TWI791750B - Polymerizable liquid crystal composition, polarizing film and method for producing the same, polarizing plate and display device - Google Patents

Abstract

An objective of the present invention is to provide a polymerizable liquid crystal composition suitable for forming a polarizing film (polarizer) which has a high suppressing effect on the denaturation of a dichroic dye when exposed to sunlight and can suppress the deterioration of the polarization performance with time.

The polymerizable liquid crystal composition of the present invention comprises a polymerizable liquid crystal compound having at least one polymerizable group and exhibiting smectic liquid crystallinity, a dichroic dye and an antioxidant; wherein, the polymerizable group contained in the polymerizable liquid crystal compound is a radical polymerizable group, and the antioxidant satisfies the formula (1) in relation to the polymerizable liquid crystal compound. 0.8℃ ≦ T1-T2 (1) [In the formula, T1 is a phase transition temperature to liquid crystal phase developed at the lowest temperature side when the phase transition temperature is measured while cooling to 23℃ at 5℃/min after heating the polymerizable liquid crystal compound to 130℃ in the atmosphere; T2 is a phase transition temperature to liquid crystal phase developed at the lowest temperature side when the phase transition temperature is measured while cooling to 23℃ at 5℃/min after heating a mixture consisting of 100 parts by mass of the polymerizable liquid crystal compound and 1 part by mass of the antioxidant to 130℃ in the atmosphere.]

Description

Polymerizable liquid crystal composition, polarizing film, manufacturing method thereof, polarizing plate, and display device

The present invention relates to a polymerizable liquid crystal composition, a polarizing film and a manufacturing method thereof, a polarizing plate, and a display device equipped with the polarizing plate.

Conventionally, in various image display panels such as liquid crystal display panels and organic electroluminescence (organic EL) display panels, polarizing plates are used by being bonded to image display elements such as liquid crystal cells or organic EL display elements. As for such a polarizing plate, a polarizing plate having a structure in which a protective layer such as a triacetyl cellulose film is laminated on at least one side of the polarizing plate with an adhesive layer interposed therebetween; the aforementioned polarizing plate is made of a polyvinyl alcohol-based resin film The adsorption orientation is formed by compounds showing dichroism such as iodine or dichroic dyes.

In recent years, displays such as image display panels have been continuously required to be thinner, and polarizers or polarizers, which are one of their constituent elements, have also been required to be thinner. To meet such demands, for example, thin host-guest polarizers composed of a polymerizable liquid crystal compound and a compound exhibiting dichroism have been proposed (Patent Document 1 and Patent Document 2).

[Prior Art Literature] [Patent Document]

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

[Patent Document 2] Japanese Unexamined Patent Publication No. 2013-37353

Furthermore, as displays are used in various places including outdoors in recent years, development of polarizers excellent in light resistance has been demanded.

Therefore, the object of the present invention is to provide a polymerizable liquid crystal composition which has a high inhibitory effect on the modification of dichroic pigments when exposed to sunlight, and is suitable for forming polarized light which can suppress the degradation of polarizing performance over time. film (polarizer).

The inventors of the present invention have completed the present invention as a result of earnest research in order to solve the above-mentioned problems. That is, the present invention provides the following preferred aspects.

[1] A polymerizable liquid crystal composition comprising: a polymerizable liquid crystal compound having at least one polymerizable group and exhibiting smectic liquid crystallinity, a dichroic dye, and an antioxidant; The polymerizable group possessed by the liquid crystal compound is a free radical polymerizable group; the relationship between the aforementioned antioxidant and the aforementioned polymerizable liquid crystal compound satisfies the formula (1): 0.8°C≦T1-T2 (1)

In the formula, T1 is the phase transition to the liquid crystal phase that appears on the lowest temperature side when the temperature of the above-mentioned polymerizable liquid crystal compound is raised to 130°C in the air, and then cooled to 23°C at 5°C/min while measuring the phase transition temperature. Temperature: T2 means that the mixture formed by 100 parts by mass of the aforementioned polymerizable liquid crystal compound and 1 part by mass of the aforementioned antioxidant is heated to 130°C in the atmosphere, and then cooled to 23°C at 5°C/min while measuring the phase transition Temperature, the phase transition temperature to the liquid crystal phase that appears on the lowest temperature side.

[2] The polymerizable liquid crystal composition as described in the aforementioned item [1], which further includes a solvent.

[3] The polymerizable liquid crystal composition according to [1] or [2] above, wherein the dichroic dye is an azo dye.

[4] The polymerizable liquid crystal composition according to any one of items [1] to [3] above, wherein the polymerizable group of the polymerizable liquid crystal compound is an acryloxy group.

[5] The polymerizable liquid crystal composition according to any one of the above items [1] to [4], which contains 0.1 to 15 parts by mass of an antioxidant based on 100 parts by mass of the polymerizable liquid crystal compound.

[6] The polymerizable liquid crystal composition according to any one of items [1] to [5] above, wherein the antioxidant is selected from the group consisting of phenolic compounds, alicyclic alcohol compounds, and amine compounds. At least 1 species in the group.

[7] The polymerizable liquid crystal composition according to any one of the aforementioned items [1] to [6], wherein the antioxidant has any one of formula (2), formula (3) and formula (4) structure;

In formula (2) and formula (3), R ₁ to R ₅ are independently -H, -OH, -NH ₂ , a branched or non-branched alkyl group with 1 to 12 carbons, or a carbon number 1 to 12 branched or non-branched alkoxy groups; in formula (2) and formula (3), at least one of each of R ₁ to R ₅ is -OH or -NH ₂ .

[8] The polymerizable liquid crystal composition as described in item [7] above, wherein the antioxidant is a compound represented by formula (5); A ₁ -L ₁ -(A ₂ -L ₂ ) _n -A ₃ ( 5)

In the formula, _L1 and _L2 are independently a single bond or a divalent linking group, _A1 is the base shown in formula (2), formula (3) or formula (4), _A2 is the formula (6) Or the base shown in formula (7), A ₃ is the base shown in formula (8) or formula (9), n is an integer from 0 to 2, when n is 2, 2 A ₂ can be mutually the same, also may be different;

In formula (2) and formula (3), R ₁ to R ₅ are the same definitions as the aforementioned item [7];

In formula (6) and formula (7), R ₆ to R ₉ are independently -H, -OH, -NH ₂ , branched or non-branched alkyl with 1 to 12 carbons, or 1 carbon to 12 branched or unbranched alkoxy groups;

In formula (8) and formula (9), R ₁₀ to R ₁₄ are independently -H, -OH, -NH ₂ , a branched or non-branched alkyl group with 1 to 12 carbons, or a carbon number 1 to 12 branched or unbranched alkoxy groups.

[9] A polarizing film, which is a hardened product of a polymerizable liquid crystal composition, the polymerizable liquid crystal composition comprising: a dichroic dye, a polymerizable liquid crystal compound, and an antioxidant; and, in X-ray diffraction measurement, the polarized light The film shows a Bragg peak; the aforementioned antioxidant satisfies the formula (1) in relation to the aforementioned polymerizable liquid crystal compound: 0.8°C≦T1-T2 (1)

In the formula, T1 is the phase transition to the liquid crystal phase that appears on the lowest temperature side when the temperature of the above-mentioned polymerizable liquid crystal compound is raised to 130°C in the air, and then cooled to 23°C at 5°C/min while measuring the phase transition temperature. Temperature: T2 means that the mixture formed by 100 parts by mass of the aforementioned polymerizable liquid crystal compound and 1 part by mass of the aforementioned antioxidant is heated to 130°C in the atmosphere, and then cooled to 23°C at 5°C/min while measuring the phase transition Temperature, the phase transition temperature to the liquid crystal phase that appears on the lowest temperature side.

[10] A polarizing plate comprising the polarizing film described in [9] above, and a retardation film.

[11] The polarizing plate as described in item [10] above, wherein the retardation film satisfies formula (X), and the angle formed by the slow axis of the retardation film and the absorption axis of the polarizing film is substantially 45° ;100≦Re(550)≦180 (X)

In the formula, Re(550) represents the in-plane retardation value at a wavelength of 550 nm.

[12] The polarizing plate as described in [10] or [11] above, wherein the retardation film satisfies the formula (Y): Re(450)/Re(550)<1 (Y)

In the formula, Re(450) and Re(550) represent the in-plane retardation values at wavelengths of 450nm and 550nm, respectively.

[13] The polarizing plate according to any one of [10] to [12] above, wherein the retardation film is composed of a polymer in an aligned state of a polymerizable liquid crystal compound.

[14] A display device comprising the polarizing film described in [9] above or the polarizing plate described in any one of [10] to [13] above.

[15] A method for producing a polarizing film, comprising: forming a coating film of the polymerizable liquid crystal composition described in any one of items [1] to [8]; removing the solvent from the coating film; The liquid crystal compound is phase-transferred to a temperature above the liquid phase, and then the temperature is lowered to make the polymerizable liquid crystal compound phase-transfer to a smectic phase; and, polymerizing the polymerizable liquid crystal compound while maintaining the state of the smectic phase.

According to the present invention, a polymerizable liquid crystal composition can be provided, which has a high inhibitory effect on the modification of dichroic pigments when exposed to sunlight, and is suitable for forming a polarizing film that can suppress the degradation of polarizing performance over time.

Embodiments of the present invention will be described in detail below. In addition, the scope of the present invention is not limited to the embodiments described here, and various changes can be made without detracting from the spirit of the present invention.

<Polymerizable Liquid Crystal Composition>

The polymerizable liquid crystal composition of the present invention contains: a polymerizable liquid crystal compound having at least one polymerizable group and exhibiting smectic liquid crystallinity (hereinafter also referred to as "polymerizable liquid crystal compound (A)"). By using a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity, a polarizing film having a high degree of alignment order can be formed. The liquid crystal state exhibited by the polymerizable liquid crystal compound (A) is a smectic phase (smectic liquid crystal state). for better. Here, the high-order smectic phase means smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, Among the smectic K phase and the smectic L phase, the smectic B phase, the smectic F phase, and the smectic I phase are more preferable. The liquid crystal can be either thermotropic liquid crystal or lyotropic liquid crystal, but thermotropic liquid crystal is preferred because the film thickness can be finely controlled.

The polymerizable liquid crystal compound may be a monomer, but may also be an oligomer or a polymer in which the polymerizable group is polymerized.

The polymerizable liquid crystal compound (A) is a liquid crystal compound having at least one polymerizable group. Here, the term "polymerizable group" refers to a group capable of participating in a polymerization reaction by active radicals or acids generated by a polymerization initiator.

The polymerizable group of the polymerizable liquid crystal compound (A) includes, for example, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryl Acyloxy group, oxirane group, oxetanyl group, etc. Among them, free radical polymerizable groups are preferred, acryloxy, methacryloxy, vinyl, and vinyloxy are more preferred, and acryloxy and methacryloxy are more preferred. Preferably, acryloxy is still more preferred.

The polymerizable liquid crystal compound (A) is not particularly limited as long as it has at least one polymerizable group and exhibits smectic liquid crystallinity, and known polymerizable liquid crystal compounds can be used.

Examples of the polymerizable liquid crystal compound (A) include a compound represented by formula (A1) and a polymer of the compound (hereinafter, the compound and the polymer may be collectively referred to as "polymerizable liquid crystal compound (A1)").

U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ^{3 -W 2} -V ² -U ² (A1) [In formula (A1), X ¹ , X ² and X ³ They independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the hydrogen atom contained in the divalent aromatic group or alicyclic hydrocarbon group can be replaced by a halogen atom, a carbon number of 1 to 4 Alkyl, fluoroalkyl with 1 to 4 carbons, alkoxy with 1 to 4 carbons, cyano or nitro, the carbon atoms constituting the divalent aromatic group or divalent alicyclic hydrocarbon group can also be replaced by Oxygen atom or sulfur atom or nitrogen atom is substituted. However, at least one of X ¹ , X ² and X ³ is an optionally substituted 1,4-phenylene group or an optionally substituted cyclohexane-1,4-diyl group.

Y ¹ and Y ² are independently a single bond or a divalent linking group.

U ¹ represents a hydrogen atom or a polymerizable group.

U ² represents a polymerizable group.

W ¹ and W ² are independently a single bond or a divalent linking group.

V ¹ and V ² independently represent an alkanediyl with a carbon number of 1 to 20 that may have a substituent, and the -CH ₂ - constituting the alkanediyl can also be replaced by -O-, -CO-, -S- or NH-]

In the polymerizable liquid crystal compound (A1), X ¹ , X ² and X ³ are independent of each other, preferably 1,4-phenylene which may have substituents, or cyclohexane-1 which may have substituents, In the 4-diyl group, at least one of X ¹ , X ² and X ³ is a 1,4-phenylene group which may have a substituent, or a cyclohexane-1,4-diyl group which may have a substituent. In particular, X ¹ and X ³ are preferably cyclohexane-1,4-diyl which may have substituents, and the cyclohexane-1,4-diyl is more preferably trans-cyclohexane-1,4 - two bases. Examples of substituents that may be optionally substituted in 1,4-phenylene or cyclohexane-1,4-diyl that may have substituents include: methyl, ethyl and alkyl groups having 1 to 4 carbon atoms such as butyl groups, cyano groups, and halogen atoms such as chlorine atoms and fluorine atoms. Preferably there is no substitution. Moreover, when ^Y1 and ^Y2 have the same structure, it is preferable that at least one of ^X1 , ^X2 and ^X3 has a different structure. When at least one of X ¹ , X ² and X ³ has a different structure, smectic liquid crystallinity tends to be easily exhibited.

Y ¹ and Y ² are preferably independently of each other -CH ₂ CH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ O-, -COO-, -OCOO-, single bond, -N=N-, -CR ^a =CR ^b -, -C≡C-, -CR ^a =N-, or -CO-NR ^{a -} . R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbons. Y ¹ is more preferably -CH ₂ CH ₂ -, -COO- or a single bond, and Y ² is more preferably -CH ₂ CH ₂ - or CH ₂ O-. In addition, when X ¹ , X ² and X ³ all have the same structure, it is preferable that Y ¹ and Y ² have different structures from each other. When ^Y1 and ^Y2 have mutually different structures, there is a tendency to easily exhibit smectic liquid crystallinity.

U ² is a polymeric group. U ¹ is a hydrogen atom or a polymeric group, preferably a polymeric group. It is preferable that both ^U1 and ^U2 are polymerizable groups, more preferably both are free radical polymerizable groups. Examples of the polymerizable group include the same ones as the polymerizable group of the polymerizable liquid crystal compound (A) exemplified above. The polymerizable group represented by U ¹ and the polymerizable group represented by U ² may be different from each other, but they are preferably of the same type.

The alkanediyl groups represented by ^V1 and ^V2 can be exemplified as: methylene, ethylidene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4- Diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,10-diyl Diyl, tetradecane-1,14-diyl and eicosane-1,20-diyl, etc. 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.

As for the optional substituents of the alkanediyl, examples include cyano groups and halogen atoms, etc., but the alkanediyl is preferably unsubstituted, and unsubstituted straight-chain alkanediyl for better.

W ¹ and W ² are preferably a single bond, -O-, -S-, -COO- or -OCOO- independently of each other, more preferably a single bond or -O-.

Examples of the polymerizable liquid crystal compound (A1) include compounds represented by formula (A-1) to formula (A-25). When the polymerizable liquid crystal compound (A1) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans form.

Among them, preferably selected from formula (A-2), formula (A-3), formula (A-4), formula (A-5), formula (A-6), formula (A-7) ), formula (A-8), formula (A-13), formula (A-14), formula (A-15), formula (A-16) and formula (A-17) Group of at least 1 species. The polymerizable liquid crystal compound (A1) may be used alone or in combination of two or more.

The polymerizable liquid crystal compound (A1) can be produced by a known method such as Lub et al. described in Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156.

On the premise of not impairing the effects of the present invention, the polymerizable liquid crystal composition of the present invention may contain other polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (A). From the viewpoint of obtaining a polarizing film with a high degree of alignment order, in the polymerizable liquid crystal composition, the ratio of the polymerizable liquid crystal compound (A) to the total mass of all the polymerizable liquid crystal compounds is preferably 51% by mass or more, More preferably, it is more than 70% by mass, and more preferably, it is more than 90% by mass.

When the polymerizable liquid crystal composition of the present invention contains two or more polymerizable liquid crystal compounds (A), at least one of them may be the polymerizable liquid crystal compound (A1), or all of them may be the polymerizable liquid crystal compound (A1 ). By combining a plurality of polymerizable liquid crystal compounds, liquid crystallinity may be temporarily maintained even at a temperature lower than the liquid crystal-crystal phase transition temperature.

In the polymerizable liquid crystal composition of the present invention, the content of the polymerizable liquid crystal compound is preferably 40 to 99.9% by mass, more preferably 60 to 99% by mass, and even more preferably 70% by mass relative to the solid content of the polymerizable liquid crystal composition. to 99% by mass. When the content of the polymerizable liquid crystal compound is within the above range, the orientation of the polymerizable liquid crystal compound tends to be high.

In this specification, the so-called solid content means the total amount of components except the solvent from the polymerizable liquid crystal composition.

The polymerizable liquid crystal composition of the present invention contains a dichroic dye. Here, a dichroic dye means a dye having a property in which the absorbance in the long-axis direction of the molecule is different from the absorbance in the short-axis direction. The dichroic dye usable in the present invention is not particularly limited as long as it has the above properties, and may be a dye or a pigment. Two or more dyes or pigments may be used in combination, respectively, or a dye and a pigment may be used in combination.

色素、花青色素、萘色素、偶氮色素及蒽醌色素等。 The dichroic dye preferably has a maximum absorption wavelength (λ _MAX ) in the range of 300 to 700 nm. Examples of such dichroic pigments include: acridine pigments,

Pigments, cyanine pigments, naphthalene pigments, azo pigments and anthraquinone pigments, etc.

Azo dyes can be, for example, monoazo dyes, disazo dyes, trisazo dyes, tetrazo dyes, and stilbene azo dyes, etc., preferably disazo dyes and trisazo dyes, which can be For example, a compound represented by formula (I) (hereinafter also referred to as "compound (I)").

K ¹ -(-N=NK ² ) _p -N=NK ³ (I) [In the formula (I), K ¹ and K ³ independently represent a phenyl group that may have a substituent, a naphthalene that may have a substituent group or a monovalent heterocyclic group which may have a substituent. K ² represents a p-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, the plurality of K ² may be the same as or different from each other. In the range showing absorption in the visible light region, -N=N-bonds can be replaced by -C=C-, -COO-, -NHCO-, -N=CH-bonds. 〕

唑、苯并

唑等雜環化合物除去1個氫原子之基。2價之雜環基係可列舉從前述雜環化合物除去2個氫原子之基。 The monovalent heterocyclic group can be enumerated: from quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole,

Azole, benzo

Heterocyclic compounds such as azoles are based on the removal of one hydrogen atom. Examples of the divalent heterocyclic group include groups obtained by removing two hydrogen atoms from the aforementioned heterocyclic compound.

For the phenyl, naphthyl and 1-valent heterocyclic group in ^K1 and ^K3 , and the p-phenylene group, naphthalene-1,4-diyl and 2-valent heterocyclic group in ^K2 , any For substituents, examples include: alkyl groups with 1 to 4 carbons; alkoxy groups with 1 to 4 carbons such as methoxy, ethoxy, butoxy; and trifluoromethyl groups with 1 to 4 carbons. 4's fluorinated alkyl group; cyano group; nitro group; halogen atom; An amine group of an alkyl group with a number of 1 to 6, or an amine group where two substituted alkyl groups are bonded to each other to form an alkanediyl group with a carbon number of 2 to 8. The unsubstituted amine group is -NH ₂ ) and the like.

Among compound (I), the compound represented by any one of formula (I-1) to formula (I-6) is preferable.

〔式(I-1)至(I-8)中， B¹至B³⁰係互相獨立地表示氫原子、碳數1至6之烷基、碳數1至4之烷氧基、氰基、硝基、取代或無取代之胺基(取代胺基及無取代胺基之定義係如前述)、氯原子或三氟甲基。

[In formulas (I-1) to (I-8), B ¹ to B ³⁰ independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 4 carbons, a cyano group, A nitro group, a substituted or unsubstituted amino group (the definitions of the substituted amino group and the unsubstituted amino group are as described above), a chlorine atom or a trifluoromethyl group.

n1 to n4 independently represent an integer of 0 to 3.

When n1 is 2 or more, the plural ^B2s may be the same as or different from each other; when n2 is 2 or more, the plural ^B6s may be the same or different; when n3 is 2 or more, the plural B6s may be B ⁹ may be the same as or different from each other, and when n4 is 2 or more, a plurality of B ¹⁴ may be the same or different from each other. 〕

The aforementioned anthraquinone pigment is preferably a compound represented by formula (I-9).

〔式(I-9)中，R¹至R⁸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 (I-9), 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 carbons or an aryl group having 6 to 12 carbons. 〕

色素係以式(I-10)所示之化合物為較佳。 aforementioned

The pigment is preferably a compound represented by formula (I-10).

〔式(I-8)中， R⁹至R¹⁵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 the formula (I-8), R ⁹ to R ¹⁵ 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 carbons or an aryl group having 6 to 12 carbons. 〕

The aforementioned acridine pigment is preferably a compound represented by formula (I-11).

〔式(I-11)中，R¹⁶至R²³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 the formula (I-11), R ¹⁶ to R ²³ 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 carbons or an aryl group having 6 to 12 carbons. 〕

In formula (I-9), formula (I-10) and formula (I-11), the alkyl group of carbon number 1 to 6 of R ^x can enumerate such as methyl, ethyl, propyl, butyl, Examples of pentyl, hexyl, etc., and aryl having 6 to 12 carbon atoms include phenyl, tolyl, xylyl, and naphthyl.

The aforementioned cyanine pigments are preferably compounds represented by formula (I-12) and compounds represented by formula (I-13).

〔式(I-12)中，D¹及D²互相獨立地表示式(I-12a)至式(I-12d)中任一者所示之基。n5表示1至3之整數。

[In formula (I-12), D ¹ and D ² independently represent a group represented by any one of formula (I-12a) to formula (I-12d). n5 represents an integer of 1 to 3.

〕

〕

〔式(I-13)中，D³及D⁴互相獨立地表示式(I-13a)至式(1-13h)中之任一者所示之基。

[In formula (I-13), D ³ and D ⁴ independently represent a group represented by any one of formula (I-13a) to formula (1-13h).

n6 represents an integer of 1 to 3.

〕

〕

The polymerizable liquid crystal composition of the present invention is excellent in suppressing the photodegradation of the dichroic pigment in the polarizing film when the polarizing film is formed, so it is easy to cause photodegradation when used against light such as ultraviolet rays in sunlight. In the case of a color pigment, the effect of the present invention can be exhibited particularly remarkably. Therefore, the polymerizable liquid crystal composition of the present invention is particularly advantageous when using a dichroic dye that is prone to photodegradation. The dichroic dye contained in the polymerizable liquid crystal composition of the present invention is preferably an azo dye.

The content of the dichroic dye in the polymerizable liquid crystal composition of the present invention can be appropriately determined according to the type of dichroic dye to be used, but is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound , more preferably 0.1 to 20 parts by mass, more preferably 0.1 to 12 parts by mass. If the content of the dichroic dye is within the above range, the orientation of the polymerizable liquid crystal compound is less likely to be disturbed, and a polarizing film with a high degree of orientation order can be obtained.

The polymerizable liquid crystal composition of the present invention contains an antioxidant.

In the polymerizable liquid crystal composition of the present invention, the relationship between the antioxidant and the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition satisfies the formula (1): 0.8°C≦T1-T2 (1).

In the formula (1), T1 is when the temperature of the polymerizable liquid crystal compound contained in the aforementioned polymerizable liquid crystal composition is raised to 130°C in the air, and then cooled to 23°C at 5°C/min while measuring the phase transition temperature, The phase transition temperature to the liquid crystal phase that appears on the lowest temperature side.

T2 is a mixture of 100 parts by mass of the aforementioned polymerizable liquid crystal compound and 1 part by mass of the aforementioned antioxidant heated up to 130°C in the air, then cooled to 23°C at 5°C/min while measuring the phase transition temperature Actually, the phase transition temperature to the liquid crystal phase that appears on the lowest temperature side.

When the polymerizable liquid crystal composition of the present invention contains two or more kinds of polymerizable liquid crystal compounds, the above-mentioned T1 and T2 are polymerizable liquid crystal compounds that have the same composition as the polymerizable liquid crystal compound that constitutes the polymerizable liquid crystal composition ( mixture) was measured. The detailed measurement methods of T1 and T2 are as described in the examples below.

In general, excellent polarizing properties can be obtained when the polymerizable liquid crystal compound and the dichroic pigment are aligned with a high degree of order. However, in such an aligned state, since the dichroic dye is contained in the polymerizable liquid crystal compound, the addition of an antioxidant causes disorder in the orientation of the polymerizable liquid crystal compound, resulting in a so-called polarizing property. problem of reduction.

The polymerizable liquid crystal composition of the present invention can exert a high effect on suppressing deterioration of polarizing performance when forming a polarizing film by containing an antioxidant satisfying the above formula (1).

In the formula (1), T1-T2 becomes an indicator of the influence of the antioxidant on the phase transition temperature of the liquid crystal state. The larger the value of T1-T2, it means that the polymerizable liquid crystal compound and the antioxidant are more similar in molecular structure, and exist in a more mixed state in the liquid crystal state, and the antioxidant will interact with the polymerizable liquid crystal compound are directed together. Therefore, it is speculated that the larger the value of T1-T2, the closer the intermolecular distance between the dichroic dye and the antioxidant that exists in the state of being included in the polymerizable liquid crystal compound becomes, and the dichroic dye can be exerted. Highly inhibiting effect of light degradation, and it is difficult to disturb the orientation of the polymerizable liquid crystal compound, and a polarizing film with a high degree of orientation order can be obtained.

In the antioxidant contained in the polymerizable liquid crystal composition of the present invention, the above-mentioned value of T1-T2 is 0.8°C or higher, preferably 0.9°C or higher, more preferably 1.0°C or higher, still more preferably 1.2°C or higher, especially The best is above 1.5°C.

If the value of T1-T2 is less than 0.8°C, the molecular structure of the polymerizable liquid crystal compound is very different from that of the antioxidant, and it is difficult to orient the antioxidant and the polymerizable liquid crystal compound with a high degree of order. As a result, it is difficult to sufficiently exhibit the effect of suppressing photodegradation of the dichroic dye. On the other hand, if the value of T1-T2 is within the above range, an antioxidant can be disposed near the dichroic dye occluded in the polymerizable liquid crystal compound, and a high effect of suppressing the decrease in polarization performance can be expected.

In the present invention, although the upper limit of T1-T2 is not particularly limited, it is usually below 35°C, preferably below 30°C, more preferably below 25°C.

In the polymerizable liquid crystal composition, the antioxidant is not particularly limited as long as it satisfies the above formula (1) with the polymerizable liquid crystal compound and can exert the effect of the present invention, and known antioxidants can be used. From the viewpoint of having a high inhibitory effect on photodegradation of dichroic dyes, a so-called primary antioxidant that captures free radicals and has an effect of preventing autooxidization (autooxidized) is preferable. Therefore, the antioxidant contained in the polymerizable liquid crystal composition of the present invention is more preferably at least one selected from the group consisting of phenol compounds, alicyclic alcohol compounds and amine compounds. Antioxidants may be used alone or in combination of two or more.

。 The antioxidant system selected from the group consisting of phenolic compounds, alicyclic alcohol compounds and amine compounds can be exemplified by any one of the structures shown in formula (2), formula (3) and formula (4). compound;

.

In formula (2) and formula (3), R ₁ to R ₅ are independently -H, -OH, -NH ₂ , branched or non-branched alkyl with 1 to 12 carbons, or 1 carbon to 12 branched or non-branched alkoxy groups; in formula (2) and formula (3), at least one of R ₁ to R ₅ is -OH or -NH ₂ .

Branched or non-branched alkyl groups with 1 to 12 carbons can be exemplified: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl , Heptyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, etc.

Branched or non-branched alkoxy groups with 1 to 12 carbons can be exemplified: methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethyl Hexyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, etc.

In formula (2) and formula (3), -OH or -NH ₂ present in at least one of R ₁ to R ₅ is preferably present in R ₁ , at this time, R ₂ to R ₅ is more preferably -H, a branched or non-branched alkyl group with 1 to 12 carbons, or a branched or non-branched alkoxy group with 1 to 12 carbons, and -H is still more preferred.

The above-mentioned antioxidant system having the structure shown in formula (2), formula (3) or formula (4) can be, for example, a compound shown in formula (5): A ₁ -L ₁ -(A ₂ -L ₂ ) _n -A ₃ (5).

In formula (5), L ₁ and L ₂ are each independently a single bond or a divalent linking group.

A ₁ is a group represented by the above formula (2), formula (3) or formula (4).

〔式(6)及式(7)中，R₆至R₉分別獨立地為-H、-OH、-NH₂、碳數1至12之分枝或非分枝烷基、或碳數1至12之分枝或非分枝烷氧基〕。 A ₂ is the base shown in formula (6) or formula (7):

[In formula (6) and formula (7), R ₆ to R ₉ are independently -H, -OH, -NH ₂ , branched or non-branched alkyl with 1 to 12 carbons, or 1 carbon to 12 branched or unbranched alkoxy].

〔式(8)及式(9)中，R₁₀至R₁₄分別獨立地為-H、-OH、-NH₂、碳數1至12之分枝或非分枝烷基，或是碳數1至12之分枝或非分枝烷氧基〕。 The base shown in A ₃ series formula (8) or formula (9):

[In formula (8) and formula (9), R ₁₀ to R ₁₄ are independently -H, -OH, -NH ₂ , a branched or non-branched alkyl group with 1 to 12 carbons, or a carbon number 1 to 12 branched or unbranched alkoxy].

N is an integer from 0 to 2, and when n is 2, the two _A2s may be the same as or different from each other.

The divalent linking groups in L ₁ and L ₂ include single bond, ether group, carbonyl group, ester group, amide group, azo group and the like. L ₁ and L ₂ are preferably bonded species that have no absorption in visible light as antioxidants, more preferably single bonds, ether groups, and ester groups, and particularly preferably single bonds and ether groups.

_A1 can include the same group as the structure shown in the above-mentioned formula (2), formula (3) and formula (4) exemplified earlier, preferably the group shown in formula (2) or formula (4) , more preferably the group shown in formula (2), more preferably R ₁ is -OH, and R ₂ to R ₅ are each independently -H or -CH ₃ , especially R ₂ to R ₅ are all for -H.

Branched alkyl with ₁ to 12 carbons, non-branched alkyl with 1 to 12 carbons, branched alkoxy with 1 to 12 carbons represented by _R6 to _R14 in A2 and _A3 The group, and the non-branched alkoxy group with 1 to 12 carbons can be mentioned as the branched alkyl group with 1 to 12 carbons, the branched alkyl group with 1 to 12 carbons as previously exemplified as _R1 to _R5 in _A1 . Unbranched alkyl, branched alkoxy having 1 to 12 carbons and unbranched alkoxy having 1 to 12 carbons are the same group.

In _A2 , R ₆ to R ₉ are independently, preferably -H or -CH ₃ , more preferably -H, even more preferably all of R ₆ to R ₉ are -H or -CH ₃ , especially Best series R ₆ to R ₉ are all -H.

In _A3 , R ₁₂ is a branched or non-branched alkyl group with 1 to 12 carbons, or a branched or non-branched alkoxy group with 1 to 12 carbons, R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are independently, preferably -H or -CH ₃ , particularly preferably R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are all -H.

The weight average molecular weight of the antioxidant is preferably 600 or less, more preferably 500 or less, and more preferably 450 or less.

If the weight-average molecular weight of the antioxidant is 600 or less, the antioxidant can be arranged near the dichroic dye without significantly disturbing the orientation of the polymerizable liquid crystal compound, so the effect of inhibiting photodegradation of the dichroic dye can be further enhanced. Furthermore, when the weight average molecular weight of an antioxidant is 400 or less, since it becomes difficult to have absorption in a visible light wavelength region, and the fall of a polarizing performance can be reduced more effectively, it is still more preferable.

In the polymerizable liquid crystal composition of the present invention, the antioxidant system includes, for example, the following compounds.

Among them, an antioxidant having a molecular structure with a small steric hindrance and high linearity is preferable because it is easily oriented together with a polymerizable liquid crystal compound and tends to be excellent in the effect of inhibiting photodegradation of a dichroic dye. As far as the antioxidant in the polymerizable liquid crystal composition of the present invention is concerned, although it is not limited thereto, it is preferably 4-n-octyloxyphenol, 4-n-decyloxyphenol, 4-n-dodecyloxy Phenol, 4,4'-biphenol, 4-ethoxy-4'-hydroxybiphenyl, 4-butoxy-4'-hydroxybiphenyl, 4-octyloxy-4'-hydroxybiphenyl base, 4-decyloxy-4'-hydroxybiphenyl, 4-dodecyloxy-4'-hydroxybiphenyl.

The content of the above-mentioned antioxidant in the polymerizable liquid crystal composition of the present invention is preferably 0.1 to 15 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound; more preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass The above; more preferably less than 12 parts by mass, more preferably less than 8 parts by mass, and most preferably less than 4 parts by mass.

Photodeterioration of a dichroic dye can be effectively suppressed as content of an antioxidant is more than the said lower limit. Moreover, when content of an antioxidant is below the said upper limit, it becomes difficult to disturb the orientation of a polymerizable liquid crystal compound, and the high inhibitory effect with respect to the photodegradation of a dichroic dye can be expected.

The polymerizable liquid crystal composition of the present invention may also contain a polymerization initiator.

The polymerization initiator is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal compound, and a photopolymerization initiator is preferred in terms of initiating the polymerization reaction at a lower temperature. Specifically, examples thereof include photopolymerization initiators capable of generating active radicals or acids by the action of light, among which photopolymerization initiators that generate free radicals by the action of light are preferred. A polymerization initiator can be used individually or in combination of 2 or more types.

化合物、錪鹽及鋶鹽等。 Examples of polymerization initiators include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds,

Compounds, Odonium salts and Condium salts, etc.

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

Examples of benzophenone compounds include: benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide Ether, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone, etc.

Examples of alkyl phenone compounds include: diethoxyacetylbenzene, 2-methyl-2-morpholinyl-1-(4-methylphenylthio)propane-1-one, 2-dimethyl Amino-2-benzyl-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2 -Diphenyl-2,2-dimethoxyethan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one , oligomers of 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, etc.

Examples of acylphosphine oxide compounds include: 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, etc. .

化合物係可列舉如：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-(4-二乙基胺基-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

Compounds can be listed such as: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri

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

, 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)ethenyl]-1,3,5-tri

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

wait.

As a polymerization initiator, a commercially available one can be used. Commercially available polymerization initiators include, for example: "Irgacure (registered trademark) 907", "Irgacure (registered trademark) 184", "Irgacure (registered trademark) 651", "Irgacure (registered trademark) 819", "Irgacure (registered trademark) 250", "Irgacure (registered trademark) 369" (Ciba Japan Co., Ltd.); "Seikuol (registered trademark) BZ", "Seikuol (registered trademark) Z", "Seikuol (registered trademark) BEE" (Seiko Chemical Co., Ltd.); "Kayacure (registered trademark) BP100" (Nippon Kayaku Co., Ltd.); "Cyracure (registered trademark) UVI-6992" (Dow Corporation); "Adeka optomer SP-152", "Adeka optomer SP- 170" (ADEKA Co., Ltd.); "TAZ-A", "TAZ-PP" (Siber Hegner Corporation, Japan); and "TAZ-104" (Sanwa Chemical Corporation), etc.

When the polymerizable liquid crystal composition contains a polymerization initiator, its content may be appropriately determined according to the type of polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition and the amount of the polymerizable liquid crystal compound contained therein. Based on 100 parts by mass of the polymerizable liquid crystal compound, it is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass. When content of a polymeric initiator is in the said range, it can superpose|polymerize without disturbing the orientation of a polymerizable liquid crystal compound.

When the polymerizable liquid crystal composition contains a photopolymerization initiator, it may further contain a photosensitizer. By using a photosensitizer, the polymerization reaction of the polymerizable liquid crystal compound can be further accelerated.

及紅螢烯等。光增敏劑係可單獨使用或組合2種以上而使用。 Photosensitizers include, for example: xanthone compounds such as xanthone and thioxanthone (2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); anthracene Anthracene compounds such as anthracene (dibutoxyanthracene, etc.) containing alkoxy groups;

and rubrene, etc. A photosensitizer can be used individually or in combination of 2 or more types.

The content of the photosensitizer in the polymerizable liquid crystal composition of the present invention may be appropriately determined according to the type and amount of the photopolymerization initiator and the polymerizable liquid crystal compound, but relative to 100 parts by mass of the polymerizable liquid crystal compound , 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.

The polymerizable liquid crystal composition of the present invention may contain a leveling agent. The leveling agent has the function of adjusting the fluidity of the polymerizable liquid crystal composition to make the coating film obtained by coating the polymerizable liquid crystal composition more flat. Specifically, surfactants can be mentioned. The leveling agent is preferably at least one selected from the group consisting of a leveling agent mainly composed of a polyacrylate compound and a leveling agent mainly composed of a compound containing a fluorine atom. A leveling agent can be used individually or in combination of 2 or more types.

Leveling agents with polyacrylate compounds as the main component include: "BYK-350", "BYK-352", "BYK-353", "BYK-354", "BYK-355", "BYK- 358N", "BYK-361N", "BYK-380", "BYK-381" and "BYK-392" (BYK Chemie Company), etc.

Leveling agents with fluorine-containing compounds as main components include: "Megafac (registered trademark) R-08", Megafac "R-30", Megafac "R-90", Megafac "F-410", Megafac "F-411", Megafac "F-443", Megafac "F-445", Megafac "F-470", Megafac "F-471", Megafac "F-477", Megafac "F-479", Megafac "F-482" and Megafac "F-483" (DIC Corporation); "Surflon (registered trademark) S-381", Surflon "S-382", Surflon "S-383", Surflon "S-393", Surflon "SC-101", Surflon "SC-105", "KH-40" and "SA-100" (AGC Seimi Chemical Co., Ltd.); "E1830", "E5844" (Daikin Fine Chemical Research Institute Co., Ltd.); "EFTOP EF301", "EFTOP EF303", "EFTOP EF351" and "EFTOP EF352" (Mitsubishi Material Electron Chemicals Co., Ltd.), etc.

The content of the leveling agent in the polymerizable liquid crystal composition of the present invention is preferably 0.05 to 5 parts by mass, more preferably 0.05 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the aforementioned range, the polymerizable liquid crystal compound is easily aligned horizontally, unevenness is less likely to occur, and a smoother polarizing film tends to be obtained.

The polymerizable liquid crystal composition of the present invention may contain other additives other than polymerization initiators, photosensitizers and leveling agents. Examples of other additives include coloring agents such as release agents, stabilizers, and blueing agents, flame retardants, and lubricants. When the polymerizable liquid crystal composition contains other additives, relative to the solid content of the polymerizable liquid crystal composition, the content of other additives is preferably more than 0% and not more than 20% by mass, more preferably more than 0% and 10% by mass the following.

The polymerizable liquid crystal composition of the present invention may contain a solvent. Generally speaking, since the compound exhibiting smectic liquid crystallinity has a high viscosity, it is easy to coat by adding a solvent to the polymerizable liquid crystal composition, and as a result, it becomes easy to form a polarizing film. The solvent system can be appropriately selected according to the solubility of the polymerizable liquid crystal compound and the dichroic dye, for example: water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl celluloid, butyl celluloid Alcohol solvents such as Su and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate, etc. ; Acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, methyl isobutyl ketone and other ketone solvents; pentane, hexane, heptane and other aliphatic hydrocarbon solvents; toluene, di Aromatic hydrocarbon solvents such as toluene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorinated hydrocarbon solvents such as chloroform and chlorobenzene; etc.

These solvents can be used individually or in combination of 2 or more types. The content of the solvent is preferably 100 to 1900 parts by mass, more preferably 150 to 900 parts by mass, and still more preferably 180 to 600 parts by mass relative to 100 parts by mass of solids constituting the polymerizable liquid crystal composition.

The polymerizable liquid crystal composition of the present invention can usually be prepared by mixing and stirring a polymerizable liquid crystal compound, a dichroic dye, an antioxidant, and the above-mentioned additives and solvents as needed.

The polymerizable liquid crystal composition of the present invention is excellent in suppressing the photodegradation of dichroic pigments, and can obtain a polarizing film that is less prone to degradation of polarizing performance over time, so it can be suitably used in the manufacture of polarizing films.

With the polymerizable liquid crystal composition of the present invention, a polarizing film with a high degree of alignment order can be produced.

A polarizing film with a high degree of orientation order can obtain Bragg peaks derived from higher-order structures such as hexatic phase or crystal phase in X-ray diffraction measurement.

The so-called Bragg peaks mean peaks originating from the periodic structure of molecularly oriented planes. Therefore, in the polarizing film formed by the polymerizable liquid crystal composition of the present invention, the polymerizable liquid crystal compound or its polymer is preferably oriented in such a way that the polarizing film will show a Bragg peak in the X-ray diffraction measurement, and The "horizontal alignment" in which the molecules of the polymerizable liquid crystal compound are aligned in the direction of light absorption is more preferable. In the present invention, a polarizing film with a periodic interval of 3.0 to 6.0 Å on the molecularly oriented planes is preferred. A high degree of orientation order such as Bragg peaks can be controlled by controlling the type of polymerizable liquid crystal compound used, the type of antioxidant or the amount of the antioxidant, the type of dichroic dye or the dichroic dye The amount is achieved.

As described above, by formulating an antioxidant satisfying the formula (1) in relation to the polymerizable liquid crystal composition, it is possible to resist photodegradation of the dichroic dye while maintaining a high degree of alignment of the polymerizable liquid crystal compound. A high suppression effect is obtained, so it is possible to obtain a polarizing film with excellent polarizing performance and less prone to decrease in polarizing performance over time. Therefore, the present invention is also aimed at a polarizing film that is a hardened product of a polymerizable liquid crystal composition including a dichroic dye, a polymerizable liquid crystal compound, and an antioxidant, and the polarizing film is used in X-ray diffraction measurement. It shows a Bragg peak, and the aforementioned antioxidant satisfies the formula (1) in relation to the aforementioned polymerizable liquid crystal compound: 0.8°C≦T1-T2 (1)

[In the formula, T1 is the phase transition to the liquid crystal phase that appears on the lowest temperature side when the temperature of the above-mentioned polymerizable liquid crystal compound is raised to 130°C in the air, and then cooled to 23°C at 5°C/min while measuring the phase transition temperature. Transition temperature; T2 means that the mixture formed by 100 parts by mass of the aforementioned polymerizable liquid crystal compound and 1 part by mass of the aforementioned antioxidant is heated to 130°C in the atmosphere, and then cooled to 23°C at 5°C/min. The phase transition temperature to the liquid crystal phase that appears on the lowest temperature side at the time of the transition temperature].

In the polymerizable liquid crystal composition used to form the polarizing film of the present invention, the polymerizable liquid crystal compound, dichroic dye, and antioxidant can be exemplified above as the polymerizable liquid crystal composition contained in the present invention. The liquid crystal compound, the dichroic dye, and the antioxidant are the same. The polymerizable liquid crystal composition used to form the polarizing film of the present invention may contain a polymerization initiator, a leveling agent, other additives, and a solvent. Examples of these components include the same ones as the components contained in the polymerizable liquid crystal composition of the present invention exemplified above.

The polarizing film of the present invention can be produced, for example, by the following method, the method comprising: forming a coating film of the polymerizable liquid crystal composition of the present invention; removing the solvent from the coating film; and raising the temperature until the phase transition of the polymerizable liquid crystal compound to the liquid phase Above the temperature above, then lower the temperature to make the phase transfer of the polymerizable liquid crystal compound to the smectic phase (smectic liquid crystal state); and polymerize the polymerizable liquid crystal compound while maintaining the aforementioned smectic phase (smectic liquid crystal state) .

The coating film of the polymerizable liquid crystal composition can be formed by coating the polymerizable liquid crystal composition on the substrate or on the alignment film described later, especially the polymerizable liquid crystal composition whose viscosity is adjusted by adding a solvent (hereinafter , also known as "the composition for forming a polarizing film"). The polymerizable liquid crystal composition can also be directly coated on the retardation film or other layers constituting the polarizing plate of the present invention.

The substrate is typically a transparent substrate. When the substrate is not provided on the display surface of the display element, for example, when a laminate obtained by removing the substrate from the polarizing film is provided on the display surface of the display element, the substrate may be opaque. The so-called transparent substrate means a substrate having transparency through which light (especially visible light) can penetrate, and the so-called transparency refers to the characteristic that the transmittance to light with a wavelength of 380 to 780nm becomes more than 80%. A specific transparent base material may, for example, be a translucent resin base material. The resin system constituting the light-transmitting resin base material includes, for example, polyolefins such as polyethylene and polypropylene; cyclic olefin-based resins such as norbornene-based polymers; polyvinyl alcohol; polyethylene terephthalate; polyethylene terephthalate; Methacrylate; Polyacrylate; Cellulose esters such as triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate; Polyethylene naphthalate; Polycarbonate; Polyethylene ; Polyether sulfide; polyether ketone; polyphenylene sulfide and polyphenylene oxide (polyphenylene oxide), etc. From the viewpoint of ease of acquisition and transparency, polyethylene terephthalate, polymethacrylate, cellulose ester, cyclic olefin resin, or polycarbonate is preferable. Cellulose esters are those in which some or all of the hydroxyl groups contained in cellulose have been esterified, and are readily available on the market. In addition, cellulose ester substrates can also be easily obtained from the market. Examples of commercially available cellulose ester substrates include "Fujitac Film" (Fuji Shashin Film Co., Ltd.); "KC8UX2M", "KC8UY" and "KC4UY" (Konica Minolta Opto Co., Ltd.).

The properties required for the base material vary depending on the structure of the polarizing film, but usually a base material with as little retardation as possible is preferred. As for the base material whose phase difference is as small as possible, a cellulose ester film which does not have a phase difference, such as Zero TAC (Konica Minolta Opto Co., Ltd.) and Z TAC (Fuji Film Co., Ltd.), etc. is mentioned, for example. An unextended cyclic olefin-based resin substrate is also preferable. The surface of the base material that is not laminated with a polarizing film can also be treated with hard coating, antireflection treatment, antistatic treatment, etc.

If the thickness of the substrate is too thin, the strength will decrease and the workability will tend to be deteriorated, so it is usually 5 to 300 μm, preferably 20 to 200 μm, and more preferably 20 to 100 μm.

The method of applying the composition for forming a polarizing film to a substrate etc. includes, for example, a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, a coater ( Known methods such as coating methods such as the applicator method and printing methods such as the flexo method.

Then, under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the composition for forming a polarizing film does not polymerize, the solvent is removed by drying or the like to form a dry coating film. The drying method may, for example, be natural drying, ventilation drying, heat drying, or reduced-pressure drying.

Moreover, in order to make the phase transfer of the polymerizable liquid crystal compound to the liquid phase, the temperature is raised to above the temperature at which the polymerizable liquid crystal compound will phase transfer to the liquid phase, and then the temperature is lowered to make the phase transfer of the polymerizable liquid crystal compound to the smectic phase (lamellar phase). column liquid crystal state). Such a phase transfer may be performed after the solvent in the coating film is removed, or may be performed simultaneously with the removal of the solvent.

A cured film of the polymerizable liquid crystal composition is formed by polymerizing the polymerizable liquid crystal compound while maintaining the state of the polymerizable liquid crystal compound in a smectic liquid crystal state as a polarizing film. The polymerization method is preferably photopolymerization. In photopolymerization, the light irradiated on the dry coating film can be determined according to the type of the photopolymerization initiator contained in the dried coating film, the type of the polymerizable liquid crystal compound (especially the type of the polymerizable group contained in the polymerizable liquid crystal compound), species) and the amount of the polymerizable liquid crystal compound are appropriately selected. Specific examples thereof include one or more kinds of light or active electron rays selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays. Among them, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction, or it can be widely used as a photopolymerization device in this field, and it is more preferable to use ultraviolet light. The method of photopolymerization depends on the type of polymerizable liquid crystal compound or photopolymerization initiator contained in the polymerizable liquid crystal composition. In addition, during polymerization, the polymerization temperature can also be controlled by cooling the dry coating film and performing light irradiation by appropriate cooling means. By employing such a cooling means and performing polymerization of the polymerizable liquid crystal compound at a lower temperature, even if a base material having low heat resistance is used, a polarizing film can be formed appropriately. During photopolymerization, by performing masking or developing, etc., a patterned polarizing film can also be obtained.

The light sources of the aforementioned active energy rays can be, for example, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, and wavelengths of emitted light LED light sources ranging from 380 to 440nm, chemical lamps, black light lamps, microwave excited mercury lamps, metal halide lamps, etc.

The ultraviolet irradiation intensity is usually 10 to 3,000 mW/cm ² . The intensity of ultraviolet irradiation is preferably an intensity in a wavelength region effective for activating the photopolymerization initiator. The time for irradiating light is usually 0.1 second to 10 minutes, preferably 1 second to 5 minutes, more preferably 5 seconds to 3 minutes, and more preferably 10 seconds to 1 minute. If the ultraviolet irradiation intensity is irradiated once or multiple times, the cumulative light intensity is 10 to 3000mJ/cm ² , preferably 50 to 2000mJ/cm ² , more preferably 100 to 1000mJ/cm ² .

By performing photopolymerization, the polymerizable liquid crystal compound is polymerized while maintaining a smectic phase, preferably in a liquid crystal state maintaining a high-order smectic phase, to form a polarizing film. The polarizing film obtained by polymerizing the polymerizable liquid crystal compound while maintaining the liquid crystal state of the smectic phase is also accompanied by the effect of the aforementioned dichroic pigment. The resulting polarizing film) has the advantage of high polarizing performance. Furthermore, it has the advantage of excellent strength compared to the one coated only with a dichroic dye or a lyotropic liquid crystal.

The thickness of the polarizing film can be appropriately selected according to the applicable display device, preferably 0.1 to 10 μm, more preferably 0.3 to 4 μm, and even more preferably 0.5 to 3 μm.

The polarizing film is preferably formed on the alignment film. The alignment film has an alignment-limiting force for aligning the polymerizable liquid crystal compound in a desired direction. The orientation film is preferably solvent-resistant to the application of a composition containing a polymerizable liquid crystal compound, and has heat resistance to solvent removal or heat treatment for orientation of the polymerizable liquid crystal compound. . Such an alignment film system can include, for example: an alignment film containing an alignment polymer, a light alignment film, a groove alignment film with a concave-convex pattern or a plurality of grooves on the surface, a stretched film extending toward the alignment direction, etc. From the point of view of the accuracy and quality of the orientation angle, it is better to use a light orientation film.

唑、聚伸乙基亞胺、聚苯乙烯、聚乙烯基吡咯啶酮、聚丙烯酸及聚丙烯酸酯。其中，以聚乙烯醇為較佳。定向性聚合物係可單獨使用或組合2種以上而使用。 Orientation polymers include, for example, polyamides or gelatins having amide bonds in the molecule, polyimides having amide bonds in the molecule and polyamic acids such as polyimides and their hydrolyzates, polyamides, and polyamides. Vinyl alcohol, alkyl modified polyvinyl alcohol, polyacrylamide, poly

Azole, polyethylenimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylates. Among them, polyvinyl alcohol is preferred. The orientation polymers can be used alone or in combination of two or more.

The alignment film containing the alignment polymer is usually coated with a composition in which the alignment polymer is dissolved in a solvent (hereinafter, also referred to as "alignment polymer composition") on the substrate, and the solvent is removed, or the The directional polymer composition is coated on the substrate, and the solvent is removed, and obtained by rubbing (rubbing method). As a solvent, the thing similar to what was mentioned above as a solvent usable when forming a polarizing film is mentioned.

As for the concentration of the oriented polymer in the oriented polymer composition, as long as the oriented polymer material can be completely dissolved in the solvent, it is sufficient, but relative to the solution, it is 0.1 to 20% in terms of solid content. More preferably, it is about 0.1 to 10%.

As for the oriented polymer composition, commercially available oriented film materials can also be directly used. Examples of commercially available oriented film materials include: Sunever (registered trademark, manufactured by Nissan Chemical Industry Co., Ltd.), Optomer (registered trademark, manufactured by JSR Corporation), and the like.

The method of applying the alignment polymer composition to the substrate is the same as the method exemplified as the method of applying the composition for forming a polarizing film to the substrate.

The methods for removing the solvent contained in the directional polymer composition include, for example, natural drying, ventilation drying, heat drying, and reduced-pressure drying.

In order to impart an orientation regulating force to the orientation film, a rubbing treatment (rubbing method) may be performed as necessary.

As for the method of imparting directional control force by rubbing, for example: a method of bringing a rubbing roller into contact with a film of an oriented polymer; the rubbing roller is wound with a rubbing cloth and rotated, and the directional The film system of the object is formed on the surface of the substrate by coating the directional polymer composition on the substrate and annealing.

A photo-alignment film is usually coated with a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter also referred to as a "photo-alignment film-forming composition") on a substrate, and irradiated with polarized light (compared to The best is polarized UV). In the point that the direction of the orientation confinement force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light, a photo-alignment film is more preferable.

The photoreactive group refers to a group that produces liquid crystal alignment ability by light irradiation. Specifically, examples include those that participate in photoreactions that are the origin of liquid crystal alignment ability, such as induction of molecular orientation or isomerization reactions, dimerization reactions, photocrosslinking reactions, or photodecomposition reactions generated by light irradiation. base. Among them, a group that participates in a dimerization reaction or a photocrosslinking reaction is preferable in terms of excellent orientation. As far as the photoreactive group is concerned, it is better to have a group with an unsaturated bond (especially a double bond), to have a group selected from carbon-carbon double bond (C=C bond), carbon-nitrogen double bond (C =N bond), nitrogen-nitrogen double bond (N=N bond) and carbon-oxygen double bond (C=O bond) at least one group is particularly preferred.

(formazan)基及具有氧偶氮苯(azoxybenzene)構造之基等。具有C=O鍵之光反應性基係可舉例如二苯甲酮基、香豆素基、蒽醌基及馬來醯亞胺基等。此等基亦可具有烷基、烷氧基、芳基、烯丙氧基、氰基、烷氧基羰基、羥基、磺酸基、鹵化烷基等取代基。 The photoreactive groups with C=C bonds can be listed as: vinyl, polyalkenyl, stilbene (stilbene) base, 4-(2-styrene) pyridine (stilbazole) base, styrene pyridinium (stilbazolium) ) group, chalcone (chalcone) group and cinnamyl group, etc. Examples of photoreactive groups having a C=N bond include aromatic schiff base groups and groups having structures such as aromatic hydrazones. The photoreactive groups with N=N bonds can be listed as: azophenyl, azonaphthyl, aromatic heterocyclic azo, disazo, methyl

(formazan) groups and groups with an azoxybenzene structure, etc. The photoreactive group having a C=O bond can be, for example, a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have a substituent 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, or a halogenated alkyl group.

Among them, the photoreactive group that participates in the photodimerization reaction is preferred. In terms of the amount of polarized light irradiation necessary for photoalignment, it is easy to obtain a photoalignment film with excellent thermal stability and stability over time. Cinnamoyl and chalcone groups are preferred. The polymer having a photoreactive group is particularly preferably one having a cinnamoyl group having a cinnamic acid structure at the end of the side chain of the polymer.

By coating the composition for forming a photo-alignment film on the substrate, a photo-alignment sensing layer can be formed on the substrate. The solvent contained in the composition includes the same solvents as those exemplified above that can be used when forming a polarizing film, and can be appropriately selected according to the solubility of the polymer or monomer having a photoreactive group.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photoalignment film can be appropriately adjusted by the type of polymer or monomer and the thickness of the intended photoalignment film, but relative to photoalignment The mass of the film-forming composition is preferably at least 0.2 mass%, more preferably in the range of 0.3 to 10 mass%. The composition system for forming a photoalignment film may contain a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer within a range that does not significantly impair the properties of the photoalignment film.

As the method of applying the composition for forming a photoalignment film to a substrate, for example, the same method as the method of applying an alignment composition to a substrate can be mentioned. As the method of removing the solvent from the applied composition for forming a photoalignment film, natural drying method, ventilation drying method, heat drying method and reduced pressure drying method etc. are mentioned.

Irradiation of polarized light may be performed by directly irradiating polarized light UV with respect to the composition for forming a photoalignment film coated on the substrate with the solvent removed, or by irradiating polarized light from the substrate side and allowing the polarized light to pass through. form of exposure. The polarized light is preferably parallel light in nature. The wavelength of the polarized light to be irradiated is preferably in the wavelength region where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength of 250 to 400 nm is particularly preferred. In terms of the light source used for the polarized light irradiation, examples include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high pressure mercury lamps and metal halide lamps better. Among them, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and a metal halide lamp are preferable because the luminous intensity of ultraviolet rays with a wavelength of 313 nm is large. The light from the aforementioned light source can be irradiated with polarized light UV by passing through an appropriate polarizer. Such polarizers can use polarizing filters or Glan-Thompson (Glan-Thompson) polarizers, Glan-Taylor (Glan-Taylor) polarizers or wire grid polarizers .

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

The groove (groove) oriented film is a film with a concave-convex pattern or a plurality of grooves (grooves) on the film surface. When the polymerizable liquid crystal compound is coated on a film having a plurality of linear grooves arranged side by side at equal intervals, the liquid crystal molecules will be oriented along the direction of the grooves.

The method of obtaining the groove alignment film is, for example, exposing the surface of the photosensitive polyimide film through an exposure mask with a pattern-shaped slit, and then developing and rinsing to form a concave-convex pattern. The method of forming; on the plate-shaped original disc with groove on the surface, forming a layer of UV curable resin before hardening, and moving the formed resin layer to the base material and then hardening; A method in which a film of UV-curable resin before curing is pressed against a roll-shaped master having a plurality of grooves to form concavities and convexities, and then cured.

The thickness of the alignment film (orientation film containing alignment polymer or light alignment film) is usually in the range of 10 to 10000nm, preferably in the range of 10 to 1000nm, more preferably below 500nm, more preferably in the range of 10 to 200nm, especially The best range is from 50 to 150nm.

The present invention includes a polarizing plate (elliptical polarizing plate) comprising the polarizing film and retardation film of the present invention. In the polarizing plate of the present invention, the retardation film preferably satisfies the formula (X): 100≦Re(550)≦180 (X) [wherein, Re(550) represents the in-plane retardation value at a wavelength of 550nm]. If the retardation film has the in-plane retardation value shown in (X) above, it will function as a so-called λ/4 plate. The aforementioned formula (X) is preferably 100nm≦Re(550)≦180nm, more preferably 120nm≦Re(550)≦160nm. Moreover, Re(550) can be measured by the method described in an Example.

In the polarizing plate of the present invention, the angle formed by the slow axis of the retardation film and the absorption axis of the polarizing film is preferably substantially 45°. In addition, "substantially 45°" in the present invention means 45°±5°.

Furthermore, it is better that the retardation film satisfy the formula (Y): Re(450)/Re(550)<1 (Y) [wherein, Re(450) and Re(550) respectively represent wavelength 450nm and 550nm in-plane phase difference]. The retardation film satisfying the above formula (Y) has so-called reverse wavelength dispersion, which shows excellent polarizing performance. The value of Re(450)/Re(550) is preferably at most 0.93, more preferably at most 0.88, still more preferably at most 0.86, preferably at least 0.80, more preferably at least 0.82.

The aforementioned retardation film may be a stretched film that obtains a retardation by stretching a polymer, but from the viewpoint of thinning the polarizing plate, it is preferably a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (hereinafter also referred to as The cured product called "polymerizable liquid crystal composition (B)") is composed of a polymer in an aligned state of the aforementioned polymerizable liquid crystal compound. The polymerizable liquid crystal compound forming the retardation film (hereinafter also referred to as "polymerizable liquid crystal compound (B)") means a liquid crystal compound having a polymerizable functional group (especially a photopolymerizable functional group). The so-called photopolymerizable functional group refers to a group capable of participating in a polymerization reaction by active radicals and acids generated by a photopolymerization initiator. Examples of photopolymerizable functional groups include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, and oxirane group, oxetanyl group, etc. Among them, acryloxy, methacryloxy, vinyloxy, oxirane and oxetanyl are preferred, and acryloxy is more preferred. The liquid crystal property of the polymerizable liquid crystal compound (B) can be thermotropic liquid crystal or lyotropic liquid crystal, and the phase order structure can be nematic liquid crystal or smectic liquid crystal. The polymerizable liquid crystal compound (B) may be used alone or in combination of two or more.

The polymerizable liquid crystal compound (B) includes, for example, compounds satisfying all of the following (a) to (d) from the viewpoint of imparting ease of film formation and retardation represented by the aforementioned formula (Y).

(A) Compounds with thermotropic liquid crystallinity;

(b) Having π electrons in the long axis direction (a) of the polymerizable liquid crystal compound.

(c) There are π electrons in the direction intersecting with the major axis direction (a) [the intersecting direction (b)].

(D) Let the total of π electrons existing in the major axis direction (a) be N(πa), and the total molecular weight existing in the major axis direction be N(Aa), and define it by formula (i) The π-electron density system of the long-axis direction (a) of the polymerizable liquid crystal compound is: D(πa)=N(πa)/N(Aa) (i); the total of π-electrons existing in the crossing direction (b) is set to N(πb), and the total molecular weight present in the crossing direction (b) is set to N(Ab), and the π electron density system of the crossing direction (b) of the polymerizable liquid crystal compound defined by formula (ii): D (πb)=N(πb)/N(Ab) (ii); the π-electron density in the long axis direction (a) of the polymerizable liquid crystal compound defined by formula (i) is the same as that of the aforementioned polymerizable liquid crystal compound defined by formula (ii) The relationship of the π-electron density in the crossing direction (b) of the liquid crystal compound is: 0≦[D(πa)/D(πb)]≦1 [that is, the π-electron density in the crossing direction (b) is greater than that in the long-axis direction (a) π-electron density].

The polymerizable liquid crystal compound (B) that satisfies all of the above (a) to (d) can be coated on the alignment film formed by rubbing, and can form a nematic phase by heating above the phase transition temperature. The nematic phase formed by the alignment of the polymerizable liquid crystal compound (B) is usually aligned such that the long axis directions of the polymerizable liquid crystal compound are parallel to each other, and the long axis direction becomes the alignment direction of the nematic phase.

。前述式(II)所示之化合物可單獨使用或組合2種以上而使用。 Generally, the polymerizable liquid crystal compound (B) which has the above-mentioned characteristic shows reverse wavelength dispersibility in many cases. Compounds satisfying the characteristics of (a) to (d) above can be exemplified by compounds represented by formula (II):

. The compound represented by said formula (II) can be used individually or in combination of 2 or more types.

In formula (II), Ar represents a divalent aromatic group which may have a substituent. Here, the aromatic group is a group having a planar ring structure, and the number of π electrons in the ring structure is [4n+2] according to Hückel's rule. Here, n represents an integer. In the case of forming a ring structure containing heteroatoms such as -N= or -S-, it includes non-covalent bond electron pairs on these heteroatoms and satisfies Huckel's rule, and also includes aromaticity. Preferably, at least one of nitrogen atom, oxygen atom and sulfur atom is included in the divalent aromatic group.

G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 4 carbons, a fluoroalkyl group having 1 to 4 carbons, a to 4 alkoxy, cyano or nitro, and the carbon atoms constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may also be substituted by oxygen atom, sulfur atom or nitrogen atom.

L ¹ , L ² , B ¹ and B ² are each independently a single bond or a divalent linking group.

k and l each independently represent an integer of 0 to 3, and satisfy the relationship of 1≦k+l. Here, when 2≦k+1, B ¹ and B ² , G ¹ and G ² may be the same as or different from each other.

E ¹ and E ² independently represent an alkanediyl group having 1 to 17 carbon atoms, wherein the hydrogen atoms contained in the alkanediyl group may be replaced by halogen atoms, and the -CH ₂ - contained in the alkanediyl group may be Substituted by -O-, -S-, -Si-. ^P1 and ^P2 independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

G ¹ and G ² are independently, preferably 1,4-phenylenediyl groups which may be substituted by at least one substituent selected from the group consisting of halogen atoms and alkyl groups with 1 to 4 carbon atoms, which may be 1,4-cyclohexanediyl substituted by at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms; more preferably 1,4-phenylenediyl substituted by methyl Base, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-trans-cyclohexanediyl; especially unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-trans-cyclohexanediyl. It is preferred that at least one of G ¹ and G ² present in plural is a divalent alicyclic hydrocarbon group, more preferably at least one of G ¹ and G ² bonded to L ¹ or L ² is divalent Valence of alicyclic hydrocarbon group.

L ¹ and L ² are independent, preferably a single bond, an alkylene group with 1 to 4 carbons, -O-, -S-, -R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, R ^a7 OC=OOR ^a8 -, -N=N-, -CR ^c =CR ^d - or -C≡C-. Here, R ^a1 to R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbons, and R ^c and R ^d represent an alkyl group having 1 to 4 carbons or a hydrogen atom. L ¹ and L ² are each independently, more preferably a single bond, -OR ^a2-1 -, -CH ₂ -, -CH ₂ CH ₂ -, -COOR ^a4-1 - or -OCOR ^a6-1 -. Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent any one of a single bond, -CH ₂ -, and -CH ₂ CH ₂ -. L ¹ and L ² are each independently, and are more preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ - or -OCO-.

In a suitable embodiment of the present invention, at least one of ^G1 and ^G2 in the polymerizable liquid crystal compound used in formula (II) is a divalent alicyclic hydrocarbon group, and the divalent alicyclic The hydrocarbon group of the formula is bonded to a divalent aromatic group Ar which may have a substituent through L ¹ and/or L ² of -COO-.

B ¹ and B ² are independent, preferably a single bond, an alkylene group with 1 to 4 carbons, -O-, -S-, -R ^a9 OR ^a10 -, -R ^a11 COOR ^a12 -, -R ^a13 OCOR ^a14 -, or R ^a15 OC=OOR ^a16 -. Here, R ^a9 to R ^a16 each independently represent a single bond or an alkylene group having 1 to 4 carbons. B ¹ and B ² are each independently, more preferably a single bond, -OR ^a10-1 -, -CH ₂ -, -CH ₂ CH ₂ -, -COOR ^a12-1 -, or -OCOR ^a14-1 -. Here, R ^a10-1 , R ^a12-1 , and R ^a14-1 each independently represent any of a single bond, -CH ₂ -, and -CH ₂ CH ₂ -. B ¹ and B ² are each independently, and are more preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, -OCO-, or -OCOCH ₂ CH ₂ -.

From the point of view of reverse wavelength dispersion, k and l are preferably in the range of 2≦k+l≦6, k+l=4 is more preferable, and k=2 and l=2 are still more good. If k=2 and l=2, it is even better because of the symmetrical structure.

E ¹ and E ² are independently independent, preferably alkanediyl having 1 to 17 carbons, more preferably alkanediyl having 4 to 12 carbons.

The polymeric groups represented by ^P1 or ^P2 can be exemplified as: epoxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloxy group, formyl group Acryloxy group, oxirane group and oxetanyl group, etc. Among these, acryloxy, methacryloxy, vinyloxy, oxirane and oxetanyl are preferred, and acryloxy is more preferred.

環、嘧啶環、三唑環、三

環、吡咯啉環、咪唑環、吡唑環、噻唑環、苯并噻唑環、噻吩并噻唑環、

唑環、苯并

唑環、及啡啉環等。此等之中，以具有噻唑環、苯并噻唑環或苯并呋喃環為較佳，以具有苯并噻唑基為更佳。在Ar含有氮原子時，該氮原子以具有π電子為較佳。 Ar preferably has at least one member selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, and an electron-attracting group. Examples of the aromatic hydrocarbon ring system include benzene ring, naphthalene ring, anthracene ring, etc., with benzene ring and naphthalene ring being preferred. Examples of the aromatic heterocyclic ring system include: furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyrrole ring,

ring, pyrimidine ring, triazole ring, three

ring, pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole ring,

Azole ring, benzo

Azole ring, and phenanthroline ring, etc. Among these, it is preferable to have a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is more preferable to have a benzothiazolyl group. When Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

In formula (II), the total number N _π of the π electrons contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, more preferably 14 or more, and most preferably 14 or more. 16 or more. Preferably it is below 30, more preferably below 26, even more preferably below 24.

The aromatic group represented by Ar includes, for example, groups of formula (Ar-1) to formula (Ar-23).

In formula (Ar-1) to formula (Ar-23), the * symbol represents a linking part, and Z ⁰ , Z ¹ and Z ² independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 12 carbons, and a cyano group , nitro, alkylsulfinyl with 1 to 12 carbons, alkylsulfonyl with 1 to 12 carbons, carboxyl, fluoroalkyl with 1 to 12 carbons, alkoxy with 1 to 6 carbons , Alkylthio with 1 to 12 carbons, N-alkylamino with 1 to 12 carbons, N,N-dialkylamino with 2 to 12 carbons, N-alkyl with 1 to 12 carbons A sulfamoyl group or a N,N-dialkylsulfamoyl group with 2 to 12 carbon atoms.

Q ¹ and Q ² independently represent -CR ^2' R ^3' -, -S-, -NH-, -NR ^2' -, -CO- or -O-, R ^2' and R ^3' are independently Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

J ¹ and J ² each independently represent a carbon atom or a nitrogen atom.

Y ¹ , Y ² and Y ³ each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.

W ¹ and W ² independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.

The aromatic hydrocarbon groups in Y ¹ , Y ² and Y ³ include, for example, aromatic hydrocarbon groups with 6 to 20 carbon atoms such as phenyl, naphthyl, anthracenyl, phenanthrenyl, and biphenyl. Examples of the aromatic hydrocarbon group include: phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, etc., phenyl and naphthyl are preferred, and phenyl is more preferred.

Examples of the aromatic heterocyclic group include aromatic heterocyclic groups having 4 to 20 carbon atoms containing at least one heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom. The aromatic heterocyclic group can be enumerated such as: furyl, pyrrolyl, thienyl, pyridyl, thiazolyl, benzothiazolyl, etc., with furyl, thienyl, pyridyl, thiazolyl, benzothiazolyl as better.

Y ¹ and Y ² are independently independent, and may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group that may be substituted.

The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from a collection of aromatic rings. The polycyclic aromatic heterocyclic group is a condensed polycyclic aromatic heterocyclic group, or a group derived from a collection of aromatic rings.

Z ⁰ , Z ¹ and Z ² are independently independent, preferably a hydrogen atom, a halogen atom, an alkyl group with 1 to 12 carbons, a cyano group, a nitro group, an alkoxy group with 1 to 12 carbons, and Z ⁰ is represented by hydrogen atom, an alkyl group having 1 to 12 carbons, and a cyano group are more preferable. ^Z1 and ^Z2 are more preferably hydrogen atom, fluorine atom, chlorine atom, methyl group, or cyano group.

Q ¹ and Q ² are preferably -NH-, -S-, -NR ^2' - and -O-, and R ^2' is preferably a hydrogen atom. Q ¹ and Q ² are particularly preferably -S-, -O-, -NH-.

From the viewpoint of molecular stability, among the formulas (Ar-1) to (Ar-23), the formulas (Ar-6) and (Ar-7) are preferable.

In formulas (Ar-17) to (Ar-23), Y ¹ can form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ .

環、嘧啶環、吲哚環、喹啉環、異喹啉環、卟啉環、吡咯啶環等。該芳香族雜環基可具有取代基。Y¹可與其所鍵結之氮原子及Z⁰一起為前述取代之多環系芳香族烴基或多環系芳香族雜環基。該多環系芳香族雜環基係可列舉如：苯并呋喃環、苯并噻唑環、苯并

唑環等。前述式(II)所示之化合物係例如可依據日本特開2010-31223號公報記載之方法而製造。 As the aromatic heterocyclic group, the above-mentioned aromatic heterocyclic ring that Ar may have can be mentioned. Examples include: pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyr

ring, pyrimidine ring, indole ring, quinoline ring, isoquinoline ring, porphyrin ring, pyrrolidine ring, etc. This aromatic heterocyclic group may have a substituent. Y ¹ may be the aforementioned substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ . The polycyclic aromatic heterocyclic group can be exemplified as: benzofuran ring, benzothiazole ring, benzo

Azole ring etc. The compound represented by the aforementioned formula (II) can be produced, for example, according to the method described in JP-A-2010-31223.

The content of the polymerizable liquid crystal compound (B) in the polymerizable liquid crystal composition (B) is, for example, 70 to 99.5 parts by mass, preferably 80 to 99.5 parts by mass relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition (B). 99 parts by mass, more preferably 90 to 98 parts by mass. There exists a tendency for the orientation of a retardation film to become high that content exists in the said range.

Here, the term "solid content" refers to the total amount of components excluding volatile components such as solvents from the polymerizable liquid crystal composition (B).

The polymerizable liquid crystal composition (B) may also contain a polymerization initiator for initiating the polymerization reaction of the polymerizable liquid crystal compound (B).

Examples of the polymerization initiator include the same ones as the polymerization initiators usable in the polymerizable liquid crystal composition (A) exemplified above. The polymerizable liquid crystal composition (B) may also contain photosensitizers, leveling agents, and additives exemplified as additives contained in the polymerizable liquid crystal composition (A) as needed. Photosensitizers and leveling agents include the same ones as those contained in the polymerizable liquid crystal composition (A) exemplified above.

The retardation film system can prepare a composition by adding a solvent to the polymerizable liquid crystal composition (B) containing the polymerizable liquid crystal compound (B) and, if necessary, polymerization initiators, additives, etc., and mixing and stirring (hereinafter, Also referred to as "retardation film-forming composition"), this composition is coated on a substrate or an alignment film, and the solvent is removed by drying, so that the polymerizable liquid crystal compound (B) in the resulting coating film is Hardened by heating and/or active energy rays. The base material and/or alignment film used for production of a retardation film are the same as what was exemplified above and which can be used when producing the polarizing film of this invention.

The solvent used in the composition for forming a retardation film, the coating method of the composition for forming a retardation film, the curing conditions caused by active energy rays, etc., can all be listed as those that can be used in the production method of the polarizing film of the present invention. for the same.

The thickness of the retardation film can be appropriately selected according to the display device used, but from the viewpoint of thin film and flexibility, it is preferably 0.1 to 10 μm, more preferably 1 to 5 μm, and 1 to 3 μm. Even better.

The polarizing plate of the present invention is equipped with the polarizing film and the retardation film of the present invention, preferably a substrate, an alignment film (especially a light alignment film), the polarizing film and the retardation film of the present invention. The polarizing plate of the present invention may further contain other layers (protective layer, adhesive layer, etc.) other than these. In the polarizing plate of the present invention, the polarizing film of the present invention and the phase difference film system may be bonded via an adhesive layer or an adhesive layer. In the polarizing plate of the present invention, the retardation film can also be directly formed on the polarizing film of the present invention by directly coating the composition for forming a retardation film on the polarizing film of the present invention.

From the viewpoint of the flexibility or visibility of the display device, the thickness of the polarizing plate of the present invention is preferably from 10 to 300 μm, more preferably from 20 to 200 μm, and still more preferably from 25 to 100 μm.

The present invention is a display device including the polarizing film of the present invention or the polarizing plate of the present invention.

The display device of the present invention can be obtained, for example, by bonding the polarizing film or polarizing plate of the present invention to the surface of the display device via an adhesive layer.

The so-called display device is a device with a display mechanism, which contains a light-emitting element or a light-emitting device as a light-emitting source. The display device can be, for example, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (field emission display device (FED, etc.) , surface electric field emission display device (SED)), electronic paper (display device using electronic ink or electrophoretic elements), plasma display device, projection display device (grid light valve (grating light valve, GLV) display device, Display devices with digital micromirror devices (digital micromirror devices, DMDs, etc.), piezoelectric ceramic displays, etc. The liquid crystal display device is any one of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection type liquid crystal display device. These display devices may be display devices that display 2-dimensional images, or may be stereoscopic display devices that display 3-dimensional images. In particular, the display device of the present invention is preferably an organic EL display device and a touch panel display device, particularly preferably an organic EL display device.

[Example]

<Preparation of polymerizable liquid crystal composition (hereinafter, also referred to as "polarizing film forming composition")>

The composition (1) for polarizing film formation was obtained by mixing the following components, and stirring at 80 degreeC for 1 hour. As the dichroic dye, the azo dye described in the Examples of JP-A-2013-101328 was used. Hereinafter, "%" and "part" in the examples mean % by mass and parts by mass, respectively, unless otherwise specified.

‧Polymerizable liquid crystal compound:

‧Dichroic pigments:

Azo pigments;

‧Polymerization initiator:

2-Dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure369; manufactured by Ciba Specialty Chemicals Co., Ltd.) 6 parts

‧Leveling agent:

Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 1.2 parts

‧Solvent:

400 parts o-xylene

Furthermore, in the composition (1) for forming a polarizing film, except that the compound described below is mixed in the amount shown in Table 1 as an antioxidant, the rest is in the same manner as the composition (1) for forming a polarizing film. , and the compositions (2) to (18) for forming a polarizing film were obtained.

The addition amount of the antioxidant in Table 1 is represented by the quantity with respect to 100 mass parts of polymerizable liquid crystal compounds in the composition for polarizing film formation.

<Structure of Antioxidant>

The structure of the antioxidant used in the Example and the comparative example is as follows.

(Antioxidant A: 4-n-octyloxyphenol)

(Antioxidant B: 4,4'-biphenol)

(Antioxidant C: 4-ethoxy-4'-hydroxybiphenyl)

(Antioxidant D: 4-butoxy-4'-hydroxybiphenyl)

(Antioxidant E: 4-octyloxy-4'-hydroxybiphenyl)

(Antioxidant F: Dibutylhydroxytoluene)

(Antioxidant G: Tinuvin 770; manufactured by BASF Corporation)

(Antioxidant H: Sumilizer GP; manufactured by Sumitomo Chemical Co., Ltd.)

(Antioxidant I: p-Methoxyphenol)

<Measurement of liquid crystal phase transition temperature change T1-T2>

(1) Formation of oriented film

On a glass substrate, 2% by mass of polyvinyl alcohol (Poly(vinyl Alcohol) 1000, Completely Hydrolyzed], manufactured by Wako Pure Chemical Industries, Ltd.) was applied by spin coating The aqueous solution, after drying, forms a film with a thickness of 100 nm. Next, an orientation film was 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 type, manufactured by Changyang Engineering Co., Ltd.), with a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Chemical Co., Ltd.) with a pressing amount of 0.15 mm, rotation speed 500rpm, 16.7mm/s conditions.

(2) Determination of T1

As for the polymerizable liquid crystal compound, by stirring 90 parts of the compound represented by the formula (A-6), 10 parts of the compound represented by the formula (A-7), and 400 parts of o-xylene at 80° C. for 1 hour, Thereby, a uniformly mixed mixed composition can be obtained.

The obtained mixed composition was coated on the above-mentioned glass with an orientation film by the spin coating method, and heated and dried on a hot plate at 130° C. for 3 minutes to remove o-xylene as a solvent. Thereafter, the obtained coating film was rapidly cooled to room temperature to obtain a dry coating film of a polymerizable liquid crystal compound. After the dried film was heated to 130°C on the heating plate, the temperature was lowered at a rate of 5°C/min, and when the temperature was lowered to 23°C, it was observed with a polarizing microscope to measure the phase transition temperature. As a result, it was confirmed that the phase shifted to the nematic liquid crystal phase at 113.7°C, the phase shifted to the smectic A phase at 109.6°C, the phase shifted to the smectic B phase at 92.0°C, and the smectic B phase was maintained until it became 23 until ℃. In the above process, since the liquid crystal phase that appears on the lowest temperature side is the smectic B phase, T1 is defined as 92.0° C. of the phase transition temperature to the smectic B phase.

(3) Determination of T2

Except for adding 1 part by mass of antioxidants A to I to 100 parts by mass of the polymerizable liquid crystal compound to the above-mentioned mixed composition, the rest is determined by the same method as the measurement of T1 in (2) above. A dry film formed of a mixture of an antioxidant and a polymerizable liquid crystal compound is obtained. The phase transition temperature was measured by the same method as the measurement of T1 in (2) above, and it was found that the liquid crystal phase that appeared on the lowest temperature side in all the mixtures was the smectic B phase. Table 2 describes the phase transition temperature (T2) to the liquid crystal phase that appeared on the lowest temperature side when each antioxidant was contained.

Example 1

(1) Fabrication of light alignment film on substrate

(i) Preparation of composition for light alignment film formation

The following components described in JP 2013-033249 A were mixed, and the resulting mixture was stirred at 80° C. for 1 hour to obtain a photoalignment film-forming composition.

‧Photo-alignment polymer:

2份

2 copies

‧Solvent:

98 parts of o-xylene

(ii) Formation of light alignment film

Using a triacetyl cellulose film (KC8UX2M, manufactured by Konica Minolta Co., Ltd.) as a substrate, corona treatment was applied to the surface of the film, and the composition for forming an optical alignment film was applied and dried at 120°C to obtain a dry film. The polarized light UV was irradiated on the dry film to form a photo-alignment film, and a film with a photo-alignment film was obtained. The polarized UV treatment was performed using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.), under the condition that the intensity measured at a wavelength of 365 nm was 100 mJ.

(2) Production of polarizing film

On the film with a photo-alignment film obtained as described above, the composition (2) for forming a polarizing film was coated by the bar coating method (#9 30mm/s), and heated and dried in a drying oven at 120°C for 1 minute. After the polymerizable liquid crystal compound is phase-transferred to the liquid phase, the polymerizable liquid crystal compound is cooled to room temperature to phase-transfer the polymerizable liquid crystal compound to a smectic liquid crystal state. Then, using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.), ultraviolet rays with an exposure dose of 1000 mJ/cm ² (365 nm basis) were irradiated on the layer formed from the composition for forming a polarizing film, thereby The polymerizable liquid crystal compound contained in the dry film is polymerized while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound, and a polarizing film is formed from the dry film. The film thickness of the polarizing film at this time was measured with a laser microscope (OLS3000 manufactured by Olympus Co., Ltd.), and it was 2.3 μm. The product obtained in this way is a polarizer containing a polarizing film and a substrate. Using the X-ray diffraction device X'Pert PRO MPD (manufactured by Spectris Co., Ltd.), the same X-ray diffraction measurement was performed on this polarizing film, and the full width at half maximum (Full Width at Half Maximum, FWHM) = sharp diffraction peak (Bragg peak) of about 0.17°. Also, the same result was obtained for the incidence from the direction perpendicular to the rubbing. It was confirmed that the order period (d) obtained from the peak position was about 4.4 Å, and a structure reflecting a high-order smectic phase was formed.

(3) Production of polarizing film laminates

Further, after corona treatment was applied to the surface of the polarizing film of the polarizer obtained above, an aqueous solution (viscosity: 92 cP) was applied to the corona-treated surface with a wire bar coater (#30). 7 parts of carboxy-modified polyvinyl alcohol ["Kuraray Poval KL318" manufactured by Kuraray Co., Ltd.], water-soluble polyamide epoxy resin as a thermal crosslinking agent [" An aqueous solution of 3.5 parts of Sumilizer Resin 650 (aqueous solution with a solid content concentration of 30% by mass)]. By drying at 80° C. for 5 minutes, the aforementioned aqueous solution was dried to form a protective layer, and a polarizer with a protective layer was produced. Furthermore, glass (Corning, EagleXG) was bonded to the protective layer via an adhesive layer formed of a pressure-sensitive adhesive (Lintec Co., Ltd., film thickness: 25 μm) to obtain the polarizing film of Example 1. laminated body.

<Measurement of polarization degree Py and monomer transmittance Ty>

The degree of polarization Py and the single transmittance Ty of the polarizing film laminate of Example 1 were measured as follows. Using a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) equipped with a polarizer holder (folder), the direction of the transmission axis is measured in the wavelength range of 380nm to 780nm by the double beam method The transmittance (Ta) and the transmittance (Tb) in the direction of the absorption axis. The contrast side of the holder is provided with a screen that cuts off 50% of the light.

Use the following formulas [(Formula 1) and (Formula 2)] to calculate the monomer transmittance and polarization degree of each wavelength, and then perform photometric correction according to the 2-degree field of view (C light source) of JIS Z 8701 to calculate the photometric correction Monomer transmittance (Ty) and photometrically corrected polarization (Py).

Monomer penetration rate Ty(%)=(Ta+Tb)/2 (Equation 1)

Degree of polarization Py(%)=(Ta-Tb)/(Ta+Tb)×100 (Equation 2)

Examples were obtained by the same method except that the polarizing film forming compositions (1), (3) to (18) shown in Table 3 were used instead of the polarizing film forming composition (2). 2 to 15, the polarizing film laminates of Comparative Example 1, Comparative Example 2 and Reference Example 1.

<Evaluation of Lightfastness>

For the laminates of Examples 1 to 15, Comparative Example 1, Comparative Example 2, and Reference Example 1, the light resistance was evaluated according to the following method. The results are shown in Table 3.

Put the above-mentioned polarizing film laminate with the triacetyl cellulose film of the substrate facing up, and put it into a light fastness tester (Suntest XLS+; manufactured by ATLAS), and irradiate the accumulated light at 23070KJ/ ^m2 . Re-measure the polarization degree Py and monomer transmittance Ty of the laminate, and calculate the change rate before and after the light resistance test.

It was confirmed that the polarizing films (Examples 1 to 15) prepared from the polarizing film-forming compositions 2 to 16 (ie, the polymerizable liquid crystal composition of the present invention) had good light resistance.

Example 16

<Production of Circular Polarizer>

On the protective layer of the polarizer with a protective layer obtained in the production process of the polarizing film laminate in Example 5, an adhesive layer formed of a pressure-sensitive adhesive (manufactured by Lintec Co., Ltd., film thickness 25 μm) was interposed , to transfer the retardation film produced according to Example 1 of Japanese Patent Application Laid-Open No. 2015-143786. Then, an aluminum metal plate was bonded through an adhesive layer formed of a pressure-sensitive adhesive (manufactured by Lintec Co., Ltd., film thickness: 25 μm) to obtain an elliptically polarizing plate.

<Measurement of reflection hue a*, b*>

The reflection hue of the triacetyl cellulose film surface of the base material of the obtained ellipsoidal polarizing plate was measured with a spectrophotometer (CM-3700d, manufactured by Konica Minolta Co., Ltd.) to measure L*a*b*(CIE) Chromaticity a* and b* of the color system.

<Evaluation of Lightfastness>

Then, with the triacetyl cellulose film of the base material facing up, put it into a light resistance tester (Suntest XLS+; manufactured by ATLAS), irradiate the accumulated light at 23070KJ/ ^m2 , and then measure the laminated body again. Chromaticity a* and b*, and calculate the rate of change before and after the light fastness test. The results are shown in Table 4.

It was confirmed that the elliptically polarizing plate having the polarizing film of the present invention has a small amount of change in chromaticity and has good light resistance.

Claims (14)

A polymerizable liquid crystal composition, comprising: a polymerizable liquid crystal compound having at least one polymerizable group and exhibiting smectic liquid crystallinity, a dichroic pigment, and an antioxidant; the polymerizable group of the aforementioned polymerizable liquid crystal compound is free The above-mentioned dichroic dye is an azo dye; the above-mentioned antioxidant satisfies the formula (1) in the relationship with the above-mentioned polymerizable liquid crystal compound: 0.8 ° C ≦ T1-T2 (1) In the formula, T1 is the above-mentioned After the polymerizable liquid crystal compound is heated to 130°C in the atmosphere, when the phase transition temperature is measured while cooling to 23°C at 5°C/min, the phase transition temperature to the liquid crystal phase that appears on the lowest temperature side; T2 is based on 100 A mixture of the aforementioned polymerizable liquid crystal compound and 1 mass part of the aforementioned antioxidant is heated up to 130°C in the air, and when the phase transition temperature is measured while cooling at 5°C/min to 23°C, at the lowest temperature The phase transition temperature to the liquid crystal phase that appears on the side. As for the polymerizable liquid crystal composition described in claim 1, the polymerizable liquid crystal composition further includes a solvent. The polymerizable liquid crystal composition as described in claim 1 or 2, wherein the polymerizable group of the polymerizable liquid crystal compound is an acryloxy group. The polymerizable liquid crystal composition as described in claim 1 or 2, wherein 0.1 to 15 parts by mass of an antioxidant is contained relative to 100 parts by mass of the polymerizable liquid crystal compound. The polymerizable liquid crystal composition according to claim 1 or 2, wherein the antioxidant is at least one selected from the group consisting of phenolic compounds, alicyclic alcohol compounds, and amine compounds. The polymerizable liquid crystal composition as described in item 1 or 2 of the scope of the patent application, wherein the antioxidant has any structure shown in formula (2), formula (3) and formula (4);

In formula (2) and formula (3), R ₁ to R ₅ are independently -H, -OH, -NH ₂ , branched or non-branched alkyl with carbon number 1 to 12, or carbon number 1 to 12 branched or non-branched alkoxy groups; in formula (2) and formula (3), at least one of each of R ₁ to R ₅ is -OH or -NH ₂ . The polymerizable liquid crystal composition as described in claim 6 of the patent application, wherein the antioxidant is a compound represented by formula (5): A ₁ -L ₁ -(A ₂ -L ₂ ) _n -A ₃ (5) In the formula, _L1 and _L2 are independently a single bond or a divalent linking group, _A1 is the base shown in formula (2), formula (3) or formula (4), _A2 is the formula (6) Or the base shown in formula (7), A ₃ is the base shown in formula (8) or formula (9), n is an integer from 0 to 2, when n is 2, 2 A ₂ can be mutually the same, also may be different;

In formula (2) and formula (3), R ₁ to R ₅ are defined as the same definition as the definition described in item 7 of the scope of the patent application;

In formula (6) and formula (7), R ₆ to R ₉ are independently -H, -OH, -NH ₂ , a branched or non-branched alkyl group with 1 to 12 carbons, or a branched or non-branched alkyl group with 1 to 12 carbons. 12 branched or unbranched alkoxy;

In formula (8) and formula (9), R ₁₀ to R ₁₄ are independently -H, -OH, -NH ₂ , a branched or non-branched alkyl group with 1 to 12 carbons, or a branched or non-branched alkyl group with 1 to 12 carbons. 12 branched or unbranched alkoxy groups. A polarizing film, which is a hardened product of a polymerizable liquid crystal composition, and the polymerizable liquid crystal composition includes a dichroic pigment, a polymerizable liquid crystal compound, and an antioxidant; in X-ray diffraction measurement, the polarizing film shows a Bragg peak, the aforementioned The dichroic pigment is an azo pigment, and the aforementioned antioxidant satisfies the formula (1) in the relationship with the aforementioned polymerizable liquid crystal compound: 0.8°C≦T1-T2 (1) In the formula, T1 means that the aforementioned polymerizable liquid crystal compound is released in the atmosphere After the temperature is raised to 130°C, when the phase transition temperature is measured while cooling to 23°C at 5°C/min, the phase transition temperature to the liquid crystal phase that appears on the lowest temperature side; After the mixture of liquid crystal compound and 1 mass part of the aforementioned antioxidant is heated up to 130°C in the atmosphere, it is heated at 5°C/min. The phase transition temperature to the liquid crystal phase that appears on the lowest temperature side when the clock is cooled to 23°C and the phase transition temperature is measured at the same time. A polarizing plate comprising the polarizing film and retardation film described in item 8 of the scope of the patent application. The polarizing plate as described in item 9 of the scope of the patent application, wherein the retardation film satisfies formula (X), and the angle formed by the slow axis of the retardation film and the absorption axis of the polarizing film is substantially 45°; 100≦Re(550)≦180 (X) In the formula, Re(550) represents an in-plane retardation value at a wavelength of 550 nm. The polarizing plate as described in item 9 or 10 of the scope of the patent application, wherein the retardation film satisfies the formula (Y): Re(450)/Re(550)<1 (Y) In the formula, Re(450) and Re (550) represent the in-plane retardation values at wavelengths of 450nm and 550nm, respectively. The polarizing plate according to claim 9 or 10, wherein the retardation film is composed of a polymer in an aligned state of a polymerizable liquid crystal compound. A display device equipped with the polarizing film described in item 8 of the scope of application or the polarizing plate described in any one of items 9 to 12 of the scope of application. A method for manufacturing a polarizing film, comprising: forming a coating film of the polymerizable liquid crystal composition described in any one of claims 1 to 7 of the patent application; removing the solvent from the coating film; Raising the temperature above the temperature at which the polymerizable liquid crystal compound phase transfers to the liquid phase, and then lowering the temperature so that the polymerizable liquid crystal compound phase transfers to the smectic phase; and polymerizing the polymerizable liquid crystal compound while maintaining the state of the smectic phase.