JP2009040984A - Liquid crystal composition, retardation-controlling members using the same, and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal composition that can produce an insert type retardation layer with good homeotropic orientation in spite of formation of the retardation layer on the oriented membrane or not. <P>SOLUTION: By using a liquid crystal composition (M) that comprises a liquid crystal compound composed of a crosslinkable liquid crystal molecule and mercaptopropionic acid and/or a mercaptopropionic acid derivative, an insert type retardation layer good oriented in homeotropic can be obtained in spite of formation of the retardation layer on the oriented membrane or not. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a liquid crystal composition, a retardation control member having a retardation layer formed of the liquid crystal composition, and a liquid crystal display device incorporating the retardation control member.

  Since the liquid crystal display device has the great advantages of thinning and light weight, and low power consumption, it is actively used for image display in various devices such as a personal computer, a mobile phone, and an electronic notebook.

  The liquid crystal display device includes two substrates facing each other, and an electrode to which a voltage can be applied is provided on one of the substrates, and liquid crystal (driving liquid crystal) is applied between the two substrates according to the applied voltage. A liquid crystal layer (driving liquid crystal layer) formed by enclosing the alignment state in a controllable manner is formed to form a liquid crystal cell, and a polarizing plate is attached to the outside of the liquid crystal cell in the thickness direction. In a liquid crystal display device, the state of light passing through the polarizing plate and traveling inside the liquid crystal cell is controlled according to the birefringence of the liquid crystal layer, so that the amount of light passing through the liquid crystal cell and going outside is controlled. Then, an image is formed on the liquid crystal display screen in accordance with such a light quantity control pattern.

  The image displayed on the liquid crystal display screen of the liquid crystal display device is derived from the birefringence of the driving liquid crystal constituting the liquid crystal layer, and depends on the viewing line direction of the liquid crystal display screen and the angle formed by the liquid crystal display screen. Problems with image display stability such as image color unevenness and inversion phenomenon, that is, viewing angle dependency problems, have been pointed out. In order to solve this problem, it has been proposed so far to install a film material (retardation film) that performs optical compensation by controlling the phase difference of light passing through the driving liquid crystal layer in the liquid crystal cell. Such a retardation film is usually produced by stretching a film of polyacrylate, polycarbonate, triacetyl cellulose or the like.

  Such retardation film is installed in the liquid crystal cell by attaching the retardation film to the substrate constituting the liquid crystal cell with an adhesive. The refractive index of the adhesive used at that time Is usually different from the refractive index of the retardation film or substrate, and there is a possibility that interface reflection may occur at the contact interface between the pressure-sensitive adhesive layer and the retardation film or substrate. In addition, in the liquid crystal display device provided with the retardation film, a layer made of an adhesive is added, and the refractive index of the adhesive is further adjusted to suppress the risk of irregular reflection of light generated on the liquid crystal display screen. Necessity arises.

  As for the retardation film, when the retardation film is attached to the outside of the liquid crystal cell, the retardation film is exposed to the outside of the liquid crystal cell, so that the retardation film expands by absorbing moisture outside the liquid crystal cell. There is a problem that it ends up. Further, since the retardation film is a film material, there is a problem that the optical compensation function is changed due to shrinkage with time. Further, with the retardation film, it is difficult to perform optical compensation by patterning and arranging in accordance with the size of the pixels that form an image displayed on the liquid crystal display device, and narrowing down to a necessary position.

  In order to solve these problems and difficulties, recently, a liquid crystal cell is composed of a liquid crystal composition containing crosslinkable liquid crystal molecules or polymer liquid crystals having a roughly elongated rod-like appearance. It has been proposed that a retardation layer is formed on the inner side (in-cell side) of the substrate (in-cell side) (in-cell), and the in-cell retardation layer (in-cell type retardation layer) exhibits an optical compensation function.

  As a method for forming the in-cell type retardation layer, an alignment film is appropriately formed on the surface of a substrate or the like by using a method such as a rubbing method, a photo-alignment method, or an ion beam method, and then on the alignment film surface. A method for forming a retardation layer by applying a liquid crystal composition to form a liquid crystal coating film and curing the liquid crystal coating film has been proposed. In this method, the surface of the alignment film is a surface that is supposed to be a surface (base surface) that forms the base of the retardation layer, and the alignment film is formed by appropriately selecting the type of the alignment film that forms the base surface. The alignment of liquid crystal molecules such as a crosslinkable liquid crystal contained in a liquid crystal composition applied on the film surface is controlled (Patent Document 1). Specifically, according to this method, a vertical alignment film is used as the alignment film for forming the base surface, whereby a phase difference layer in which liquid crystal molecules are vertically aligned with respect to the base surface and homeotropically aligned is obtained. . In the present specification, the base surface is a surface forming the base of the retardation layer (retardation layer base surface) unless otherwise specified.

  By the way, regarding a method for obtaining a homeotropically aligned in-cell type retardation layer, a method for more stably vertically aligning liquid crystal molecules with respect to a base surface has been specifically studied (Patent Document 2).

  However, in the method of forming the in-cell type retardation layer using the alignment film as proposed in Patent Documents 1 and 2, a layer structure made of the alignment film is newly added. Therefore, it is necessary to add a process for forming an alignment film to increase the number of manufacturing processes for manufacturing a liquid crystal display device. In addition, the alignment film is often inferior in adhesion to the retardation layer as compared with the substrate, etc., and there is a strong demand for applying means for ensuring sufficient adhesion between the alignment film and the retardation layer. However, this is a further disadvantage for the simplification of the manufacturing process. Regarding the adhesion between the retardation layer and the alignment film, it is considered to add various additives to the liquid crystal composition to improve the adhesion between the retardation layer and the alignment film. There is a possibility that the orientation of the liquid crystal molecules contained in the product may be disturbed, and the advantage of effectively aligning the liquid crystal molecules, which is an advantage of using the alignment film, may be lost.

  For these reasons, it has been studied to obtain an in-cell type retardation layer homeotropically aligned with a liquid crystal composition containing a crosslinkable liquid crystal molecule without using an alignment film (Patent Document 3).

Japanese Patent Laid-Open No. 10-319408 JP-A-11-240890 Special table 2004-524385 gazette

  However, even if the crosslinkable liquid crystal molecules contained in the liquid crystal coating film formed on the base surface are aligned vertically in order to form a homeotropically aligned in-cell type retardation layer without using an alignment film, the crosslinkability is not improved. It has been extremely difficult to stably maintain a state in which liquid crystal molecules are vertically aligned.

  After vertically aligning the crosslinkable liquid crystal molecules contained in the liquid crystal coating film formed by coating the liquid crystal composition on the lower ground, the polymerization of the crosslinkable liquid crystal molecules proceeds sufficiently to cure the liquid crystal coating film. Since it is difficult to stably maintain the state in which the crosslinkable liquid crystal molecules are vertically aligned with respect to the plane having the normal line in the thickness direction of the liquid crystal coating film until the phase difference layer is formed, it is incorporated into the liquid crystal display Therefore, it has been difficult to efficiently obtain an in-cell type retardation layer that sufficiently exhibits the optical compensation function.

  In addition, when forming the in-cell type retardation layer, the liquid crystal composition is uniformly and uniformly applied on the base surface regardless of the type of the base surface, whether it is the substrate surface or the alignment film surface. It is important to apply it, but the surface of the base surface is washed to remove dirt such as dust adhering to the surface, and the surface of the base surface is further modified It is said that it is effective to improve the wettability. However, if such a cleaning process or a modification process is performed more effectively, there is a high possibility that the surface of the base surface becomes unfavorable when the liquid crystal molecules are vertically aligned, and a sufficient optical compensation function is achieved. There is a problem that it is difficult to form a phase difference layer.

  The present invention has been made in view of these problems, and it is possible to obtain an in-cell type retardation layer that is well homeotropically oriented regardless of whether or not the retardation layer is formed on the orientation film. In particular, it is desirable to provide a liquid crystal composition to be prepared, and in particular, by subjecting the base surface, which is to be the base of the retardation layer, to a cleaning treatment and / or a modification treatment, Even when the state changes and the state of the base surface is not good for vertically aligning the crosslinkable liquid crystal molecules contained in the liquid crystal composition, the liquid crystal molecules are effectively vertically aligned and sufficient An object of the present invention is to provide a liquid crystal composition capable of stably forming a homeotropically aligned retardation layer. Still another object of the present invention is to provide a retardation control member provided with a retardation layer formed using the liquid crystal composition of the present invention, and a liquid crystal display device incorporating the retardation control member.

  The state in which the liquid crystal molecules are vertically aligned is the direction of the optical axis of the liquid crystal molecules with respect to the plane Q, assuming a plane Q having a normal line parallel to the thickness direction of the layer structure constituting the base surface. Is standing vertically or substantially vertically. Specifically, the angle between the longitudinal direction of the liquid crystal molecules and the normal of the plane Q is within 3 degrees (ideally coincident state). It shall be shown. A state in which the liquid crystal molecules are completely vertically aligned is formed in a state where the optical axis of the liquid crystal molecules and the normal line of the plane Q are completely coincident. Unless otherwise specified, the direction of the optical axis of the liquid crystal molecules is aligned with the longitudinal direction of the elongated rod-like liquid crystal molecules.

  The homeotropic orientation indicates the state of the optical axis of the retardation layer. When a plane S having a normal line parallel to the thickness direction of the retardation layer is assumed, the light in the retardation layer with respect to the plane S is assumed. It shall indicate that the shaft is fully upright. Further, the state where the optical axis of the retardation layer is sufficiently raised means that the direction of the optical axis of the retardation layer is standing perpendicularly or substantially perpendicular to the plane S, and the optical axis and A state in which the angle formed with the normal line of the plane S is within a predetermined angle (3 degrees), ideally a state in which the angle rises vertically (the optical axis direction of the retardation layer and the normal direction of the plane S) In the same state).

  In such a case, assuming an xyz orthogonal coordinate system in which the thickness direction of the retardation layer is the z-axis, the refractive index of the retardation layer is expressed as nx, ny, nz in the x-axis direction, the y-axis direction, and the z-axis direction, respectively. If so, the smaller the angle formed between the direction of the optical axis of the retardation layer and the normal line of the plane S, the more the value of nx and the value of ny become approximately equal. Therefore, corresponding to the small angle formed between the direction of the optical axis of the retardation layer and the normal line of the plane S, the light is generated when the light is irradiated in the direction where the inclination from the z-axis direction is 0 °. The phase difference value becomes small. That is, the smaller the retardation value, the better the retardation layer is homeotropically oriented. Here, specifically, when the retardation layer is homeotropically aligned well, the retardation value is 4 nm or less, preferably 3.5 nm or less, more preferably 3 nm or less. .

  The present invention includes (1) a liquid crystal composition comprising a liquid crystal compound comprising a crosslinkable liquid crystal molecule, and a composition (M) comprising a mercaptopropionic acid and / or a mercaptopropionic acid derivative, 2) The liquid crystal composition according to the above (1), wherein the crosslinkable liquid crystal molecule has at least one (meth) acryloyl group in at least one molecule, and (3) the composition (M) is a value in terms of a compound. The liquid crystal composition according to (1) or (2), wherein the mercaptopropionic acid derivative is α-mercaptopropionic acid methyl ester or ethyl α-mercaptopropionic acid. Ester, α-mercaptopropionic acid butyl ester, β-mercaptopropionic acid methyl ester, β-mercaptopropionic acid ethyl ester, β-mercaptopropio 2-ethylhexyl acid ester, β-mercaptopropionic acid n-octyl ester, β-mercaptopropionic acid methoxybutyl ester, β-mercaptopropionic acid stearyl ester, β-mercaptopropionic acid isononyl ester, trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate The liquid crystal composition according to any one of (1) to (3) above, (5) the liquid crystal composition according to any one of (1) to (4), further including a silane coupling agent. Liquid crystal composition, (6) a photopolymerization initiator The liquid crystal composition according to any one of the above (1) to (5), (7) 99.79 to 70% by weight (compared to a blend) comprising crosslinkable liquid crystal molecules containing a (meth) acryloyl group (Converted value) 0.01 to 10% by weight (compared to compound converted value) silane coupling agent and 0.1 to 10% by weight (compared to compound converted value) ), And the composition (M) is contained in an amount of 0.1 to 10% by weight (compared to the equivalent of the compound), (8) A retardation control member comprising a substrate having optical transparency and a retardation layer formed directly or indirectly on the substrate, wherein the retardation layer is formed on the substrate. It is formed by curing the liquid crystal composition according to any one of (1) to (7). (9) The retardation control member according to (8), further comprising a colored layer, (10) The retardation layer is formed on the substrate ( The liquid crystal composition according to any one of 1) to (7) is applied to form a liquid crystal coating film, the active radiation is irradiated toward the surface of the liquid crystal coating film, and the crosslinking contained in the liquid crystal coating film (8) The retardation control member according to (8) or (9), which is formed by curing a liquid crystal molecule, (11) The retardation layer is a layer having homeotropic alignment (8) ) To (10) The phase difference control member according to any one of (10) and (12) A driving liquid crystal layer is formed between two opposing substrates in which liquid crystal is sealed so as to be capable of orientation control according to a change in voltage. In the liquid crystal display device, any one of the above (8) to (11) is provided on one of the two substrates. The gist of the present invention is a liquid crystal display device in which the phase difference control member described above is incorporated.

  In the present specification, the liquid crystal composition includes an embodiment (first embodiment) composed of a mixture of each composition (liquid crystal compound or the like) constituting the liquid crystal composition, and each composition constituting the liquid crystal composition. Any of the aspects (second aspect) configured by a liquid obtained by dissolving or suspending the mixed mixture in a solvent is included.

  Further, in this specification, the value converted to the formulation for each formulation of the liquid crystal composition is when the total weight of the liquid crystal composition is 100 when the liquid crystal composition is the first aspect. When the liquid crystal composition is in the second embodiment, the weight percentage of each compound (solid) compounded as a component constituting the liquid crystal composition is shown. From the total weight of the liquid crystal composition of the present invention, When the amount obtained by subtracting the weight of the solvent (that is, the total weight of the mixture before being dissolved or suspended in the solvent) is defined as 100% by weight of each compound (solid) compounded as a component constituting the liquid crystal composition It shall be shown.

  According to the present invention, the liquid crystal composition includes a composition composed of mercaptopropionic acid and / or a mercaptopropionic acid derivative (referred to as composition (M)), so that the base of the retardation layer is formed. Improves the reactivity of the cross-linkable polymerization reaction of the cross-linkable liquid crystal molecules contained in the liquid crystal coating film formed by coating the liquid crystal composition on the underlying surface (substrate surface, colored layer surface, alignment film surface, etc.) A liquid crystal composition capable of better aligning the crosslinkable liquid crystal molecules in the liquid crystal coating film and capable of easily forming a phase difference layer having good homeotropic alignment without using an alignment film. In addition, it is possible to obtain a liquid crystal composition that can stably form a retardation layer that is homeotropically aligned even if a surface treatment or a modification treatment is applied to the base surface.

  The liquid crystal composition contains a composition (M) made of mercaptopropionic acid and / or a mercaptopropionic acid derivative, so that the crosslinkable liquid crystal molecules contained in the liquid crystal coating film made of the liquid crystal composition are in contact with the base surface. Although the detailed mechanism regarding the good vertical alignment is not clear, it is thought that the mechanism is as follows. First, using this liquid crystal composition, when the liquid crystal composition is applied onto the base surface to form a liquid crystal coating film, the interface side of the liquid crystal coating film with the base surface or air (or a predetermined gas) It is conceivable that not only the crosslinkable liquid crystal molecules existing on the interface side, but also the crosslinkable liquid crystal molecules present in the vicinity of the middle position in the thickness direction of the liquid crystal coating film are well aligned. As described above, the crosslinkable liquid crystal molecules existing in the vicinity of the middle position in the thickness direction of the liquid crystal coating film separated from the base surface are well aligned vertically, so that the state of the base surface is poor when the crosslinkable liquid crystal molecules are aligned vertically. Even in such a state, the alignment regulating force accompanying the vertical alignment of a large number of crosslinkable liquid crystal molecules existing in the vicinity of the middle position in the thickness direction of the liquid crystal coating film may be affected by the interface side of the liquid crystal coating film with the base surface or air. The alignment state of the crosslinkable liquid crystal molecules existing on the interface side of the film is ordered, and the crosslinkable liquid crystal molecules are also vertically aligned. Eventually, the group of crosslinkable liquid crystal molecules contained in the liquid crystal coating film is in a state where the alignment is not greatly disturbed as a whole, and is well aligned vertically.

  Further, according to the present invention, since the liquid crystal compound contained in the liquid crystal composition is composed of crosslinkable liquid crystal molecules, the liquid crystal composition is coated on the base surface to form a liquid crystal coating film, and the liquid crystal coating film is applied to the liquid crystal coating film. A retardation layer having a polymer (liquid crystal polymer) structure of crosslinkable liquid crystal molecules can be formed by polymerizing (crosslinking polymerization) the crosslinkable liquid crystal molecules contained therein. Therefore, according to the present invention, the heat resistance and the birefringence characteristics indicating the optical characteristics of the retardation layer are not easily affected by heat. For example, even in an environment where the temperature is relatively high, such as in a car. There is an effect that a retardation layer capable of easily exhibiting an optical compensation function can be formed. Such an effect becomes particularly large when the crosslinkable liquid crystal molecule is a polymerizable liquid crystal molecule capable of three-dimensional crosslink polymerization because the polymer structure constituting the retardation layer becomes stronger.

  According to the present invention, as the crosslinkable liquid crystal molecules constituting the liquid crystal compound contained in the liquid crystal composition, those having a (meth) acryloyl group in the molecular structure are used to efficiently form a liquid crystal polymer structure. The effect which becomes possible is produced.

  In the present invention, in the liquid crystal composition, the composition (M) composed of mercaptopropionic acid and / or a mercaptopropionic acid derivative is contained in an amount of 0.1 to 10% by weight in terms of the formulation, so that the crosslinkable liquid crystal The molecules can be effectively vertically aligned and the state thereof can be maintained satisfactorily, and a phase difference layer having a homeotropic alignment can be stably formed.

  In the liquid crystal composition of the present invention, the mercaptopropionic acid derivative is a mercaptopropionic acid derivative, is α-mercaptopropionic acid methyl ester, α-mercaptopropionic acid ethyl ester, α-mercaptopropionic acid butyl ester, β-mercapto. Propionic acid methyl ester, β-mercaptopropionic acid ethyl ester, β-mercaptopropionic acid 2-ethylhexyl ester, β-mercaptopropionic acid n-octyl ester, β-mercaptopropionic acid methoxybutyl ester, β-mercaptopropionic acid stearyl ester, β-mercaptopropionic acid isononyl ester, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), By being selected from pentaerythritol hexakis (3-mercaptopropionate) and tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate, the composition (M) contains a mercaptopropionic acid derivative. In this case, it is possible to satisfactorily align the liquid crystal compound composed of the crosslinkable liquid crystal molecules while efficiently crosslinking the crosslinkable liquid crystal molecules.

  The liquid crystal composition of the present invention may contain a silane coupling agent. In this case, the composition (M) comprising a mercaptopropionic acid and / or a mercaptopropionic acid derivative and a silane coupling agent Synergistically, the effect of satisfactorily vertically aligning the crosslinkable liquid crystal molecules can be obtained.

  The liquid crystal composition of the present invention may further contain a photopolymerization initiator, and in this case, the crosslinking polymerization of the crosslinkable liquid crystal molecules can be performed more quickly and sufficiently.

  According to the present invention, it is possible to obtain a retardation control member having a retardation layer formed by vertically aligning and fixing crosslinkable liquid crystal molecules contained in a liquid crystal composition, so that it can be incorporated into a liquid crystal display device. In addition, a phase difference control member capable of exhibiting an optical compensation function can be obtained efficiently.

  According to the present invention, the phase difference control member is further provided with a colored layer, whereby a color filter that can be used by being incorporated in a liquid crystal display device can be obtained.

  Furthermore, according to the present invention, a liquid crystal display device in which an in-cell type retardation layer is formed on the substrate can be obtained by incorporating the retardation control member into the substrate constituting the liquid crystal display device, and the optical compensation function can be obtained. Liquid crystal display device and various devices capable of liquid crystal display without performing a process of creating a member such as a film material having a retardation layer separately and attaching the member to a substrate. Can be designed. Furthermore, according to the present invention, it is possible to eliminate the need for an adhesive or the like that is required when a phase difference control member is provided separately, and thus it is possible to reduce the risk of light scattering by the adhesive. . And according to this invention, since the layer of an adhesive can be made unnecessary, a liquid crystal display device can be reduced in thickness.

  The liquid crystal composition of the present invention includes a liquid crystal compound composed of liquid crystal molecules and a composition (M) composed of mercaptopropionic acid and / or a mercaptopropionic acid derivative.

  Examples of the liquid crystal molecules constituting the liquid crystal compound include liquid crystal molecules capable of forming a nematic liquid crystal phase and liquid crystal molecules capable of forming a smectic liquid crystal phase.

  As the liquid crystal molecule, a polymerizable liquid crystal molecule having an unsaturated double bond as a polymerizable functional group in the structure of the liquid crystal molecule is used, and a polymerizable liquid crystal molecule capable of crosslinking polymerization in a liquid crystal phase state from the viewpoint of heat resistance ( Cross-linkable polymerizable liquid crystal molecules or cross-linkable liquid crystal molecules) are used.

  As the crosslinkable liquid crystal molecules, those having an unsaturated double bond at the end of the molecular structure are used, but those having an unsaturated double bond at both ends of the molecular structure (having two or more unsaturated double bonds) Are preferred). When the retardation layer is formed using crosslinkable liquid crystal molecules, a crosslinked polymer structure formed by crosslinking the crosslinkable liquid crystal molecules is formed in the retardation layer.

  More specifically, examples of the crosslinkable liquid crystal molecules include nematic liquid crystal molecules having crosslinkability (crosslinkable nematic liquid crystal molecules). Examples of the crosslinkable nematic liquid crystal molecules include monomers, oligomers, and polymers having at least one polymerizable functional group such as (meth) acryloyl group, epoxy group, octacene group, and isocyanate group in one molecule. As such a crosslinkable liquid crystal molecule, more specifically, one compound (compound (I)) or two or more compounds represented by the following general formula (1) Mixture, one compound (compound (II)) or a mixture of two or more compounds represented by general formula (2) shown in the following chemical formula 2 (compound (III)) 1) or a mixture of two or more thereof, or a combination thereof. The (meth) acryloyl group is a generic name for a methacryloyl group and an acryloyl group.

In the general formula (1) shown in Chemical Formula 1, R ¹ and R ² each represent hydrogen or a methyl group, but at least R ¹ and R ^{2 in} order to broaden the temperature range at which the crosslinkable liquid crystal molecules exhibit a liquid crystal phase. It is preferred that either one of R ² is hydrogen, and more preferred that both are hydrogen. X in the general formula (1) and Y in the general formula (2) may be any of hydrogen, chlorine, bromine, iodine, an alkyl group having 1 to 4 carbon atoms, a methoxy group, a cyano group, or a nitro group. Is preferably a chlorine or methyl group. Moreover, a and b which show the chain length of the alkylene group between the (meth) acryloyloxy group and aromatic ring of the both ends of the molecular chain of General formula (1), and d and e in General formula (2) are respectively 1 Although an arbitrary integer can be taken in the range of -12, it is preferable that it is the range of 4-10, and it is further more preferable that it is the range of 6-9. The compound (I) of the general formula (1) in which a = b = 0 or the compound (II) of the general formula (2) in which d = e = 0 has poor stability and is easily hydrolyzed, and the compound (I) or (II) itself has high crystallinity. In addition, compound (I) or compound (II) in which a and b, or d and e are each 13 or more, have a low isotropic phase transition temperature (TI). For this reason, both of these compounds have a narrow temperature range in which liquid crystal molecules stably exhibit liquid crystallinity (temperature range for maintaining a liquid crystal phase), and are not preferable for use in a retardation layer.

  As the crosslinkable liquid crystal molecules, the above-mentioned chemical formula 1, chemical formula 2, chemical formula 3, and chemical formula 4 exemplify the monomer of the liquid crystal having a polymerizability (polymerizable liquid crystal). These may also be used, and for these, well-known ones such as the above-mentioned oligomers, chemicals 2, chemicals 3, chemicals 4 and the like can be appropriately selected and used.

  Considering that the retardation amount and orientation characteristics of the retardation layer are determined by the birefringence Δn of the crosslinkable liquid crystal molecule and the thickness of the retardation layer, the birefringence Δn of the crosslinkable liquid crystal molecule is 0.03. It is preferable that it is about -0.20, and it is further more preferable that it is about 0.05-0.15.

  In the liquid crystal composition, a composition (M) composed of mercaptopropionic acid and / or a mercaptopropionic acid derivative is blended.

  The mercaptopropionic acid is preferably a compound selected from β-mercaptopropionic acid and α-mercaptopropionic acid.

  Mercaptopropionic acid derivatives include α-mercaptopropionic acid methyl ester, α-mercaptopropionic acid ethyl ester, α-mercaptopropionic acid butyl ester esterified product of β-mercaptopropionic acid, β-mercaptopropionic acid methyl ester, β- Mercaptopropionic acid ethyl ester, β-mercaptopropionic acid 2-ethylhexyl ester, β-mercaptopropionic acid n-octyl ester, β-mercaptopropionic acid methoxybutyl ester, β-mercaptopropionic acid stearyl ester, β-mercaptopropionic acid isononyl Esters, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hex A compound selected from an esterified product of β-mercaptopropionic acid, such as saquis (3-mercaptopropionate) and tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate, is preferable.

  In the liquid crystal composition of the present invention, an appropriate amount of a liquid crystal compound composed of liquid crystal molecules such as the above-mentioned compound (I), compound (II) and compound (III), and mercaptopropionic acid and / or mercaptopropionic acid derivative It can be produced as a mixed mixture.

  In the liquid crystal composition of the present invention, the compounding amount of the liquid crystal compound is preferably 70% by weight or more, and more preferably 75% by weight or more in terms of the amount of the compound. When the compounding amount of the liquid crystal compound is 70% by weight (vs. the compound equivalent value) or more, the liquid crystal property of the liquid crystal compound is improved. Even if alignment failure occurs, the proportion of liquid crystal molecules that have generated alignment failure can be suppressed to a rate that can be relatively ignored when the retardation layer sufficiently exhibits the optical compensation function. In addition, if the compounding quantity of a liquid crystal compound is 70 weight% (vs. compound conversion value) or more, about the upper limit, it can set suitably by balance with structural components other than the liquid crystal compound contained in a liquid crystal composition. it can.

  The composition (M) composed of mercaptopropionic acid and / or a mercaptopropionic acid derivative is preferably contained in the liquid crystal composition in an amount of 0.1 to 10% by weight in terms of the formulation.

  When the composition (M) is blended in the liquid crystal composition in an amount of 0.1% by weight (vs. the compound-converted value) or more, a sufficiently stable homeotropically aligned retardation layer is formed from the liquid crystal composition. When the composition (M) is blended in an amount of 10% by weight or less (as a blended value), the crosslinkable liquid crystal molecules contained in the retardation layer are formed when the retardation layer is formed of the liquid crystal composition. The occurrence of alignment defects can be suppressed, and furthermore, the deterioration of the insulating properties of the retardation layer is suppressed, so that when a voltage is applied to the liquid crystal cell in which the retardation layer is incorporated, it is applied to the liquid crystal cell. Therefore, the possibility that the liquid crystal display cannot maintain the potential and causes the display failure of the liquid crystal screen is suppressed.

  In the liquid crystal composition of the present invention, the compounding ratio of the liquid crystal compound and the composition (M) is preferably 100: 6.5 in the ratio of (weight of liquid crystal compound) :( weight of composition (M)). More preferably, it is 100: 3.5.

  In the liquid crystal composition of the present invention, additives may be appropriately added as necessary. As this additive, a method parallel to the thickness direction of the retardation layer containing a liquid crystal compound composed of a crosslinkable liquid crystal molecule, except for the mercaptopropionic acid and the mercaptopropionic acid derivative as described above (except for the composition (M)). Alignment (vertical alignment) is performed so that the optical axis of the crosslinkable liquid crystal molecules stands up to the plane when a plane having a line is assumed (ideally, the crosslinkable liquid crystal molecules are perfectly vertically aligned). Specific examples include agents (sometimes referred to as vertical alignment aids), photopolymerization initiators, polymerization inhibitors, and sensitizers. Specific examples of the vertical alignment aid contained in the liquid crystal composition include polyimide, surfactants, and coupling agents.

  By including such a vertical alignment aid in the liquid crystal composition, a crosslinkable liquid crystal contained in the liquid crystal composition synergistically with the composition (M) comprising the mercaptopropionic acid or mercaptopropionic acid derivative contained in the liquid crystal composition. It is possible to obtain an effect of better vertically aligning the molecules.

  When polyimide is used as the vertical alignment aid, it is preferable that the polyimide has a long-chain alkyl group because the thickness of the retardation layer to be formed can be selected within a wide range. When the vertical alignment aid is polyimide, specific examples of the polyimide include SE-7511 and SE-1211 manufactured by Nissan Chemical Industries, and JALS-2021-R2 manufactured by JSR.

  In the case of using a surfactant as the vertical alignment aid, the surfactant is not particularly limited as long as the crosslinkable liquid crystal molecules can be vertically aligned, but the liquid crystal molecules are converted into a liquid crystal phase when the retardation layer is formed. Since it is necessary to heat to the transition temperature, it is required to have heat resistance to such an extent that it is not decomposed even at the transition temperature to the liquid crystal phase. In addition, since liquid crystal molecules may be dissolved in an organic solvent when forming the retardation layer, in such a case, it is required that the affinity with the organic solvent for dissolving the liquid crystal molecules is good. The As long as these requirements are met, the surfactant is not limited to nonionic, cationic, anionic, etc., and only one type of surfactant may be used, or a plurality of types of surfactants may be used. An agent may be used in combination.

  When a coupling agent is added as a vertical alignment aid, a silane coupling agent can be preferably used as the coupling agent, specifically, n-octyltrimethoxysilane, n-octyltriethoxysilane, Silane coupling agents obtained by hydrolyzing silane compounds such as decyltrimethoxysilane, decyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, Examples of the amino silane coupling agent include a silane coupling agent containing fluorine in the molecular structure, and it is more preferable to use an amino silane coupling agent. A plurality of these coupling agents may be selected and added to the liquid crystal composition.

  In this specification, the amino silane coupling agent is a silane coupling agent comprising a primary amine, a secondary amine, or a tertiary amine, and a silane cup having a ketimine structure in the molecular structure. The generic name of the ring agent shall be indicated.

  As such an amino silane coupling agent, more specifically, for example, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane (KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd., TSL8345 manufactured by Toshiba Silicone), N-2 (aminoethyl) 3-aminopropyltrimethoxysilane (Shin-Etsu Chemical KBM-603, Toshiba Silicone TSL8340), 3-aminopropyltriethoxysilane (Shin-Etsu Chemical KBE-603, Toshiba Silicone TSL8331), 3-aminopropyltrimethoxysilane (KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-aminopropyltriethoxysilane (KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-triethoxysilyl-N- (1,3- Dimethyl-butylidene) propylamine (Shin-Etsu Chemical KBE-9103) , N- phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. KBM-573), and the like.

  In the liquid crystal composition, the coupling agent such as a silane coupling agent is 0.01 to 10% by weight (compared to the compound equivalent), preferably 0.01 to 5% by weight (compared to the compound equivalent), and more preferably. Is added in an amount of 0.01 to 2% by weight (compared to the equivalent of the compound), and particularly preferably 0.1 to 2% by weight (compared to the equivalent of the compound). By making the addition amount of the silane coupling agent 0.01% by weight (compared to the equivalent of the compound) or more, it is possible to impart sufficient alignment stability to the retardation layer. By making the addition amount 10% by weight or less (vs. compound equivalent value) or less, liquid crystal display due to poor alignment of liquid crystal molecules in the retardation layer due to the addition of the silane coupling agent or a decrease in electrical reliability of the retardation layer. It is possible to suppress the deterioration of the image quality of the image displayed on the screen to a level that can be ignored.

  In the liquid crystal composition of the present invention, the compounding ratio of the liquid crystal compound and the silane coupling agent is preferably 100: 5.5, in the ratio of (weight of liquid crystal compound) :( weight of silane coupling agent). The ratio is preferably 100: 3.3, particularly preferably 100: 2.2.

  In the liquid crystal composition of the present invention, when the crosslinkable liquid crystal molecule has photopolymerizability, a photopolymerization initiator may be appropriately added to the liquid crystal composition as necessary. The photopolymerization initiator is an initiator that promotes a polymerization reaction of crosslinkable liquid crystal molecules contained in the liquid crystal composition when the liquid crystal composition is irradiated with active radiation such as ultraviolet rays when forming the retardation layer using the liquid crystal composition. It works as an agent. As the photopolymerization initiator, a radical polymerizable initiator can be used. Radical polymerizable initiators are compounds that generate free radicals by the energy of ultraviolet rays, for example, benzophenone derivatives such as benzoin and benzophenone or derivatives thereof; xanthone and thioxanthone derivatives; chlorosulfonyl, chloromethyl polynuclear aromatic compounds Halogen-containing compounds such as chloromethyl heterocyclic compounds and chloromethylbenzophenones; triazines; fluorenones; haloalkanes; redox couples of photoreductive dyes and reducing agents; organic sulfur compounds; It is done. As photopolymerization initiators, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 907 (all manufactured by Ciba Specialty Chemicals), Darocur (Merck), Adeka 1717 (Asahi Denka Kogyo Co., Ltd.) ), 2,2′-bis (o-chlorophenyl) -4,5,4′-tetraphenyl-1,2′-biimidazole (manufactured by Kurokin Kasei Co., Ltd.), etc. Is preferred. These photopolymerization initiators can be used alone or in combination of two or more. When using 2 or more types together, it is preferable to combine initiators having different absorption wavelengths so as not to inhibit the absorption spectral characteristics.

  When the photopolymerization initiator is added to the liquid crystal composition, the liquid crystal composition is coated on the lower surface of the retardation layer such as the substrate surface to form a liquid crystal coating film, and the cross-linking present in the liquid crystal coating film After aligning the liquid crystal molecules, the cross-linked liquid crystal molecules can be cross-linked and efficiently polymerized by irradiating the liquid crystal coating film with light having a photosensitive wavelength of the photopolymerization initiator. .

  The photopolymerization initiator needs to be added within a range that does not significantly impair the orientation of the crosslinkable liquid crystal molecules contained in the liquid crystal composition. In consideration of this point, the blending amount of the photopolymerization initiator in the liquid crystal composition (the total amount of the photopolymerization initiator used when two or more photopolymerization initiators are used in combination) is 0.1-10. % By weight (vs. compound equivalent), preferably 0.5 to 8% by weight (vs. compound equivalent), more preferably 1 to 5% by weight (vs. compound equivalent).

  In the case where a photopolymerization initiator is added to the liquid crystal composition, the liquid crystal composition is a polymerization inhibitor that suppresses the polymerization rate in a controllable manner as long as the function of the photopolymerization initiator is not greatly impaired. Or a sensitizer for assisting absorption of electromagnetic waves such as ultraviolet rays may be added. Polymerization inhibitors include p-benzoquinone, hydroquinone, pt-butylcatechol, di-t-butyl paracresol, 2,4,6-tri-tert-butylphenol, hydroquinone monomethyl ether, α-naphthol or acetani Gin acetate or the like can be specifically used.

  Further, when a sensitizer is blended in the liquid crystal composition, the blending amount of the sensitizer can be appropriately selected within a range that does not significantly impair the orientation of the crosslinkable liquid crystal molecules, specifically 0.01 to 1% by weight. Is selected within the range. Only one type of polymerization inhibitor and sensitizer may be used, or two or more types may be used in combination.

  The liquid crystal composition of the present invention may contain a compound (T) composed of polyfunctional molecules. The polyfunctional molecule forming this compound (T) is a molecule having two or more polymerizable functional groups in the molecular structure, and as this polyfunctional molecule, a polyfunctional molecule having an alcoholic hydroxyl group in the molecular structure is preferably used. And polyfunctional (meth) acrylates can be preferably used. Furthermore, as the polyfunctional (meth) acrylate, a polyfunctional (meth) acrylate having an alcoholic hydroxyl group in the molecular structure can be more preferably used.

  Examples of the polyfunctional (meth) acrylate having an alcoholic hydroxyl group include monomers, oligomers and polymers having at least one alcoholic hydroxyl group in one molecule. As such a polyfunctional (meth) acrylate, specifically, one compound or a mixture of two or more of the compounds represented by the general formula shown below (compound (IV)) is used. Can do.

In the general formula shown in Chemical Formula 5, m represents an integer of 1 or more, n represents an integer of 2 or more, R ¹ represents an organic hydrocarbon structure having 1 or more carbon atoms, and R ² represents hydrogen or a methyl group, respectively. Indicates. More specifically, examples of the compound (IV) satisfying the general formula shown in Chemical formula 5 include pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, and dipentaerythritol hydroxypentaacrylate. The compound (IV) is not limited to the compound having the molecular weight and can be used by being added to the liquid crystal composition, but the molecular weight is 1000 or less from the viewpoint of compatibility with the crosslinkable liquid crystal molecules. Is preferred.

  The compound (T) needs to be added in a range that does not significantly impair the orientation of the crosslinkable liquid crystal molecules contained in the liquid crystal composition, and is generally 5.0 to 30 weights in terms of the compound. %, Preferably 10 to 15% by weight, is added to the liquid crystal composition. When the compounding amount of the compound (T) is 5.0% by weight or less (vs. compound conversion value), the hardness in the thickness direction of the retardation layer obtained when the retardation layer is formed using the liquid crystal composition is When the compounding amount of the compound (T) is not more than 30% by weight (compared to the compound equivalent), the crosslinkable liquid crystal molecules are used when the crosslinkable liquid crystal molecules contained in the liquid crystal composition are to be aligned. There is a risk that the orientation of the film tends to be disturbed.

  In the liquid crystal composition of the present invention, the compounding amounts of the liquid crystal compound, the composition (M), and the silane coupling agent, and further the photopolymerization initiator are within the numerical ranges indicating the preferred contents described above, respectively. The combination can be adjusted as appropriate, and can be adjusted as appropriate depending on the type of other compounds used. For example, the liquid crystal composition contains a liquid crystal compound composed of a crosslinkable liquid crystal molecule containing a (meth) acryloyl group, a composition (M), an amino silane coupling agent, and a photopolymerization initiator. In this case, the amount of each substance contained in the liquid crystal composition is such that the liquid crystal compound is 99.79 to 70% by weight (compared to the compound equivalent), and the amino silane coupling agent is 0.01 to 10% by weight ( (Composition conversion value), and the composition (M) comprising 0.1 to 10% by weight of photopolymerization initiator (vs. compound conversion value) and comprising a mercaptopropionic acid and / or a mercaptopropionic acid derivative. 0.1 to 10% by weight (vs. compound equivalent) is preferably contained.

  The liquid crystal composition of the present invention is not limited to a mixture composed of the liquid crystal compound and the composition (M) as described above, or a mixture in which such an additive as described above is appropriately blended. In addition, a mixture may be appropriately added to a mixture or a mixture obtained by adding an additive to the mixture. In this case, the liquid crystal composition may be configured in a solution in which a liquid crystal compound or the like is dissolved in a solvent, or may be configured in a suspension in which the liquid crystal compound is suspended. When the liquid crystal composition is configured in the form of a solution or suspension as described above, the liquid crystal composition is applied onto the base surface using a conventionally known method, and the crosslinkable liquid crystal is applied onto the base surface. It becomes easy to distribute molecules approximately uniformly, and it becomes easy to form an approximately homogeneous retardation layer.

  As a solvent used in the liquid crystal composition, a solvent capable of dissolving the composition (M) contained in the liquid crystal composition and the liquid crystal compound (added when an additive is added to the liquid crystal composition) The agent can also be dissolved), specifically, hydrocarbons such as benzene, toluene, xylene, n-butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, Ethers such as diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2,4-pentanedione, ethyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Esters such as tate, γ-butyrolactone, amide solvents such as 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, tritrichloroethylene, tetrachloroethylene , Halogen solvents such as chlorobenzene and orthodichlorobenzene, alcohols such as t-butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monomethyl ether, ethyl cellosolve, and butyl cellosolve 1 type, or 2 or more types, such as phenols, phenols, such as phenol and parachlorophenol, can be used. If only one kind of solvent is used, the solubility of compound components such as crosslinkable liquid crystal molecules is insufficient, or a material (for example, constituting a base material) that is a counterpart of application when applying a liquid crystal composition. In the case where there is a risk of the material being attacked, these disadvantages can be avoided by using a mixture of two or more solvents. Among the above-mentioned solvents, hydrocarbon solvents and glycol monoether acetate solvents are preferable as the sole solvent, and preferable solvents are ethers or ketones and glycols mixed. It is a mixed solvent. When the liquid crystal composition includes a solvent, the concentration of the liquid crystal composition is usually different depending on various conditions such as the solubility of the liquid crystal compound to be used in the solvent and the layer thickness desired for the retardation layer. It is 1 to 60% by weight, preferably 3 to 40% by weight. The concentration of the liquid crystal composition is obtained by dividing (the value obtained by subtracting the weight of the solvent from the total weight of the liquid crystal composition composed of the solution) by (the total weight of the liquid crystal composition composed of the solution). It is calculated as a value obtained by multiplying the obtained value by 100.

  By using the liquid crystal composition of the present invention, a retardation layer can be formed on various objects such as a substrate, and a retardation control member capable of exhibiting an optical compensation function is formed as shown below. be able to.

  The phase difference control member obtained by using the liquid crystal composition of the present invention will be described.

  The retardation control member 1 can be configured by laminating a retardation layer 4 formed of a liquid crystal composition directly or indirectly with respect to the base material 2. In the example of FIG. The substrate 2 is formed directly on the substrate 2, and the surface of the substrate 2 forms the lower ground of the retardation layer.

  The base material 2 is made of a light-transmitting base material forming material, and the base material forming material may be composed of a single layer or a plurality of types of base material forming materials. The light transmittance of the substrate 2 can be appropriately selected.

  The base material forming material is preferably configured to be optically isotropic. The base material forming material may be provided with a region having optical anisotropy or light shielding properties locally as necessary. Specifically, as the substrate forming material, a plate, a sheet, or a film formed of an inorganic material or an organic material can be used. Examples of the inorganic material include glass, silicon, and quartz. In particular, when the retardation control member 1 is used for a liquid crystal display device, it is preferable to use an alkali-free glass containing no alkali component in the glass as an inorganic material. Quartz is preferred as the inorganic material from the viewpoint of low thermal expansibility and good dimensional stability and excellent workability in high-temperature heat treatment. On the other hand, examples of the organic material include acrylic such as polymethyl methacrylate, polyamide, polyacetal, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, or syndiotactic polystyrene, polyphenylene sulfide, polyether ketone, poly Ether ether ketone, fluorine resin, polyether nitrile, etc., polycarbonate, modified polyphenylene ether, polycyclohexene, polynorbornene resin, etc., or polysulfone, polyethersulfone, polypropylene, polyarylate, polyamideimide, polyetherimide, Examples thereof include polyether ketones or thermoplastic polyimides. It can be used those composed of specific plastics. About the thickness of a base material formation material, it can select suitably according to a use, and specifically, the thing of about 5 micrometers-3 mm is used, for example.

  The retardation layer 4 is a layer in which light can travel inside the retardation layer 4 in the thickness direction, and has a function of birefringing light traveling inside the retardation layer 4 when traveling. It is a layer having.

  Specifically, the retardation layer 4 satisfies nx <nz and ny <nz with respect to the refractive indexes nx, ny, and nz, and nx and ny are equal or almost equal to each other, so-called “+ C plate” ( Functions as a positive C plate). However, with respect to the refractive index of the retardation layer 4, the z-axis (z in FIG. 5) is taken in the thickness direction of the retardation layer 4 (normal direction of the retardation layer 4), and the in-plane direction (position) of the retardation layer 4. The x-axis (x in FIG. 5) and y-axis (y in FIG. 5) perpendicular to the in-plane direction (direction parallel to the plane) of a plane having a normal line parallel to the thickness direction of the phase difference layer 4 ) And an xyz space is assumed, the refractive indexes of light in the x-axis, y-axis, and z-axis directions are defined as nx, ny, and nz, respectively.

  The retardation layer 4 has a polymer structure formed by crosslinking polymerization of crosslinkable liquid crystal molecules constituting the liquid crystal compound contained in the liquid crystal composition of the present invention. The crosslinkable liquid crystal molecule has an optical axis corresponding to its molecular structure, and has birefringence characteristics determined according to the state of the optical axis, and the optical axis of the crosslinkable liquid crystal molecule is directed in a specific direction ( That is, by aligning the crosslinkable liquid crystal molecules) to form a polymer structure and fixing the direction of the optical axis of the crosslinkable liquid crystal molecules, a layer structure having a birefringence characteristic corresponding to the alignment state can be formed. .

  The retardation layer 4 is formed as a layer having a homeotropic alignment, ie, a layer having a function of a so-called positive C plate, in which a polymer structure is formed in a state where crosslinkable liquid crystal molecules are vertically aligned.

  That is, the retardation layer 4 has an optical axis (a in FIG. 5) that faces the z-axis direction in the xyz space assumed above, that is, the value of the angle θ is zero or almost zero in FIG. Thus, it is formed by aligning and fixing positively birefringent anisotropic crosslinkable liquid crystal molecules contained in the liquid crystal composition.

  Regarding the polymer structure of the retardation layer 4, the degree of polymerization of the crosslinkable liquid crystal molecules is preferably about 80 or more, and more preferably about 90 or more. When the degree of polymerization of the crosslinkable liquid crystal molecules constituting the retardation layer 4 is greater than 80, it is possible to maintain a homeotropically aligned state. In addition, the said polymerization degree shows the ratio consumed by the polymerization reaction including the crosslinking reaction and polymerization reaction of a crosslinkable liquid crystal molecule among the polymerizable functional groups of a crosslinkable liquid crystal molecule.

  The retardation layer 4 has crosslinkability existing at different positions in the thickness direction and in-plane direction of the retardation layer 4 with respect to the tilt angle of each crosslinkable liquid crystal molecule constituting the polymer structure (crosslinked polymer structure). The tilt angle between the liquid crystal molecules is preferably approximately zero degrees (ideally zero degrees). In this case, when the optical axis of each crosslinkable liquid crystal molecule included in the retardation layer 4 is approximately aligned in the thickness direction of the retardation layer 4 and a plane having a normal line in the thickness direction of the retardation layer 4 is assumed, The optical axis of the retardation layer 4 stands up with respect to the plane (ideally, the optical axis of the retardation layer 4 stands upright), and the retardation layer 4 has uniform birefringence characteristics. Thus, there is little unevenness in the in-plane direction, and the optical compensation function as a positive C-plate can be achieved almost uniformly.

  The thickness of the retardation layer 4 is not particularly limited, but is preferably about 0.5 to 10 μm in consideration of productivity and the like.

  The retardation layer 4 can be specifically formed as follows, for example.

  First, the liquid crystal composition is adjusted as described above. Specifically, a liquid crystal compound and a mercaptopropionic acid and / or mercaptopropionic acid derivative are appropriately mixed, and if necessary, an additive such as a photopolymerization initiator or a silane coupling agent is added in an appropriate amount to obtain a mixture ( G) is obtained. This mixture is dissolved in a solvent to prepare a solution (R). Both the mixture (G) and the solution (R) obtained here correspond to the liquid crystal composition of the present invention. However, in forming the phase difference 4 of the phase difference control member 1 shown in FIG. Suppose that it is in the state of a solution. For further convenience, the liquid crystal composition in a solution state may be referred to as a liquid crystal composition solution.

  When the liquid crystal composition solution is prepared, this liquid crystal composition solution is then applied on the lower ground of the retardation layer 4 to form a liquid crystal coating film. In the example of the phase difference control member 1 shown in FIG. 1, the surface of the substrate 2 corresponds to the base surface, and a liquid crystal composition solution is applied onto the surface of the substrate 2 to form a liquid crystal coating film. Is done.

  Examples of the application method of the liquid crystal composition solution include a gravure printing method, an offset printing method, a relief printing method, a screen printing method, a transfer printing method, an electrostatic printing method, a plateless printing method, and a gravure coating method. , Roll coating method, knife coating method, air knife coating method, bar coating method, dip coating method, kiss coating method, spray coating method, die coating method, comma coating method, inkjet coating method, or a combination thereof, as appropriate. Can be used.

When the liquid crystal coating film is formed on the lower ground, the liquid crystal coating film is dried (drying process). This drying process may be carried out by a process (natural drying process) in which a liquid crystal coating film formed on the substrate 2 is left under atmospheric pressure, but a liquid crystal coating film is formed on the substrate 2. When the process is performed in a process (vacuum drying process) in which the pressure in the container is reduced to about 1.5 × 10 ⁻¹ Torr or less in a sealed container, It is preferable because the solvent can be vaporized better.

  In the above-described drying treatment of the liquid crystal coating film, particularly in the reduced pressure drying treatment, the crosslinkable liquid crystal molecules contained in the liquid crystal coating film are aligned in the vertical direction (alignment treatment) at the time of the drying treatment. Is possible. In the drying under reduced pressure, the liquid crystal coating film can be brought into a supercooled state by being placed under a reduced pressure state, and in this state, the crosslinkable liquid crystal molecules contained in the liquid crystal coating film are vertically aligned, and then the crosslinkable liquid crystal molecules. The liquid crystal coating film is brought to about room temperature while maintaining the vertical alignment state. Thereby, the crosslinkable liquid crystal molecules can be efficiently maintained in a vertically aligned state until the crosslink polymerization is performed in a later step.

  The alignment treatment is not limited to the method performed in combination with the above-described reduced-pressure drying treatment, and a method generally known as an alignment treatment for vertically aligning the crosslinkable liquid crystal molecules, for example, the coating film On the other hand, a method of applying an electric field or a magnetic field from a predetermined direction can be selected as appropriate.

  After the drying treatment, before the polymerization of the crosslinkable liquid crystal molecules contained in the liquid crystal coating film, if the solvent remains in the liquid crystal coating film, it is included in the liquid crystal coating film to remove the solvent. In order to more reliably maintain the vertical alignment state of the crosslinkable liquid crystal molecules, the liquid crystal coating film may be baked (pre-baking treatment). The pre-baking treatment is not particularly limited, but for example, a liquid crystal coating film formed on the base material 2 is placed on a hot plate, and the temperature is in the range of 70 ° C. to 120 ° C. Specifically, it can be carried out by a method of baking for about 30 minutes to 30 minutes.

Next, crosslinking polymerization of the crosslinkable liquid crystal molecules contained in the liquid crystal coating film is performed (crosslinking polymerization treatment), and the alignment state of the crosslinkable liquid crystal molecules in the liquid crystal coating film is fixed. This cross-linking polymerization treatment can proceed by irradiating the liquid crystal coating film surface with light. The wavelength of light applied to the liquid crystal coating film is appropriately selected according to the absorption wavelength of the liquid crystal composition constituting the liquid crystal coating film, for example, the absorption wavelength of the crosslinkable liquid crystal molecules. In particular, when a photopolymerization initiator is included in the liquid crystal composition, it is preferably selected as appropriate according to the absorption wavelength of the photopolymerization initiator. The light applied to the liquid crystal coating film is not limited to monochromatic light, but may be light having a certain wavelength range including the photosensitive wavelength of the crosslinkable liquid crystal molecules and the photopolymerization initiator. Specifically, the light applied to the liquid crystal coating film is generally actinic radiation such as ultraviolet rays. Furthermore, when the cross-linkable liquid crystal molecules are crosslinked and polymerized by irradiating the liquid crystal coating film with ultraviolet rays, the ultraviolet rays having a wavelength of about 200 to 500 nm are generally irradiated. As the ultraviolet ray, an ultraviolet ray emitted from an ultraviolet ray source is usually used. As the ultraviolet ray source, a high pressure mercury lamp, a xenon lamp, a metal halide lamp or the like is used. The amount of light applied to the liquid crystal coating film depends on the type and composition of the crosslinkable liquid crystal molecules in the liquid crystal coating film (if the photopolymerization initiator is present in the liquid crystal coating film, Usually, it is about 10 to 3000 mJ / cm ² , although it varies depending on the composition and the type and amount of the photopolymerization initiator.

  In the cross-linking polymerization treatment, the cross-linkable liquid crystal molecules are heated while heating the base material 2 on which the liquid crystal coating film is formed to a temperature 1 to 10 ° C. lower than the temperature at which the cross-linkable liquid crystal molecules transition from the liquid crystal phase to the isotropic phase. It is preferable to carry out the crosslinking polymerization. By doing so, it is possible to reduce the disorder of the vertical alignment of the crosslinkable liquid crystal molecules during the crosslinking polymerization treatment. From this point of view, the temperature at which the crosslinking polymerization is performed is more preferably 3 to 6 ° C. lower than the temperature at which the crosslinkable liquid crystal molecules undergo a phase transition from the liquid crystal phase to the isotropic phase.

  As another method for cross-linking polymerization of the cross-linkable liquid crystal molecules, the cross-linkable liquid crystal molecules (or photopolymerization) is performed while heating the substrate 2 on which the liquid crystal coating film is formed to the liquid crystal phase temperature in an inert gas atmosphere. And a method of irradiating the liquid crystal coating film with light having a photosensitive wavelength of the initiator. In this method, cross-linking polymerization of cross-linkable liquid crystal molecules is performed in an inert gas atmosphere, and the substrate in the liquid crystal coating film is compared with the case where cross-linking polymerization of cross-linkable liquid crystal molecules is performed in an air atmosphere. It is preferable in that the disorder of the vertical alignment of the crosslinkable liquid crystal molecules (that is, the liquid crystal molecules close to the surface of the liquid crystal coating film) located away from 2 can be suppressed.

  Furthermore, as another method for crosslinking polymerization of the crosslinkable liquid crystal molecules, the following methods can be mentioned. That is, in the inert gas atmosphere or the air atmosphere, the substrate 2 on which the liquid crystal coating film is formed is heated to the liquid crystal phase temperature, and the liquid crystal coating film is irradiated with light having a photosensitive wavelength of the crosslinkable liquid crystal molecule to perform crosslinking polymerization. The reaction is allowed to proceed partially (referred to as a partial crosslinking step), and after the partial crosslinking step, the substrate 2 on which the liquid crystal coating film has been formed is cooled to a temperature (Tc) at which the crosslinkable liquid crystal molecules become a crystalline phase, In this state, the liquid crystal coating film is further irradiated with light having a photosensitive wavelength of the crosslinkable liquid crystal molecules to advance the crosslinking polymerization reaction to be completed. The temperature Tc described above is a temperature at which the crosslinkable liquid crystal molecules become a crystal phase in the liquid crystal coating film before the crosslinking polymerization reaction proceeds.

  In the partial cross-linking step, even when the substrate 2 on which the liquid crystal coating film is formed is cooled to the temperature Tc, the state in which the cross-linkable liquid crystal molecules included in the liquid crystal coating film are vertically aligned is maintained. The crosslinking polymerization reaction of the crosslinkable liquid crystal molecules proceeds. Accordingly, the degree of progress of the cross-linking polymerization reaction in the partial cross-linking step is appropriately selected according to the type of cross-linkable liquid crystal molecules 5 contained in the liquid crystal coating film, the film thickness of the liquid crystal coating film, and the like. It is preferable to proceed the crosslinking polymerization reaction until the degree of polymerization of the conductive liquid crystal molecules becomes 5-50.

  Thus, the liquid crystal coating film becomes a layer having a structure in which the crosslinkable liquid crystal molecules are fixed in a vertically aligned state on the substrate 2, and the layer forms a homeotropically aligned retardation layer 4. In this way, the retardation control member 1 in which the homeotropically aligned retardation layer 4 is formed can be manufactured.

  In the phase difference control member 1, the phase difference layer 4 is not limited to the case where the phase difference layer 4 is formed as a whole surface with respect to the base surface, and may be formed partially.

  As a method of partially forming the retardation layer 4 on the base surface, for example, in addition to various printing methods, a method of patterning and forming on the substrate 2 by a photolithography method using a photomask is specifically exemplified. It can be illustrated. According to this, it is possible to determine a predetermined region in advance such as a region forming a pixel in the phase difference control member 1 and form the phase difference layer 4 in a predetermined pattern aiming at the region.

  Specifically, the retardation layer 4 can be formed in a predetermined pattern as follows.

  That is, when the liquid crystal coating film is cured, the crosslinking polymerization of the crosslinkable liquid crystal molecules is in a state where the crosslinkable liquid crystal molecules contained in the liquid crystal coating film exhibit a liquid crystal phase, and the active radiation such as light having a photosensitive wavelength of the photopolymerization initiator Is irradiated (exposed) through a photomask having a light-shielding pattern to cause the polymerization reaction to partially proceed (referred to as a partial polymerization step). After the partial polymerization step, a crosslinkable liquid crystal The liquid crystal coating film is heated to a temperature (Ti) at which molecules are in an isotropic phase, and in this state, the liquid crystal coating film is further irradiated with actinic radiation such as light having a photosensitive wavelength, or a polymerization reaction is advanced. A method of proceeding the polymerization reaction of the crosslinkable liquid crystal molecules contained in the liquid crystal coating film to a predetermined degree of polymerization by performing a process of thermally polymerizing the crosslinkable liquid crystal molecules by heating the liquid crystal coating film to a temperature Ti or higher after the step Carried out in The By doing so, it is possible to pattern-form a region in which the crosslinkable liquid crystal molecules are given orientation in the retardation layer and a region in which the crosslinkable liquid crystal molecules are not given orientation. The temperature Ti described above is a temperature at which the crosslinkable liquid crystal molecules are in an isotropic phase in the liquid crystal coating film before the crosslinking polymerization reaction is advanced.

  In addition, when the cross-linking polymerization of the cross-linkable liquid crystal molecules is performed through a partial polymerization process using a photomask, after the partial polymerization process is performed on the base material on which the liquid crystal coating film is formed, the base material Is immersed in a solution in which the liquid crystal compound in which the polymerization reaction of the liquid crystal molecules is insufficient and in an uncured state can be dissolved, whereby the portion of the liquid crystal coating film where the polymerization of the crosslinkable liquid crystal molecules has not progressed It is also possible to form (pattern) a layer structure including crosslinkable liquid crystal molecules in a liquid crystal phase in a predetermined pattern on the substrate.

  For the retardation control member 1 obtained as described above, the crosslinkable liquid crystal molecules contained in the liquid crystal coating film are subjected to crosslinking polymerization to form the liquid crystal coating film as the retardation layer 4, and then the polymerized crosslinking is performed. It is preferable that the retardation layer 4 containing the crystalline liquid crystal molecules is further heated (post-polymerization heating treatment) because the hardness of the retardation layer 4 and the adhesion to the underlying surface can be improved. However, when the post-polymerization heat treatment is performed, since the base material 2 needs to have heat resistance, a glass substrate having heat resistance is preferably used as the base material forming material constituting the base material 2.

  In performing the post-polymerization heat treatment, the heating temperature of the retardation layer 4 is 200 to 250 ° C., and the post-polymerization heat treatment is more effectively hardened than the post-polymerization heat treatment before the post-polymerization heat treatment. It is preferable from the viewpoint that can be performed. About the time which performs heat processing after superposition | polymerization, it is preferable from the viewpoint similar to the said viewpoint about the heating temperature at the time of performing heat processing after superposition | polymerization that it is 30 to 150 minutes. When the heating temperature is 250 ° C. or the heating time exceeds 150 minutes, the hardness / strength of the retardation layer 4 is increased, but the possibility that the retardation layer 4 itself is strongly yellowed increases, while the heating temperature is 150 ° C. When the temperature is less than 30 minutes, the possibility that sufficient hardness / strength and adhesion cannot be obtained increases.

  The retardation layer 4 is heated and then cooled.

  Such post-polymerization heat treatment can be specifically carried out by introducing the base material 2 on which the retardation layer 4 is formed into a baking apparatus such as an oven apparatus and baking it under conditions of atmospheric pressure and air atmosphere. In addition, it can implement also by the method by infrared irradiation.

  In addition, in performing the post-polymerization heat treatment step, it is preferable that the temperature increase during the heating of the retardation layer 4 and the temperature decrease after the heating are performed gradually.

  In forming the retardation layer 4, when the underlying surface of the retardation layer 4 is in a state of high water repellency or oil repellency, a liquid crystal composition is applied in advance (that is, on the base surface). Before forming the liquid crystal coating film to form the retardation layer 4), the liquid crystal is subjected to UV cleaning treatment or plasma treatment within a range in which the crosslinkable liquid crystal molecules can be vertically aligned with respect to the base surface. You may improve the wettability of the base surface surface which is going to apply | coat a composition previously.

When subjected to UV cleaning process on the underlying surface of the retardation layer 4, the irradiation amount of ultraviolet rays irradiated toward an underlying surface ^{500mJ / cm 2 ~3000mJ / cm 2} , more preferably 900mJ ^/ cm 2 ~3000mJ / Cm ² . By ultraviolet rays are irradiated at 500 mJ / cm ² or more dose, the wettability to the substrate surface can be sufficiently imparted, by ultraviolet rays are irradiated at 3000 mJ / cm ² or more dose, the underlying surface It is possible to effectively suppress the possibility of problems such as discoloration of the layer structure itself constituting the.

Here, when subjected to UV cleaning process on the underlying surface of the retardation layer 4, the base surface at the irradiation amount of 900 mJ / cm ² or more 3000 mJ / cm ² or less of ultraviolet light is cleaned, the wettability of the underlying surface is Although it is particularly preferably improved, on the other hand, under the influence of ultraviolet irradiation, the state of the base surface becomes a state in which it is difficult to vertically align the crosslinkable liquid crystal molecules. As a result, conventionally, when the base surface is cleaned with an ultraviolet irradiation amount of 900 mJ / cm ² or more, a liquid crystal coating film is formed on the base surface to crosslink the liquid crystal vertically. It was difficult to satisfactorily align the liquid crystal in the vertical direction, and it was not possible to stably obtain a phase difference layer having a good homeotropic alignment. In this regard, in the liquid crystal composition of the present invention, the crosslinkable liquid crystal molecules in the liquid crystal composition are formed on the base surface even if it is on the base surface that has been subjected to UV cleaning treatment with an ultraviolet irradiation amount of 900 mJ / cm ² or more. It is possible to satisfactorily vertically align the film, and it is possible to stably form a phase difference layer having a good homeotropic alignment, and to obtain a phase difference control member capable of exhibiting a good optical compensation function. Can do.

  The retardation control member 1 obtained using the liquid crystal composition of the present invention may be provided with a colored layer.

  Then, next, the phase difference control member 1 provided with the colored layer will be described. In particular, for the retardation control member 1, a colored layer 13 having a color pattern and a black matrix 15 is formed on the surface of the substrate 2, and the surface of the colored layer 13 constitutes the ground of the retardation layer 4. The case where the retardation layer 4 is indirectly formed on the substrate will be described as an example (FIGS. 2 and 3). 2 and 3 are a schematic cross-sectional view and a schematic plan view, respectively, illustrating a cross-section for explaining one of the embodiments of the phase difference control member 1 including the colored layer 13. In FIG. 3, the phase difference layer 4 is omitted for convenience of explanation.

  In the phase difference control member 1, a light-shielding black matrix 15 is coated on one surface of a base material 2 in a grid pattern (lattice pattern) so that a non-formation region of the black matrix 15 serves as an opening 20. A large number of lattice points are formed. At this time, the formation region of the black matrix 15 corresponds to a light shielding part, and the opening 20 corresponds to a transmission part.

  The black matrix 15 can be formed, for example, by patterning a metal thin film having a light shielding property or light absorption property such as a metal chromium thin film or a tungsten thin film on the surface of the substrate 2. The black matrix 15 can also be formed by printing an organic material such as a resin containing a black pigment in a predetermined shape.

  On the base material 2 on which the black matrix 15 is arranged, three color patterns 16, 17, 18 are arranged in a strip shape so as to cover the opening 20, and these color patterns 16, 17, 18 and the black matrix are arranged. 15, a colored layer 13 is formed (FIGS. 2 and 3). The color patterns 16, 17, and 18 are light-transmitting, and the visible light that is transmitted is split into red (R), green (G), and blue (B) light, respectively. Therefore, as shown by a two-dot chain line in FIG. 3, each of the three color patterns of RGB (red (R) color pattern 16, green (G) color pattern 17, blue (B) color pattern 18) is covered. The apertures 20 are formed to form pixels, and the three apertures 20 covered by the three color patterns 16, 17, and 18 are combined to form one picture element 21.

  The color patterns 16, 17, and 18 are formed by applying, to the base material 2, a coloring material dispersion liquid in which a coloring material formed by blending a pigment corresponding to each color type and a resin is dispersed in a solvent for each color type. In addition to being formed by patterning a coating film to be formed into a predetermined shape such as a strip shape by a photolithography method, for example, by applying a coloring material dispersion liquid to the substrate 2 in a predetermined shape using an inkjet method or the like Can also be formed.

  When the black matrix 15 is formed in the colored layer 13, the black matrix 15 has a function of preventing color mixing of the color patterns 16, 17, and 18 applied in a roughly strip shape as a light shielding portion, and an opening. The function of partitioning the section 20 in plan view to sharpen the outline of the picture element 21, and also used for driving the liquid crystal that is normally arranged in the liquid crystal cell when the phase difference control member 1 is incorporated in the liquid crystal cell It also has a function of concealing a driving circuit such as a TFT from transmitted light.

  In some cases, the phase difference control member 1 does not require the black matrix 15 depending on its application and optical specifications (in this case, the colored layer 13 is configured by a color pattern).

  In the phase difference control member 1 of the present invention, the arrangement shape of the black matrix 15 is not limited to a rectangular lattice shape, and may be formed in a stripe shape or a triangular lattice shape. Further, the color pattern constituting the colored layer 13 can also be a CMY system which is a complementary color system in addition to the RGB system of three colors, and further, in the case of a single color or two colors, or four or more colors. Cases can also be taken. In addition to the case where the color pattern is formed in a strip shape, a variety of patterns may be adopted depending on the purpose, such as a pattern in which a large number of fine patterns such as a rectangular shape or a triangular shape are dispersedly arranged on the substrate 2. sell.

  The phase difference control member 1 has a layer structure composed of a switching element such as a TFT and a transparent electrode such as an ITO film, and the surface of these layer structures is used as the ground of the phase difference layer 4. It may be configured. The transparent electrode can be formed by appropriately selecting a known means such as a sputtering method and appropriately patterning on the substrate surface.

  In the example of FIGS. 2 and 3, the retardation control member 1 is described in which the colored layer 13 is provided on the substrate 2 and the colored layer 13 is interposed between the substrate 2 and the retardation layer 4. The retardation control member 1 is not limited to this, and may be configured such that the retardation layer 4 is interposed between the base material 2 and the colored layer 13, for example. That is, the colored layer 13 may be further laminated on the retardation layer 4 (air interface side) of the retardation control member 1 shown in FIG.

  The retardation control member 1 provided with such a colored layer 13 can be used as a color filter incorporated in one of the two substrates constituting the liquid crystal display device.

  The retardation control member 1 of the present invention may be formed by arranging columnar structures (columns) in a predetermined arrangement pattern directly or indirectly on the retardation layer 4. The arrangement pattern is appropriately selected according to the design of the phase difference control member 1.

  The column body is a photo in which a photo-curing photosensitive paint is applied on the retardation layer 4 to form a photosensitive paint coating film and dried to form a pattern corresponding to a predetermined arrangement pattern. It is exposed by irradiating actinic radiation such as ultraviolet rays toward the photosensitive paint coating film through a mask, and the exposed and unexposed areas are cured and uncured areas are formed. It is formed by removing the portion by etching treatment and firing the cured portion. Examples of the photosensitive paint having photocurability include conventionally known material compositions, for example, material compositions that form polymers such as acrylic polymers, amide polymers, and ester polymers containing polyfunctional acrylates. Can do.

  Further, the retardation control member 1 of the present invention may be formed by laminating a protective layer on the retardation layer 4. In this case, the protective layer is formed by applying the photosensitive paint on the phase difference layer 4 using the same photosensitive paint as the photosensitive paint that can be used when forming the column body. It is possible to form specifically by.

Next, a liquid crystal display device incorporating the phase difference control member 1 of the present invention will be described.
In addition, as a liquid crystal display device, it is an IPS mode, and demonstrates the case where the phase difference control member 1 which makes the colored layer 13 a base surface is incorporated (FIG. 4) as an example. FIG. 4 is a diagram for explaining the liquid crystal display device 51.

  As shown in FIG. 4, the liquid crystal display device 51 of the present invention is driven in accordance with a change in the electric field while being placed in an electric field between a pair of opposing substrates 25 (opposing substrate 22 and TFT array substrate 23). A driving liquid crystal layer 28 is formed by enclosing a liquid crystal composition for driving a liquid crystal display device (driving liquid crystal composition 24) in such a manner that the orientation can be changed. The liquid crystal display device 51 includes a backlight (not shown) that emits light from the outer position of the TFT array substrate 23 toward the TFT array substrate 23 in the thickness direction of the TFT array substrate 23. ing.

  The counter substrate 22 is formed by laminating a colored layer 13 having a black matrix 15 and color patterns 16, 17, and 18 on the base material 2, and covering the surface of the colored layer 13 to form the retardation layer 4. Yes.

  Further, on the retardation layer 4, the column body 3 has the base portion (the upper portion in FIG. 4) placed at a predetermined position on the surface of the retardation layer 4 (column body formation planned position) as described above. It distributes using well-known methods, such as. The columnar formation planned position is appropriately determined in a portion (non-pixel portion) excluding a portion to be a pixel in the phase difference control member 1.

  On the counter substrate 22, a linearly polarizing plate 33 is disposed on the surface of the substrate 2 in the thickness direction on the surface where the colored layer 13 is not formed.

  The TFT array substrate 23 is for driving for switching driving whether or not voltage is applied to the liquid crystal 44 of the driving liquid crystal layer 28 on the surface of the transparent substrate 41 on the in-cell side (side where the driving liquid crystal composition 24 is sealed). A TFT forming a circuit and a liquid crystal driving electrode for controlling the amount of voltage applied to the driving liquid crystal layer 28 are provided (not shown). The liquid crystal driving electrode generates an electric field in the in-plane direction of the driving liquid crystal layer 28 and changes the orientation of the liquid crystal 44 in the in-plane direction of the driving liquid crystal layer 28.

  Furthermore, the TFT array substrate 23 is in contact with the tip portions (downward in the figure) of a large number of pillars 3 on the outermost surface on the in-cell side. The backlight side substrate 23 is provided with a linearly polarizing plate 42 on the out-cell side (opposite side of the in-cell side).

  In the liquid crystal display device 51, the linearly polarizing plate 33 of the counter substrate 22 and the linearly polarizing plate 42 of the TFT array substrate 23 are arranged so that their transmission axes are orthogonal to each other. In the figure, the transmission axes of the linearly polarizing plates 33 and 42 are indicated by arrows.

  In this liquid crystal display device 51, the counter substrate 22 is provided with a layer structure in which the base material 2, the colored layer 13, and the retardation layer 4 are laminated, and this layer structure is the retardation control member 1 in the present invention. Configure. That is, the liquid crystal display device 51 is configured by incorporating the phase difference control member 1.

  In the liquid crystal display device 51, the retardation film 30 may be disposed inside the linear polarizing plate 33 in the counter substrate 22 as necessary. In the example shown in FIG. 4, as the liquid crystal display device 51, the retardation control member 1 in which the retardation layer 4 is formed as a layer having an optical compensation function of a positive C plate is incorporated, and the retardation film 30 is positive. One having an optical compensation function as an A plate is shown. In FIG. 4, the birefringence characteristics defining the optical compensation function of the retardation layer 4 and the retardation film 30 are indicated by refractive index ellipsoids 100 and 101, respectively.

  In the liquid crystal display device 51, a plurality of retardation films 30 may be interposed in a plurality of types as required. Therefore, for example, the liquid crystal display device 51 incorporates the retardation control member 1 in which the retardation layer 4 is formed as a layer having an optical compensation function of a positive C plate, and as the retardation film 30 as a positive A plate. It may be configured by laminating two or more of those having the above optical compensation function and those having other functions.

  In the present specification, the case where the liquid crystal display device incorporating the phase difference control member 1 is in the IPS mode has been described. This is because the phase difference control member 1 is, for example, in an MVA mode or an OCB mode (Optically Compensated Birefringence mode). This is not to deny use in liquid crystal display devices in other modes such as.

Example 1
A liquid crystal material composition having the following composition by mixing a liquid crystal compound composed of cross-linkable polymerizable liquid crystal molecules as shown in the following compounds (a) to (d), a surfactant, a photopolymerization initiator, and a polymerization inhibitor. A was adjusted. In addition, the weight ratio (% by weight) of each constituent component such as a liquid crystal compound and a surfactant constituting the liquid crystal material composition A shown below is the weight ratio of each constituent component to the total weight of the liquid crystal material composition A. Show.

<Composition of liquid crystal material composition A>
Compound (a) 32.67% by weight
Compound (b) 18.67% by weight
Compound (c) 21.0% by weight
Compound (d) 21.0% by weight
Surfactant 1.02% by weight
(Dodecanol)
Photopolymerization initiator 5.6 wt%
(Irgacure 907, manufactured by Ciba Specialty Chemicals)
Polymerization inhibitor 0.04% by weight
(BHT (2,6-di-tert-butyl-4-hydroxytoluene))

  With respect to the liquid crystal material composition A, a mercaptopropionic acid derivative (pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd., PEMP)) as a composition (M) Product equivalent value)) was added to obtain a liquid crystal composition of the present invention.

  The obtained liquid crystal composition was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to obtain a 20% concentration solution (liquid crystal composition solution). Here, the concentration of 20% indicates that the weight ratio (% by weight) of the liquid crystal composition to the total weight of the solution is 20% by weight.

  Using this liquid crystal composition solution, a retardation control member having a retardation layer formed on a colored layer was produced as follows.

[Formation of colored layer]
A glass substrate (vertical 100 × width 100 mm, thickness 0.7 mm) (manufactured by Corning, 1737 material) as a base material was prepared, washed in advance, and a colored layer was formed on the glass substrate surface. In forming the colored layer, a red (R) colored material dispersion was prepared. A pigment dispersion type photoresist was used as the coloring material dispersion.

  Preparation of the pigment dispersion type photoresist is performed by adding beads to the dispersion composition (containing pigment, dispersant and solvent) and dispersing for 3 hours with a disperser (paint shaker (manufactured by Asada Tekko Co., Ltd.)). A pigment-dispersed photoresist was obtained by mixing the removed dispersion and the clear resist composition (containing polymer, monomer, additive, initiator and solvent). A pigment dispersion type photoresist having the following composition was used.

(Red (R) pigment-dispersed photoresist)
・ Red pigment: 4.8 parts by weight (CIPR254 (manufactured by Ciba Specialty Chemicals, Chromophthal DPP Red BP))
・ Yellow pigment: 1.2 parts by weight (CI PY139 (manufactured by BASF, Paliotor Yellow D1819))
・ Dispersant: 3.0 parts by weight (manufactured by Zeneca Corporation, Solsperse 24000)
・ Monomer: 4.0 parts by weight (Sartomer Co., Ltd., SR399)
-Polymer 1-5.0 parts by weight-Initiator-1.4 parts by weight (Irgacure 907, manufactured by Ciba Geigy)
・ Initiator: 0.6 parts by weight (2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole)
・ Solvent: 80.0 parts by weight (propylene glycol monomethyl ether acetate)

  The adjusted red pigment-dispersed photoresist is applied onto the glass substrate surface by spin coating, pre-baked (pre-baked) at 90 ° C. for 3 minutes, alignment exposure (100 mJ / cm 2), and then at 230 ° C., 30 Post-baking was performed for a minute to form a red monochromatic colored layer (thickness: 2.0 μm). This colored layer was formed on the entire surface of the glass substrate.

After forming a colored layer on the glass substrate, a UV cleaning treatment was performed. The UV cleaning treatment was performed by irradiating the colored layer surface with ultraviolet rays (wavelength 254 nm, exposure amount 1 J / cm ² ). In addition, the ultraviolet-ray cleaning apparatus (Iwasaki Electric company make, OC-2506) was used for UV cleaning process.

  After the UV cleaning treatment, the glass substrate on which the colored layer was formed was placed on a spin coater (manufactured by Mikasa Co., Ltd., 1H-360S), and the surface of the colored layer was used as a base surface and adjusted as described above. A liquid crystal coating film was prepared by spin coating the liquid crystal composition solution.

[Formation of liquid crystal phase state for liquid crystal compound contained in liquid crystal coating film]
The substrate on which the liquid crystal coating film was formed was dried under reduced pressure (room temperature, pressure at the time of pressure reduction of 20 Pa), thereby bringing the liquid crystal compound into a liquid crystal phase and distilling off the solvent in the liquid crystal coating film.

[Crosslinking polymerization reaction of liquid crystal molecules]
Next, ultraviolet rays (365 nm) with an output of 20 mW / cm ² are irradiated for 10 seconds on the entire surface of the liquid crystal coating film in an air atmosphere by using an ultraviolet irradiation device having a super high pressure mercury lamp (TORISURE 751 manufactured by Harrison Toshiba Lighting Co., Ltd.). Then, the liquid crystal molecules in the liquid crystal coating film are cross-linked and fixed in a state where the cross-linkable liquid crystal molecules are vertically aligned, and further subjected to post-polymerization baking treatment by baking in an oven at 230 ° C. for 30 minutes, A phase difference control member was obtained. Regarding the obtained retardation control member, the thickness of the retardation layer was 1.0 μm. The thickness of the retardation layer was measured using a stylus thickness meter Alphastep (manufactured by Tencor).

  The homeotropic orientation and optical compensation function of the retardation layer of the obtained retardation control member were evaluated as follows.

[Evaluation of homeotropic orientation]
The alignment state of the crosslinkable liquid crystal molecules constituting the retardation layer was evaluated based on the measured retardation value when light having a wavelength of 589 nm was transmitted through the retardation layer. For measurement of the phase difference, RETS-1250AV manufactured by Otsuka Electronics Co., Ltd. was used.

  That is, first, a z-axis is assumed in the thickness direction of the retardation layer of the retardation control member, a plane having a normal line in the z-axis direction is taken, and the x axis and the y axis are orthogonal to each other in the plane Assuming an xyz space coordinate system. And the phase difference of the phase difference layer was measured about the direction inclined in the x-axis direction and the y-axis direction with respect to the z-axis direction and the z-axis. Whether or not the phase difference generated in the retardation layer exhibits symmetry with respect to the z-axis when measured in the direction inclined in the x-axis direction and when measured in the direction inclined in the y-axis direction. Was measured. Based on these measurement results, the quality of the orientation as to whether or not the retardation layer had a good homeotropic orientation was evaluated as follows.

The phase difference shows symmetry in both the x-axis direction and the y-axis direction, and the value of the phase difference in the z-axis direction is 4 nm or less.
The phase difference exhibits symmetry in both the x-axis direction and the y-axis direction, or the phase difference value in the z-axis direction satisfies 4 nm or less.
The phase difference is disturbed in symmetry in both the x-axis direction and the y-axis direction, and the value of the phase difference in the z-axis direction is larger than 4 nm.

  The result of evaluation of homeotropic orientation with respect to the retardation layer of the retardation control member was ◎, and it was confirmed that the retardation layer was well homeotropically oriented.

[Evaluation of optical compensation function]
Regarding whether or not the phase difference control member effectively exerts the optical compensation function, the phase difference control member is used to observe the presence or absence of light leakage and to measure the luminance ratio. Evaluation was based on the values.

  Regarding the presence or absence of light leakage, first, using a polarizing microscope (Olympus Co., CPX31-P), a phase difference control member is placed on a sample stage on which the sample is mounted, and the eyepiece side and the light source are sandwiched between the sample stages. The polarizing plates provided at both predetermined positions on the side are set in a crossed Nicols state, light is irradiated from the light source toward the phase difference control member through the polarizing plate on the light source side, and the eyepiece side when the irradiation is performed The light leakage from the polarizing plate was observed with the naked eye (observation during dark display). In addition, the luminance at this time was also measured.

  Next, the polarizing plates provided on the eyepiece side and the light source side were set so that the transmission axes of the light were aligned with each other, and the same light as in the dark display observation was irradiated from the light source, and the light leakage was visually observed. (Observation during bright display). The luminance at this time was also measured. Then, a luminance ratio (that is, Ton / Toff) between the luminance at the time of dark display (Toff) and the luminance at the time of bright display (Ton) was calculated. In general, it is said that an excellent display can be provided when the luminance ratio is 1000 or more. Therefore, an extremely excellent display is provided at a value exceeding 1100. Is in a state of being able to. Therefore, based on the calculated luminance ratio value, the optical compensation function of the phase difference control member was evaluated as follows. The luminance was measured using EZ contrast 160 (manufactured by ELDIM).

The presence or absence of light leakage is not observed with the naked eye, and (Ton / Toff) is 1100 or more.
The presence or absence of light leakage is not observed with the naked eye, and (Ton / Toff) is 1000 or more and less than 1100 ...
Obvious light leakage is observed, or (Ton / Toff) is less than 1000 ...

  The result of evaluation of the optical compensation function regarding the phase difference control member was ◎, and it was confirmed that the phase difference control member exhibits the optical compensation function satisfactorily.

Example 2
Example 1 except that the blending amount of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd., PEMP) constituting the liquid crystal composition was changed to 0.1% by weight (compared to the equivalent of the blend). A liquid crystal composition was prepared in the same manner as described above, and a liquid crystal composition solution and a retardation control member were prepared in the same manner as in Example 1 using this liquid crystal composition.

  Regarding the obtained retardation control member, the homeotropic orientation and the optical compensation function of the retardation layer were evaluated in the same manner as in Example 1. As a result, the homeotropic orientation of the retardation layer was evaluated as ◎, and the optical compensation function was evaluated as ○. Therefore, it was confirmed that the retardation control member of Example 2 was well homeotropically aligned with respect to the retardation layer and exhibited an optical compensation function.

Example 3
Example 1 except that the blending amount of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd., PEMP) constituting the liquid crystal composition was changed to 10% by weight (compared to the equivalent of the blend). A liquid crystal composition was prepared, and using this liquid crystal composition, a liquid crystal composition solution and a retardation control member were prepared in the same manner as in Example 1.

  Regarding the obtained retardation control member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Example 1. As a result, the homeotropic orientation of the retardation layer was evaluated as ◎, and the optical compensation function was evaluated as ○. Therefore, it was confirmed that the retardation control member of Example 3 was well homeotropically aligned with respect to the retardation layer and exhibited an optical compensation function.

Example 4
A liquid crystal composition was prepared in the same manner as in Example 1 except that a mercaptopropionic acid derivative β-mercaptopropionic acid methyl ester (manufactured by Sakai Chemical Co., Ltd., MPM) was used as the composition (M) constituting the liquid crystal composition. Using this liquid crystal composition, a liquid crystal composition solution and a retardation control member were produced in the same manner as in Example 1.

  Regarding the obtained retardation control member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Example 1. As a result, the homeotropic orientation of the retardation layer was evaluated as ◎, and the optical compensation function was evaluated as ○. Therefore, it was confirmed that the retardation control member of Example 4 was well homeotropically aligned with respect to the retardation layer and exhibited an optical compensation function.

Example 5
A liquid crystal composition was prepared in the same manner as in Example 1 except that the mercaptopropionic acid derivative β-mercaptopropionic acid ethyl ester (manufactured by Sakai Chemical Co., Ltd., EPM) was used as the composition (M) constituting the liquid crystal composition. Using this liquid crystal composition, a liquid crystal composition solution and a retardation control member were produced in the same manner as in Example 1.

  Regarding the obtained retardation control member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Example 1. As a result, the homeotropic orientation of the retardation layer was evaluated as ◎, and the optical compensation function was evaluated as ○. Therefore, it was confirmed that the retardation control member of Example 5 was well homeotropically aligned with respect to the retardation layer and exhibited an optical compensation function.

Example 6
A liquid crystal composition was prepared in the same manner as in Example 1 except that β-mercaptopropionic acid was used in place of the mercaptopropionic acid derivative as the composition (M) constituting the liquid crystal composition, and this liquid crystal composition was used. A liquid crystal composition solution and a retardation control member were produced in the same manner as in Example 1.

  Regarding the obtained retardation control member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Example 1. As a result, the homeotropic orientation of the retardation layer was evaluated as ◎, and the optical compensation function was evaluated as ○. Therefore, it was confirmed that the retardation control member of Example 6 was well homeotropically aligned with respect to the retardation layer and exhibited an optical compensation function.

Example 7
A liquid crystal composition was prepared in the same manner as in Example 1 except that α-mercaptopropionic acid methyl ester as a mercaptopropionic acid derivative was used as the mercaptopropionic acid derivative as the composition (M) constituting the liquid crystal composition. A liquid crystal composition solution and a retardation control member were produced using the composition in the same manner as in Example 1.

  Regarding the obtained retardation control member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Example 1. As a result, the homeotropic orientation of the retardation layer was evaluated as ◎, and the optical compensation function was evaluated as ○. Therefore, it was confirmed that the retardation control member of Example 7 was well homeotropically aligned with respect to the retardation layer and exhibited an optical compensation function.

Example 8
A liquid crystal composition was prepared in the same manner as in Example 1 except that α-mercaptopropionic acid was used in place of the mercaptopropionic acid derivative as the composition (M) constituting the liquid crystal composition, and this liquid crystal composition was used. In the same manner as in Example 1, a liquid crystal composition solution and a retardation control member were produced.

  Regarding the obtained retardation control member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Example 1. As a result, the homeotropic orientation of the retardation layer was evaluated as ◎, and the optical compensation function was evaluated as ○. Therefore, it was confirmed that the retardation control member of Example 8 was well homeotropically aligned with respect to the retardation layer and exhibited an optical compensation function.

Example 9
As a composition (M) constituting the liquid crystal composition, β-mercaptopropionic acid (manufactured by Sakai Chemical Co., Ltd., BMPA) (blending amount 3% by weight (compared to the compound equivalent)) and mercaptopropionic acid derivative (manufactured by Sakai Chemical Co., Ltd., PEMP) (a blending amount of 0.1% by weight (compared to a blended value)), and a liquid crystal composition was prepared in the same manner as in Example 1 except that both were added to the liquid crystal material composition A. Using this liquid crystal composition, a liquid crystal composition solution and a retardation control member were produced in the same manner as in Example 1.

  Regarding the obtained retardation control member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Example 1. As a result, the homeotropic orientation of the retardation layer was evaluated as ◎, and the optical compensation function was evaluated as ◎. Therefore, it was confirmed that the retardation control member of Example 9 was well homeotropically aligned with respect to the retardation layer and exhibited an optical compensation function.

Example 10
To the liquid crystal material composition A of Example 1, a polyfunctional (meth) acrylate (manufactured by Toagosei Co., Ltd., M305) (blending amount 10% by weight (vs. blended value)) was further added. A liquid crystal composition was obtained. A liquid crystal composition solution and a retardation control member were produced using this liquid crystal composition in the same manner as in Example 1.

  Regarding the obtained retardation control member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Example 1. As a result, the homeotropic orientation of the retardation layer was evaluated as ◎, and the optical compensation function was evaluated as ◎. Therefore, it was confirmed that the retardation control member of Example 10 was well homeotropically aligned with respect to the retardation layer and exhibited an optical compensation function.

Example 11
Mercaptopropionic acid derivative (pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd., PEMP)) as a composition (M) for the liquid crystal material composition A of Example 1 (blending amount 3 wt. % (Vs. compound conversion value)), and 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (KBE-9103 manufactured by Shin-Etsu Chemical Co., Ltd.) (blending amount 3 wt% (vs. compound conversion) Value)) was added to obtain a liquid crystal composition of the present invention. A liquid crystal composition solution and a retardation control member were produced using this liquid crystal composition in the same manner as in Example 1.

  Regarding the obtained retardation control member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Example 1. As a result, the homeotropic orientation of the retardation layer was evaluated as ◎, and the optical compensation function was evaluated as ◎. Therefore, it was confirmed that the retardation control member of Example 11 was well homeotropically aligned with respect to the retardation layer and exhibited an optical compensation function.

Comparative Example 1
A liquid crystal composition was prepared in the same manner as in Example 1 except that neither the mercaptopropionic acid nor the mercaptopropionic acid derivative was added to the liquid crystal material composition A (the composition (M) was not added). Using this liquid crystal composition, a liquid crystal composition solution (comparative solution) was prepared in the same manner as in Example 1. In addition, the liquid crystal compound contained in the comparative solution was cured by the same method as the method for producing the retardation control member of Example 1, except that the liquid crystal composition solution of Example 1 was replaced with a comparative solution. A comparative member having a layer structure formed on the colored layer surface was prepared.

  Regarding the comparative member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Example 1. As a result, it was evaluated that the homeotropic orientation of the layer structure made of the comparative solution and the optical compensation function of the comparative member were both x. Therefore, it was confirmed that the comparative member of Comparative Example 1 was not well homeotropically aligned with respect to the layer structure obtained by curing the liquid crystal compound contained in the comparative solution, and did not sufficiently exhibit the optical compensation function. .

Comparative Example 2
In the same manner as in Example 1 except that thioglycolic acid (manufactured by Sakai Chemical Industry Co., Ltd., TGA) was added to the liquid crystal material composition A instead of adding the mercaptopropionic acid derivative as the composition (M). A composition was made. Using this liquid crystal composition, a liquid crystal composition solution (comparative solution) was prepared in the same manner as in Comparative Example 1, and a layer structure formed by curing the liquid crystal compound contained in the comparative solution was provided on the colored layer surface. A comparative member was prepared.

  Regarding the comparative member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Comparative Example 1. As a result, it was evaluated that the homeotropic orientation of the layer structure made of the comparative solution and the optical compensation function of the comparative member were both x. Therefore, it was confirmed that the comparative member of Comparative Example 2 was not well homeotropically aligned with respect to the layer structure obtained by curing the liquid crystal compound contained in the comparative solution, and did not sufficiently exhibit the optical compensation function. .

Comparative Example 3
Example 1 except that ammonium thioglycolate (manufactured by Sakai Chemical Industry Co., Ltd., ATG) was added to the liquid crystal material composition A instead of adding the mercaptopropionic acid derivative as the composition (M). A liquid crystal composition was prepared. Using this liquid crystal composition, a liquid crystal composition solution (comparative solution) was prepared in the same manner as in Comparative Example 1, and a layer structure formed by curing the liquid crystal compound contained in the comparative solution was provided on the colored layer surface. A comparative member was prepared.

  Regarding the comparative member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Comparative Example 1. As a result, it was evaluated that the homeotropic orientation of the layer structure made of the comparative solution and the optical compensation function of the comparative member were both x. Therefore, it was confirmed that the comparative member of Comparative Example 3 was not well homeotropically aligned with respect to the layer structure obtained by curing the liquid crystal compound contained in the comparative solution, and did not sufficiently exhibit the optical compensation function. .

Reference example 1
A liquid crystal composition was prepared in the same manner as in Example 1 except that the amount of the composition (M) added to the liquid crystal material composition A was 0.08% by weight (compared to the equivalent of the compound). Using this liquid crystal composition, a liquid crystal composition solution (comparative reference solution) was prepared in the same manner as in Comparative Example 1, and a layer structure formed by curing the liquid crystal compound contained in the comparative reference solution was formed on the colored layer surface. A comparative reference member prepared for was prepared.

  For this comparative reference member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Comparative Example 1. As a result, it was evaluated that both the homeotropic orientation of the layer structure composed of the comparative reference solution and the optical compensation function of the comparative reference member were good. Therefore, when compared with Example 1, the comparative reference member of Reference Example 1 is not sufficiently homeotropically aligned with respect to the layer structure obtained by curing the liquid crystal compound contained in the comparative reference solution. It was confirmed that the optical compensation function was not fully exhibited.

Reference example 2
A liquid crystal composition was prepared in the same manner as in Example 1, except that the amount of the composition (M) added to the liquid crystal material composition A was 11% by weight (compared to the equivalent of the compound). Using this liquid crystal composition, a liquid crystal composition solution (comparative reference solution) was prepared in the same manner as in Comparative Example 1, and a layer structure formed by curing the liquid crystal compound contained in the comparative reference solution was formed on the colored layer surface. A comparative reference member prepared for was prepared.

  For the comparative reference member, the homeotropic orientation and the optical compensation function were evaluated in the same manner as in Comparative Example 1. As a result, it was evaluated that both the homeotropic orientation of the layer structure composed of the comparative reference solution and the optical compensation function of the comparative reference member were good. Therefore, the comparative reference member of Reference Example 2 is not sufficiently homeotropically aligned with respect to the layer structure obtained by curing the liquid crystal compound contained in the comparative reference solution when compared with Example 1. It was confirmed that the optical compensation function was not fully exhibited.

It is a schematic sectional drawing explaining the example of the phase difference control member of this invention. It is a schematic sectional drawing explaining the example of a phase difference control member in case this foundation layer is a colored layer in this invention. It is a schematic plan view explaining the example of a phase difference control member in case this foundation layer is a colored layer in this invention. It is a schematic exploded perspective view for demonstrating the liquid crystal display device incorporating the phase difference control member of this invention. It is a figure for demonstrating the x-axis, y-axis, and z-axis which are assumed with the state of an optical axis about the phase difference layer of the phase difference control member of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Phase difference control member 2 Base material 4 Phase difference layer 13 Colored layer 15 Black matrix 16, 17, 18 Color pattern 51 Liquid crystal display device

Claims (12)

  A liquid crystal composition comprising: a liquid crystal compound comprising a crosslinkable liquid crystal molecule; and a composition (M) comprising a mercaptopropionic acid and / or a mercaptopropionic acid derivative.   The liquid crystal composition according to claim 1, wherein the crosslinkable liquid crystal molecule has at least one (meth) acryloyl group in at least one molecule.   The liquid crystal composition according to claim 1 or 2, wherein the composition (M) is contained in an amount of 0.1 to 10% by weight in terms of a compound.   Mercaptopropionic acid derivatives are α-mercaptopropionic acid methyl ester, α-mercaptopropionic acid ethyl ester, α-mercaptopropionic acid butyl ester, β-mercaptopropionic acid methyl ester, β-mercaptopropionic acid ethyl ester, β-mercaptopropionic acid. Acid 2-ethylhexyl ester, β-mercaptopropionic acid n-octyl ester, β-mercaptopropionic acid methoxybutyl ester, β-mercaptopropionic acid stearyl ester, β-mercaptopropionic acid isononyl ester, trimethylolpropane tris (3-mercapto Propionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), The [(3-mercapto-propionyl b carboxymethyl) - ethyl] isocyanurate, are more selected, the liquid crystal composition according to any one of claims 1 to 3.   The liquid crystal composition according to claim 1, further comprising a silane coupling agent.   The liquid crystal composition according to claim 1, further comprising a photopolymerization initiator.   99.79 to 70% by weight (compared to the compound equivalent) of a liquid crystal compound composed of a crosslinkable liquid crystal molecule containing a (meth) acryloyl group, and 0.01 to 10% by weight (relative to a compound based on an amino silane coupling agent). A silane coupling agent of (compound conversion value) and a photopolymerization initiator of 0.1 to 10% by weight (vs. compound conversion value), and the composition (M) is 0.1 to 10 The liquid crystal composition according to claim 1, wherein the liquid crystal composition is contained in an amount of% by weight (compared to a compound equivalent). A retardation control member comprising a base material having optical transparency and a retardation layer formed directly or indirectly on the base material,
A retardation layer is formed by curing the liquid crystal composition according to any one of claims 1 to 7 on a base material.   The phase difference control member according to claim 8, further comprising a colored layer.   A retardation layer is formed by applying the liquid crystal composition according to claim 1 on a substrate to form a liquid crystal coating film, and irradiating active radiation toward the surface of the liquid crystal coating film. The retardation control member according to claim 8 or 9, which is formed by curing crosslinkable liquid crystal molecules contained in the liquid crystal coating film.   The retardation control member according to claim 8, wherein the retardation layer is a layer having homeotropic alignment.   12. In a liquid crystal display device in which a driving liquid crystal layer is formed between two opposing substrates, in which liquid crystal is sealed so as to be capable of orientation control in accordance with a change in voltage, one of the two substrates is provided with one of claims 8 to 11. A liquid crystal display device, wherein any one of the retardation control members is incorporated.

Images