CN118047890A - Composition for forming phase difference film, method for producing phase difference film, and phase difference plate - Google Patents
Composition for forming phase difference film, method for producing phase difference film, and phase difference plate Download PDFInfo
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- CN118047890A CN118047890A CN202311478745.4A CN202311478745A CN118047890A CN 118047890 A CN118047890 A CN 118047890A CN 202311478745 A CN202311478745 A CN 202311478745A CN 118047890 A CN118047890 A CN 118047890A
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Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/12—Esters of phenols or saturated alcohols
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- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
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- G—PHYSICS
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- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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- C09K19/3001—Cyclohexane rings
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Abstract
The invention relates to a composition for forming a phase difference film, a method for producing a phase difference film, and a phase difference plate. Provided is a composition for forming a phase difference film, which can be formed into a film by using a step of removing a solvent at a lower temperature than conventional methods, for example, at a temperature lower than 100 ℃, and which can suppress the occurrence of unevenness in the film formation and can form a phase difference film excellent in optical characteristics. A composition for forming a retardation film, which comprises a polymerizable liquid crystal compound, and at least 2 organic solvents A and B having different boiling points from each other, wherein the polymerizable liquid crystal compound has a nematic liquid crystal phase transition temperature of 100 ℃ to 200 ℃, the nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound is X, the boiling point of the organic solvent A is Ta, and the boiling point of the organic solvent B is Tb, and satisfies the formulas (1) to (3): tb-Ta is more than or equal to 10 (DEG C) (1), ta is less than X-30 (DEG C) (2), tb is more than X-70 (DEG C) (3).
Description
Technical Field
The present invention relates to a composition for forming a retardation film, a method for producing a retardation film using the composition for forming a retardation film, and a retardation plate comprising a cured film of the composition for forming a retardation film.
Background
As one of the characteristics of a retardation film (retardation film) used in various image display devices, it is required to be able to perform polarization conversion in a full wavelength region, and for example, it is known that the same polarization conversion can be theoretically performed in a wavelength region exhibiting inverse wavelength dispersibility of [ Re (450)/Re (550) ] < 1. For example, polymerizable liquid crystal compounds having a so-called T-shaped or H-shaped molecular structure tend to exhibit reverse wavelength dispersibility when polymerized and cured, and have been used as materials for forming retardation films (for example, patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2019-191504
Disclosure of Invention
Problems to be solved by the invention
The retardation film formed of the polymerizable liquid crystal compound can be obtained, for example, by: after a coating solution obtained by dissolving a polymerizable liquid crystal compound in a solvent is applied to a support substrate to form a coating film, the polymerizable liquid crystal compound contained in the coating film is converted into a liquid crystal phase state, and the solvent is distilled off. In general, the film forming method includes a heat drying step for removing a solvent by distillation, but in recent years, a low temperature at the time of film forming is demanded from the viewpoint of reducing environmental load.
However, according to the studies of the present inventors, it has been found that in a conventional composition for forming a retardation film using a polymerizable liquid crystal compound having a high nematic phase transition temperature, for example, a nematic phase transition temperature higher than 100 ℃, when the drying temperature at the time of solvent removal is lowered, the distribution of the in-plane retardation of the obtained retardation film tends to deteriorate, and phase-difference unevenness may occur.
The purpose of the present invention is to provide a composition for forming a retardation film, which can be used for film formation by removing a solvent at a lower temperature than conventional ones, for example, at a lower temperature than 100 ℃, and which can suppress the occurrence of unevenness in film formation and form a retardation film having excellent optical characteristics.
Means for solving the problems
The present invention provides the following preferred embodiments.
[1] A composition for forming a retardation film, which comprises a polymerizable liquid crystal compound having a nematic liquid crystal phase transition temperature in a range of 100 ℃ to 200 ℃ inclusive, and at least 2 organic solvents A and B having different boiling points from each other,
The following formulas (1) to (3) are satisfied when the nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound is X (. Degree. C.), the boiling point of the organic solvent A is Ta (. Degree. C.), and the boiling point of the organic solvent B is Tb (. Degree. C.):
Tb-Ta≥10(℃) (1)
Ta<X-30(℃) (2)
Tb>X-70(℃) (3)。
[2] The composition for forming a retardation film according to the above [1], wherein the polymerizable liquid crystal compound comprises a polymerizable liquid crystal compound (I) represented by the following formula (I).
[ Chemical formula 1]
P1-E1-(B1-G1)k-L1-Ar-L2-(G2-B2)1-E2-P2 (I)
In the formula (I) of the formula (I),
L 1、L2、B1 and B 2 each independently represent a single bond or a divalent linking group,
G 1 and G 2 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group in which a hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, a carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom,
K and l each independently represent an integer of 0 to 3 and satisfy the relation 1.ltoreq.k+l,
E 1 and E 2 each independently represent an alkanediyl group having 1 to 17 carbon atoms, wherein hydrogen atoms contained in the alkanediyl group may be substituted with halogen atoms, the alkanediyl group may contain-CH 2 -which is optionally replaced by-O-, -S-, -C (=o) -substitution,
P 1 and P 2 each independently represent a polymerizable group or a hydrogen atom (wherein at least 1 of P 1 and P 2 is a polymerizable group),
Ar is a group represented by any one of formulas (Ar-1) to (Ar-5),
[ Chemical formula 2]
[ In the formulae (Ar-1) to (Ar-5),
* Represents a bonding portion;
Q 1 represents-S-, -O-or-NR 11-,R11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent,
Q 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent;
W 1 and W 2 each independently represent-O-; -S-, -CO-, -NR 11-,R11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent;
Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
Y 2 represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, a hydrogen atom contained in the alkyl group may be substituted with a halogen atom, -CH 2 -contained in the alkyl group may be substituted by-O-, -CO-, -O-CO-or-CO-O-;
Z 1、Z2 and Z 3 each independently represents a hydrogen atom or an aliphatic hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms having 1 valence, a halogen atom, a cyano group, a nitro group, -NR 12R13 or-SR 14,Z1, and Z 2 may be bonded to each other to form an aromatic ring or an aromatic heterocyclic ring, and R 12～R14 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Ax represents an organic group having at least 1 aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring and having 2 to 30 carbon atoms, ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having at least 1 aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring and having 2 to 30 carbon atoms, and Ax and Ay may be bonded to each other to form a ring;
Y 3 and Y 4 each independently represent a group selected from the following formula (Y 3 -1).
[ Chemical formula 3]
[ In (Y 3 -1) ],
R Y1 represents a hydrogen atom OR an alkyl group having 1 to 6 carbon atoms, which may be substituted with 1 OR more substituents X 3, wherein the substituents X 3 represent a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a sulfur pentafluoride group (pentafluorosulfuranyl group), a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group (thioisocyano group), OR 1-CH 2 -OR 2 OR more non-adjacent-CH 2 -groups may each independently be replaced with a linear OR branched alkyl group having 1 to 20 carbon atoms of -O-、-S-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-CH＝CH-COO-、-CH＝CH-OCO-、-COO-CH＝CH-、-OCO-CH＝CH-、-CH＝CH-、-CF＝CF- OR-C≡C-, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, OR may be a group represented by-B 3-F3-P3 (wherein B 3 represents -CR16R17-、-CH2-CH2-、-O-、-S-、-CO-O-、-O-CO-、-O-CO-O-、-C(＝S)-O-、-O-C(＝S)-、-O-C(＝S)-O-、-CO-NR18-、-NR18-CO-、-O-CH2-、-CH2-O-、-S-CH2-、-CH2-S- OR a single bond, and R 16～R18 independently represents a hydrogen atom, a fluorine atom OR an alkyl group having 1 to 4 carbon atoms; F 3 represents an alkanediyl group having 1 to 12 carbon atoms, wherein hydrogen atoms contained in the alkanediyl group are optionally substituted with-OR 19 OR a halogen atom, R 19 represents an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and-CH 2 -contained in the alkanediyl group may be replaced with-O-OR-CO-; P 3 represents a hydrogen atom OR a polymerizable group),
U 1 represents an organic group having 2 to 30 carbon atoms and having an aromatic hydrocarbon group, any carbon atom of which may be replaced with a heteroatom, and the aromatic hydrocarbon group may be substituted with 1 or more substituents X 3;
T 1 represents-O-, -S-, -COO-, -OCO-O-, -NU 2-、-N＝CU2-、-CO-NU2-、-OCO-NU2 -or O-NU 2-,U2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms a cycloalkenyl group having 3 to 12 carbon atoms, an organic group having 2 to 30 carbon atoms and an aromatic hydrocarbon group (any carbon atom of the aromatic hydrocarbon group may be replaced with a hetero atom), or (E 3-A3)q-B3-F3-P3, the alkyl, cycloalkyl, cycloalkenyl and aromatic hydrocarbon groups each being unsubstituted or substituted by more than 1 substituent X 3, the alkyl group being optionally substituted by the cycloalkyl or cycloalkenyl group, 1-CH 2 -or more than 2 non-adjacent-CH 2 -of the alkyl group being optionally substituted by -O-、-S-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-SO2-、-O-CO-O-、-CO-NH-、-NH-CO-、-CH＝CH-COO-、-CH＝CH-OCO-、-COO-CH＝CH-、-OCO-CH＝CH-、-CH＝CH-、-CF＝CF- or-C≡C-, in the cycloalkyl or cycloalkenyl group, 1-CH 2 -or 2 or more non-adjacent-CH 2 -may be replaced by-O-, -CO-, -COO-, -OCO-or-O-CO-O-, E 3 is defined in the same manner as in the above-mentioned B 3, A 3 represents a 2-valent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a 2-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, the alicyclic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, -R 20、-OR21, cyano group or nitro group, R 20 represents a hydrogen atom, fluorine atom or alkyl group having 1 to 4 carbon atoms, R 21 represents alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, B 3、F3 and P 3 each have the same meaning as those of B 3、F3 and P 3, q represents an integer of 0 to 4, and when plural groups E 3 and/or A 3 are present, each may be the same or different, and U 1 and U 2 may be bonded to form a ring ]
[3] The composition for forming a retardation film according to the above [1] or [2], wherein the hansen solubility parameter distance calculated using the hansen solubility parameter (δd A、δPA、δHA) of the organic solvent a and the hansen solubility parameter (δd B、δPB、δHB) of the organic solvent B is 10 or less.
[4] The composition for forming a retardation film according to the above [2] or [3], wherein the polymerizable liquid crystal compound further comprises a rod-like polymerizable liquid crystal compound.
[5] The composition for forming a retardation film according to any one of the above [1] to [4], wherein the solid content concentration is 5% by mass or more.
[6] The composition for forming a retardation film according to any one of the above [1] to [5], wherein the total content of the organic solvent A and the organic solvent B is 80% by mass or more relative to the total mass of the solvents contained in the composition for forming a retardation film.
[7] The composition for forming a retardation film according to any one of the above [1] to [6], wherein the organic solvent A is an ether-based organic solvent or a ketone-based solvent.
[8] The composition for forming a retardation film according to any one of the above [1] to [7], which contains a leveling agent.
[9] A method for producing a retardation film, comprising the steps of:
A process for forming a coating film of the composition for forming a retardation film according to any one of the above [1] to [8],
A step of drying the coating film at a drying temperature Td (DEG C) to obtain a dried coating film, and
A step of curing the dried coating film to obtain a retardation film;
The drying temperature Td (c) satisfies the formula (4) and (5):
Ta < Td < Tb (4)
X-80 ≤ Td ≤ X-20 (5)。
[10] the production method as described in the above [9], wherein the drying temperature Td is 70℃or more and less than 130 ℃.
[11] A retardation plate comprising a cured film of the composition for forming a retardation film according to any one of the above [1] to [8 ].
Effects of the invention
According to the present invention, it is possible to provide a composition for forming a retardation film, which can be used for forming a film by removing a solvent at a lower temperature than the conventional one, for example, at a lower temperature than 100 ℃, and which can suppress the occurrence of unevenness in the film formation and can form a retardation film excellent in optical characteristics.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described herein, and various modifications may be made without departing from the spirit of the present invention.
< Composition for Forming phase-difference film >
The composition for forming a retardation film of the present invention comprises a polymerizable liquid crystal compound having a nematic liquid crystal phase transition temperature in a range of 100 ℃ to 200 ℃ inclusive, and at least 2 organic solvents A and B having different boiling points from each other. In the composition for forming a retardation film of the present invention, the following formulas (1) to (3) are satisfied when the nematic phase transition temperature of the polymerizable liquid crystal compound is X ℃, the boiling point of the organic solvent a is Ta ℃, and the boiling point of the organic solvent B is Tb ℃.
Tb-Ta≥10(℃) (1)
Ta<X-30(℃) (2)
Tb>X-70(℃) (3)
In the present disclosure, an organic solvent having a relatively low boiling point among solvents contained in the phase difference film-forming composition is referred to as "organic solvent a", and an organic solvent having a relatively high boiling point is referred to as "organic solvent B". When 3 or more organic solvents are contained in the composition for forming a retardation film, it is necessary to contain at least 2 organic solvents satisfying all of the above-mentioned formulae (1) to (3) in relation to the nematic liquid crystal phase transition temperature X ℃ of the polymerizable liquid crystal compound contained in the composition for forming a retardation film.
In the case where the composition for forming a phase difference film contains a plurality of polymerizable liquid crystal compounds, the nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compounds is a temperature measured using a mixture of polymerizable liquid crystal compounds obtained by mixing all the polymerizable liquid crystal compounds constituting the composition for forming a phase difference film at the same ratio as the composition in the composition for forming a phase difference film.
In general, when the drying temperature for removing the organic solvent from the coating film of the composition (coating liquid) containing the polymerizable liquid crystal compound and the organic solvent is low, the evaporation rate of the organic solvent is low, and the drying oven is susceptible to the influence of the air quantity and the like, and the appearance defects such as the occurrence of the wind streaks on the coating surface are liable to occur. Conventionally, an organic solvent used for dissolving a polymerizable liquid crystal compound having a molecular structure such as a T-type or H-type, which exhibits inverse wavelength dispersibility, often has a high boiling point of more than 100 ℃, and it is difficult to reduce the drying temperature without causing defects in appearance such as moire and the like during film formation. In contrast, the composition for forming a retardation film of the present invention contains the organic solvent a and the organic solvent B satisfying the above-described formulas (1) to (3) in relation to the polymerizable liquid crystal compound, and thus, compared with the case where the same polymerizable liquid crystal compound is used in the past, the occurrence of unevenness and alignment defects on the coated surface can be suppressed and a retardation film excellent in appearance and optical characteristics can be formed even when the drying step for removing the solvent is performed at a low temperature.
The formula (1) shows that the boiling point of the organic solvent B is 10 ℃ or higher than that of the organic solvent A. By including at least 2 organic solvents having boiling points differing by 10 ℃ or more, a difference in volatilization speed of each organic solvent is generated, and the volatilization speed of the solvent as a whole of the composition can be easily controlled with respect to the drying temperature. Thus, even when the drying temperature is low, the liquid crystal composition is not easily affected by wind or the like in the drying furnace, occurrence of wind streak unevenness due to the wind streak unevenness can be suppressed, and further, the evaporation of the organic solvent can be prevented from becoming faster than necessary, and occurrence of crystallization and alignment defects of the liquid crystal composition due to the evaporation of the solvent can be suppressed. If the difference between Ta and Tb is moderate, the timing of removing the organic solvent a and the organic solvent B in the drying step can be controlled, and the aforementioned effects can be easily obtained, and therefore, the difference is preferably 20 ℃ or higher, more preferably 30 ℃ or higher, and may be, for example, 40 ℃ or higher or 50 ℃ or higher. On the other hand, if the difference between Ta and Tb is excessively large, it may be difficult to sufficiently remove each organic solvent in a preferable drying temperature range. Therefore, the difference between Ta and Tb is usually 150℃or less, preferably 120℃or less, more preferably 100℃or less, still more preferably 90℃or less, and may be 80℃or less, for example. When the composition for forming a retardation film contains 3 or more organic solvents, the difference in boiling point between at least 1 combination among the combinations of 2 organic solvents satisfying the relationship between the organic solvent of formula (2) and the organic solvent of formula (3) is preferably within the above range.
If the boiling point of the organic solvent a satisfies the formula (2) and the boiling point of the organic solvent B satisfies the formula (3) in relation to the nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound contained in the composition for forming a retardation film in addition to the formula (1), a solvent (organic solvent a) having a boiling point lower than the phase transition temperature of the polymerizable liquid crystal compound by a certain degree or more and a solvent (organic solvent B) having a boiling point higher than the solvent by a certain degree or more are mixed and present. This makes it possible to properly remove the solvent in the drying step at the time of film formation, thereby suppressing crystallization of the liquid crystal compound and occurrence of alignment defects, and suppressing uneven wind marks caused by hot air in the drying furnace, and to obtain a retardation film excellent in appearance and optical characteristics.
The boiling point Ta of the organic solvent a may be lower than the nematic liquid crystal phase transition temperature X ℃ of the polymerizable liquid crystal compound by, for example, 40 ℃ or more, 50 ℃ or more, or 60 ℃ or more. If Ta is too low, the solvent evaporation rate becomes high in a preferable drying temperature range, and crystallization and alignment defects of the polymerizable liquid crystal compound tend to occur easily. On the other hand, if Ta is too high, defects such as moire tend to be easily generated in the preferable drying temperature range. Therefore, ta is usually 40 ℃ or higher, preferably 50 ℃ or higher, for example, 60 ℃ or higher, although it also varies depending on the nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound.
The difference between the boiling point Tb of the organic solvent B and the nematic liquid crystal phase transition temperature X ℃ of the polymerizable liquid crystal compound is preferably smaller than the difference between Ta and X ℃, more preferably Tb is lower than X ℃, and the difference between Tb and X ℃ is within 60 ℃, still more preferably within 50 ℃. If Tb is too low, crystallization and alignment defects of the polymerizable liquid crystal compound tend to occur in the drying step, and if Tb is too high, removal of the solvent in a preferable drying temperature range is not easy, and appearance defects such as wind streaks tend to occur easily. Accordingly, tb also varies depending on the nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound, but is preferably lower than the phase transition temperature X℃and in the range of X-40℃or higher.
The above-described effects of suppressing crystallization, moire, and the like are more easily obtained particularly when the boiling point Ta of the organic solvent a is lower than the drying temperature (hereinafter, also sometimes referred to as "Td") for removing the solvent when the phase difference film is formed from the phase difference film-forming composition, and the boiling point Tb of the organic solvent B is higher than the drying temperature Td. Therefore, in one embodiment of the present invention, the boiling point Ta of the organic solvent a and the boiling point Tb of the organic solvent B are preferably in a relationship satisfying the formula (4) in terms of the relationship with the drying temperature Td.
Ta<Td<Tb (4)
In other words, the composition for forming a retardation film of the present invention is suitably used in a film forming step in which the drying temperature for removing the solvent is higher than Ta and lower than Tb.
In one embodiment of the present invention, in the drying step, the nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the coating film is preferably lower than the boiling point of the organic solvent B, and more preferably lower than the drying temperature, from the viewpoint that the optical characteristics such as orientation and low haze can be improved. Since the nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound tends to be lowered in the organic solvent, the nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound (alone) measured with the polymerizable liquid crystal compound tends to be higher than the nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the coating film (including the organic solvent).
In the present invention, the drying temperature Td may be appropriately determined in consideration of the nematic phase transition temperature of the polymerizable liquid crystal compound to be used, the boiling point of the organic solvent contained in the composition for forming a retardation film, and the like. The drying temperature is, for example, a temperature range of about 20 to 80℃lower than the nematic phase transition temperature of the polymerizable liquid crystal compound to be used, specifically, preferably 70 to 140℃and more preferably 80 to 130℃and may be, for example, 120℃or lower, 110℃or lower, further 100℃or lower, 95℃or lower, or 90℃or lower. The composition for forming a phase difference film of the present invention, which contains at least 2 organic solvents having different boiling points from each other so that the boiling point of each organic solvent and the nematic phase transition temperature of the polymerizable liquid crystal compound satisfy the above-mentioned formulas (1) to (3), is particularly easy to obtain the following effects: when the drying step is performed in the above-mentioned temperature range, volatilization and removal of the organic solvent a and the organic solvent B are appropriately performed based on the relationship with the drying temperature, and thus crystallization and alignment defects of the liquid crystal compound are suppressed and uneven air streaks due to hot air in the drying furnace are suppressed.
The organic solvent a may be appropriately selected in consideration of the nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound to be used, the solubility of the polymerizable liquid crystal compound, the temperature conditions of a desired drying process, and the like. In one embodiment of the present invention, the temperature range of the boiling point Ta of the organic solvent a may be, for example, 100 ℃ or less, preferably 40 to 100 ℃, more preferably 50 to 100 ℃, still more preferably 60 to 90 ℃, still more preferably 65 to 80 ℃. When the organic solvent a having a boiling point in the above range is contained, the effect of suppressing the occurrence of wind streak unevenness in drying can be obtained even when the film is formed at a low drying temperature, for example, 100 ℃ or less, preferably 95 ℃ or less, and more preferably 90 ℃ or less, which is preferable from the viewpoint of reducing the environmental load.
The organic solvent B may be appropriately selected in consideration of the nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound to be used, the solubility of the polymerizable liquid crystal compound, the temperature conditions of a desired drying process, and the like. In one embodiment of the present invention, the temperature range of the boiling point Tb of the organic solvent B may be, for example, more than 100 ℃, preferably more than 100 ℃ and 300 ℃ or less, more preferably 120 to 250 ℃, still more preferably 120 to 200 ℃, still more preferably 120 to 150 ℃. When the organic solvent B having a boiling point in the above range is contained, for example, in combination with the organic solvent a having a low boiling point of 100 ℃ or lower, crystallization of the liquid crystal compound and occurrence of alignment defects can be suppressed, and even when a film is formed at a low drying temperature of preferably 100 ℃ or lower, preferably 95 ℃ or lower, more preferably 90 ℃ or lower from the viewpoint of reduction in environmental load, a retardation film excellent in appearance characteristics can be obtained.
The hansen solubility parameter distance (hereinafter, sometimes simply referred to as "HSP distance") calculated using the hansen solubility parameter (δd A、δPA、δHA) of the organic solvent a and the hansen solubility parameter (δd B、δPB、δHB) of the organic solvent B is preferably 10 or less. If the compatibility of solvents is low, the solvents are partially separated in the solvent drying step, and thus, unevenness (mesh-like unevenness) in the mesh pattern due to the low compatibility of the solvents is likely to occur, and there is a possibility that appearance defects different from the aforementioned unevenness in the wind pattern due to the influence of wind in the drying furnace may occur. When the HSP distance is 10 or less, the compatibility between the organic solvent a and the organic solvent B becomes high, and the occurrence of mesh-like unevenness due to the compatibility of the solvents can be effectively suppressed. From the viewpoint of suppressing the mesh unevenness, the HSP distance is preferably 9.5 or less, more preferably 9.0 or less. The lower limit of the HSP distance is not particularly limited, but is usually 1.0 or more, preferably 2.0 or more.
Hansen (Hansen) solubility parameters are parameters that divide the solubility parameters introduced by hilbert (Hildebrand) into 3 components of dispersion term (δd), polar term (δp), hydrogen bond term (δh) and represent in three-dimensional space. The dispersion term (δd) represents the effect due to the dispersion force, the polar term (δp) represents the effect due to the dipole force, and the hydrogen bond term (δh) represents the effect of the hydrogen bond force.
Definition and calculation of hansen solubility parameters is described in Charles m.hansen, hansen Solubility Parameters: a Users Handbook (CRC press, 2007). Further, by using computer software Hansen Solubility PARAMETERS IN PRACTICE (hsPIP), the hansen solubility parameter can be easily estimated from the chemical structure of a solvent whose literature value is unknown. In the present invention, when determining hansen solubility parameters of the organic solvent a and the organic solvent B, the values of the registered hansen solubility parameters are used with respect to the solvents registered in the database.
For example, when δd A、δPA、δHA is the coordinate of hansen solubility parameter of organic solvent a and δd B、δPB、δHB is the coordinate of hansen solubility parameter of organic solvent B, the HSP distance can be calculated from the following equation.
HSP distance ＝[4(δDA-δDB)2+(δPA-δPB)2+(δHA-δHB)2]1/2
In the present invention, the organic solvent a and the organic solvent B may be selected as appropriate from known organic solvents capable of dissolving the polymerizable liquid crystal compound based on the phase transition temperature, the envisaged drying temperature, and the like of the polymerizable liquid crystal compound to be used so as to satisfy the above-described formulas (1) to (3), and preferably so that the HSP distance falls within the above-described range. Examples of the organic solvents a and B include the following solvents (() having boiling points):
Ketone solvents such as methyl isobutyl ketone (116 ℃), cyclohexanone (156 ℃), cyclopentanone (130 ℃), methyl amyl ketone (151 ℃), isophorone (215 ℃) and gamma-butyrolactone (GBL) (204 ℃);
Aromatic solvents such as xylene (144 ℃), mesitylene (165 ℃), cumene (152 ℃), ethylbenzene (136 ℃), anisole (154 ℃), aniline (184 ℃), benzaldehyde (178 ℃), benzyl alcohol (205 ℃), methyl benzoate (199 ℃), ethyl benzoate (213 ℃), propyl benzoate (230 ℃), butyl benzoate (250 ℃), nitrobenzene (211 ℃) and tetralin (207 ℃);
octane (125 ℃), nonane (151 ℃), decane (174 ℃), undecane (196 ℃) and dodecane (216 ℃) and the like.
Glycol monomethyl ether (124 ℃), glycol monoethyl ether (135 ℃), glycol n-propyl ether (151 ℃), glycol isopropyl ether (141 ℃), glycol n-butyl ether (171 ℃), diethylene glycol dimethyl ether (162 ℃), diethylene glycol diethyl ether (189 ℃), dipropylene glycol dimethyl ether (171 ℃), diethylene glycol monomethyl ether (194 ℃), diethylene glycol monoethyl ether (202 ℃), diethylene glycol monobutyl ether (230 ℃), diethylene glycol ethyl methyl ether (176 ℃), diethylene glycol butyl methyl ether (212 ℃), propylene glycol monomethyl ether (120 ℃), propylene glycol dimethyl ether (97 ℃), dipropylene glycol monomethyl ether (188 ℃), dipropylene glycol dimethyl ether (171 ℃), tripropylene glycol dimethyl ether (215 ℃), triethylene glycol monomethyl ether (249 ℃), triethylene glycol dimethyl ether (216 ℃), tetraethylene glycol dimethyl ether (276 ℃), propylene glycol monomethyl ether acetate (146 ℃), ethylene glycol monomethyl ether acetate (145), diethylene glycol monoethyl ether acetate (217), diethylene glycol monobutyl ether acetate (245 ℃), and other glycol solvents;
Ester solvents such as propyl acetate (102 ℃), butyl acetate (126 ℃), amyl acetate (142 ℃), ethyl lactate (155 ℃), methyl methoxypropionate (143 ℃), ethyl ethoxypropionate (170 ℃), isoamyl propionate (156 ℃), isoamyl isobutyrate (170 ℃), ethyl butyrate (121 ℃), propyl butyrate (143 ℃), butyl butyrate (165 ℃), ethylene carbonate (244 ℃) and propylene carbonate (242 ℃);
Amide solvents such as N, N-dimethylformamide (153 ℃), N-dimethylacetamide (165 ℃), N-methyl-2-pyrrolidone (202 ℃) and γ -butyrolactam (245 ℃); and
Halogen solvents such as monochlorobenzene (132 ℃), 1,2, -tetrachloroethane (147 ℃) and sulfur-containing solvents such as dimethyl sulfoxide (189 ℃) and dimethyl sulfone (238 ℃);
Ether solvents such as tetrahydrofuran (66 ℃), 1, 3-dioxolane (77 ℃), 2-methyltetrahydrofuran (80 ℃), 1, 4-dioxane (101 ℃), cyclopentylmethyl ether (106 ℃) and tetrahydropyran (88 ℃).
As the organic solvents a and B, it is more advantageous to select organic solvents which have high solubility in the polymerizable liquid crystal compound to be used and are inactive to the polymerization reaction of the polymerizable liquid crystal compound, respectively. In a preferred embodiment of the present invention, the organic solvent a is an ether-based organic solvent or a ketone-based solvent, more preferably an ether-based solvent, and still more preferably a cyclic ether-based solvent. In a preferred embodiment of the present invention, the organic solvent B is selected from the group consisting of ketone solvents, aromatic solvents, halogen solvents and amide solvents, more preferably ketone solvents or halogen solvents, and still more preferably ketone solvents. In a preferred embodiment of the present invention, the combination of the organic solvent a being an ether-based solvent and the organic solvent B being a ketone-based solvent is preferred.
The content ratio of the organic solvent a and the organic solvent B can be appropriately set depending on the types of the organic solvent a and the organic solvent B used, their boiling points, the envisaged drying temperature, drying conditions, and the like. Although the amount of the organic solvent a and the amount of the organic solvent B are also dependent on the type of the organic solvent a and the organic solvent B, the boiling point, the drying conditions, and the like, in general, if the amount of the organic solvent a is high, the effect of suppressing occurrence of moire unevenness tends to be improved, and if the amount of the organic solvent B is high, the effect of suppressing occurrence of crystallization and alignment defects of the liquid crystal compound tends to be improved. In one embodiment of the present invention, the content ratio of the organic solvent a to the organic solvent B (mass ratio, organic solvent a: organic solvent B) is preferably 20: 80-80: 20, more preferably 30: 70-70: 30, more preferably 35: 65-65: 35, particularly preferably 40: 60-60: 40.
The composition for forming a retardation film of the present invention may contain an organic solvent other than the organic solvent a and the organic solvent B (hereinafter, also referred to as "other organic solvent") as long as the effect of the present invention is not impaired. When the composition for forming a retardation film contains 3 or more organic solvents, the relationship of the formulae (1) to (3) may be satisfied, and the organic solvent a and the organic solvent B may be obtained from the 2 solvents in the relationship. In the present disclosure, among the combinations of 2 organic solvents that satisfy the relationship between the organic solvent of formula (2) and the organic solvent of formula (3), the combination of 2 types having the largest proportion with respect to the total mass of all solvents included in the composition for forming a phase difference film may be regarded as the organic solvent a and the organic solvent B, and the organic solvents other than them may be regarded as other organic solvents. In this case, the organic solvent a and the organic solvent B are preferably arranged in this order from the organic solvent having a low boiling point and are adjacent to each other. Since the control of boiling points and the like between various solvents becomes complicated, the types of organic solvents contained in the composition for forming a retardation film of the present invention are usually 4 or less, preferably 3 or less, more preferably 2.
The other organic solvent is an organic solvent different from the organic solvent a and the organic solvent B used, and may be selected from known organic solvents such as the organic solvents exemplified above as the organic solvent a and the organic solvent B. As the other organic solvent, it is more advantageous to select an organic solvent which has high solubility for the polymerizable liquid crystal compound and is inactive to the polymerization reaction of the polymerizable liquid crystal compound.
From the viewpoint of sufficiently obtaining the effect of the present invention, the total content of the organic solvent a and the organic solvent B is preferably 80 mass% or more, more preferably 85 mass% or more, still more preferably 90 mass% or more, or 100 mass% or more, relative to the total mass of the solvents contained in the composition for forming a phase difference film (that is, the organic solvents contained in the composition for forming a phase difference film may be only the organic solvent a and the organic solvent B). In other words, the content of the other organic solvent is preferably 20 mass% or less, more preferably 15 mass% or less, still more preferably 10 mass% or less, based on the total mass of the solvents contained in the composition for forming a retardation film, and may be substantially free of other organic solvents. If the content of the other organic solvent is within the above range, the solvent can be removed without heating more than necessary in the drying step, and the amount of the residual solvent can be reduced, so that a retardation film excellent in appearance can be obtained.
The composition for forming a retardation film of the present invention preferably contains an organic solvent in such an amount that the solid content concentration thereof is 5 mass% or more. When the solid content concentration is 5 mass% or more, the effect of suppressing occurrence of wind streak unevenness is easily improved. From this viewpoint, the solid content concentration in the composition for forming a phase difference film of the present invention is more preferably 8 mass% or more, and still more preferably 10 mass% or more. The upper limit of the solid content concentration is not particularly limited, but is usually 40 mass% or less, preferably 30 mass% or less, from the viewpoint of coatability and the like. In other words, the content of the organic solvent (the total amount of the organic solvents a and B and the other organic solvents when the other organic solvents are included) in the composition for forming a retardation film of the present invention is preferably 60 to 95 mass% or less with respect to the total mass of the composition for forming a retardation film. If the content of the organic solvent is within the above range, moire is less likely to occur, and the solvent can be dried and removed without heating more than necessary in the drying step, so that the amount of the residual solvent can be reduced, and thus a retardation film excellent in appearance and optical characteristics can be obtained.
The composition for forming a retardation film of the present invention comprises a polymerizable liquid crystal compound (hereinafter, also referred to as "polymerizable liquid crystal compound (x)") having a nematic liquid crystal phase transition temperature in a range of 100 ℃ to 200 ℃. The polymerizable liquid crystal compound (x) is a liquid crystal compound having a polymerizable group, particularly a photopolymerizable group, and as the polymerizable liquid crystal compound (x), a polymerizable liquid crystal compound conventionally known in the field of optical films can be used. The liquid-crystalline property exhibited by the polymerizable liquid-crystalline compound (x) may be a thermotropic liquid crystal or a lyotropic liquid crystal, but is preferably a thermotropic liquid crystal in view of enabling precise film thickness control. The polymerizable liquid crystal compound (x) exhibits nematic liquid crystal properties as a phase-ordered structure, and thus has an advantage of easy alignment control.
The polymerizable liquid crystal compound (x) includes all compounds satisfying the following (a) to (D).
(A) A compound capable of forming a nematic phase;
(B) The polymerizable liquid crystal compound has pi electrons in the long axis direction (a).
(C) Pi electrons are present in a direction intersecting the long axis direction (a) [ intersecting direction (b) ].
(D) The pi electron density in the long axis direction (a) of the polymerizable liquid crystal compound defined by the following formula (i) by taking the total of pi electrons present in the long axis direction (a) as N (pi a) and the total of molecular weights present in the long axis direction as N (Aa):
d (pi a) =n (pi a)/N (Aa) (i), and,
The pi electron density in the cross direction (b) of the polymerizable liquid crystal compound defined by the following formula (ii) by taking the sum of pi electrons present in the cross direction (b) as N (pi b) and the sum of molecular weights present in the cross direction (b) as N (Ab):
D(πb)＝N(πb)/N(Ab) (ii)
There is a relationship of 0.ltoreq.D (pi a)/D (pi b). Ltoreq.1 (i.e., pi electron density in the cross direction (b) is greater than pi electron density in the long axis direction (a)).
The polymerizable liquid crystal compounds satisfying all of the above (a) to (D) may be applied to an alignment film and heated to a temperature equal to or higher than the phase transition temperature to form a nematic phase, for example. The nematic phase formed by aligning the polymerizable liquid crystal compound is generally aligned such that the long axis directions of the polymerizable liquid crystal compound are parallel to each other, and the long axis directions are alignment directions of the nematic phase.
The polymerizable liquid crystal compound having the above-mentioned characteristics is usually a compound having reverse wavelength dispersibility in a liquid crystal cured film obtained by polymerizing the compound alone. The polymerizable liquid crystal compound is preferably a liquid crystal having a mesogenic structure in a T-shape or H-shape, which further has birefringence in a direction perpendicular to the molecular long axis direction, from the viewpoint of exhibiting reverse wavelength dispersibility, and is more preferably a T-shape liquid crystal from the viewpoint of obtaining stronger dispersion. Specific examples of the compound satisfying the characteristics (a) to (D) include compounds represented by the following formula (I).
[ Chemical formula 4]
P1-E1-(B1-G1)k-L1-Ar-L2-(G2-B2)1-E2-P2 (I)
In the composition for forming a retardation film of the present invention, the polymerizable liquid crystal compound (x) preferably contains the polymerizable liquid crystal compound represented by the above formula (I) (hereinafter, also referred to as "polymerizable liquid crystal compound (I)") in view of the fact that the same polarization conversion and excellent optical characteristics are easily obtained in the retardation film exhibiting reverse wavelength dispersibility. These polymerizable liquid crystal compounds may be used singly or in combination of 2 or more.
In formula (I), L 1、L2、B1 and B 2 each independently represent a single bond or a divalent linking group.
L 1 and L 2 are each independently preferably a single bond, an alkylene group 、-O-、-S-、-Ra1ORa2-、-Ra3COORa4-、-Ra5OCORa6-、-Ra7OC＝OORa8-、-N＝N-、-CRc＝CRd-、 having 1 to 4 carbon atoms or-C.ident.C-. Here, R a1～Ra8 each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R c and R d each represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. L 1 and L 2 are each independently more preferably a single bond, -OR a2-1-、-CH2-、-CH2CH2-、-COORa4-1 -, OR OCOR a6-1 -. Here, R a2 -1、Ra4-1、Ra6-1 each independently represents any one of a single bond, -CH 2-、-CH2CH2 -. L 1 and L 2 are each independently further preferably a single bond, -O-, -CH 2CH2-、-COO-、-COOCH2CH2 -, or-OCO-.
B 1 and B 2 are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, a-O-, -S-, -R a9ORa10-、-Ra11COORa12-、-Ra13OCORa14 -, or-R a15OC＝OORa16 -. Here, R a9～Ra16 each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms. More preferably, each of B 1 and B 2 is independently a single bond, -OR a10-1-、-CH2-、-CH2CH2-、-COORa12 -1 -, OR OCOR a14-1 -. Here, R a10-1、Ra12-1、Ra14-1 each independently represents any one of a single bond, -CH 2-、-CH2CH2 -. B 1 and B 2 are each independently further preferably a single bond-O-, -CH 2CH2-、-COO-、-COOCH2CH2 -, -OCO-, or-OCOCH 2CH2 -.
G 1 and G 2 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and the carbon atoms constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom. Each of G 1 and G 2 is independently preferably a1, 4-phenylenediyl group which may be substituted with at least 1 substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, a1, 4-cyclohexanediyl group which may be substituted with at least 1 substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably a1, 4-phenylenediyl group substituted with a methyl group, an unsubstituted 1, 4-phenylenediyl group, or an unsubstituted 1, 4-trans-cyclohexanediyl group, particularly preferably an unsubstituted 1, 4-phenylenediyl group, or an unsubstituted 1, 4-trans-cyclohexanediyl group.
It is preferable that at least 1 of G 1 and G 2 in the plurality of groups is a divalent alicyclic hydrocarbon group, and it is more preferable that at least 1 of G 1 and G 2 bonded to L 1 or L 2 is a divalent alicyclic hydrocarbon group.
K and l each independently represent an integer of 0 to 3, and satisfy a relationship of 1.ltoreq.k+l. From the viewpoint of exhibiting inverse wavelength dispersibility, k and l are preferably in the range of 2.ltoreq.k+l.ltoreq.6, k+l=4 is preferred, k=2 is more preferred, and l=2 is preferred. k=2 and l=2 are preferably symmetrical.
E 1 and E 2 each independently represent an alkanediyl group having 1 to 17 carbon atoms, wherein hydrogen atoms contained in the alkanediyl group may be substituted with halogen atoms, the-CH 2 -contained in the alkanediyl group may be substituted by-O-, -S-, -C (=o) -. E 1 and E 2 are each independently preferably an alkanediyl group having 1 to 17 carbon atoms, more preferably an alkanediyl group having 4 to 12 carbon atoms.
P 1 and P 2 each independently represent a polymerizable group or a hydrogen atom. Among them, at least 1 of P 1 and P 2 is a polymerizable group, and from the viewpoint of film hardness of the obtained retardation film, it is preferable that P 1 and P 2 are both polymerizable groups. Examples of the polymerizable group represented by P 1 or P 2 include an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxetanyl group, and an oxetanyl group. Among them, a radical polymerizable group or a cation polymerizable group is preferable, and from the viewpoints of operability and ease of production, acryloyloxy, methacryloyloxy, vinyloxy, oxetanyl and oxetanyl are preferable, and acryloyloxy is more preferable.
Ar is a group represented by any one of formulas (Ar-1) to (Ar-5). These groups are common in the following respects: in the polymerizable liquid crystal compound represented by the formula (I), a molecular structure having a large volume in a direction intersecting the long axis direction is imparted, and the absorption wavelength in the short axis direction is long wavelength, and the retardation due to the aligned liquid crystal molecules tends to have inverse wavelength dispersibility.
[ Chemical formula 5]
The total number N π of pi electrons contained in the 2-valent group containing an aromatic hydrocarbon ring or an aromatic heterocycle represented by the formulas (Ar-1) to (Ar-5) is preferably 12 or more, more preferably 16 or more, still more preferably 18 or more, and particularly preferably 20 or more. The content is preferably less than 36, more preferably 32 or less, further preferably 30 or less, and particularly preferably 26 or less.
In the formulae (Ar-1) to (Ar-5), the bond with L 1 or L 2 in the formula (I) is represented.
In the formula (Ar-1), Q 1 represents-S-, -O-or-NR 11-,R11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. In the formulae (Ar-3) and (Ar-4), Q 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
In the formula (Ar-2), W 1 and W 2 each independently represent-O-; -S-, -CO-, -NR 11-,R11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
In the formula (Ar-1), Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent. In the formula (Ar-2), Y 2 represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent. Here, the hydrogen atom contained in the alkyl group may be substituted with a halogen atom, the-CH 2 -contained in the alkyl group may be replaced by-O-; -CO-, -O-CO-, or-CO-O-substitution.
In the formulae (Ar-1) to (Ar-5), Z 1、Z2 and Z 3 each independently represent a hydrogen atom, an aliphatic hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms in 1 valence, a halogen atom, a cyano group, a nitro group, -NR 12R13, or-SR 14,Z1, and Z 2 may be bonded to each other to form an aromatic ring or an aromatic heterocyclic ring. R 12～R14 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
In the formulae (Ar-3) and (Ar-4), ax represents an organic group having at least 1 aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring and having 2 to 30 carbon atoms, ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having at least 1 aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring and having 2 to 30 carbon atoms, and Ax and Ay may be bonded to form a ring.
In the formula (Ar-1), Y 1 is preferably an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent. The aromatic hydrocarbon group or aromatic heterocyclic group which may have a substituent is preferably a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted. In the present disclosure, the "polycyclic aromatic hydrocarbon group" refers to an aromatic hydrocarbon group having at least 2 aromatic rings, and examples thereof include a condensed aromatic hydrocarbon group formed by condensing 2 or more aromatic rings and an aromatic hydrocarbon group formed by bonding 2 or more aromatic rings. The "polycyclic aromatic heterocyclic group" refers to an aromatic heterocyclic group having at least 1 heteroaromatic ring and at least 1 ring selected from the group consisting of aromatic rings and heteroaromatic rings, and examples thereof include an aromatic heterocyclic group formed by fusing 1 or more aromatic heterocyclic rings to 1 or more rings selected from the group consisting of aromatic rings and heteroaromatic rings and an aromatic heterocyclic group formed by bonding at least 1 heteroaromatic ring to at least 1 ring selected from the group consisting of aromatic rings and heteroaromatic rings.
Examples of the substituent that the aromatic hydrocarbon group or the aromatic heterocyclic group may have include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group (alkylsulfanyl) having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 4 carbon atoms, an N, N-dialkylamino group having 2 to 8 carbon atoms, a sulfamoyl group, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, and an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
Examples of Y 1 include groups represented by the following formula (Y 1-1)～(Y1 -7).
[ Chemical formula 6]
In the formulae (Y 1 -1) to (Y 1 -7), the "part" represents a linking part.
In the formulae (Y 1 -1) to (Y 1 -7), Z 4 each independently represents a halogen atom or an organic group having 1 to 20 carbon atoms, and for example, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a cyano group, a nitro group, a sulfo group, a nitroxide group (nitroxide), a carboxyl group, a trifluoromethyl group, a methoxy group, a thiomethyl group, an N, N-dimethylamino group, an N-methylamino group, a halogen atom, a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a cyano group, a nitro group, a trifluoromethyl group, and particularly a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a pentyl group, a hexyl group are preferable.
In the formulae (Y 1 -1) to (Y 1 -7), V 1 and V 2 each independently represents-CO-, -S-, -NR 15 -, -O-, -Se-or-SO 2 -, preferably-S-; -NR 15 -or-O-. R 15 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formulae (Y 1 -1) to (Y 1 -7), W 3～W7 each independently represents-c=or-n=.
In the formulae (Y 1 -1) to (Y 1 -7), preferably, at least 1 of V 1、V2 and W 3～W7 represents a group containing S, N or O.
In the formulae (Y 1 -1) to (Y 1 -7), a independently represents an integer of 0 to 3, preferably 0 or 1.b each independently represents an integer of 0 to 2, preferably 0.
Any one of the groups represented by the formulas (Y 1 -1) to (Y 1 -7) is preferably any one of the groups represented by the following formulas (Y 1 -8) to (Y 1 -13), and more preferably a group represented by the formula (Y 1 -8). Note that the "part" indicates a connection part.
[ Chemical formula 7]
In the formulae (Y 1 -8) to (Y 1 -13), Z 4、a、b、V1、V2 and W 3 have the same meanings as those of Z 4、a、b、V1、V2 and W 3 in the formulae (Y 1 -1) to (Y 1 -7).
Specific examples of Y 1 include groups represented by the formulae (ar-1) to (ar-840) described in JP-A2019-003177. Among them, preferred is a group represented by the following formula.
[ Chemical formula 8]
In one embodiment of the present invention, the group represented by the formula (Ar-1) is specifically a group represented by the following formula (Ar 1-1)～(Ar1 -126). Wherein, the moiety represents a linking moiety with L 1 or L 2 in formula (I).
[ Chemical formula 9]
[ Chemical formula 10]
[ Chemical formula 11]
[ Chemical formula 12]
[ Chemical formula 13]
[ Chemical formula 14]
In one embodiment of the present invention, the group represented by the formula (Ar-2) is specifically a group represented by the following formula (Ar 2-1)～(Ar2 -13). Wherein, the moiety represents a linking moiety with L 1 or L 2 in formula (I).
[ Chemical formula 15]
In one embodiment of the present invention, the group represented by the formula (Ar-3) is specifically a group represented by the following formula (Ar 3-1)～(Ar3 -23). Wherein, the moiety represents a linking moiety with L 1 or L 2 in formula (I).
[ Chemical formula 16]
[ Chemical formula 17]
The groups represented by the formulas (Ar-1) to (Ar-4) may be, for example, those described in Japanese patent application laid-open No. 2011-207765, japanese patent application laid-open No. 2008-107767, WO2014/010325, etc., in addition to those exemplified in the above examples.
In the formula (Ar-5), Y 3 and Y 4 are each independently selected from the group represented by the following formula (Y 3 -1).
[ Chemical formula 18]
In the formula (Y 3 -1), R Y1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group may be substituted with 1 or more substituents X 3.
The substituent X 3 represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a sulfur pentafluoride group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or 1-CH 2 -or 2 or more non-adjacent-CH 2 -groups each independently of which may be replaced with a linear or branched alkyl group having 1 to 20 carbon atoms of -O-、-S-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-CH＝CH-COO-、-CH＝CH-OCO-、-COO-CH＝CH-、-OCO-CH＝CH-、-CH＝CH-、-CF＝CF- or-C≡C-, any hydrogen atom in the alkyl group may be replaced with a fluorine atom, or a group represented by-B 3-F3-P3. B 3 represents -CR16R17-、-CH2-CH2-、-O-、-S-、-CO-O-、-O-CO-、-O-CO-O-、-C(＝S)-O-、-O-C(＝S)-、-O-C(＝S)-O-、-CO-NR18-、-NR18-CO-、-O-CH2-、-CH2-O-、-S-CH2-、-CH2-S- or a single bond, R 16～R18 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms; f 3 represents an alkanediyl group having 1 to 12 carbon atoms, wherein hydrogen atoms contained in the alkanediyl group are optionally substituted with-OR 19 OR a halogen atom, R 19 represents an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, -CH 2 -contained in the alkanediyl may be replaced by-O-OR-CO-; p 3 represents a hydrogen atom or a polymerizable group.
As the substituent X 3, a fluorine atom, a chlorine atom, -CF 3、-OCF3 or a cyano group is preferable. R Y1 is preferably an unsubstituted or a C1-6 alkyl group substituted with 1 or more fluorine atoms, more preferably a hydrogen atom.
In the formula (Y 3 -1), U 1 represents an organic group having 2 to 30 carbon atoms and having an aromatic hydrocarbon group. Any carbon atom of the aromatic hydrocarbon group may be replaced with a heteroatom, and U 1 is an organic group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring and having 2 to 30 carbon atoms. The aromatic hydrocarbon group may be substituted with 1 or more substituents X 3 described above.
From the viewpoint of good wavelength dispersibility, U 1 is preferably an organic group having an aromatic heterocycle in which 1 or more of carbon atoms are replaced with a heteroatom. From the viewpoint of obtaining good wavelength dispersibility and exhibiting high birefringence, U 1 is more preferably an organic group having an aromatic heterocycle as a condensed ring of a 5-membered ring and a 6-membered ring.
Specifically, as U 1, an organic group having a group represented by the following formula is preferable. In the following formula, these groups have a bond to T 1 at any position.
[ Chemical formula 19]
In the formula (Y 3 -1), T 1 represents-O-, -S-, -COO-, -OCO-O-, -NU 2-、-N＝CU2-、-CO-NU2-、-OCO-NU2 -or O-NU 2-,U2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an organic group having 2 to 30 carbon atoms and having an aromatic hydrocarbon group (any carbon atom of the aromatic hydrocarbon group may be replaced with a hetero atom), or (E 3-A3)q-B3-F3-P3. The alkyl group, cycloalkyl group, cycloalkenyl group and aromatic hydrocarbon group may be each unsubstituted or substituted with 1 or more substituents X 3, 1-CH 2 -or more than 2-CH 2 -in the alkyl group may each independently be replaced by -O-、-S-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-SO2-、-O-CO-O-、-CO-NH-、-NH-CO-、-CH＝CH-COO-、-CH＝CH-OCO-、-COO-CH＝CH-、-OCO-CH＝CH-、-CH＝CH-、-CF＝CF- or-C≡C-, 1-CH 2 -or more than 2 non-adjacent-CH 2 -in the cycloalkyl or cycloalkenyl group may be replaced by-O-, -CO-, -COO-, -OCO-or-O-CO-O-. E 3, as defined above for B 3, A 3 represents a 2-valent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a 2-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, the hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by halogen atoms, -R 20、-OR21, cyano groups or nitro groups, R 20 represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, r 21 represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom. B 3、F3 and P 3 have the same meanings as those of B 3、F3 and P 3, respectively, and q represents an integer of 0 to 4. Where there are multiple E 3 and/or A 3, they may each be the same or different.
From the viewpoint of good birefringence and easy synthesis, T 1 is preferably-O-, -S-, -n=cu 2 -or-NU 2 -, from the viewpoint of easy improvement of wavelength dispersion and birefringence, T 1 is more preferably-O-; -S-or-NU 2 -.
U 2 is preferably: 1-CH 2 -or 2 or more non-adjacent-CH 2 -which may be substituted with 1 or more of the substituents X 3 and each independently may be replaced with an alkyl or alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a cycloalkenyl group having 3 to 12 carbon atoms; or the aforementioned alkyl or alkenyl group which may be substituted with the cycloalkyl group, cycloalkenyl group or aryl group.
Among them, U 2 is more preferable from the viewpoints of birefringence and solvent solubility: the hydrogen atom may be substituted by fluorine atom and 1-CH 2 -or 2 or more non-adjacent-CH 2 -may each independently be replaced by-O-; -CO-, -COO-, or-OCO-is a linear alkyl group having 1 to 20 carbon atoms.
U 1 and U 2 may be bonded to form a ring. In this case, for example, a cyclic group represented by-NU 1U2 or a cyclic group represented by-n=cu 1U2 may be mentioned.
From the viewpoints of easy availability of raw materials, good solubility, and high birefringence, each of Y 3 and Y 4 particularly preferably represents a group selected from the following formulae (Y 3' -1) to (Y 3' -47).
[ Chemical formula 20]
[ Chemical formula 21]
[ Chemical formula 22]
The following are specific examples of the group represented by the formula (Ar-5) from the viewpoints of improving the orientation of the polymerizable liquid crystal compound (x), facilitating industrial production, and improving productivity. The following (Ar 5-1)～(Ar5 -20) represents a bond to L 1 or L 2 in formula (I).
[ Chemical formula 23]
[ Chemical formula 24]
[ Chemical formula 25]
In the formulae (Ar-1) to (Ar-5), the group represented by any one of the formulae (Ar-1), (Ar-2) and (Ar-5) is more preferable, and the group represented by the formula (Ar-1) is even more preferable. Examples of the polymerizable liquid crystal compound represented by the formula (I) include those described in Japanese patent application laid-open No. 2019-003177 and Japanese patent application laid-open No. 2019-073496.
The nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound (I) when measured alone is preferably 100℃to 200 ℃. The nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound (I) is preferably 110 ℃ or higher, more preferably 120 ℃ or higher, for example, 130 ℃ or higher, and further 140 ℃ or higher.
In the present invention, the nematic liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature adjustment stage, a Differential Scanning Calorimeter (DSC), a thermogravimetric differential thermal analysis apparatus (TG-DTA), or the like.
In the present invention, the composition for forming a retardation film may contain a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (I). Examples of the polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (I) include rod-like polymerizable liquid crystal compounds. Here, the term "rod-like polymerizable liquid crystal compound" refers to a polymerizable liquid crystal compound having a molecular structure which can be regarded as a rod, and in the present disclosure, refers to a polymerizable liquid crystal compound having a positive wavelength dispersibility due to a phase difference which is generally generated by aligned liquid crystal molecules.
In the present invention, as the polymerizable liquid crystal compound forming the liquid crystal cured film, for example, a compound containing a group represented by the following formula (II) (hereinafter, also referred to as "polymerizable liquid crystal compound (II)") can be used. The polymerizable liquid crystal compound (II) generally tends to exhibit positive wavelength dispersibility. These polymerizable liquid crystal compounds may be used singly or in combination of 2 or more.
P4-B4-E4-B5-A4-B6-(II)
In the formula (Y), P 4 represents a polymerizable group.
A 4 represents a 2-valent alicyclic hydrocarbon group or a 2-valent aromatic hydrocarbon group.
B 4 represents-O-, -S-; -CO-O- -O-CO-, -O-CO-O-, -CO-NR 22-、-NR22 -CO-, -CS-, or a single bond. R 22 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
B 5 and B 6 each independently represent -C≡C-、-CH＝CH-、-CH2-CH2-、-O-、-S-、-C(＝O)-、-C(＝O)-O-、-O-C(＝O)-、-O-C(＝O)-O-、-CH＝N-、-N＝CH-、-N＝N-、-C(＝O)-NR22-、-NR22-C(＝O)-、-OCH2-、-OCF2-、-CH2O-、-CF2O-、-CH＝CH-C(＝O)-O-、-O-C(＝O)-CH＝CH-、-H、-C≡N or a single bond.
E 4 represents an alkanediyl group having 1 to 12 carbon atoms, wherein hydrogen atoms contained in the alkanediyl group are optionally substituted by alkoxy groups having 1 to 5 carbon atoms, and wherein hydrogen atoms contained in the alkoxy groups are optionally substituted by halogen atoms. In addition, in the case of the optical fiber, -CH 2 forming the alkanediyl group-may be replaced by-O-or-CO-. ]
The number of carbon atoms of the aromatic hydrocarbon group and alicyclic hydrocarbon group of a 4 is preferably in the range of 3 to 18, more preferably in the range of 5 to 12, and particularly preferably 5 or 6. The hydrogen atom contained in the 2-valent alicyclic hydrocarbon group and the 2-valent aromatic hydrocarbon group represented by a 4 may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, and the alkyl group having 1 to 6 carbon atoms and the hydrogen atom contained in the alkoxy group having 1 to 6 carbon atoms may be substituted with a fluorine atom. As A 4, cyclohexane-1, 4-diyl, 1, 4-phenylene is preferred.
E 4 is preferably a linear alkanediyl group having 1 to 12 carbon atoms. the-CH 2 -constituting the alkanediyl group may be replaced by-O-.
Specifically, examples thereof include straight-chain alkanediyl groups having 1 to 12 carbon atoms such as methylene, ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl, undecane-1, 11-diyl and dodecane-1, 12-diyl, ;-CH2-CH2-O-CH2-CH2-、-CH2-CH2-O-CH2-CH2-O-CH2-CH2- and -CH2-CH2-O-CH2-CH2-O-CH2-CH2-O-CH2-CH2-.
As a result of the fact that as a B 4, preferably-O-, -S-; -CO-O-, -O-CO-, -and of these, -CO-O-is more preferable.
As B 5 and B 6, each independently is preferably-O-, -S-, -C (=o) -O-, -O-C (=o) -O-, wherein, more preferably-O-or-O-C (=o) -O-.
The polymerizable group represented by P 4 may be a group polymerizable with the polymerizable liquid crystal compound (I), and examples thereof include a vinyl group, a vinyloxy group, a P-stilbene group, an acryl group, an acryloyloxy group, a methacryl group, a methacryloyloxy group, a carboxyl group, an acetyl group, a hydroxyl group, a carbamoyl group, an amino group, an alkylamino group having 1 to 4 carbon atoms, an epoxy group, an oxetanyl group, a formyl group, -n=c=o, and-n=c=s. From the viewpoint of high polymerization reactivity, particularly photopolymerization reactivity, a radical polymerizable group or a cation polymerizable group is preferable. The group represented by P 4-B4 -is preferably an acryloyloxy group, methacryloyloxy group or vinyloxy group, from the viewpoint of easy handling and easy production of the liquid crystal compound itself.
As the polymerizable liquid crystal compound (II), there may be mentioned compounds represented by the formula (II-1), the formula (II-2), the formula (II-3), the formula (II-4), the formula (II-5) or the formula (II-6).
P4-B4-E4-B5-A4-B6-A5-B7-A6-B8-A7-B9-E5-B10-P5(II-1)
P4-B4-E4-B5-A4-B6-A5-B7-A6-B8-A7-F4(II-2)
P4-B4-E4-B5-A4-B6-A5-B7-A6-B8-E5-B10-P5(II-3)
P4-B4-E4-B5-A4-B6-A5-B7-A6-F4(II-4)
P4-B4-E4-B5-A4-B6-A5-B7-E5-B10-P5(II-5)
P4-B4-E4-B5-A4-B6-A5-F4(II-6)
[ In the above-mentioned, a method for producing a semiconductor device,
A 4、B4～B6 and P 4 have the same meaning as above,
Each of a 5～A7 is independently synonymous with a 4, each of B 7～B9 is independently synonymous with B 5, B 10 is synonymous with B 4, E 5 is synonymous with E 4, and P 5 is synonymous with P 4.
F 4 represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxyl group, a hydroxymethyl group, a formyl group, a sulfo group (-SO 3 H), a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms or a halogen atom, and-CH 2 -constituting the alkyl group and the alkoxy group may be replaced by-O-. ]
Specific examples of the polymerizable liquid crystal compound (II) include compounds having a polymerizable group among compounds described in "3.8.6 networks (fully crosslinked)", "6.5.1 liquid crystal materials b..polymerizable nematic liquid crystal materials" of liquid crystal stool (edited by the liquid crystal stool edit committee, release of charpy (10/30) 2000), and polymerizable liquid crystals described in japanese patent application laid-open nos. 2010-31223, 2010-270108, 2011-6360 and 2011-207765.
The polymerizable liquid crystal compound (II) is preferably a liquid crystal compound exhibiting nematic liquid crystal properties. When the polymerizable liquid crystal compound (II) exhibits nematic liquid crystal properties, the nematic liquid crystal phase transition temperature may be 100℃or more and 200℃or less, or may be outside the above range, for example, less than 100 ℃.
In the present invention, when the composition for forming a retardation film contains a plurality of polymerizable liquid crystal compounds, the nematic liquid crystal phase transition temperature of the mixture of polymerizable liquid crystal compounds may be 100 ℃ to 200 ℃. The nematic liquid crystal phase transition temperature of the mixture is preferably 110℃or higher, more preferably 120℃or higher, for example 130℃or higher, and further 140℃or higher.
The content of the polymerizable liquid crystal compound (I) in the composition for forming a retardation film of the present invention can be appropriately determined depending on the kind, combination, etc. of the polymerizable liquid crystal compound to be used, and is preferably 20 to 100 parts by mass, more preferably 40 to 100 parts by mass, still more preferably 50 to 100 parts by mass, and particularly preferably 55 to 100 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound contained in the composition for forming a retardation film. When the content of the polymerizable liquid crystal compound (I) is within the above range, the obtained retardation film tends to have inverse wavelength dispersibility, and is advantageous in terms of optical characteristics. When the composition for forming a retardation film contains 2 or more kinds of polymerizable liquid crystal compounds (I), the total amount of all polymerizable liquid crystal compounds (I) contained in the composition for forming a retardation film is preferably within the above-described content range.
The content of the polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (I) in the composition for forming a phase difference film of the present invention is preferably less than 50 parts by mass, more preferably 40 parts by mass or less, still more preferably 20 parts by mass or less, particularly preferably 10 parts by mass or less, and may be substantially 0 part by mass, based on 100 parts by mass of the polymerizable liquid crystal compound contained in the composition for forming a phase difference film. In one embodiment of the present invention, the content of the polymerizable liquid crystal compound (II) is preferably within the aforementioned range.
The total content of the polymerizable liquid crystal compound in the composition for forming a phase difference film is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 99 parts by mass, and even more preferably 90 to 98 parts by mass, per 100 parts by mass of the solid content of the composition for forming a phase difference film. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of alignment accuracy of the obtained retardation film. When the composition for forming a retardation film contains 2 or more polymerizable liquid crystal compounds, the total amount of all liquid crystal compounds contained in the composition for forming a retardation film is preferably within the above-described content range. In the present specification, the solid content of the composition for forming a retardation film means all components obtained by removing volatile components such as an organic solvent from the composition for forming a retardation film.
The composition for forming a retardation film of the present invention may contain a polymerization initiator. The polymerization initiator is a compound capable of initiating a polymerization reaction of a polymerizable liquid crystal compound or the like, and is preferably a photopolymerization initiator that generates a living radical by the action of light from the viewpoint of not depending on the phase state of the thermotropic liquid crystal.
The photopolymerization initiator may be a compound capable of initiating polymerization of the polymerizable liquid crystal compound, and a known photopolymerization initiator may be used. Specifically, a photopolymerization initiator capable of generating a living radical or an acid by the action of light is exemplified, and among them, a photopolymerization initiator capable of generating a radical by the action of light is preferable. The photopolymerization initiator may be used alone or in combination of 2 or more.
As the photopolymerization initiator, known photopolymerization initiators can be used, and as the photopolymerization initiator generating active radicals, for example, self-cleaving benzoin compounds, acetophenone compounds, hydroxyacetophenone compounds, α -aminoacetophenone compounds, oxime ester compounds, acylphosphine oxide compounds, azo compounds and the like can be used, and hydrogen abstraction benzophenone compounds, alkylbenzene ketone compounds, benzoin ether compounds, benzil ketal compounds, dibenzosuberone compounds, anthraquinone compounds, xanthone compounds, thioxanthone compounds, halogenated acetophenone compounds, dialkoxyacetophenone compounds, halogenated bisimidazole compounds, halogenated triazine compounds, triazine compounds and the like can be used. As the photopolymerization initiator for generating an acid, iodonium salts, sulfonium salts, and the like can be used. From the viewpoint of excellent reaction efficiency at low temperatures, a self-cleaving photopolymerization initiator is preferable, and acetophenone-based compounds, hydroxyacetophenone-based compounds, α -aminoacetophenone-based compounds, and oxime ester-based compounds are particularly preferable.
The content of the photopolymerization initiator may be appropriately adjusted depending on the type and amount of the polymerizable liquid crystal compound, and is usually 0.1 part by mass to 30 parts by mass, preferably 0.5 part by mass to 10 parts by mass, and more preferably 0.5 part by mass to 8 parts by mass, based on 100 parts by mass of the total amount of the polymerizable liquid crystal compound contained in the composition for forming a retardation film. If the amount is within the above range, the reaction of the polymerizable group proceeds sufficiently without disturbing the alignment of the polymerizable liquid crystal compound.
The composition for forming a retardation film may contain a leveling agent. The leveling agent is an additive having a function of adjusting the fluidity of the composition and flattening a film obtained by coating the composition, and examples thereof include organomodified silicone oils, polyacrylate esters and perfluoroalkyl groups. Among them, a polyacrylate-based leveling agent and a perfluoroalkyl-based leveling agent are preferable.
The content of the leveling agent in the composition for forming a retardation film is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, the polymerizable liquid crystal compound tends to be horizontally aligned, and the resulting cured film tends to be smoother. If the content of the leveling agent with respect to the polymerizable liquid crystal compound exceeds the above range, unevenness tends to occur easily in the obtained cured film. The composition for forming a retardation film may contain 2 or more leveling agents.
The composition for forming a retardation film of the present invention may contain additives such as an antioxidant, a photosensitizing agent, and a reactive additive, in addition to the organic solvent, the polymerizable liquid crystal compound, and the polymerization initiator and leveling agent, if necessary. These components may be used alone in combination of 1 kind or 2 or more kinds. When the phase difference film-forming composition contains an additive, the content thereof is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, relative to the solid content of the phase difference film-forming composition.
The composition for forming a retardation film can be obtained by mixing the organic solvent a and the organic solvent B with the polymerizable liquid crystal compound, and if necessary, a polymerization initiator, a leveling agent, and other components at a predetermined temperature.
< Method for producing retardation film >
The composition for forming a retardation film of the present invention can be used for forming a film by removing a solvent at a lower temperature than the conventional one, for example, at a lower temperature than 100 ℃, and is excellent in the effect of suppressing the occurrence of unevenness in the film formation, and therefore is suitable as a material (composition) for forming a retardation film excellent in optical characteristics.
In the case of forming a retardation film using the composition for forming a retardation film of the present invention, for example, it is advantageous to employ a method comprising the steps of:
A step of forming a coating film of the composition for forming a retardation film of the present invention,
A step of drying the coating film at a drying temperature Td (DEG C) to obtain a dried coating film, and
A step of curing the dried coating film to obtain a retardation film;
The drying temperature Td (c) satisfies the formula (4) and (5):
Ta<Td<Tb (4)
X-80≤Td≤X-20 (5)。
accordingly, the present invention also provides a method for producing a phase difference film, comprising the steps of:
A step of forming a coating film of the composition for forming a retardation film of the present invention,
A step of drying the coating film at a drying temperature Td (DEG C) to obtain a dried coating film, and
A step of curing the dried coating film to obtain a retardation film;
The drying temperature Td (c) satisfies the formula (4) and (5):
Ta<Td<Tb (4)
X-80≤Td≤X-20 (5)。
The coating film of the composition for forming a retardation film can be formed by coating the mixed composition on a substrate, an alignment film, or the like. As the substrate, a substrate known in the art such as a glass substrate and a resin film substrate can be suitably selected and used. From the viewpoint of processability, a resin film base material is preferable. Examples of the resin constituting the resin film base material include polyolefin such as polyethylene, polypropylene, and norbornene polymer; a cyclic olefin resin; polyvinyl alcohol; polyethylene terephthalate; a polymethacrylate; a polyacrylate; cellulose esters such as cellulose triacetate, cellulose diacetate and cellulose acetate propionate; polyethylene naphthalate; a polycarbonate; polysulfone; polyether sulfone; polyether ketone; polyphenylene sulfide, polyphenylene ether, and the like.
The alignment film preferably has solvent resistance that does not dissolve in the organic solvents a and B due to the application of the composition for forming a retardation film, and also has heat resistance against heat treatment in a drying step described later. Examples of the alignment film include a rubbing alignment film containing an alignment polymer, a photo-alignment film, a groove alignment film having a concave-convex pattern on the surface and a plurality of grooves, a stretched film, and the like. The photo-alignment film is preferable in that the alignment direction can be easily controlled more precisely. As such an alignment film, an alignment film generally used in the production of an optical film (particularly, a retardation film) can be suitably selected and used. Specifically, for example, a rubbing alignment film described in japanese patent application laid-open publication No. 2019-191504, a photo-alignment film formed of a (co) polymer including a structural unit having a photoreactive group and a structural unit having a polymerizable group described in japanese patent application laid-open publication No. 2021-196514, or the like can be used.
Examples of the method of applying the composition for forming a phase difference film to a substrate or the like include known methods such as spin coating, extrusion, gravure coating, die coating, bar coating, coater, and other coating methods, and flexography, and other printing methods.
Then, the organic solvent is dried and removed, thereby forming a dried coating film. The drying method includes natural drying, ventilation drying, heating drying, and reduced pressure drying, and is preferably heating drying in view of efficiently forming a retardation film, and the composition for forming a retardation film of the present invention is excellent in the effect of suppressing wind streak unevenness, and thus can be suitably used for heating drying by hot air such as a drying oven. In the present invention, the drying temperature Td (c) at this time is preferably controlled so that the formulas (4) and (5) are satisfied in the relationship between the boiling point Ta (c) of the organic solvent a constituting the composition for forming a retardation film, the boiling point Tb (c) of the organic solvent B, and the nematic liquid crystal phase transition temperature X (c) of the polymerizable liquid crystal compound.
Ta<Td<Tb (4)
X-80≤Td≤X-20 (5)
By setting the drying temperature to be higher than Ta and lower than Tb and within a certain range as compared with the phase transition temperature of the polymerizable liquid crystal compound, the effects of suppressing the occurrence of the aforementioned wind streak unevenness due to the influence of wind in the drying furnace, crystallization of the liquid crystal compound due to volatilization of the solvent, and occurrence of alignment defects can be obtained. Thus, a retardation film having excellent appearance characteristics and optical characteristics can be obtained.
In the drying step, the solvent can be removed from the coating film by heating the coating film obtained from the composition for forming a retardation film, and the polymerizable liquid crystal compound can be oriented in a desired direction (for example, in a horizontal direction) with respect to the plane of the coating film. In the present invention, as a drying temperature for removing the solvent contained in the composition for forming a phase difference film and bringing the polymerizable liquid crystal compound into a desired alignment state, a temperature lower than the liquid crystal phase transition temperature (nematic liquid crystal phase transition temperature) of the polymerizable liquid crystal compound contained in the composition, for example, a temperature lower than the phase transition temperature of the polymerizable liquid crystal compound used by about 20 to 80 ℃ is preferably used. By performing the drying step under such conditions, the following effects are particularly easily obtained: the volatilization and removal of the organic solvent A and the organic solvent B are appropriately performed based on the relationship between the drying temperature, thereby suppressing crystallization of the liquid crystal compound and occurrence of alignment defects, and suppressing uneven air marks caused by hot air in the drying furnace.
The drying temperature Td can be appropriately determined in consideration of the material of the polymerizable liquid crystal compound to be used, the substrate for forming the coating film, and the like. In one embodiment of the present invention, the drying temperature Td is preferably 70 ℃ or higher and lower than 130 ℃. The drying temperature Td is more preferably 120 ℃ or less, still more preferably 110 ℃ or less, particularly preferably 100 ℃ or less, for example, may be lower than 100 ℃, and further may be 90 ℃ or less, from the viewpoint of suppressing excessive consumption of heat energy and improving production efficiency. By using a low heating temperature, there is also an advantage that the range of choices for the support substrate to which the composition for forming a retardation film is applied is widened.
The drying time can be appropriately determined depending on the heating temperature, the kind of the polymerizable liquid crystal compound contained, the kind of the organic solvent, the boiling point thereof, the amount thereof, and the like, and is usually 15 seconds to 10 minutes, preferably 0.5 to 5 minutes.
Next, in the obtained dry coating film, the polymerizable liquid crystal compound is polymerized while maintaining the alignment state of the polymerizable liquid crystal compound, thereby forming a liquid crystal cured film (retardation film) which is a polymer of the polymerizable liquid crystal compound existing in a desired alignment state. As the polymerization method, a photopolymerization method is generally used. In photopolymerization, the light to be irradiated to the dried coating film may be appropriately selected depending on the kind of the polymerization initiator contained in the dried coating film, the kind of the polymerizable liquid crystal compound, and the amount thereof. Specific examples thereof include 1 or more light and active electron beams 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 preferable from the viewpoint of easy control of the progress of polymerization reaction and the use of a device widely used in the art as a photopolymerization device, and the types of polymerizable liquid crystal compound and polymerization initiator contained in the composition for forming a retardation film are preferably selected in advance so that photopolymerization can be performed by ultraviolet light. In addition, in the polymerization, the polymerization temperature can be controlled by cooling the dried coating film by an appropriate cooling means and simultaneously irradiating the film with light. If the polymerizable liquid crystal compound is polymerized at a lower temperature by using such a cooling means, a retardation film can be formed appropriately even if a substrate having low heat resistance is used as the substrate. In addition, the polymerization reaction can be accelerated by increasing the polymerization temperature within a range where defects due to heat at the time of light irradiation (deformation of the base material due to heat, etc.) do not occur. In photopolymerization, a patterned cured film can also be obtained by masking, developing, or the like.
Examples of the light source of the active energy ray include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, an LED light source that emits light in a wavelength range of 380 to 440nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.
The ultraviolet irradiation intensity is usually 10 to 3,000mW/cm 2. The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activation of the photopolymerization initiator. The time for irradiation of light is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and still more preferably 0.1 seconds to 1 minute. When the irradiation is performed 1 or more times at such ultraviolet irradiation intensity, the cumulative light amount thereof is 10 to 3,000mJ/cm 2, preferably 50 to 2,000mJ/cm 2, more preferably 100 to 1,000mJ/cm 2.
The thickness of the retardation film may be appropriately selected according to the display device or the like to be used. Preferably 0.2 to 5. Mu.m, more preferably 0.2 to 3. Mu.m. The thickness may be measured by an interferometric film thickness meter, a laser microscope, or a stylus film thickness meter.
The composition for forming a retardation film of the present invention can form a retardation film in a relatively low temperature range, and therefore, by using the composition for forming a retardation film of the present invention, it is possible to form a film at a low temperature without deteriorating the optical characteristics that can be exhibited by the polymerizable liquid crystal compound, and a retardation film having excellent optical characteristics can be obtained. Accordingly, the present invention also relates to a retardation plate comprising a retardation film which is a cured film of the composition for forming a retardation film of the present invention and which is formed by curing a polymerizable liquid crystal compound in the composition in an aligned state. The retardation plate comprising the cured film of the composition for forming a retardation film can sufficiently exhibit the optical characteristics that the polymerizable liquid crystal compound used can originally exhibit, and can be a retardation plate having high optical performance.
The liquid crystal cured film (retardation film) constituting the retardation plate of the present invention may be composed of a homopolymer of the polymerizable liquid crystal compound (I) in an aligned state, or may be composed of a copolymer in an aligned state of a mixture of other polymerizable liquid crystal compounds such as the polymerizable liquid crystal compound (I) and the polymerizable liquid crystal compound (II).
In one embodiment of the present invention, the retardation film constituting the retardation plate of the present invention is a cured film of the composition for forming a retardation film of the present invention, and preferably satisfies the optical characteristics represented by the following formulas (a), (b) and (c). Such a liquid crystal cured film is generally a cured film in which a polymerizable liquid crystal compound is cured in a state of being oriented in a horizontal direction with respect to the plane of the liquid crystal cured film.
Re(450)/Re(550)≤1.00 (a)
1.00≤Re(650)/Re(550) (b)
100nm≤Re(550)≤180nm (c)
[ Formula (λ) represents an in-plane phase difference value at a wavelength λnm of the retardation film, re= (nx (λ) -ny (λ)) ×d (d represents a thickness of the retardation film), nx represents a principal refractive index at a wavelength λnm in a direction parallel to a plane of the retardation film in a refractive index ellipsoid formed of the retardation film, ny represents a refractive index at a wavelength λnm in a direction parallel to the plane of the retardation film and orthogonal to the direction of the nx in the refractive index ellipsoid formed of the retardation film). A kind of electronic device
When the retardation film satisfies the formulas (a) and (b), the retardation film exhibits so-called inverse wavelength dispersibility in which the in-plane phase difference at a short wavelength is smaller than the in-plane phase difference at a long wavelength. From the viewpoint of improving the inverse wavelength dispersibility and further improving the optical characteristics of the retardation film, re (450)/Re (550) is preferably 0.80 or more and less than 1.0, more preferably 0.80 or more and less than 0.92. The ratio Re (650)/Re (550) is preferably 1.00 or more, more preferably 1.01 or more.
The in-plane retardation value can be adjusted by the thickness d of the retardation film. Since the in-plane phase difference value is defined by the above formula Re (λ) = (nx (λ) -ny (λ)) ×d, the three-dimensional refractive index and the film thickness d may be adjusted so as to obtain a desired in-plane phase difference value (Re (λ): in-plane phase difference value of the retardation film at wavelength λ (nm)).
When the retardation film satisfies the formula (c), the retardation film including the retardation film functions as a λ/4 plate, and the effect of improving the front reflection hue (the effect of suppressing coloring) is excellent when the circularly polarizing plate including the retardation film is applied to an optical display or the like. A more preferable range of the in-plane phase difference value is 120 nm.ltoreq.Re (550). Ltoreq.170 nm, and a further preferable range is 130 nm.ltoreq.Re (550). Ltoreq.150 nm.
The retardation plate of the present invention can be used in various display devices such as a liquid crystal display device, an organic Electroluminescence (EL) display device, an inorganic Electroluminescence (EL) display device, a flexible image display device, a touch panel display device, an electron emission display device (for example, an electric field emission display device (FED), a surface electric field emission display device (SED)), an electronic paper (a display device using electronic ink, an electrophoretic element, a plasma display device, a projection display device (for example, a Grating Light Valve (GLV) display device, a display device having a Digital Micromirror Device (DMD)) and a piezoceramic display in the form of a circularly polarizing film, and is particularly suitably used in an organic Electroluminescence (EL) display device and an inorganic Electroluminescence (EL) display device.
The circular polarizing plate and various members (e.g., polarizing film, display element, etc.) in the display device, and the constitution thereof may be appropriately selected from known materials and techniques.
Examples
Hereinafter, the present invention will be described more specifically with reference to examples. Unless otherwise specified, "%" and "parts" in examples refer to mass% and mass parts, respectively.
[ Preparation of composition for Forming photo-alignment film ]
The light-oriented material (weight average molecular weight: 50000, m: n=50:50) having the following structure was produced according to the method described in japanese patent application laid-open No. 2021-196514. The photo-alignment film-forming composition was prepared by mixing 2 parts of photo-alignment material and 98 parts of cyclopentanone (solvent) as components and stirring the resultant mixture at 80 ℃ for 1 hour.
Light-oriented material:
[ chemical formula 26]
[ Production of polymerizable liquid Crystal Compound ]
Polymerizable liquid crystal compounds (A1) to (A3) having the structures shown below were prepared, respectively. The polymerizable liquid crystal compound (A1) was prepared in the same manner as described in JP-A2010-31223. The polymerizable liquid crystal compound (A2) is prepared in the same manner as described in Japanese patent application laid-open No. 2019-73496. The polymerizable liquid crystal compound (A3) is prepared in the same manner as described in Japanese patent application laid-open No. 2016-81035.
Polymerizable liquid crystal compound (A1)
[ Chemical formula 27]
Polymerizable liquid crystal compound (A2)
[ Chemical formula 28]
Polymerizable liquid crystal compound (A3)
[ Chemical formula 29]
[ Measurement of nematic liquid Crystal phase transition temperature of polymerizable liquid Crystal Compound ]
The polymerizable liquid crystal compounds (A1) to (A3) thus produced were weighed 1g into vials, and 2g of chloroform was further added thereto to dissolve the compounds. The resulting solution was applied to a glass substrate with a PVA alignment film subjected to a rubbing treatment, and dried. The substrate was placed in a cooling and heating apparatus (LNP 94-2 manufactured by JAPAN in the company "koku"), and the temperature was raised from room temperature to 180 ℃ and then cooled to room temperature. The morphology of the liquid crystal layer at the time of temperature change was observed with a polarizing microscope (LEXT, olympus corporation), and the temperature at which the liquid crystal layer became a nematic liquid crystal phase was measured as a nematic liquid crystal phase transition temperature. The results obtained are shown in Table 1.
In the case where 2 or more kinds of polymerizable liquid crystal compounds are used in combination in the examples, a mixture of all polymerizable liquid crystal compounds constituting the composition for forming a retardation film and a mixture of polymerizable liquid crystal compounds obtained by mixing the same ratio as the composition in the composition for forming a retardation film is used for the above-mentioned nematic liquid crystal phase transition temperature, and the measurement is carried out in the same manner as in the case of using 1 kind of polymerizable liquid crystal compounds.
TABLE 1
Example 1]
[ Preparation of composition (1) for Forming a retardation film ]
According to Table 2, 0.1 part of a leveling agent "BYK-361N" (manufactured by BM Chemie Co., ltd.) and 3 parts of "Irgacure OXE-03" (manufactured by BASF Japan Ltd.) as a photopolymerization initiator were added to 100 parts of the polymerizable liquid crystal compound (A1). Further, the organic solvent a was added so that the solid content concentration became 9%: tetrahydrofuran (Ta: 66 ℃ C.)/organic solvent B: cyclopentanone (Tb: 130 ℃ C.) mixed solvent (20/80 in mass ratio). The mixture was stirred at a temperature of 50℃for 1 hour, thereby preparing a composition (1) for forming a retardation film. The HSP distance between tetrahydrofuran and cyclopentanone was calculated as 7.1 according to the following method.
TABLE 2
[ Calculation method of HSP distance ]
The hansen solubility parameter (δd A：16.8,δPA：5.7,δHA:8.0) of tetrahydrofuran and the hansen solubility parameter (δd B：17.9,δPB：11.9,δHB:5.2) of cyclopentanone, which have been registered in the database, were used for HSP distance, and calculated using the following formula.
HSP distance ＝[4(δDA-δDB)2+(δPA-δPB)2+(δHA-δHB)2]1/2
[ Production of retardation film ]
The composition for forming a photo-alignment film was applied to a biaxially stretched polyethylene terephthalate (PET) film (Diafoil mitsubishi resin (ltd)) as a base material by a bar coater. The obtained coating film was dried in a drying oven at 120℃for 2 minutes, and then cooled to room temperature to form a dried film. Then, a UV irradiation apparatus (SPOTCURE SP-9; manufactured by USHIO INC.) was used to irradiate polarized ultraviolet light of 100mJ/cm 2 (based on 313 nm) to obtain a photo-alignment film. The film thickness of the photo-alignment film was 200nm as measured by using an ellipsometer (ellipsometer) M-220 manufactured by Nippon Spectrophotometer Co.
The composition (1) for forming a retardation film was applied to the obtained photo-alignment film by a bar coater to form a coating film. The coated film was heated and dried in a drying oven at 90℃for 1 minute, and then cooled to room temperature to obtain a dried film. Subsequently, a retardation film formed BY curing a polymerizable liquid crystal compound in a state of being oriented in a horizontal direction with respect to the substrate surface was formed BY irradiating the dried film with ultraviolet light having an exposure of 500mJ/cm 2 (based on 365 nm) under a nitrogen atmosphere using a high-pressure mercury lamp (U.S. Pat. No. Unicure VB-15201 BY-A), and a retardation plate (1) formed of a substrate, a photo-alignment film and a retardation film was obtained. The film thickness of the retardation film was 2.0 μm as measured by using a laser microscope LEXT OLS4100 manufactured by Olympus corporation.
< Evaluation of unevenness due to wind streaks >
A pair of linear polarizers are overlapped on a light table (light table) so as to be crossed nicols. The retardation plates obtained in examples and comparative examples were placed between the linear polarizers provided on the optical table as described above. At this time, the slow axis of the retardation film is set to be substantially 45 ° with respect to the absorption axis of the polarizer when viewed from the thickness direction. Then, by visual observation, the degree of unevenness caused by moire was observed from the uniformity in the observed image (uniformity of phase difference). The results are shown in Table 4.
< Evaluation criterion >
A: no wind streak unevenness is observed at all
B: a small amount of wind streak unevenness was observed in the range of less than 30% of the area of the retardation plate
C: the wind streak unevenness was observed in the range of less than 30% of the area of the retardation plate
D: uneven wind streaks were observed in the whole retardation plate
E: serious wind streak unevenness was observed in the whole retardation plate
< Evaluation of orientation >
The obtained retardation plate was observed at 400 Xmagnification using a polarizing microscope (BX 51, manufactured by Olympus Co., ltd.). The orientation was evaluated according to the following criteria. The results are shown in Table 4.
< Evaluation criterion >
A: absence of disorder of crystallization and alignment of liquid crystal compound
B: the disorder of crystallization and orientation of the liquid crystal compound was slightly observed
C: the disturbance of crystallization and orientation of the liquid crystal compound was strongly observed
< Evaluation of mesh unevenness >
A pair of linear polarizers are overlapped on the optical table in such a manner as to be crossed nicols. The retardation plates obtained in examples and comparative examples were placed between the linear polarizers provided on the optical table as described above. In this case, the slow axis of the retardation film is set to be substantially 45 ° with respect to the absorption axis of the polarizer when viewed from the thickness direction. Then, the degree of mesh unevenness was observed by visual observation based on the uniformity (uniformity of phase difference) in the observed image. The results are shown in Table 4.
< Evaluation criterion >
A: no mesh unevenness was observed at all
B: several mesh-like irregularities were observed
C: serious mesh-like unevenness was observed
< Measurement of wavelength dispersibility >
An adhesive layer (an adhesive containing an acrylic polymer) and a glass substrate are sequentially bonded to the surface of the retardation plate on the opposite side to the photo-alignment film side, and then the substrate (PET film) and the photo-alignment film constituting the retardation plate are peeled together, and then the adhesive layer and the COP film (transfer object) subjected to corona treatment are sequentially bonded to the surface of the retardation plate. Thus, a laminate having a glass substrate, an adhesive layer, a retardation film, an adhesive layer, and a COP film (transfer object) in this order was obtained. The in-plane phase difference values of the laminate were measured for light having a wavelength of 450nm, 550nm, and 650nm using KOBRA-WR manufactured by Kabushiki Kaisha. The in-plane phase difference values for the light having wavelengths of 450nm, 550nm and 650nm were obtained by using the Cauchy dispersion formula obtained from the measurement results of the in-plane phase difference values for the light having wavelengths of 448.2nm, 498.6nm, 548.4nm, 587.3nm, 628.7nm and 748.6 nm.
For the measured value of Re (450)/Re (550) [ Re (450) represents an in-plane phase difference value for light having a wavelength of 450nm, re (550) represents an in-plane phase difference value for light having a wavelength of 550nm ], a case of 0.80 or more and less than 0.92 was evaluated as a, a case of 0.92 or more and less than 1.0 was evaluated as B, and a case of 1.0 or more was evaluated as C. The results are shown in Table 4.
< Example 2 and 3>
The phase difference film-forming compositions (2) and (3) and the phase difference plates (2) and (3) were obtained in the same manner as in example 1, except that the mixing ratio of the organic solvent a and the organic solvent B was changed as shown in table 4. The obtained retardation plate was evaluated in the same manner as in example 1. The results are shown in Table 4.
Example 4 ]
A composition (4) for forming a retardation film and a retardation plate (4) were obtained in the same manner as in example 1 except that the mixing ratio of the organic solvent a and the organic solvent B was changed to 40/60 (mass ratio) and the solid content concentration was changed to 5%, as described in table 4. The obtained retardation plate was evaluated in the same manner as in example 1. The results are shown in Table 4.
Example 5 ]
A composition (5) for forming a retardation film and a retardation plate (5) were obtained in the same manner as in example 1 except that the mixing ratio of the organic solvent a and the organic solvent B was changed to 40/60 (mass ratio) and the solid content concentration was changed to 12%, as described in table 4. The obtained retardation plate was evaluated in the same manner as in example 1. The results are shown in Table 4.
< Examples 6 to 9>
As the solvent, an organic solvent a containing the following mixture ratio shown in table 4 was used: tetrahydrofuran/organic solvent B: cyclopentanone/other organic solvents: in the same manner as in example 1 except that the solid content concentration of the mixed solvent of N-methyl-2-pyrrolidone (NMP, boiling point: 202 ℃ C.) was changed to 12%, phase difference film-forming compositions (6) to (9) and phase difference plates (6) to (9) were obtained. The obtained retardation plate was evaluated in the same manner as in example 1. The results are shown in Table 4.
< Examples 10 to 12>
Phase difference film-forming compositions (10) to (12) and phase difference plates (10) to (12) were obtained in the same manner as in example 1 except that the mixing ratio of the organic solvent a and the organic solvent B was changed to a solid content concentration of 12% as shown in table 4. The obtained retardation plate was evaluated in the same manner as in example 1. The results are shown in Table 4.
< Examples 13 to 18>
Phase difference film-forming compositions (13) to (18) and phase difference plates (13) to (18) were obtained in the same manner as in example 1 except that the types and mixing ratios of the organic solvents were changed to 12% in accordance with the descriptions in table 4. The obtained retardation plate was evaluated in the same manner as in example 1. The results are shown in Table 4.
The boiling point of the solvent used is as follows.
2-Methyltetrahydrofuran: 80 DEG C
1, 3-Dioxolane: 77 DEG C
Monochlorobenzene: 132 DEG C
Anisole: 154 DEG C
Dimethyl sulfoxide (DMSO): 189 DEG C
In addition, the HSP distance between the organic solvent a and the organic solvent B in each example was calculated. The calculation results are shown in table 4.
< Example 19 and 20>
Phase difference film forming compositions (19) and (20) and phase difference plates (19) and (20) were obtained in the same manner as in example 5, except that the polymerizable liquid crystal compound (A2) and the polymerizable liquid crystal compound (A3) were used as the polymerizable liquid crystal compound, respectively. The obtained retardation plate was evaluated in the same manner as in example 1. The results are shown in Table 4.
< Examples 21 to 24>
As the polymerizable liquid crystal compound, a liquid crystal compound LC242 (registered trademark of BASF corporation) represented by the following formula (LC 242) was used. The nematic liquid crystal phase transition temperature of LC242 was 63 ℃.
[ Chemical formula 30]
A composition for forming a retardation film (21) to (24) and a retardation plate (21) to (24) were obtained in the same manner as in example 5 except that the polymerizable liquid crystal compound (A1) and the polymerizable liquid crystal compound (LC 242) were mixed and used in the mass ratio shown in table 3. The obtained retardation plate was evaluated in the same manner as in example 1. The nematic liquid crystal phase transition temperature of the mixture of polymerizable liquid crystal compounds is shown in table 4.
TABLE 3
< Reference example >
A composition (25) for forming a retardation film and a retardation plate (25) were obtained in the same manner as in example 1, except that LC242 was used as a polymerizable liquid crystal compound, the solvent was tetrahydrofuran alone, the solid content concentration was 12%, and the drying temperature was 70 ℃. The obtained retardation plate was evaluated in the same manner as in example 1. The results are shown in Table 4.
Comparative example 1]
A composition (26) for forming a retardation film and a retardation plate (26) were obtained in the same manner as in example 1 except that the solvent was NMP alone, the solid content concentration was 12%, and the drying temperature was 120 ℃. The obtained retardation plate was evaluated in the same manner as in example 1. The results are shown in Table 4.
Comparative examples 2 to 5]
A composition (27) to (30) for forming a retardation film and a retardation plate (27) to (30) were obtained in the same manner as in example 1 except that the types of solvents and the solid concentration were changed as described in table 4. The obtained retardation plate was evaluated in the same manner as in example 1. The results are shown in Table 4.
TABLE 4
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Claims (11)
1. A composition for forming a retardation film, which comprises a polymerizable liquid crystal compound having a nematic liquid crystal phase transition temperature in a range of 100 ℃ to 200 ℃ inclusive, and at least 2 organic solvents A and B having different boiling points from each other,
The following formulas (1) to (3) are satisfied when the nematic liquid crystal phase transition temperature of the polymerizable liquid crystal compound is X (. Degree. C.), the boiling point of the organic solvent A is Ta (. Degree. C.), and the boiling point of the organic solvent B is Tb (. Degree. C.):
Tb-Ta≥10(℃) (1)，
Ta<X-30(℃) (2)，
Tb>X-70(℃) (3)。
2. The composition for forming a retardation film according to claim 1, wherein the polymerizable liquid crystal compound comprises a polymerizable liquid crystal compound (I) represented by the following formula (I),
[ Chemical formula 1]
P1-E1-(B1-G1)k-L1-Ar-L2-(G2-B2)1-E2-P2 (1)
In the formula (I) of the present invention,
L 1、L2、B1 and B 2 each independently represent a single bond or a divalent linking group,
G 1 and G 2 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group in which a hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, a carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom,
K and l each independently represent an integer of 0 to 3 and satisfy the relation 1.ltoreq.k+l,
E 1 and E 2 each independently represent an alkanediyl group having 1 to 17 carbon atoms, wherein hydrogen atoms contained in the alkanediyl group may be substituted with halogen atoms, the alkanediyl group may contain-CH 2 -which is optionally replaced by-O-, -S-, -C (=o) -substitution,
P 1 and P 2 each independently represent a polymerizable group or a hydrogen atom (wherein at least 1 of P 1 and P 2 is a polymerizable group),
Ar is a group represented by any one of formulas (Ar-1) to (Ar-5),
[ Chemical formula 2]
In the formulae (Ar-1) to (Ar-5),
* Represents a bonding portion;
Q 1 represents-S-, -O-or-NR 11-,R11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent,
Q 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent;
W 1 and W 2 each independently represent-O-; -S-, -CO-, -NR 11-,R11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent;
Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
Y 2 represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have a substituent, a hydrogen atom contained in the alkyl group may be substituted with a halogen atom, -CH 2 -contained in the alkyl group may be substituted by-O-, -CO-, -O-CO-or-CO-O-;
Z 1、Z2 and Z 3 each independently represents a hydrogen atom or an aliphatic hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms having 1 valence, a halogen atom, a cyano group, a nitro group, -NR 12R13 or-SR 14,Z1, and Z 2 may be bonded to each other to form an aromatic ring or an aromatic heterocyclic ring, and R 12～R14 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Ax represents an organic group having at least 1 aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring and having 2 to 30 carbon atoms, ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an organic group having at least 1 aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring and having 2 to 30 carbon atoms, and Ax and Ay may be bonded to each other to form a ring;
y 3 and Y 4 each independently represent a group selected from the following formula (Y 3 -1),
[ Chemical formula 3]
In the formula (Y 3 -1),
R Y1 represents a hydrogen atom OR an alkyl group having 1 to 6 carbon atoms, which may be substituted with 1 OR more substituents X 3, wherein the substituents X 3 represent a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a sulfur pentafluoride group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, OR 1-CH 2 -, OR2 OR more non-adjacent-CH 2 -, each independently may be substituted with -O-、-S-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-CH＝CH-COO-、-CH＝CH-OCO-、-COO-CH＝CH-、-OCO-CH＝CH-、-CH＝CH-、-CF＝CF- OR-C≡C-linear OR branched alkyl groups having 1 to 20 carbon atoms, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, OR may be a group represented by-B 3-F3-P3 (wherein, B 3 represents -CR16R17-、-CH2-CH2-、-O-、-S-、-CO-O-、-O-CO-、-O-CO-O-、-C(＝S)-O-、-O-C(＝S)-、-O-C(＝S)-O-、-CO-NR18-、-NR18-CO-、-O-CH2-、-CH2-O-、-S-CH2-、-CH2-S- OR a single bond, R 16～R18 represents a hydrogen atom, a fluorine atom, OR an alkyl group having 1 to 4 carbon atoms; F 3 represents a dialkyl group having 1 to 12 carbon atoms, which may be substituted with a halogen atom OR-C≡C-C5 may be substituted with a hydrogen atom, OR-C3998 represents a halogen atom in the alkyl group having 2 to C-C may be substituted with a halogen atom, OR-C3998,
U 1 represents an organic group having 2 to 30 carbon atoms and having an aromatic hydrocarbon group, any carbon atom of which may be replaced with a heteroatom, and the aromatic hydrocarbon group may be substituted with 1 or more substituents X 3;
T 1 represents-O-; -S-, -COO-, -OCO-, -OCO-O-, -NU 2-、-N＝CU2 -, and,
-CO-NU 2-、-OCO-NU2 -or O-NU 2-,U2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group (any carbon atom of the aromatic hydrocarbon group may be replaced with a hetero atom), or (E 3-A3)q-B3-F3-P3) an alkyl group, a cycloalkyl group, a cycloalkenyl group and an aromatic hydrocarbon group each of which is unsubstituted or may be substituted with 1 or more substituent groups X 3, an alkyl group of which may be substituted with the cycloalkyl group or the cycloalkenyl group, 1-CH 2 -or 2 or more non-adjacent-CH 2 -in the alkyl group may each be independently replaced with -O-、-S-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-SO2-、-O-CO-O-、-CO-NH-、-NH-CO-、-CH＝CH-COO-、-CH＝CH-OCO-、-COO-CH＝CH-、-OCO-CH＝CH-、-CH＝CH-、-CF＝CF- or-c≡c-, in the cycloalkyl or cycloalkenyl group, 1-CH 2 -or 2 or more non-adjacent-CH 2 -may be replaced by-O-, -CO-, -COO-, -OCO-or-O-CO-O-, E 3 is defined in the same manner as in the above-mentioned B 3, A 3 represents a 2-valent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a 2-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, the hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a halogen atom, -R 20、-OR21, cyano group or nitro group, R 20 represents a hydrogen atom, fluorine atom or alkyl group having 1 to 4 carbon atoms, R 21 represents alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted with fluorine atom, b 3、F3 and P 3 have the same meaning as that of B 3、F3 and P 3, q represents an integer of 0 to 4, and when a plurality of E 3 and/or A 3 are present, each may be the same or different, and U 1 and U 2 may be bonded to form a ring.
3. The composition for forming a retardation film according to claim 1, wherein the hansen solubility parameter distance calculated using the hansen solubility parameter (δd A、δPA、δHA) of the organic solvent a and the hansen solubility parameter (δd B、δPB、δHB) of the organic solvent B is 10 or less.
4. The composition for forming a retardation film according to claim 2, wherein the polymerizable liquid crystal compound further comprises a rod-like polymerizable liquid crystal compound.
5. The composition for forming a retardation film according to claim 1, wherein the solid content concentration is 5% by mass or more.
6. The composition for forming a retardation film according to claim 1, wherein the total content of the organic solvent A and the organic solvent B is 80% by mass or more relative to the total mass of the solvents contained in the composition for forming a retardation film.
7. The composition for forming a retardation film according to claim 1, wherein the organic solvent A is an ether-based organic solvent or a ketone-based solvent.
8. The composition for forming a retardation film as claimed in claim 1, comprising a leveling agent.
9. A method for producing a retardation film, comprising the steps of:
a process for forming a coating film of the composition for forming a retardation film according to any one of claims 1 to 8,
A step of drying the coating film at a drying temperature Td (DEG C) to obtain a dried coating film, and
A step of curing the dried coating film to obtain a retardation film;
the drying temperature Td (c) satisfies the formula (4) and (5):
Ta < Td < Tb (4)，
X-80 ≤ Td ≤ X-20 (5)。
10. The manufacturing method according to claim 9, wherein the drying temperature Td is 70 ℃ or higher and lower than 130 ℃.
11. A retardation plate comprising a cured film of the composition for forming a retardation film according to any one of claims 1 to 8.
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