have a polymerizable group and has a molecular weight of, for example, 1000 or less. According to the present invention, since the compound showing dichroism can be inhibited from transferring to the protective layer even if it is not polymerized, a polarizing film having excellent polarizing performance can be obtained.

[solvent]

The polarizer-forming composition may contain a solvent. The solvent is preferably one that can completely dissolve the non-colorable polymerizable liquid crystal compound, and is preferably a solvent inactive to the polymerization reaction of the non-colorable polymerizable liquid crystal compound.

Examples of solvents include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol Ester solvents such as methyl ether acetate, γ-butyrolactone or propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl Ketone solvents such as isobutyl ketone and isophorone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; tetrahydrofuran and dimethyl benzene Ether solvents such as oxyethane; chlorine-containing solvents such as chloroform and chlorobenzene, etc.

These solvents may be used alone or in combination of two or more.

The solvent content is preferably 50 to 98% by mass with respect to the total amount of the above-mentioned polarizer-forming composition. In other words, the solid content in the polarizer-forming composition is preferably 2 to 50% by mass. When the content of the solid content is 50 mass % or less, the viscosity of the polarizer-forming composition becomes low, and the thickness of the polarizer becomes approximately uniform, so that the polarizer tends to be less uneven. In addition, the content of such solid content can be determined in consideration of the thickness of the polarizer to be produced.

[Polymerization initiator]

The composition for forming a polarizer may contain a polymerization initiator. A polymerization initiator is a compound which can start the polymerization reaction of a non-colorable polymerizable liquid crystal compound, etc.. The polymerization initiator is preferably a photopolymerization initiator that generates active radicals by the action of light.

化合物、碘鎓鹽及鋶鹽等。 Examples of the polymerization initiators include benzoin compounds, diphenyl ketone compounds, alkyl phenyl ketone compounds, acylphosphine oxide compounds, triphenyl ketone compounds, and triphenyl ketone compounds.

Compounds, iodonium salts and peronium salts, etc.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

For example, the benzophenone compound includes benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl) diphenyl ketone and 2,4,6-trimethyl diphenyl ketone, etc.

Examples of the alkyl phenyl ketone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl- 2-Dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl yl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1- Oligomers of hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, etc.

Examples of the acyl phosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, and the like.

化合物例如可列舉2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(4-二乙胺基-2-甲基苯基)乙烯基]-1,3,5-三

及2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三

等。 three

Examples of the compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris

, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tris

, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-tri

and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri

Wait.

Commercially available ones can be used as polymerization initiators. Commercially available polymerization initiators include Irgacure (registered trademark) 907, 184, 651, 819, 250, and 369 (manufactured by Ciba Specialty Chemicals Co., Ltd.); SEIKUOL (registered trademark) BZ, Z, and BEE (Seiko Chemical Co., Ltd.) Co.); Kayacure (registered trademark) BP100, and UVI-6992 (Dow Chemical Co., Ltd.); ADEKA OPTOMER SP-152, and SP-170 (ADEKA Co., Ltd.); TAZ-A, and TAZ-PP (Japan SiberHegner Co., Ltd.); and, TAZ-104 (Sanwa Chemical Co., Ltd.), etc.

The content of the polymerization initiator in the polarizer-forming composition can be appropriately adjusted according to the type and amount of the non-coloring polymerizable liquid crystal compound, and is usually 100 parts by mass relative to the content of the non-coloring polymerizable liquid crystal compound. It is 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass. When the content of the polymerization initiator is within the above range, the polymerization can be performed without disturbing the alignment of the non-colorable polymerizable liquid crystal compound.

[Sensitizer]

及紅螢烯(rubrene)等。 The composition for forming a polarizer may contain a sensitizer. The sensitizer is preferably a photosensitizer. Examples of the sensitizer include xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthene, etc.) ketone, etc.); anthracene and alkoxy-containing anthracene (such as dibutoxyanthracene, etc.) and other anthracene compounds;

And rubrene (rubrene) and so on.

When the composition for forming a polarizer contains a sensitizer, the polymerization reaction of the polymerizable liquid crystal compound contained in the composition for forming a polarizer can be further accelerated. Relative to the content of 100 parts by mass of the non-colorable polymerizable liquid crystal compound, the usage amount of this sensitizer is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass good.

[polymerization inhibitor]

From the viewpoint of stable progress of the polymerization reaction, the composition for forming a polarizer may contain a polymerization inhibitor. The degree of progress of the polymerization reaction of the non-colorable polymerizable liquid crystal compound can be controlled by the polymerization inhibitor.

Examples of the above-mentioned polymerization inhibitor include hydroquinone, alkoxy-containing hydroquinone, alkoxy-containing catechol (for example, butylcatechol, etc.), gallicol, 2,2,6,6-tetramethyl -Radical scavengers such as 1-piperidinyloxy radicals; thiophenols; β-naphthylamines and β-naphthols, etc.

When the polarizer-forming composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the non-colorable polymerizable liquid crystal compound content , and more preferably 0.5 to 8 parts by mass. When the content of the polymerization inhibitor is within the above range, the polymerization can be performed without disturbing the alignment of the non-colorable polymerizable liquid crystal compound.

[leveler]

The composition for forming a polarizer may contain a leveling agent. The leveling agent has the function of adjusting the fluidity of the composition for forming a polarizer and making the film obtained by applying the composition for forming a polarizer more flat, and for example, surfactants are exemplified. More preferable leveling agents include a leveling agent containing a polyacrylate compound such as "BYK-361N" (manufactured by BYK-Chemie Co., Ltd.) as a main component, and a leveling agent containing SURFLON (registered trademark) "S-381" (AGC SEIMI CHEMICAL Co., Ltd.), "MEGAFACE F-556", "MEGAFACE F-554" (manufactured by DIC Co., Ltd.) and other fluorine atom-containing compounds as a leveling agent as the main component.

When the composition for forming a polarizer contains a leveling agent, the content of the leveling agent is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the content of the non-colorable polymerizable liquid crystal compound, More preferably, it is 0.4 to 3 parts by mass. When the content of the leveling agent is within the above range, the alignment of the non-colorable polymerizable liquid crystal compound in the horizontal direction (horizontal alignment) is easy, and the resulting polarizer tends to be smoother. In the non-colorable polymerizable liquid crystal compound, when the content of the leveling agent is larger than the above-mentioned range, the obtained polarizer tends to be uneven. Moreover, the composition for polarizer formation may contain 2 or more types of leveling agents.

[Reactive Additives]

唑啉基、碳二亞胺基、吖環丙烷基、醯亞胺基、異氰酸酯基、硫異氰酸酯基、順丁烯二酸酐基等。反應性添加劑所具有之碳-碳不飽和鍵及活性氫反應性基的個數通常為各自1至20個，更佳為各自1至10個。 The polarizer-forming composition may contain reactive additives. The reactive additive preferably has a carbon-carbon unsaturated bond and an active hydrogen reactive group in its molecule. Here, the "active hydrogen-reactive group" refers to a group having reactivity with a group having active hydrogen such as a carboxyl group (-COOH), a hydroxyl group (-OH), an amine group (-NH ₂ ), and the like, and a representative example thereof is a ring oxypropyl,

An oxazoline group, a carbodiimide group, an aziridine group, an imide group, an isocyanate group, a thioisocyanate group, a maleic anhydride group, and the like. The number of carbon-carbon unsaturated bonds and active hydrogen reactive groups possessed by the reactive additive is usually 1 to 20 each, more preferably 1 to 10 each.

Preferably, there are at least two active hydrogen reactive groups in the reactive additive, and in this case, the active hydrogen reactive groups present in a plurality may be the same or different.

The carbon-carbon unsaturated bond possessed by the reactive additive may be a carbon-carbon double bond or a carbon-carbon double bond, or a combination thereof, preferably a carbon-carbon double bond. Among them, the reactive additive preferably contains a carbon-carbon unsaturated bond as a vinyl group and/or a (meth)acryloyl group. Moreover, the active hydrogen reactive group is preferably at least one reactive additive selected from the group consisting of epoxy group, glycidyl group and isocyanate group, and more preferably the reactive additive having acrylyl group and isocyanate group good.

唑啉、異丙烯基

唑啉等具有乙烯基及

唑啉基之化合物；丙烯酸異氰酸基甲酯、甲基丙烯酸異氰酸基甲酯、丙烯酸2-異氰酸基乙酯及甲基丙烯酸2-異氰酸基乙酯等具有(甲基)丙烯醯基及異氰酸酯基之化合物的寡聚物等。又，可列舉甲基丙烯酸酐、丙烯酸酐、順丁烯二酸酐及乙烯基順丁烯二酸酐等具有乙烯基、伸乙烯基及酸酐之化合物等。尤其是以甲基丙烯醯氧基環氧丙基醚、丙烯醯氧基環氧丙基醚、丙烯酸異氰酸基甲酯、甲基丙烯酸異氰酸基甲酯、乙烯基

唑啉、丙烯酸2-異氰酸基乙酯、甲基丙烯酸2-異氰酸基乙酯及上述的寡聚物為佳、丙烯酸異氰酸基甲酯、丙烯酸2-異氰酸基乙酯及上述的寡聚物為特佳。 Specific examples of the reactive additive include compounds having a (meth)acryloyl group and an epoxy group, such as methacryloyloxyglycidyl ether and acryloxyglycidyl ether; oxetane Acrylates, oxetane methacrylates and other compounds with (meth)acryloyl and oxetanyl groups; lactone acrylates, lactone methacrylates, etc. with (meth)acryloyl groups and lactone-based compounds; vinyl

oxazoline, isopropenyl

oxazoline etc. have vinyl and

Compounds of oxazoline groups; isocyanatomethyl acrylate, isocyanatomethyl methacrylate, 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate, etc. with (methyl methacrylate) ) oligomers of compounds of acrylyl and isocyanate groups, etc. Moreover, the compound etc. which have a vinyl group, a vinyl group, and an acid anhydride, such as methacrylic anhydride, an acrylic anhydride, maleic anhydride, and vinyl maleic anhydride, are mentioned. Especially with methacryloyloxyglycidyl ether, acryloxyglycidyl ether, isocyanatomethyl acrylate, isocyanatomethyl methacrylate, vinyl

oxazoline, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate and the above-mentioned oligomers are preferred, isocyanatomethyl acrylate, 2-isocyanatoethyl acrylate And the above-mentioned oligomers are particularly preferred.

Specifically, it is preferably a compound represented by the following formula (Y).

[式(Y)中，n表示1至10的整數，R^1’表示碳數2至20的二價脂肪族或脂環式烴基、或碳數5至20的二價芳香族烴基。各重複單元之2個R^2’係一方為-NH-，另一方為>N-C(=O)-R^3’表示之基。R^3’表示具有羥基或碳-碳不飽和鍵之基。

[In formula (Y), n represents an integer of 1 to 10, and R ^1′ represents a divalent aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 5 to 20 carbon atoms. One of the two R ^2' of each repeating unit is -NH-, and the other is a group represented by ^{>NC(=O)-R 3'.} R ^3' represents a group having a hydroxyl group or a carbon-carbon unsaturated bond.

^{Among R 3'} in formula (Y), at least one R ^3' is a group having a carbon-carbon unsaturated bond].

Among the reactive additives represented by the above formula (Y), a compound represented by the following formula (YY) (hereinafter, sometimes referred to as compound (YY)) is particularly preferred (also, n means the same meaning as above).

Compound (YY) can be used directly or purified as necessary. As a commercial item, Laromer (registered trademark) LR-9000 (made by BASF Corporation) is mentioned, for example.

When the polarizer-forming composition contains a reactive additive, the content of the reactive additive is usually 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

<Alignment film>

The alignment film of the present invention is a film composed of a polymer compound, which aligns the liquid crystal of a non-colorable polymerizable liquid crystal compound in a desired direction and has alignment regulation power.

The alignment film system can facilitate the liquid crystal alignment of the non-colorable polymerizable liquid crystal compound. The liquid crystal alignment states of horizontal alignment, vertical alignment, hybrid alignment, oblique alignment, etc. vary by the properties of the alignment film and the non-colorable polymerizable liquid crystal compound, and the combination thereof can be arbitrarily selected. For example, if the alignment film uses a material that exhibits horizontal alignment as the alignment regulatory force, the non-colored polymerizable liquid crystal compound can form a horizontal alignment or a mixed alignment; if it is a material that exhibits vertical alignment, the non-colored polymerizable liquid crystal compound The system can form a vertical alignment or an oblique alignment.

Expressions such as horizontal and vertical represent the long-axis direction of the non-colorable polymerizable liquid crystal compound aligned with the polarizer plane as a reference. For example, vertical alignment refers to having the long axis of the polymerizable liquid crystal compound aligned in the direction perpendicular to the plane of the polarizer. The vertical system here means 90°±20° to the plane of the polarizer.

When the alignment film is formed of an alignment polymer, the alignment regulatory force can be arbitrarily adjusted according to the surface state and friction conditions, and when the alignment film is formed of a photo-alignment polymer, it can be arbitrarily adjusted according to the polarized light irradiation conditions and the like. In addition, the liquid crystal alignment can also be controlled by selecting physical properties such as surface tension and liquid crystallinity of the non-colorable polymerizable liquid crystal compound.

The alignment film system formed between the base material or the protective layer and the polarizer is insoluble in the solvent used for forming the polarizer on the alignment film, and has heat resistance during solvent removal and heat treatment for liquid crystal alignment. good. As the alignment film, an alignment film composed of an alignment polymer, a photo-alignment film, a groove alignment film, and the like are mentioned, and a photo-alignment film is more preferable.

The thickness of the alignment film is usually in the range of 10 nm to 500 nm, preferably in the range of 10 nm to 200 nm, and more preferably in the range of 30 to 100 nm.

唑、聚乙烯亞胺(polyethylene imine)、聚苯乙烯、聚乙烯吡咯啶酮、聚丙烯酸及聚丙烯酸酯類等。尤其是以聚乙烯醇為佳。該等配向性聚合物可單獨使用，亦可組合2種以上而使用。 Alignment polymers include polyamide and gelatin which have amide bonds in the molecule, polyimide which has amide bonds in the molecule and their hydrolyzates, that is, polyamic acid, Polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polypropylene amide, poly

azoles, polyethylene imine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylate, etc. In particular, polyvinyl alcohol is preferred. These alignment polymers may be used alone or in combination of two or more.

When the alignment film is composed of an alignment polymer, the alignment film can usually be obtained by the following steps: coating a composition containing an alignment polymer and a solvent (hereinafter, also referred to as an "alignment polymer composition") The step of disposing on the substrate or protective layer and removing the solvent; or the step of coating the oriented polymer composition on the substrate or protective layer, removing the solvent and rubbing (rubbing method).

The above-mentioned solvents include water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl seleux, butyl selenium and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethyl acetate, etc. Glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and Ketone solvents such as 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 ; Chlorine-substituted hydrocarbon solvents such as chloroform and chlorobenzene, etc. These solvents may be used alone or in combination of two or more.

The concentration of the alignment polymer in the alignment polymer composition is in the range where the alignment polymer can be completely dissolved in the solvent, and the solid content conversion is preferably 0.1 to 20 mass % relative to the solution, and 0.1 to 10 mass % % is better.

The alignment polymer composition can also use a commercially available alignment film material as it is. Commercially available alignment film materials include SUNEVER (registered trademark) (manufactured by Nissan Chemical Industries, Ltd.), OPTOMER (registered trademark) (manufactured by JSR Corporation), and the like.

The method of coating the oriented polymer composition on the substrate or the protective layer includes spin coating, extrusion, gravure coating, die coating, bar coating, and coater methods. A coating method; and a conventional method such as a printing method such as a flexo method. When the polarizing film of an embodiment of the present invention is manufactured by a continuous manufacturing method in the form of Roll-to-Roll (roll-to-roll), the coating method can usually be a gravure coating method, a die coating method or a flexographic printing method. method of printing, etc.

By removing the solvent contained in the alignment polymer composition, a dry film of the alignment polymer can be formed. As a method of removing the solvent, a natural drying method, a ventilation drying method, a heating drying method, a vacuum drying method, and the like are mentioned.

The rubbing method includes a method of contacting a rubbing roll wound with a rubbing cloth and rotating a film of the oriented polymer formed on the base material or the protective layer by coating the oriented polymer composition on the base material or the protective layer and annealing the film. method.

The photo-alignment film is usually formed by coating a composition containing a polymer or monomer with a photoreactive group and a solvent (hereinafter, also referred to as a "photo-alignment film-forming composition") on a substrate or protective layer, Furthermore, it is obtained by irradiating polarized light (more preferably, polarized light UV). It is possible to arbitrarily control the direction of the alignment regulatory force by selecting the polarization direction of the irradiated polarized light, preferably a photo-alignment film.

The photoreactive group refers to a group that produces liquid crystal alignment ability by irradiating light. Specifically, by irradiating light, photoreactions such as molecular alignment induction or dissociation reaction, dimerization reaction, photocrosslinking reaction, or photolysis reaction are generated, which are the origin of liquid crystal alignment ability. Among the photoreactive groups, those having excellent alignment properties are preferably those that cause a dimerization reaction or a photocrosslinking reaction. The reactive group that can produce the above reaction is preferably an unsaturated bond, especially a double bond, which is selected from the group consisting of carbon-carbon double bond (C=C bond), carbon-nitrogen double bond (C=N bond) ), nitrogen-nitrogen double bond (N=N bond), and at least one group of the group consisting of carbon-oxygen double bond (C=O bond) is more preferable.

Examples of the photoreactive group having a C=C bond include a vinyl group, a polyalkenyl group, a stilbene group, a stilbazole, a stilbazolium group, a chalcone group, and a cinnamyl group. Examples of the photoreactive group having a C=N bond include groups having structures such as an aromatic Schiff base and an aromatic hydrazone. Examples of the photoreactive group having an N=N bond include an azophenyl group, an azonaphthyl group, an aromatic heterocyclic azo group, a disazo group, a formazan group, and the like, and an azobenzene oxide group. as the basic constructor. As a photoreactive group which has a C=O bond, a diphenyl ketone group, a coumarin group, an anthraquinone group, a maleimide group, etc. are mentioned. These groups may also have substituents such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.

The solvent of the composition for forming a photo-alignment film is preferably one that dissolves the polymer and monomer having a photoreactive group, and examples of the solvent include the solvents exemplified as the solvent of the above-mentioned alignment polymer composition.

The content of the polymer or monomer having a photoreactive group relative to the composition for forming a photoalignment film can be determined according to the type of the polymer or monomer having a photoreactive group and the thickness of the photoalignment film to be produced. It is suitably adjusted, and it is preferable to set it as 0.2 mass % or more, and it is especially preferable to set it as the range of 0.3-10 mass %. Moreover, you may contain polymer materials, such as polyvinyl alcohol and polyimide, and a photosensitizer in the range which does not impair the characteristic of a photoalignment film remarkably.

The method of applying the composition for forming a photo-alignment film to the substrate or the protective layer includes the same method as the method of applying the alignment polymer composition to the substrate or the protective layer. As the method of removing the solvent from the coated photo-alignment film-forming composition, for example, the same method as the method of removing the solvent from the alignment polymer composition can be exemplified.

Irradiation with polarized light can be in the form of direct irradiation of polarized light to the photo-alignment film-forming composition coated on the substrate or protective layer after removing the solvent; it can also be irradiated with polarized light from the side of the substrate or protective layer. And make the polarized light transmit and irradiate the form. Moreover, it is especially preferable that this polarized light system is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably a wavelength region in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) having a wavelength of 250 to 400 nm is particularly preferred. The light source used for the polarized light irradiation includes a xenon lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an ultraviolet laser such as KrF, and ArF, and the like, and a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and a metal halide lamp are more preferable. It is better because the luminous intensity of the ultraviolet light with the wavelength of 313 nm is higher. Polarized light can be irradiated by irradiating light from the above-mentioned light source through an appropriate polarizer. As such polarizers, polarizing filters, polarizers such as Glan-Thomson, Glan-Tayler, and wire grid polarizers can be used.

In addition, when rubbing or polarized light irradiation is performed, if shielding is performed, a plurality of regions (patterns) having different liquid crystal alignment directions can be formed.

The groove alignment film is a film with a concave-convex pattern or a plurality of grooves on the film surface. When liquid crystal molecules are arranged in a film having a plurality of linear grooves arranged at equal intervals, the liquid crystal molecules are aligned along the direction of the grooves.

The method for obtaining the trench alignment film may include the following methods: after exposing the surface of the photosensitive polyimide film through an exposure mask having a slit in the shape of a pattern, developing and rinsing to form a concave-convex pattern; The UV-curable resin layer before curing is formed on a plate-shaped master disk with grooves on the surface, and the resin layer is transferred to the substrate or protective layer and then cured; The UV-curable resin film is a method of pressing a roll-shaped master plate with a plurality of grooves to form unevenness, and then curing it. Specifically, the method described in Japanese Patent Laid-Open No. 6-34976 and Japanese Patent Laid-Open No. 2011-242743, etc. can be mentioned.

In order to obtain alignment with less alignment disorder, the width of the convex portion of the trench alignment film is preferably 0.05 μm to 5 μm, the width of the concave portion is preferably 0.1 μm to 5 μm, and the depth of the unevenness is preferably 2 μm or less. 0.01 μm to 1 μm is more preferable.

<protective layer>

In the polarizing film of one embodiment of the present invention, the protective layer is a cured film of a composition containing a polymerizable compound (hereinafter, also referred to as "the composition for forming a protective layer") and is laminated on one side of the polarizer or sides. The cured film of the composition for forming a protective layer refers to a film obtained by applying the composition for forming a protective layer to obtain a coating film, and then polymerizing the polymerizable compound contained in the coating film, that is, forming the protective layer The cured film of the composition is a film formed of a polymer containing the polymerizable compound. The protective layer helps to prevent the shrinkage and expansion of the polarizer, and the deterioration of the polarizer caused by temperature, humidity, ultraviolet rays, etc. The polarizer of one embodiment of the present invention can be stabilized by having a protective layer in the polarizer. polarizing properties. In a suitable embodiment of the present invention, from the viewpoint of obtaining a thin polarizing film, it is preferable to laminate the protective layer on one side of the polarizer.

In one embodiment of the present invention, the composition for forming a protective layer contains a monofunctional polymerizable compound (hereinafter, also referred to as "polymerizable compound (a)") as a polymerizable compound. That is, the protective layer is a cured film of the composition for forming a protective layer containing the polymerizable compound (a). In the present invention, the protective layer of the cured film of the composition for forming a protective layer is obtained by curing (polymerizing) a coating film obtained by coating the composition for forming a protective layer on a substrate or a polarizer. The cured film of the composition for forming a protective layer contains a polymer, and the polymer contains a structural unit derived from the polymerizable compound (a). In the present invention, it is not necessary to dry a coating film obtained by coating the composition for forming a protective layer on a base material or a polarizer. The above-mentioned protective layer is a layer obtained by polymerizing without drying a coating film obtained by coating the composition for forming a protective layer on a substrate or a polarizer (that is, the solvent in the composition for forming a protective layer). When the content is within the range described later), the resulting polarizing film can exhibit high polarizing performance. When the drying step (heating step) is performed in the production of the protective layer, the alignment of the compound exhibiting dichroism contained in the polarizer may become disordered, but in the present invention, it is considered that the alignment disorder can be suppressed because the drying step is unnecessary. .

The content of the polymerizable compound (a) in the composition for forming a protective layer is 60 mass % or more, preferably 70 mass % or more, more preferably, relative to the total polymerizable compounds contained in the composition for forming a protective layer. It is 80 mass % or more, More preferably, it is 85 mass % or more, Especially preferably, it is 88 mass % or more. When the content of the polymerizable compound (a) contained in the composition for forming a protective layer is not less than the above lower limit value, even if the composition for forming a protective layer does not contain a solvent, the fluidity of the composition for forming a protective layer is good. It is not necessary to perform a drying step, the polarization performance of the polarizer accompanying the drying step can be suppressed from being lowered, and a thin polarizing film excellent in workability can be obtained. Moreover, the upper limit of the content of the polymerizable compound (a) in the composition for forming a protective layer is more preferably 100 mass % or less with respect to the total amount of polymerizable compounds contained in the composition for forming a protective layer.

The molecular weight of the polymerizable compound (a) is preferably 300 or less, more preferably 250 or less, and still more preferably 210 or less. When the molecular weight of the polymerizable compound (a) contained in the composition for forming a protective layer is equal to or less than the above-mentioned upper limit value, the composition for forming a protective layer can be made uniform because the fluidity of the composition for forming a protective layer is more favorable. And thinly coated on the substrate or polarizer to obtain a more uniform thickness and thin protective layer. The lower limit value of the molecular weight of the polymerizable compound (a) contained in the composition for forming a protective layer is usually 80 or more. Moreover, when there are plural kinds of polymeric compounds (a) contained in the composition for forming a protective layer, the molecular weights of all kinds of polymeric compounds (a) contained in the composition for forming a protective layer are within the above-mentioned range. better.

In one embodiment of the present invention, the polymerizable compound (a) includes a compound having a (meth)acryloyl group, a compound having an epoxy group, a compound having a vinyl group, and the like. In the present invention, the polymerizable compound (a) is preferably a compound having a (meth)acryloyl group from the viewpoint of having high polymerizability and obtaining good protective performance. In addition, when the polymerizable compound (a) contains a compound having a (meth)acryloyl group, the protective layer is composed of a polymer containing a structural unit derived from a compound having a (meth)acryloyl group (for example, from A polymer composed of structural units derived from a compound having a (meth)acryloyl group).

Monofunctional compounds having a (meth)acryloyl group include, for example, (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate Alkyl esters of (meth)acrylic acid carbon number 1 to 16 such as 2-butyl acrylate and 3-butyl (meth)acrylate; cyclohexyl (meth)acrylate, 2-methyl (meth)acrylate cyclohexyl ester, tricyclo[5.2.1.02,6]decane-8-yl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate and isobornyl (meth)acrylate, etc. ( Cycloalkyl meth)acrylate with 4 to 16 carbon atoms; β-carboxyalkyl ester of (meth)acrylate with 2 to 14 carbon atoms; alkylated phenyl ester of (meth)acrylate with 2 to 14 carbon atoms; methyl Oxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate; (di)alkyl (meth)acrylamides having 4 to 16 carbon atoms; 2 to 16 carbon atoms β-Carboxyalkyl(meth)acrylamides of 14; alkylated phenyl(meth)acrylamides with carbon numbers from 2 to 14; methoxypolyethylene glycol(meth)acrylamides; benzene Oxypolyethylene glycol (meth)acrylamide, etc.

In a more preferred embodiment of the present invention, the polymerizable compound (a) is preferably a compound having a (meth)acryloyl group and a hydroxyl group from the viewpoint of obtaining better protective performance. Moreover, when the polymerizable compound (a) contains a compound having a (meth)acryloyl group and a hydroxyl group, the protective layer is composed of a polymer containing a structural unit derived from a compound having a (meth)acryloyl group and a hydroxyl group. (For example, a polymer composed of a structural unit derived from a compound having a (meth)acryloyl group and a hydroxyl group), more preferably a structural unit and a source derived from a compound having a (meth)acryloyl group A polymer derived from a structural unit of a compound having a (meth)acryloyl group and a hydroxyl group (for example, a structural unit derived from a compound having a (meth)acryloyl group and a structural unit derived from a compound having a (meth)acryloyl group and a hydroxyl group) The polymer is composed of the structural units of the compound).

In one aspect of the present invention, the content of the compound having a (meth)acryloyl group and a hydroxyl group is preferably 5% by mass or more relative to the total polymerizable compounds contained in the composition for forming a protective layer. , more preferably 30 mass % or more, still more preferably 50 mass % or more, preferably 99 mass % or less, more preferably 95 mass % or less. When the content of the compound having a (meth)acryloyl group and a hydroxyl group in the composition for forming a protective layer is equal to or more than the above lower limit value, the hydroxyl group has the effect of suppressing dissolution. In addition, it is possible to suppress a decrease in the polarization performance of the protective layer over time. When the content of the compound having a (meth)acryloyl group and a hydroxyl group in the composition for forming a protective layer is equal to or less than the above-mentioned upper limit value, the number of hydrogen bonds formed by the hydroxyl group is reduced, and the viscosity can be lowered.

The compound having a (meth)acryloyl group and a hydroxyl group is more preferably a compound represented by the following formula (1):

[In the formula, n represents an integer of 1 to 12, A ¹ represents O or NH, X ¹ represents a methylene group which may have a substituent, and when n is an integer of 2 or more, at least one of the methylene groups may also be replaced by Oxygen atom replacement, the above-mentioned substituents may be the same or different]. When the compound having a (meth)acryloyl group and a hydroxyl group is the compound represented by the above formula (1), more favorable protective performance can be obtained. It is presumed that this is because when the compound exhibiting dichroism dissolves/diffuses into the protective layer, the effect of suppressing dissolution is further obtained by the hydroxyl group at the molecular end of the polymer of the compound having a (meth)acryloyl group and a hydroxyl group in the protective layer. play.

In the above formula (1), n generally represents an integer of 1 to 12, preferably an integer of 2 to 10, more preferably an integer of 3 to 8, more preferably an integer of 4 to 6. When n is greater than or equal to the lower limit value, the hydroxyl group at the molecular end is not easily affected by the polymer main chain, and the effect of inhibiting dissolution of the hydroxyl group is easily exhibited, and when n is less than or equal to the upper limit value, since the X ¹ part is not easily aggregated, it is easy to It exerts the effect of hydroxyl group to inhibit dissolution. When n of the main chain is within the above range, when the compound exhibiting dichroism dissolves/diffuses into the protective layer, it is obtained from the hydroxyl group at the molecular end of the polymer of the compound having a (meth)acryloyl group and a hydroxyl group in the protective layer The anti-dissolution effect is easy to be further exerted.

In the above formula (1), A ¹ usually represents O or NH, more preferably O.

In the above formula (1), X ¹ represents a methylene group which may have a substituent. When n is an integer of 2 or more, at least one of the methylene groups may be substituted with an oxygen atom, and the above-mentioned substituents may be the same or different. Examples of the aforementioned substituent include an aliphatic or alicyclic hydrocarbon group having 2 to 10 carbon atoms (eg, 2 to 5 carbon atoms), or an aromatic hydrocarbon group having 5 to 20 carbon atoms (eg, 5 to 11). ^{X 1} in which at least one methylene group is replaced by an oxygen atom, for example, -(CH ₂ CH ₂ O) _m -CH ₂ CH ₂ -, -(CH ₂ CH(CH ₃ )O) _m -CH ₂ CH( CH ₃ )-[in the formula, m is an integer of 1 to 3] and the like.

In one embodiment of the present invention, the content of the compound represented by the above formula (1) is preferably 40% by mass or more, more preferably 50% by mass relative to the total polymerizable compounds contained in the composition for forming a protective layer. Above, it is more preferably 65 mass % or more, more preferably 99 mass % or less, more preferably 95 mass % or less. When the content of the compound represented by the above formula (1) in the composition for forming a protective layer is not less than the above lower limit value, due to the effect of suppressing dissolution obtained by the hydroxyl group, the decrease in polarization performance of the protective layer over time can be suppressed, and , since the fluidity of the composition for forming a protective layer is particularly good, the deterioration of the polarization performance of the polarizer accompanying the drying step can be further suppressed. When the content of the compound represented by the above formula (1) in the composition for forming a protective layer is equal to or less than the above upper limit value, hydrogen bonds formed by hydroxyl groups are reduced, and the viscosity can be lowered.

Examples of compounds having a (meth)acryloyl group and a hydroxyl group include hydroxyalkyl (meth)acrylates having 4 to 16 carbon atoms, hydroxycycloalkyl (meth)acrylates having 4 to 16 carbon atoms, and (meth)acrylates. Hydroxyalkylated phenyl acrylates having 2 to 14 carbon atoms, polyethylene glycol (meth)acrylates, and hydroxy(di)alkyl (meth)acrylamides having 4 to 16 carbon atoms, 2 to 16 carbon atoms 14 Hydroxyalkylated phenyl (meth) acrylamide, polyethylene glycol (meth) acrylamide, etc. More preferably, hydroxycycloalkyl (meth)acrylate having 4 to 6 carbon atoms and hydroxycycloalkyl (meth)acrylate having 4 to 16 carbon atoms, more preferably hydroxyalkyl acrylate having 4 to 6 carbon atoms and acrylic acid Hydroxycycloalkyl esters having 4 to 16 carbon atoms.

In a suitable embodiment of the present invention, the composition for forming a protective layer may contain, in addition to the polymerizable compound (a), a polymerizable compound having two or more functions (hereinafter, also referred to as "polymerizable compound (b)" ”) as a polymerizable compound, that is, a cured film that is a composition for forming a protective layer of a protective layer, may contain a structural unit derived from the polymerizable compound (a) and a structure derived from the polymerizable compound (b) A polymer composed of units.

In one embodiment of the present invention, the polymerizable compound (b) is, like the polymerizable compound (a), a compound having a (meth)acryloyl group, a compound having an epoxy group, and a compound having an epoxy group. Vinyl compounds, etc. In the present invention, the polymerizable compound (b) is preferably a compound having a (meth)acryloyl group from the viewpoint of having high polymerizability and obtaining favorable protective performance.

The bifunctional polymerizable compound includes, for example, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene Glycol diacrylate, bis(acrylooxyethyl) ether of bisphenol A, ethoxylated bisphenol A di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylic acid Esters, ethoxylated neopentyl glycol di(meth)acrylate and 3-methylpentanediol di(meth)acrylate, and methylenebisacrylamide, etc.

Trimethylolpropane tri(meth)acrylate; neopentaerythritol tri(meth)acrylate; sine(2-hydroxyethyl)trimeric isocyanate tris(meth)acrylate, for example, trifunctional or more polymerizable compounds ethoxylated trimethylolpropane tri(meth)acrylate; propoxylated trimethylolpropane tri(meth)acrylate; neotaerythritol tetra(meth)acrylate ; Dipiveaerythritol penta(meth)acrylate; Dipiveaerythritol hexa(meth)acrylate; Tripiveerythritol tetra(meth)acrylate; Acrylates; Tripivalerythritol Hexa (meth)acrylate; Tripivalerythritol Hepta (meth)acrylate; Tripivalerythritol Octa (meth)acrylate; Neopentaerythritol Tris (meth)acrylate ) The reactant of acrylate and acid anhydride; The reactant of dipival erythritol penta(meth)acrylate and acid anhydride; The reactant of tripivalerythritol hepta(meth)acrylate and acid anhydride; Caprolactone modification Trimethylolpropane tri(meth)acrylate; caprolactone-modified neotaerythritol tri(meth)acrylate; caprolactone-modified tris(2-hydroxyethyl)trimeric isocyanate tris(methyl) ) acrylate; caprolactone-modified neopentaerythritol tetra (meth)acrylate; caprolactone-modified dipepentaerythritol penta (meth)acrylate; (Meth)acrylate; Caprolactone-modified Trinepentaerythritol Tetra (meth)acrylate; Caprolactone-modified Trinepentaerythritol Penta (meth)acrylate; Caprolactone-modified Sanxin Pentaerythritol hexa(meth)acrylate; Caprolactone-modified Trinepentaerythritol Hepta(meth)acrylate; Caprolactone-modified Trinepentaerythritol Octa(meth)acrylate; Caprolactone The reactant of modified neopentaerythritol tri(meth)acrylate and acid anhydride; the reactant of caprolactone-modified dipivalerythritol penta(meth)acrylate and acid anhydride, and caprolactone-modified three new The reaction product of pentaneerythritol hepta(meth)acrylate and acid anhydride, etc. In addition, in the specific example of the polyfunctional acrylate shown here, (meth)acrylate type means acrylate or methacrylate. In addition, the caprolactone-modified system means that a ring-opened body of caprolactone or a ring-opened polymer is introduced between a (meth)acrylate compound-derived alcohol moiety and a (meth)acryloyloxy group .

In the present invention, from the viewpoint of obtaining a protective layer having a high surface hardness, the composition for forming a protective layer preferably contains a polymerizable compound (b) having a bifunctional or more functionalities, in particular, a trifunctional or more functional compound. More preferably, the composition contains a hexafunctional polymerizable compound (b). Moreover, the composition for protective layer formation may contain 1 type or 2 or more types of polymerizable compounds (b). When the composition for forming a protective layer contains the polymerizable compound (b), the polymer of the polymerizable compound contained in the protective layer is cross-linked, so that not only the surface hardness of the protective layer is increased, but also the polarizing film can be less exposed to the external environment. the dependency.

When the composition for forming a protective layer contains the polymerizable compound (b), the content of the polymerizable compound (b) contained in the composition for forming a protective layer is based on the total amount of polymerizable compounds contained in the composition for forming a protective layer. 20 mass % or less is preferable, 15 mass % or less is more preferable, 12 mass % or less is further more preferable, 1 mass % or more is preferable, 5 mass % or more is more preferable, and 8 mass % or more is more preferable. When the content of the polymerizable compound (b) contained in the composition for forming a protective layer is not more than the above-mentioned upper limit value, the fluidity of the composition for forming a protective layer is good even when the composition for forming a protective layer does not contain a solvent, Therefore, it is not necessary to perform a drying step, and the polarization performance of the polarizer can be suppressed from being lowered due to the drying step, and a thin polarizing film can be obtained. When the content of the polymerizable compound (b) contained in the composition for forming a protective layer is equal to or more than the above lower limit value, a protective layer having high surface hardness can be obtained.

In addition, the composition for preparing the protective layer has conventionally contained a large amount of polymerizable compounds of dichroism or more, especially trifunctional or more (more particularly, hexafunctional or more). The surface hardness of the protective layer can be improved. On the other hand, since the polymerizable compound of bifunctional or higher, especially trifunctional or higher (in particular, hexafunctional or higher) has a relatively bulky structure, in order to obtain a uniform and thin protective layer, it is necessary to increase the amount of the protective layer in the protective layer. The solvent content improves flowability. However, the transfer of the compound showing dichroism is induced by the added solvent. In a more preferred embodiment of the present invention, by using the above-mentioned specific composition for forming a protective layer, the transfer of the compound exhibiting dichroism can be suppressed, and a uniform and thin protective layer can be obtained.

In the present invention, the content of the structural unit derived from the polymerizable compound (a) in the protective layer is preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 70% by mass or more, relative to the polymer constituting the protective layer. 80 mass % or more is preferable, 85 mass % or more is especially preferable, 88 mass % or more is especially preferable, and 100 mass % or less is more preferable. When the content of the structural unit derived from the polymerizable compound (a) in the protective layer is not less than the above lower limit value, even if the composition for forming a protective layer does not contain a solvent, the fluidity of the composition for forming a protective layer is good. , it is not necessary to carry out a drying step, the polarization performance of the polarizer can be suppressed from being lowered due to the drying step, and a thinner polarizing film can be obtained with excellent workability.

The composition for forming a protective layer may contain a polymer or oligomer obtained by polymerizing a polyfunctional acrylate. Examples of polymers or oligomers obtained by polymerizing polyfunctional acrylates include aliphatic, alicyclic, or aromatic urethane acrylate polymers or oligomers.

The content of a polymer or oligomer obtained by polymerizing a polyfunctional acrylate in the composition for forming a protective layer is preferably 20% by mass or less, more preferably 15% by mass or less, relative to the solid content of the composition for forming a protective layer. , more preferably 10 mass % or less, more preferably 1 mass % or more, more preferably 5 mass % or more, more preferably 8 mass % or more. When the content of the polymer or oligomer is equal to or less than the upper limit, the fluidity of the composition for forming a protective layer is good, and a uniform and thin protective layer can be obtained. When content of the said polymer or oligomer is more than the said lower limit, the time-dependent fall of the polarizing performance of the polarizing film obtained can be suppressed further. In addition, the solid content system means the total component after removing a solvent from the composition for protective layer formation.

The composition system for forming a protective layer may contain a solvent. The solvent content in the composition for forming a protective layer is preferably 5 mass % or less, more preferably 3 mass % or less, more preferably 1 mass % or less, and particularly preferably 0 with respect to the total amount of the protective layer-forming composition. quality%. When the solvent content in the composition for forming a protective layer is not more than the above-mentioned upper limit value, the solvent content in the protective layer can be kept low even if the drying step is not performed when manufacturing the polarizing film of one embodiment of the present invention. There is no decrease in the polarization performance of the polarizing film due to the drying step, and the decrease in the polarization performance of the time-dependent polarizing film can be further suppressed. Moreover, the solvent content of the composition for forming a protective layer is particularly preferably 0 mass % (more preferably 5 mass % or less). Even if the composition does not contain a solvent (or the solvent content in the protective layer-forming composition is very small), a uniform and thin coating film can be obtained. The lower limit value of the solvent content in the composition for forming a protective layer is usually 0 mass % or more with respect to the total amount of the composition for forming a protective layer.

According to the present invention, the protective layer can be produced without performing the drying step, and since the solvent content in the composition for forming the protective layer can be made very small as described above, the polarization performance of the polarizing film can be suppressed from decreasing in the production step of the polarizing film. , and it is also possible to suppress the degradation of the polarizing performance of the polarizing film over time.

Moreover, the composition for protective layer formation may contain the additive normally used for a curable composition as needed. Examples of such additives include the above-mentioned polymerization initiators, sensitizers, polymerization inhibitors, levelers, and reactive additives, as well as ion scavengers, antioxidants, chain transfer agents, polymerization accelerators (polyols, etc.), Sensitivity additives, light stabilizers, adhesion imparting agents, thermoplastic resins, fillers, flow regulators, plasticizers, defoaming agents, silane coupling agents, pigments, antistatic agents, and ultraviolet absorbers, etc.

The content of the polymerization initiator in the composition for forming a protective layer can be appropriately adjusted according to the type and amount of the polymerizable compound, and is based on 100 parts by mass of the content of the polymerizable compound from the viewpoint of initiator efficiency , the starting agent is usually 0.1 to 40 parts by mass, preferably 0.2 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0.5 to 8 parts by mass.

When the composition for forming a protective layer contains a leveling agent, from the viewpoint of smoothing the obtained protective layer, the content of the leveling agent in the composition for forming a protective layer with respect to 100 parts by mass of the polymerizable compound content It is preferably 0 to 6 parts by mass, more preferably 0.01 to 5 parts by mass, still more preferably 0.05 to 5 parts by mass, and particularly preferably 0.08 to 3 parts by mass. The leveling agent may contain 2 or more types.

The viscosity of the composition for forming a protective layer is preferably 120 cps or less at 27° C., more preferably 80 cps or less, and more preferably 50 cps or less. When the viscosity of the composition for forming a protective layer at 27°C is less than or equal to the above upper limit value, the fluidity of the composition for forming a protective layer is more favorable, so that the composition for forming a protective layer can be uniformly and thinly coated on the base. On the material or polarizer, a protective layer with a more uniform thickness and a thin shape can be obtained, and the pump efficiency is excellent in the manufacturing process of the polarizing film. Moreover, the lower limit value of the viscosity of the composition for protective layer formation is normally 5 cps or more. The viscosity can be measured according to JIS K7367.

In a more preferred embodiment, when the solvent content in the composition for forming a protective layer is within the above range, the viscosity of the composition for forming a protective layer is equal to or less than the above upper limit value.

The solid content of the composition for forming a protective layer is preferably 95% by mass or more, more preferably 100% by mass, with respect to the total mass of the composition for forming a protective layer. When the solid content of the above-mentioned composition is more than the above-mentioned lower limit value, the composition for forming the protective layer can be uniformly and thinly coated on the base material or the polarizer even without a drying step, so that a thicker film can be obtained. It is a uniform and thin protective layer, so a polarizing film with excellent polarization performance and heat resistance can be obtained.

The thickness of the protective layer is not particularly limited, and is usually 10 μm or less, preferably 0.15 to 5 μm, more preferably 0.5 to 4 μm, and even more preferably 1.0 to 3 μm.

The surface of the polarizer without the protective layer may also have a surface treatment layer, for example, an optical layer such as a hard coat layer, an anti-reflection layer, an anti-adhesion layer, an anti-glare layer or a diffusion layer.

The purpose of the hard coat layer is to prevent scratches on the surface of the polarizing film. For example, a hard coat with excellent hardness and sliding properties can be obtained by using ultraviolet curable resins such as acrylic and polysiloxane. form the surface of the protective layer, etc. The purpose of the anti-reflection layer is to prevent the reflection of external light on the surface of the polarizing film, which can be achieved according to the formation of the conventional anti-reflection film. In addition, the purpose of the anti-adhesion layer is to prevent adhesion with the adjacent layer.

In addition, the anti-glare layer prevents the reflection of external light on the surface of the polarizing film and hinders the identification of the transmitted light of the polarizing film. In this way, the surface of the protective layer is formed by imparting a fine concavo-convex structure. The fine particles contained to form the above-mentioned surface fine concavo-convex structure include, for example, silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, indium oxide, cadmium oxide, antimony oxide, etc. having an average particle size of 0.5 to 50 μm. Inorganic microparticles that may have electrical conductivity; transparent microparticles such as organic microparticles composed of cross-linked or uncross-linked polymers. When the surface fine concavo-convex structure is formed, the content of fine particles is usually 2 to 50 parts by mass, preferably 5 to 25 parts by mass, relative to 100 parts by mass of the transparent resin forming the surface fine concave and convex structure. The anti-glare layer may also serve as a diffusion layer (viewing angle widening function, etc.) for expanding the viewing angle by diffusing the light transmitted through the polarizing film.

In addition, the anti-reflection layer, anti-adhesion layer, diffusion layer, anti-glare layer and the like may be provided on the protective layer itself and integrated, or may be provided separately from the protective layer as an optical layer.

In one embodiment of the present invention, the polarizing film system has excellent heat resistance. Here, heat resistance means that the polarization performance of the polarizing film is not easily changed over time under high temperature conditions, for example, the change rate of the visual sensitivity correction polarization degree Py after being kept at 150°C dry and in an atmospheric environment for 1 hour. (The rate of change of polarization degree), based on the corrected polarization degree Py of the visual sensitivity before holding, it is preferably 10% or less, more preferably 5% or less, and more preferably 3% or less. After holding under the same conditions for 1 hour The change rate of the visual sensitivity corrected single transmittance Ty (single transmittance change rate), based on the visual sensitivity corrected single transmittance Ty before holding, is preferably 10% or less, more preferably 5% or less, More preferably, it is 3% or less. In the method of manufacturing a display device using a polarizing film, there is a step of heating the polarizing film. Due to this step, the polarization performance of the polarizing film may be deteriorated. Since the polarizing film system of an embodiment of the present invention has excellent heat resistance, the polarization performance is not easily deteriorated in the process of manufacturing the display device, and a product with A display device with excellent image display function. In addition, the lower limit values of the polarization degree change rate and the individual transmittance change rate are each usually 0% or more.

The sensitivity-corrected transmittance (Ty) and the sensitivity-corrected polarization (Py) in this specification can be measured as follows.

The transmittance (T ¹ ) and ^{Transmittance (T 2} ) in the direction of the absorption axis. The reference side of the fixture is provided with a filter screen with 50% of the cutting light. The transmittance at each wavelength was calculated using the following formula (2), and the sensitivity-corrected transmittance (Ty) was calculated by correcting the sensitivity according to the 2-degree field of view (C light source) of JIS Z 8701. The degree of polarization at each wavelength was calculated using the following formula (3). Then, the sensitivity correction was performed according to the 2-degree field of view (C light source) of JIS Z 8701, and the sensitivity correction polarization degree (Py) was calculated.

Monomer transmittance (%)=(T ¹ +T ² )/2 (2)

Polarization (%)={(T ¹ -T ² )/(T ¹ +T ² )}×100 (3)

The above-mentioned polarizing film system can be produced, for example, according to a method comprising the following steps: The above-mentioned composition for forming a protective layer containing a polymerizable compound is coated on the above-mentioned polarizer containing the above-mentioned compound exhibiting dichroism to form a coating film. The coating step; and • the polymerizing step of polymerizing the polymerizable compound to form a protective layer. Moreover, the coating film is hardened by the polymerization of the polymerizable compound.

In the polymerization step, the polymerizable compound can be polymerized by heating and irradiating active energy rays. In a more preferred embodiment of the present invention, from the viewpoint of improving the polarization performance and heat resistance of the polarizing film obtained, the polymerizable compound can be polymerized by irradiating active energy rays. The active energy rays include ultraviolet rays, electron beams, and the like.

In the present invention, a drying step of drying the polarizing film is unnecessary. If the drying step (heating step) is performed during the preparation of the protective layer, the alignment of the dichroic compound contained in the polarizer may be disturbed. According to the present invention, since the drying step is unnecessary, the alignment disturbance can be suppressed. As a result, a thin polarizing film having a protective layer with a low solvent content can be produced, and the obtained polarizing film has excellent polarizing performance and heat resistance. Moreover, although heating may be performed, for example, it is preferable to perform heating at a temperature of 40° C. or lower.

In addition, the above-mentioned polarizing film may be produced by another method. For example, it may be produced by a method including the following steps: - Coating the above-mentioned composition for forming a protective layer containing a polymerizable compound on a substrate to form a coating film the coating step; the polymerization step of polymerizing the polymerizable compound to form a protective layer; and the polarizer forming step of forming a polarizer on the protective layer. The polarizer can also be formed after the alignment film is formed on the protective layer. Moreover, after forming a protective layer, you may remove a base material. In addition, after the polarizer forming step, a polarizing film in which protective layers are arranged on both sides of the polarizer can also be produced by performing the following steps: coating the above-mentioned composition for forming a protective layer containing a polymerizable compound on the polarizer A coating step to form a coating film; and a polymerization step to polymerize the polymerizable compound to form a protective layer. Instead of the base material, an adherend such as a display device body can also be used.

In the present invention, a glass substrate and a plastic substrate are mentioned as the substrate, and a plastic substrate is more preferable. Plastic substrates are better than glass substrates in terms of roll-to-roll processability and higher productivity. Examples of plastics constituting the plastic base material include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylates ; polyacrylate; cellulose triacetate, cellulose diacetate and cellulose acetate propionate and other cellulose esters; polyethylene naphthalate; polycarbonate; Ketones; plastics such as polyphenylene sulfide and polyphenylene ether.

Commercially available cellulose ester substrates include "FUJITAC FILM" (manufactured by Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY", and "KC4UY" (the above, manufactured by Konica Minolta Opto Co., Ltd.).

Commercially available cyclic olefin resins include "Topas" (registered trademark) (manufactured by Ticona Corporation (independent)), "ARTON" (registered trademark) (manufactured by JSR Corporation), "ZEONOR" (registered trademark), "ZEONEX" ” (registered trademark) (above, Japan ZEON Co., Ltd.) and “APEL” (registered trademark) (Mitsui Chemicals Co., Ltd.). Such a cyclic olefin-based resin can be formed into a film by conventional means such as a solvent casting method and a melt extrusion method as a base material. Commercially available cyclic olefin-based resin substrates can also be used. Commercially available cyclic olefin resin substrates include "S-SINA" (registered trademark), "SCA40" (registered trademark) (above, manufactured by Sekisui Chemical Industry Co., Ltd.), "ZEONOR FILM" (registered trademark) (OPTES Joint-stock company) and "ARTON FILM" (registered trademark) (JSR joint-stock company).

Another embodiment of the present invention provides an elliptical polarizing plate and a circular polarizing plate including the above-described polarizing film and retardation film. In one embodiment of the present invention, when a retardation film is laminated on the polarizing film, it is preferable to laminate so that the slow axis (optical axis) of the retardation film and the absorption axis of the polarizing film are substantially 45°. . By laminating the slow axis (optical axis) of the retardation film and the absorption axis of the polarizing film at substantially 45°, a function as a circularly polarizing plate can be obtained. In addition, the slow axis of the retardation film and the absorption axis of the polarizing film may be laminated so as to be substantially coincident or orthogonal. By making the slow axis of the retardation film and the absorption axis of the polarizing film substantially the same or orthogonal, it can also function as an optical compensation film. In addition, substantially 45° generally means the range of 45±5°, and substantially coincident or orthogonal generally means the range of 0±5° or the range of 90±5°.

The elliptically polarizing plate and the circularly polarizing plate can be produced by, for example, a step including a step of applying an adhesive to one side of a polarizing film and bonding the polarizing film to a retardation film through the adhesive.

The retardation film is an optical film showing optical anisotropy, and is a thin film used to convert linearly polarized light into circularly polarized light and elliptically polarized light, or vice versa. The retardation film can be, for example, made of polyvinyl alcohol, polycarbonate, polyester, polyarylate, polymethacrylate, polyimide, polyolefin, polycycloolefin (norbornene, polymers of tetracyclododecene or derivatives of these), polystyrene, polystilbene, polyethertene, polyvinylidene fluoride/polymethyl methacrylate, liquid crystal polyester, acetic acid A polymer film composed of polymers such as cellulose, ethylene-vinyl acetate copolymer saponification, polyvinyl chloride, etc., stretched film obtained by stretching about 1.01 to 6 times, etc. In particular, a polymer film obtained by uniaxially or biaxially stretching a polycarbonate film and a polycycloolefin film is preferable. Moreover, the thin film which expresses optical anisotropy by coating/alignment of a liquid crystal compound can also be used as a retardation film.

The above retardation film is preferably to satisfy the following formula (X): Re(450nm)/Re(550nm)<1 (X) In this case, since the retardation film has reverse wavelength dispersion, the retardation film is provided The display device can reduce coloring during black display.

The value of Re(450nm)/Re(550nm) can be appropriately selected. In addition, Re(λ) represents the front retardation value with respect to light of wavelength λnm.

Another embodiment of the present invention can also provide a display device including the above-mentioned polarizing film, elliptical polarizing plate or circular polarizing plate. A display device refers to a device having a display element, including a light-emitting element or a light-emitting device as a light-emitting source. The display device includes a liquid crystal display device, an electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (for example, an electric field emission display device (FED), a surface electric field emission device) Display device (SED)), electronic paper (display device using electronic ink and electrophoresis element, plasma display device, projection display device (such as GLV; Grating Light Valve) display device, with digital micromirror element (DMD; display device of digital micromirror device) and piezoelectric ceramic displays, etc. Liquid crystal display devices also include transmissive liquid crystal display devices, transflective liquid crystal display devices, reflective liquid crystal display devices, direct-view liquid crystal display devices and Any of projection type liquid crystal display devices, etc. These display devices can be display devices that display two-dimensional images, and can also be stereoscopic display devices that display three-dimensional images. In particular, the above-mentioned polarizing films, elliptically polarizing plates and circular polarizing plates can be It is effectively used in liquid crystal display devices and electroluminescence (EL) display devices. Since the display device of another embodiment of the present invention has a polarizing film with excellent polarization performance and heat resistance, it has excellent image display function, and even after It is also stable and can play this function.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples at all. In addition, "%" and "part" in an Example and a comparative example mean "mass %" and "mass part", respectively, unless it is notified in advance.

[Manufacture of the composition for forming a polarizer]

The following components were mixed and stirred at 80° C. for 1 hour to obtain a composition for forming a polarizer. As the compound showing dichroism, the azo dye described in the Examples of JP-A No. 2015-165302 was used.

(Non-colorable polymerizable liquid crystal compound)

(compounds exhibiting dichroism)

(other ingredients)

‧Polymerization initiator; 6 parts of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (IRGACURE369; manufactured by Ciba Specialty Chemicals)

‧Leveling agent; polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 0.5 part

‧Solvent; 350 parts of o-xylene

[Measurement of phase transition temperature]

A 2 mass % aqueous solution (alignment polymer composition) of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied on a glass substrate by spin coating and dried , forming a film with a thickness of 100 nm. Next, an alignment film is formed by subjecting the obtained film surface to a rubbing treatment. The friction treatment system uses a semi-automatic friction device (trade name: LQ-008, manufactured by Changyang Engineering Co., Ltd.), and a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Chemical Co., Ltd.) is used, and the pressing amount is 0.15 mm. , under the conditions of 500rpm and 16.7mm/s.

The composition for forming a polarizer was coated on the alignment film produced as described above by spin coating, heated and dried on a hot plate at 120° C. for 1 minute, and then rapidly cooled to room temperature to form the above-mentioned composition. The coating is dried on the alignment film. The temperature of the dry film was again raised to 120° C. on a hot plate, and then observed with a polarizing microscope at the time of cooling, and the phase transition temperature was measured. As a result, it was confirmed that the phase transitioned to a nematic liquid crystal phase at 115°C, to a smectic A phase at 105°C, and to a smectic B phase at 74°C.

[Production of protective layer-forming composition (coating liquids (1) to (14))]

The components shown in Table 1 were mixed at the stated mass ratios and stirred at room temperature for 1 hour to obtain coating liquids (1) to (14) as protective layer-forming compositions, respectively. The viscosities of the obtained coating liquid (1) to the coating liquid (14) were measured according to JIS K7367. It shows the results in Table 1.

In Table 1, A1 is isobornyl acrylate, A2 is 4-hydroxybutyl acrylate, A3 is 1,4-cyclohexanedimethanol monoacrylate, A4 is dimethylacrylamide, and A5 is dipivaloyl Tetraol hexaacrylate, B1 is UV-5650B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., B2 is UV-3000B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., C1 is 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxy ring Hexyl methyl ester C2 is 2-ethylhexyl glycidyl ether, D1 is IRGACURE907 made by BASF, D2 is CPI-100P made by SAN-APRO, and E1 is MEGAFACE F-554 made by DIC.

[Example 1] Manufacture and evaluation of polarizer 1. Formation of polarizer

The above-mentioned composition for forming a polarizer was coated on the above-obtained alignment film by a spin coating method, heated and dried on a hot plate at 120° C. for 1 minute, and then rapidly cooled to room temperature (a smectic shape was displayed when the temperature was lowered). temperature of the liquid crystal phase) or lower, and a first dry coating is formed on the alignment film. The liquid crystal state of the non-colorable polymerizable liquid crystal compound contained in the first dry film is a smectic B phase.

^{Next, the first dried film was irradiated with ultraviolet rays at an exposure amount of 2,400 mJ/cm 2} (365 nm reference) using a UV irradiation device (SPOT CURE SP-7; manufactured by USHIO Electric Co., Ltd.), so that the first dried film contained in the first dried film. The non-colorable polymerizable liquid crystal compound is polymerized while maintaining the liquid crystal state of the above-mentioned non-colorable polymerizable liquid crystal compound, and a polarizer is formed from the first dry film to obtain a laminate 1 . The thickness of the polarizer at this time was measured to be 1.8 μm using a laser microscope (OLS3000 manufactured by Olympus Co., Ltd.).

2. X-ray diffraction measurement

With respect to the polarizer of the obtained laminated body 1, X-ray diffraction was measured using an X-ray diffraction apparatus X'Pert PRO MPD (manufactured by Spectris Co., Ltd.). Under the conditions of using Cu as the target, X-ray tube current of 40 mA, and X-ray tube voltage of 45 kV, the generated X-ray transmission fixed divergence slit 1/2° is incident from the rubbing direction, and the scanning range 2θ=4.0 to 40.0 As a result of measuring the range of ° with a displacement scan of 2θ=0.01671°, a sharp diffraction peak (Bragg peak) with a peak width at half maximum (FWHM)=about 0.187° can be obtained around 2θ=20.22°. Also, the same result was obtained from the incident in the direction perpendicular to the rubbing direction. The order cycle (d) obtained from the tip position is about 4.39 Å, which indicates that a structure reflecting a higher-order smectic liquid crystal phase is formed.

3. Polarizing film manufactured by forming a protective layer

The above-mentioned coating liquid (1) was applied as a composition for forming a protective layer on the polarizer of the laminate 1 by spin coating, and a UV irradiation apparatus (SPOT CURE SP-7; manufactured by USHIO Electric Co., Ltd.) was used. The polarizing film (1) was produced by irradiating ultraviolet rays with an exposure amount of 400 mJ/cm ² (365 nm reference) to form a protective layer on the polarizer. The thickness of the protective layer at this time was measured to be 2.8 μm by using a laser microscope (OLS3000 manufactured by Olympus Co., Ltd.).

4. Heat resistance test of polarizing film

Using a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation), the visibility correction polarization degree Py and the visibility correction monomer transmittance Ty of the obtained polarizing film (1) were measured. Next, the polarizing film (1) was put into a dry oven at 150° C. and 1 hour later, the sensitivity-corrected polarization degree Py and the sensitivity-corrected single transmittance Ty were measured again to calculate the rate of change before and after the heat resistance test. The results are shown in Table 2.

[Examples 2 to 12]

Polarizing films (2) to (12) were each produced in the same manner as in Example 1, except that each of the coating liquids (2) to (12) was used instead of the coating liquid (1). Durability tests of polarizing films (2) to (12) were carried out. The results are shown in Table 2. In addition, the thicknesses of the protective layers of the polarizing films (2) to (12) were each 2.8 μm.

[Comparative Examples 1 and 2]

Polarizing films (13) and (14) were each produced in the same manner as in Example 1, except that the coating liquid (13) or the coating liquid (14) was used instead of the coating liquid (1). Durability tests of polarizing films (13) and (14) were carried out. The results are shown in Table 2. Moreover, the thickness of the protective layer of the polarizing films (13) and (14) is 2.8 micrometers, respectively.

Based on the total polymerizable compounds in the coating liquids (1) to (14), the content of the monofunctional polymerizable compound (content of the polymerizable compound (a)) and the content of the compound having a methacryloyl group and a hydroxyl group ( content of the hydroxyl-containing compound) and content of the compound represented by formula (1) (compound (1) content). It shows the results in Table 2.

In Examples 1 to 12, the rate of change of the polarization degree Py and the individual transmittance Ty was small, and the temporal change of the polarization performance was suppressed. On the other hand, in Comparative Examples 1 and 2, the rate of change of the polarization degree Py and the single transmittance Ty was large.

1‧‧‧Polarizer

2‧‧‧Protective layer

3‧‧‧Protective layer

10‧‧‧Polarizing film

Claims (10)

A polarizing film, which is a polarizing film formed by laminating a polarizer and a protective layer of a polymer containing a compound showing dichroism and a non-coloring polymerizable liquid crystal compound, the protective layer is a hardening of a composition containing a polymerizable compound film, and the content of the monofunctional polymerizable compound in the composition is 60% by mass or more relative to the total polymerizable compounds contained in the composition. The polarizing film according to claim 1, wherein the viscosity of the composition is 120 cps or less at 27°C. The polarizing film according to claim 1 or 2, wherein the monofunctional polymerizable compound contains a (meth)acryloyl group-containing compound. The polarizing film according to claim 1 or 2, wherein the monofunctional polymerizable compound contains a compound having a (meth)acryloyl group and a hydroxyl group. The polarizing film according to claim 4, wherein the compound having a (meth)acryloyl group and a hydroxyl group is represented by the following formula (1):

In the formula, n represents an integer of 1 to 12, A ¹ represents O or NH, X ¹ represents a methylene group which may also have a substituent, and when n is an integer of 2 or more, at least one of the methylene groups may also be replaced by oxygen. Atoms are substituted and the aforementioned substituents may be the same or different. The polarizing film according to claim 1 or 2, wherein the polarizer is a polymer containing 80% by mass or more of a non-colorable polymerizable liquid crystal compound relative to the total mass of the polarizer, and the non-colorable polymer The polymer system of the polymerizable liquid crystal compound exhibits a smectic liquid crystal phase, and the compound exhibiting dichroism is oriented to and contained in the polymer of the non-colorable polymerizable liquid crystal compound. The polarizing film according to claim 1 or 2, wherein the compound exhibiting dichroism is an azo dye. A circular polarizing plate is provided with the polarizing film and retardation film as described in any one of claims 1 to 7 of the patent application scope. The circularly polarizing plate according to claim 8, wherein the retardation film system satisfies the following formula (X): Re(450nm)/Re(550nm)<1 (X) In the formula, Re(λ) Indicates the frontal retardation value for light of wavelength λnm. A display device is provided with the polarizing film as described in any one of claims 1 to 7 of the scope of the application, or the circular polarizing plate as described in claim 8 or 9 of the scope of the application.

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