JP2007332260A - Liquid crystal composition, color filter and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal composition from which a phase difference layer excellent in adhesion to a base material, and prevented from the occurrence of a fuzzy pattern on the surface can be produced; and to provide a color filter using the composition, and a liquid crystal display using the color filter. <P>SOLUTION: The liquid crystal composition obtained by dissolving one or more kinds of crosslinkable liquid crystal molecules, and a silane coupling agent containing at least one kind selected from a sulfide group, a mercapto group, an amino group and a (meth)acryloyl group in a solvent having 5-30 specific evaporation rate when the evaporation rate of n-butyl acetate at 25°C is defined as 100. The color filter 1 has the phase difference layer 3 formed by coating the composition on the base material. The liquid crystal display has the color filter as a display-side substrate. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid crystal composition, a color filter having a retardation layer made of the liquid crystal composition, and a liquid crystal display device using the color filter.

  In recent years, liquid crystal display devices have a great advantage of being thin and light and have low power consumption, and thus are actively used in display devices such as personal computers, mobile phones, and electronic notebooks. These liquid crystal display devices perform light switching by utilizing the birefringence of the driving liquid crystal material. Therefore, the liquid crystal display device has a viewing angle dependency derived from the birefringence of the driving liquid crystal material, and various retardation layer forming films have been developed to solve this problem. This retardation layer-forming film is usually prepared by stretching a film of polyacrylate, polycarbonate, triacetyl cellulose or the like, and is placed outside a liquid crystal cell in which a driving liquid crystal material is sandwiched between two substrates. Recently, a method of installing a retardation layer inside a liquid crystal cell using a crosslinkable liquid crystal material or a polymer liquid crystal material has been proposed (Patent Document 1), and the retardation layer is installed inside a liquid crystal cell. Thus, the film becomes unnecessary, so that high mechanical strength and heat resistance can be obtained, and further moisture absorption deformation can be suppressed.

JP 2000-221506 A

However, the retardation layer formed by cross-linking the cross-linkable liquid crystal material has poor adhesion to the substrate inside the liquid crystal cell because the cross-linkable liquid crystal material itself has few sites involved in adhesion, and long-term adhesion reliability. There was a problem that it was scarce.
In order to solve this adhesion problem, an adhesive layer for increasing the adhesion between the substrate and the retardation layer is formed between the substrate and the retardation layer, or a crosslinkable liquid crystal material is used. A method of forming a layer for modifying the substrate surface using a substance having high adhesiveness is also conceivable. However, these methods result in an increase in the thickness of the liquid crystal display device, which is not desirable from the viewpoint of reducing the thickness and weight, and has the problem of increasing the number of manufacturing steps. Also, forming an anisotropic layer between the equipment and the retardation layer may cause irregular reflection of light transmitted through the liquid crystal device.

In order to solve the above problems, the present inventors have found that a liquid crystal composition in which a specific silane coupling agent is added to a liquid crystal composition containing a crosslinkable liquid crystal molecule has a phase difference excellent in adhesion to a substrate over a long period of time. The present inventors have found that a layer can be formed and solved the above problems. However, it was recognized that this has the following secondary problems.

  That is, a composition obtained by adding a silane coupling agent to a liquid crystal composition containing a crosslinkable liquid crystal molecule is applied to the surface of a substrate to form a coating film, which is dried to evaporate the solvent, thereby causing a retardation layer. When the film was formed, there was a problem that the mist was uneven on the surface of the retardation layer. Although the mechanism of the occurrence of the above-mentioned moire is not clear, the addition of a silane coupling agent reduces the smoothness of the coating surface, and the occurrence of drying unevenness in the solvent drying process causes the occurrence of moire on the surface of the retardation layer. it seems to do. In the case where it is necessary to provide a higher quality display in a liquid crystal display device or the like provided with the retardation layer, it is desirable to prevent the occurrence of the fog.

  The present invention has been made in view of the above-mentioned problems, prevents occurrence of haze on the surface of the retardation layer, and without forming a third layer between the substrate and the retardation layer, A liquid crystal composition, a color filter using the liquid crystal composition, and a liquid crystal display device using the color filter, which can be provided with an image display device such as a liquid crystal display having a phase difference layer excellent in adhesion with a substrate for a long period of time. It is intended to provide.

  In the present invention, a silane coupling agent having at least one selected from a sulfide group, a mercapto group, an amino group, and a (meth) acryloyl group is added to a liquid crystal composition containing a crosslinkable liquid crystal molecule, If a liquid crystal composition in which a solute component such as a crosslinkable liquid crystal molecule or a silane coupling agent is dissolved using a solvent having a specific evaporation rate of 5 to 30, a retardation layer is formed on a substrate using the composition. This is based on the knowledge that when the film is formed, the adhesion between the base material and the retardation layer can be sufficiently increased, and the occurrence of fog on the surface of the retardation layer can be prevented.

That is, the present invention
(1) A silane coupling agent having at least one kind of a crosslinkable liquid crystal molecule and at least one kind selected from a sulfide group, a mercapto group, an amino group, and a (meth) acryloyl group at 25 ° C. a liquid crystal composition characterized by being dissolved in a solvent having a specific evaporation rate of 5 to 30 when the evaporation rate of n-butyl acetate is 100;
(2) The liquid crystal composition according to (1), wherein the crosslinkable liquid crystal molecule has at least one (meth) acryloyl group in at least one molecule,
(3) A silane coupling agent containing a sulfide group, a silane coupling agent containing a mercapto group, or a silane coupling agent having a (meth) acryloyl group, or a total of 1 to 10% by weight. (Vs. compound equivalent value) The liquid crystal composition according to (1) or (2),
(4) The liquid crystal composition according to (1) or (2), which contains a silane coupling agent containing an amino group in an amount of 0.01 to 5% by weight (compared to a compound equivalent).
(5) As a silane coupling agent, a silane coupling agent containing an amino group, a silane coupling agent containing a sulfide group, a silane coupling agent containing a mercapto group, or a silane coupling agent having a (meth) acryloyl group. The liquid crystal composition according to (1) or (2), containing a total of 0.01 to 5% by weight (compared to the compound equivalent) of one or more agents.
(6) A liquid crystal composition as described in any one of (1) to (5), which contains a vertical alignment aid,
(7) The liquid crystal composition according to any one of (1) to (6), wherein the liquid crystal composition is used for forming a retardation layer that is homeotropically aligned,
(8) A retardation layer and a colored layer are provided on a transparent substrate, and the retardation layer is applied to the substrate by applying the liquid crystal composition according to any one of (1) to (7) to a coating film. A color filter formed by curing crosslinkable liquid crystal molecules contained in the coating film,
(9) The retardation layer is at least 98.9 to 70% by weight (vs. compound equivalent) of (meth) acryloyl group-containing crosslinkable liquid crystal molecules, 0.1 to 10% by weight (vs. compound equivalent). A liquid crystal composition containing a photopolymerization initiator and a sulfide group-containing silane coupling agent in an amount of 1 to 5% by weight (compared to the formulation) is applied to the upper surface of the substrate to form a coating film. The crosslinkable liquid crystal molecules contained are formed by photocuring and baking, and the peel strength of the retardation layer after an accelerated life test at a temperature of 100 ° C. and a humidity of 100% for 1 hour is evaluated according to JISK5600-5-6. And the color filter according to (8), which is 1 or less,
(10) The retardation layer is at least 98.9 to 70% by weight (vs. compound equivalent) of (meth) acryloyl group-containing crosslinkable liquid crystal molecules, 0.1 to 10% by weight (vs. compound equivalent). A liquid crystal composition containing a photopolymerization initiator and a mercapto group-containing silane coupling agent in an amount of 1 to 5% by weight (vs. the compound equivalent) is applied to the upper surface of the substrate to form a coating film. The crosslinkable liquid crystal molecules contained are formed by photocuring and baking, and the peel strength of the retardation layer after an accelerated life test at a temperature of 100 ° C. and a humidity of 100% for 1 hour is evaluated according to JISK5600-5-6. And the color filter according to (8), which is 1 or less,
(11) The retardation layer is at least 99.89 to 70% by weight (vs. compound equivalent) of (meth) acryloyl group-containing crosslinkable liquid crystal molecules, 0.1 to 10% by weight (vs. compound equivalent). A coating film is formed by applying a liquid crystal composition containing a photopolymerization initiator and an amino group-containing silane coupling agent in an amount of 0.01 to 5% by weight (based on the formulation) to the upper surface of the substrate. It is formed by photocuring and baking crosslinkable liquid crystal molecules contained therein, and the peel strength of the retardation layer after an accelerated life test of 1 hour at a temperature of 100 ° C. and a humidity of 100% is JISK5600-5-6. The color filter according to (8), which is 1 or less on an evaluation standard,
(12) The retardation layer is at least 98.9 to 70% by weight (vs. compound equivalent) of (meth) acryloyl group-containing crosslinkable liquid crystal molecules, 0.1 to 10% by weight (vs. compound equivalent). A liquid crystal composition containing a photopolymerization initiator and 1 to 5% by weight (compared to the compound equivalent value) of a (meth) acryloyl group-containing silane coupling agent is applied to the upper surface of the substrate to form a coating film, It is formed by photocuring and baking crosslinkable liquid crystal molecules contained in the film. The peel strength of the retardation layer after an accelerated life test of 1 hour at a temperature of 100 ° C. and a humidity of 100% is JISK5600-5-6. The color filter according to (8), which is 1 or less based on the evaluation criteria of
(13) The retardation layer is at least 99.89 to 70% by weight (vs. compound equivalent) (meth) acryloyl group-containing crosslinkable liquid crystal molecules, and 0.1 to 10% by weight (vs. compound equivalent). Photopolymerization initiator, silane coupling agent selected from amino group-containing silane coupling agent, sulfide group-containing silane coupling agent, mercapto group-containing silane coupling agent and (meth) acryloyl group-containing silane coupling agent A cross-linking liquid crystal contained in the coating film is formed by applying a liquid crystal composition containing two or more kinds of agents in a total amount of 0.01 to 5% by weight (compared to the formulation) to the upper surface of the substrate. It is formed by photocuring and baking molecules, and the peel strength of the retardation layer after an accelerated life test of 1 hour at a temperature of 100 ° C. and a humidity of 100% is 1 or less according to the evaluation standard of JISK5600-5-6. (8) The color filter described in
(14) The color filter according to any one of (8) to (13), wherein the S / N ratio of the light intensity when the surface unevenness inspection of the retardation layer is performed is 2 or less ,
(15) The color filter according to any one of (8) to (14), wherein the retardation layer is homeotropically oriented.
(16) A liquid crystal display device in which a display side substrate and a liquid crystal driving side substrate are opposed to each other, and liquid crystal is sealed between the two, and the display side substrate is any one of (8) to (15). A liquid crystal display device, characterized in that the color filter according to claim 1,
Is a summary.

In addition, some terms used in this specification are defined as follows.
The “liquid crystal composition” includes at least a crosslinkable liquid crystal molecule and a silane coupling agent having at least one selected from a sulfide group, a mercapto group, an amino group, and a (meth) acryloyl group, and further a retardation layer It means a composition in the form of a solution prepared by dissolving or suspending a mixture containing other substances used to form the liquid in a solvent having a specific evaporation rate of 5 to 30. In the present specification, the liquid crystal composition of the present invention which is the “composition in the solution state” is also referred to as “liquid crystal composition solution” for convenience.

The “(meth) acryloyl group” is used as a general term for two functional groups, “acryloyl group” and “methacryloyl group”. Examples of acryloyl groups include acrylate groups (acryloyloxy groups), and methacryloyl groups include methacrylate groups.

“Comparison value in terms of formulation” means that the weight obtained by subtracting the weight of the solvent from the liquid crystal composition of the present invention (that is, the total weight of each formulation before being dissolved or suspended in the solvent) is 100. It means the weight ratio of the formulation.

The “retardation layer” means a layer having a retardation control function capable of optically compensating for a change in retardation of light.

“Homeotropic alignment” refers to an alignment state in which the optical axes of liquid crystal molecules constituting the retardation layer rise perpendicularly or substantially perpendicularly to the substrate surface. Further, “the retardation layer is homeotropically aligned” means that liquid crystal molecules constituting the retardation layer are homeotropically aligned. In the present invention, the ideal homeotropic alignment of the liquid crystal molecules means that the xyz orthogonal coordinate is assumed in the x-axis direction when the xyz orthogonal coordinate is assumed with the thickness direction of the retardation layer as the z-axis. The case where the refractive index ny is substantially the same and the phase difference value when the measurement angle is 0 ° is 4 nm or less, preferably 3.5 nm or less, more preferably 3 nm or less. .

  In the present invention, at least a crosslinkable liquid crystal molecule and a silane coupling agent having at least one of a sulfide group, a mercapto group, an amino group, and a (meth) acryloyl group are used, and the evaporation rate of n-butyl acetate at 25 ° C. is 100. It was possible to form a retardation layer exhibiting an excellent viewing angle improvement effect on a substrate such as a glass substrate by dissolving in a solvent having a specific evaporation rate of 5 to 30.

  That is, at least a crosslinkable liquid crystal molecule and a silane coupling agent having at least one of a sulfide group, a mercapto group, an amino group, and a (meth) acryloyl group had an evaporation rate of n-butyl acetate at 25 ° C. of 100. When a retardation layer is formed on a substrate such as a glass substrate, a colored layer or an alignment film using a liquid crystal composition that dissolves in a solvent having a specific evaporation rate of 5 to 30, the addition of the silane coupling agent Due to the effect, it is possible to form a retardation layer having excellent adhesion to these substrates, and since the solute component is dissolved in a solvent having a specific evaporation rate in the above preferred range, the surface of the retardation layer It is possible to satisfactorily prevent the formation of moisture unevenness. Therefore, when the retardation layer formed using the liquid crystal composition of the present invention is used in a color filter or a liquid crystal display device using this color filter as a display-side substrate, an excellent viewing angle over a long period of time. An improvement effect can be exhibited.

  In addition, the above effect is obtained by directly applying the liquid crystal composition of the present invention on a substrate to form a coating film, and aligning and curing the crosslinkable liquid crystal composition contained in the coating film to form a retardation layer. It can be obtained simply by forming. As a result, it is not necessary to form another layer such as an adhesive layer between the base material and the retardation layer. Therefore, it is advantageous without particularly increasing the number of manufacturing steps and without increasing the thickness of the color filter having the base material, the retardation layer and the colored layer.

  The liquid crystal composition of the present invention dissolves solute components such as crosslinkable liquid crystal molecules and silane coupling agents in a solvent having a specific evaporation rate of 5 to 30 when the evaporation rate of n-butyl acetate at 25 ° C. is 100. It is characterized by damaging.

<About crosslinkable liquid crystal molecules>
As the crosslinkable liquid crystal molecule used in the liquid crystal composition of the present invention, a crosslinkable nematic liquid crystal can be used. As the crosslinkable nematic liquid crystal, for example, (meth) acryloyl group, epoxy group, octacene group, Monomers, oligomers, polymers and the like having at least one polymerizable group such as an isocyanate group can be mentioned. Examples of such crosslinkable liquid crystal molecules include one compound or a mixture of two or more compounds (I) represented by the general formula (1) represented by the following chemical formula 1, and compounds represented by the chemical formula 2 and the chemical formula 3. One compound of (II), a mixture of two or more kinds, or a mixture of these can be used.

In the general formula (1) shown in Chemical Formula 1, R ¹ and R ² each represent hydrogen or a methyl group, but R ¹ or R ² is preferably hydrogen because of the wide temperature range showing the liquid crystal phase. More preferably, ¹ and R ² are both hydrogen. X 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, but is preferably a chlorine or methyl group. In addition, a and b indicating the chain length of the alkylene group that is a spacer between the (meth) acryloyloxy group and the aromatic ring at both ends of the molecular chain of the compound (I) each independently take an arbitrary integer in the range of 2 to 12. However, it is preferably in the range of 4-10, more preferably in the range of 6-9. The compound of the general formula (1) in which a = b = 0 is poor in stability, is susceptible to hydrolysis, and has high crystallinity. Further, the compound of the general formula (1) in which a and b are each 13 or more has a low isotropic phase transition temperature (TI). For this reason, both of these compounds are not preferable because the temperature range showing liquid crystallinity becomes narrow. In the above-mentioned chemical formula 1, chemical formula 2, and chemical formula 3, the monomer of the crosslinkable liquid crystal molecule is exemplified, but the oligomer of the crosslinkable liquid crystal molecule, the polymer of the crosslinkable liquid crystal molecule, and the like are appropriately selected from those conventionally used. Can be used. In general, the retardation amount and orientation characteristics of the retardation film are determined by the birefringence Δn of the crosslinkable liquid crystal molecules and the film thickness of the retardation layer. The Δn of the crosslinkable liquid crystal molecules is about 0.03 to 0.20. Is preferable, and about 0.05 to 0.15 is more preferable.

By achieving such a birefringence, a desired phase difference such as λ / 4 or λ / 2 is obtained when visible light having a wavelength λ is transmitted by applying a liquid crystal composition using a general coating apparatus. A retardation layer is formed.

In the liquid crystal composition of the present invention, the crosslinkable liquid crystal molecules are preferably contained so as to be 70% by weight (compared to the compound equivalent) or more preferably 75% by weight (compared to the compound equivalent). By making the addition amount 70% by weight (vs. compound conversion value) or more, the liquid crystallinity is improved, and the occurrence of poor alignment of the crosslinkable liquid crystal molecules in the retardation layer can be reduced to a negligible level. When the addition of the crosslinkable liquid crystal molecules is 70% by weight or more (as a value in terms of the compound), there is no particular problem from the viewpoint of the orientation of the liquid crystal molecules. The addition amount can be determined as appropriate based on the balance. However, when it is necessary to add a specific additive to the crosslinkable liquid crystal molecule or to add a further additive for imparting a specific function to the retardation layer formed using the liquid crystal composition of the present invention. The amount of crosslinkable liquid crystal molecules added is not limited to the above. In such a case, the addition amount of the crosslinkable liquid crystal molecules may be appropriately determined in consideration of the addition amount of other additives. For example, in the case of obtaining a so-called negative C plate that is generally formed by adding the following chiral agent, it is not excluded that the addition amount of the crosslinkable liquid crystal molecules is less than 70% by weight.

<About Chiral Agent>
In the present invention, a chiral nematic liquid crystal having cholesteric regularity in which a chiral agent is added to the crosslinkable nematic liquid crystal can also be suitably used. The chiral agent is used to form a so-called negative C plate in which the optical axis of liquid crystal molecules is parallel to the retardation layer and has an extraordinary ray refractive index smaller than the ordinary ray refractive index in the normal direction of the retardation layer. It is done.

The chiral agent is a low molecular weight compound having an optically active site, and a compound having a molecular weight of 1500 or less is preferable. The chiral agent is used for the purpose of inducing a helical pitch in the positive uniaxial nematic regularity expressed by the compound (I) shown in Chemical Formula 1 or the compound (II) shown in Chemical Formula 2 and Chemical Formula 3. Examples of the chiral agent include the compounds shown in Chemical Formula 4 below, but are compatible with the compound (I) shown in Chemical Formula 1 and the compound (II) shown in Chemical Formula 2 and Chemical Formula 3 in the solution state or in the molten state. However, the compound shown in Chemical Formula 4 is not limited as long as the helical pitch can be induced without impairing the liquid crystallinity of the crosslinkable nematic liquid crystal. However, those having a crosslinkable functional group at both ends of the molecule are preferred for obtaining an optical element having good heat resistance. It is important that the chiral agent is a compound having an optically active site in the molecule.

Examples of the chiral agent that can be used in the present invention include a compound having one or more asymmetric carbons, a compound having an asymmetric point on a heteroatom such as a chiral amine, a chiral sulfoxide, or the like. And compounds having axial asymmetry such as binaphthol. For example, commercially available chiral nematic liquid crystal, more specifically, S-811 manufactured by Merck Co., etc. can be used. Depending on the properties of the selected chiral agent, nematic regularity may be destroyed and the orientation may be reduced. In the case of a non-polymerizable chiral agent, the curability of the crosslinkable liquid crystal molecules may be reduced, and the electrical reliability of the cured film may be reduced. The use of a large amount of a chiral agent having an optically active site leads to an increase in cost. Therefore, as the chiral agent used in the present invention, it is preferable to select a chiral agent having a large effect of inducing a helical pitch in the alignment of the liquid crystalline polymer. Specifically, the general formulas (2) to (2) described in Chemical Formula 4 are used. It is preferable to use a low molecular compound that is a compound represented by 4) and has axial asymmetry in the molecule.

In the general formulas (2) to (4), R ⁴ represents hydrogen or a methyl group, and Y is any one of (i) to (xxiv) shown in the following chemical formulas 5 and 6; (I), (ii), (iii), (v) and (vii) are preferred. Further, it is more preferable that c and d, which indicate the repetition of the alkylene group, are each in the range of 2 to 12 individually. A compound in which the value of either or both of c and d is 0 or 1 lacks stability, is susceptible to hydrolysis, and has high crystallinity. On the other hand, a compound having both c or d values of 13 or more has a low melting point (Tm). In other words, when a chiral agent having both values of c and d in the above preferred range is used, there is an advantage that sufficient compatibility with the crosslinkable liquid crystal monomer exemplified in the compound (I) and the compound (II) can be obtained. .

The optimum range of the amount of the chiral agent is determined in consideration of the helical pitch inducing ability and the cholesteric property of the finally obtained retardation layer. The specific range of the blending amount varies greatly depending on the type of the crosslinkable liquid crystal and the like, but is generally 0.01 to 30% by weight, preferably 0.1 to 20% by weight in terms of the blended liquid crystal composition. %, More preferably 0.5 to 15% by weight. A particularly preferred amount of the chiral agent is such that the content in the formulation is 1 to 10% by weight. When the ratio of the amount of the chiral agent is less than 0.01% by weight in terms of the compound, sufficient cholesteric properties may not be imparted to the liquid crystal composition, and when it exceeds 30% by weight, the crosslinkable liquid crystal The orientation of the molecules is hindered, and there is a risk of adverse effects such as a decrease in the curing rate and a decrease in the crosslinking density when curing. In particular, when the blending amount of the chiral agent is 1 to 10% by weight, both the orientation of the negative C plate and the crosslinking curability can be sufficiently enhanced, and good optical characteristics of the retardation layer can be obtained.
The chiral agent used in the present invention is not particularly required to have crosslinkability. However, in consideration of the thermal stability of the obtained retardation layer, the chiral agent is polymerized with the above-described crosslinkable liquid crystal material and cholesteric. It is preferable to use a crosslinkable chiral agent capable of fixing the regularity. In particular, it is preferable to have a crosslinkable functional group at both ends of the molecule in order to obtain an optical element having good heat resistance.

<Silane coupling agent>
<Silane coupling agent>
As the silane coupling agent to be blended in the liquid crystal composition, at least one silane coupling agent having any of a sulfide group, a mercapto group, an amino group, and a (meth) acryloyl group, or a mixture of two or more types may be used. Can be used.
Examples of such mercapto-based silane coupling agents include 3-mercaptopropylmethyldimethoxysilane (KBM-802 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-mercaptopropyltrimethoxysilane (KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd., Toshiba Silicone Co., Ltd.). TSL8380), 3-mercaptopropyltriethoxysilane (SIM 6475.0 manufactured by Gelest), 11-mercaptoundecyltrimethoxysilane (SIM6480.0 manufactured by Gelest), mercaptomethylmethyldiethoxysilane (SIM6473.0 manufactured by Gelest) ), S- (octanoyl) mercaptopropyltriethoxysilane (SIM 6704.0 manufactured by Gelest), and the like.
Examples of the sulfide-based silane coupling agent include bis [3- (triethoxysilyl) propyl] tetrasulfide (KBE-846 manufactured by Shin-Etsu Chemical Co., Ltd.), bis [3- (triethoxysilyl) propyl] disulfide (Gelest). SIB1824.6), bis [m- (2-triethoxysilylethyl) tolyl] polysulfide (SIB1820.5 manufactured by Gelest), and the like.
Examples of the amino silane coupling agent include N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane (KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd., TSL8345 manufactured by Toshiba Silicone Co., Ltd.), N-2 (aminoethyl) 3 -Aminopropyltrimethoxysilane (KBE-603 manufactured by Shin-Etsu Chemical Co., Ltd., TSL8340 manufactured by Toshiba Silicone), 3-aminopropyltriethoxysilane (KBE-603 manufactured by Shin-Etsu Chemical Co., Ltd., TSL8331 manufactured by Toshiba Silicone), 3-aminopropyltri Methoxysilane (Shin-Etsu Chemical KBM-903), 3-aminopropyltriethoxysilane (Shin-Etsu Chemical KBE-903), 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (Shin-Etsu) Chemicals KBE-9103), N-phenyl-3- Mino trimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-573), and the like.
Examples of the (meth) acryloyl-based silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane (KBM-502 manufactured by Shin-Etsu Chemical Co., Ltd., TSL8375 manufactured by Toshiba Silicone Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.). KBM-503 manufactured by Toshiba Silicone Co., Ltd. TSL8370), 3-methacryloxypropylmethyldiethoxysilane (KBE-502 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltriethoxysilane (KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-acryloxypropyltrimethoxysilane (KBE-5103 manufactured by Shin-Etsu Chemical Co., Ltd.), (3-acryloxypropyl) trimethoxysilane (SIA0200.0 manufactured by Gelest), methacryloxymethyltriethoxysilane (64 manufactured by Gelest) 2.0), it can be exemplified methacryloxy methyl trimethoxy silane (Gelest Inc. 6483.0) or the like.
Two or more different silane coupling agents can be used in combination. As the silane coupling agent used in the present invention, a silane coupling agent having an amino group is used to achieve the intended purpose of the present invention. Most preferred.

When any one or two or more of a silane coupling agent containing a sulfide group, a silane coupling agent having a (meth) acryloyl group, and a silane coupling agent containing a mercapto group are used in combination Although it may be added so that the content in the product is 1 to 20% by weight, it is added so as to be 1 to 10% by weight, more preferably 1 to 5% by weight. By adding 1% by weight or more, particularly the adhesion between the retardation layer and the substrate can be made sufficient. From the viewpoint of adhesion, good adhesion can be obtained even when the silane coupling agent is added in an amount of about 20% by weight. However, in order to obtain a better anti-moisture effect, it is preferable to add 1 to 10% by weight of the silane coupling agent. In particular, when the added amount is 1 to 5% by weight, it is possible to obtain a good anti-noisy effect without economic disadvantage.

When the silane coupling agent having an amino group is contained alone, or the silane coupling agent having an amino group, the silane coupling agent containing a sulfide group, the silane coupling agent containing a mercapto group, (meta) When one or more silane coupling agents having an acryloyl group are used in combination, they may be added so that the content in these total formulations is 0.01 to 20% by weight, It is more preferable to add so that it may become 0.01 to 5 weight%, It is more preferable to add 0.01 to 2 weight%, It is more preferable to add 1-2 weight%. By adding 0.01% by weight or more, particularly the adhesion between the retardation layer and the substrate can be made sufficient. From the viewpoint of adhesion, good adhesion can be obtained even if a silane coupling agent is added in an amount of about 20% by weight. However, in order to further obtain the effect of preventing mottle, it is preferable that the addition amount of the silane coupling agent having an amino group is 0.01 to 5% by weight. In particular, when the added amount is 0.01 to 2% by weight, it is possible to obtain a good anti-moy effect without economical disadvantage.

<About photopolymerization initiator>
When the liquid crystal composition of the present invention is polymerized and cured by irradiation with ultraviolet rays, a photopolymerization initiator may be added. As the photopolymerization initiator, a radical polymerization initiator can be used. The radical polymerization initiator is a compound that generates free radicals by the energy of ultraviolet rays, and includes, 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; peroxides . 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 polymerization 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.
The liquid crystal composition of the present invention blended with the photopolymerization initiator is applied onto a substrate to form a coating film, the crosslinkable liquid crystal molecules present in the coating film are aligned, and then the photopolymerization is started. By irradiating the coating film with light having a photosensitive wavelength of the agent, the aligned crosslinkable liquid crystal molecules can be well crosslinked.

The photopolymerization initiator needs to be added within a range that does not significantly impair the alignment of the liquid crystal, and is 0.01 to 15% by weight, preferably 0.1 to 10% by weight, in terms of the formulation of the liquid crystal composition. More preferably, it is added so as to be 0.5 to 10% by weight.

In addition to the photopolymerization initiator, other additives may be appropriately added to the liquid crystal composition of the present invention as long as the purpose is not impaired. For example, a polymerization inhibitor that can control the polymerization rate in a controllable manner may be added, and a sensitizer for assisting absorption of electromagnetic waves such as ultraviolet rays may be added. Examples of polymerization inhibitors include p-benzoquinone, hydroquinone, pt-butylcatechol, di-t-butyl paracresol, 2,4,6-tri-tert-butylphenol, hydroquinone monomethyl ether, α-naphthol or Acetanidin acetate or the like can be used.

<About solvent>
The liquid crystal composition of the present invention is a solute component such as a crosslinkable liquid crystal molecule or a specific silane coupling agent in a solvent having a specific evaporation rate of 5 to 30 when the evaporation rate of n-butyl acetate at 25 ° C. is 100. It is important that is dissolved. The evaporation rate of the solvent is such that when one type of solvent is used, the specific evaporation rate of the solvent is used, and when two or more types of solvents are mixed, the specific evaporation rate of the solvent after mixing is within 5-30. It is necessary to be.
Specifically, 1,2-dichlorobenzene (specific evaporation rate 12), ethylene glycol monoethyl ether acetate (specific evaporation rate 21), ethyl 3-ethoxypropionate (specific evaporation rate 12), 3-methyl-3- Methoxybutyl acetate (specific evaporation rate 10), cyclohexanone (specific evaporation rate 23), 4-hydroxy-4-methyl-2-pentanone (specific evaporation rate 14), 3-methoxybutyl acetate (specific evaporation rate 14), 2, 6-dimethyl-4-hebutanone (specific evaporation rate 18), ethylene glycol mono-tbutyl ether (specific evaporation rate 19), ethylene glycol monobutyl ether (specific evaporation rate 6), 3-methyl-3-methoxybutanol (specific evaporation rate) 5) and the like. The said solvent may be used independently or may be used in mixture of 2 or more types. In particular, when two or more solvents are mixed and used, the solubility of solute components such as cross-linkable liquid crystal molecules is insufficient or the other material to be coated is not used only by using a single solvent. When there is a possibility of being attacked, these disadvantages can be avoided by using a mixture of two or more solvents. The concentration of the liquid crystal composition solution varies depending on the solubility of the solute component used in the liquid crystal composition, the desired film thickness of the retardation film, and the like, but is usually in the range of 1 to 60% by weight, preferably 3 to 40% by weight. The amount of solvent is determined so that

<About the specific evaporation rate of the solvent>
The solvent used in the liquid crystal composition of the present invention preferably has a specific evaporation rate of 5 to 30 measured using a gravimetric method in which the evaporation rate of n-butyl acetate at 25 ° C. is 100, and 10 to 30 It is more preferable that it is, and it is especially preferable that it is 10-25. When the specific evaporation rate of the solvent is 5 to 30, when the retardation layer is formed from the liquid crystal composition of the present invention prepared using the solvent, the formation of haze unevenness is prevented well on the surface of the retardation layer. The If the specific evaporation rate is in the range of 10 to 30, after the liquid crystal composition of the present invention is applied on a substrate to form a coating film, the coating film is dried by heating or dried under reduced pressure and is present in the coating film. When the solvent to be evaporated is evaporated, unevenness in drying is difficult to occur, and it is possible to satisfactorily prevent the occurrence of unevenness on the surface of the coating film, that is, the surface of the retardation layer. When the specific evaporation rate is 10 or more, it is possible to prevent the liquid crystal composition applied to the substrate surface from being dried for a long time, and the remaining dryness is reduced. Is inferred. On the other hand, with a solvent having a specific evaporation rate of 30 or less, it is possible to uniformly dry the liquid crystal composition applied to the substrate surface at an appropriate rate, thereby preventing or reducing the occurrence of drying unevenness. Can do. Thereby, it is guessed that generation | occurrence | production of haze unevenness is suppressed. If the specific evaporation rate is in the range of 10 to 30, the above haze is likely to be suitably prevented regardless of the type of solvent. Furthermore, when the specific evaporation rate is in the range of 10 to 25, the effect of preventing unevenness is remarkable, which is particularly preferable.

<About the dynamic surface tension of the solvent>
In the liquid crystal composition solution of the present invention, the dynamic surface tension of the solvent is preferably in the range of 27 mN / m to 50 mN / m with a surface lifetime of 10 ms. If it is a solvent which has the dynamic surface tension of the said range, it will be easy to obtain the dynamic surface tension of the suitable range of the liquid-crystal composition solution mentioned later.
As described above, the solvent in the liquid crystal composition solution of the present invention may be a mixture of two or more solvents. In such a case, even if any or all of the solvents to be mixed are out of the above-mentioned preferable dynamic surface tension value range, the dynamic surface tension of the solvent after mixing should be in the above-mentioned preferable value range. .

<Dynamic surface tension of liquid crystal composition solution>
In the liquid crystal composition solution of the present invention described above, the dynamic surface tension of the liquid crystal composition solution itself is preferably in the range of 31 mN / m to 50 mN / m with a surface life of 10 ms. If it is a liquid crystal composition solution exhibiting a dynamic surface tension in the above preferred range, it is possible to more effectively prevent the occurrence of fog on the retardation layer formed using this liquid crystal composition solution.
Although such a mechanism is not yet clear, when the dynamic surface tension of the liquid crystal composition solution of the present invention is within 50 mN / m, the liquid crystal composition solution is applied on a substrate to form a coating film. It is conceivable that the unevenness of the coating film surface that naturally occurs in the coating process is easily adjusted smoothly by its own gravity, making it easy to obtain a smooth coating film surface. On the other hand, if the dynamic surface tension of the liquid crystal composition solution is 31 mN / m or more, it is considered that the smoothness of the coating film surface before drying is easily maintained without being influenced by the wind pressure of the outside air. By obtaining the smoothness of the surface of the coating film, it is presumed that the effect of preventing mottle is easy to obtain due to a synergistic effect with the solvent having an evaporation rate within the above preferred range.

In this specification, “dynamic surface tension” means the surface tension of a moving liquid, and in this specification, this is measured by the maximum bubble pressure method. The maximum bubble pressure method is a method for determining the surface tension of a liquid by measuring the pressure of bubbles generated in the liquid from the tip of a capillary. In this measurement, the pressure is measured immediately after the bubble surface is formed, so that it is possible to obtain a more dynamic surface tension, that is, a dynamic surface tension. In this specification, this elapsed time is “ A very small value of “surface life” of 10 ms is adopted. Such dynamic surface tension can be measured using a bubble pressure dynamic surface tension meter (trade name: BP-2, manufactured by KRUSS).

Measurement of dynamic surface tension using the above bubble pressure dynamic surface tension meter,
Capillary diameter: φ0.228mm
Measurement temperature: 23 ° C
Liquid volume: 60cc
Surface life: 10ms
Capillary immersion depth: 10mm
Setting density: 1.00 g / cm ³
Can be performed under the following conditions. An outline of the bubble pressure dynamic surface tension meter is shown in FIG.

  The dynamic surface tension of the liquid crystal composition defined in the present specification means a value when subjected to a coating process by a slit die coating method, and is present in a concentrated state, for example, during production and distribution of the liquid crystal composition. It does not mean the value in the case of doing.

<Dynamic viscosity of liquid crystal composition solution>
The liquid crystal composition solution of the present invention described above preferably has a dynamic viscosity in the range of 2.0 mPa · s to 4.0 mPa · s when the shear rate is 100 s ⁻¹ . If the liquid crystal composition solution has a dynamic viscosity in the above preferred range, when the retardation layer is formed using the liquid crystal composition solution, the surface of the retardation layer can be satisfactorily prevented. . Although such a mechanism is not yet clear, it is considered that a liquid crystal composition solution exhibiting the above-mentioned preferable range of dynamic viscosity tends to easily obtain the above-described preferable range of dynamic surface tension.

The dynamic viscosity of the liquid crystal composition of the present invention is determined using, for example, a double cylinder type rheometer (manufactured by TA Instruments Japan Co., Ltd., trade name: ARES) with a share rate of 100 s ⁻¹ , 23 ° C. The value measured at a liquid volume of 10 cc can be used. An outline of the double cylindrical rheometer is shown in FIG.

  Adjustment of the dynamic viscosity of the liquid crystal composition can be performed by adjusting the concentration of the mixture of the liquid crystal composition solution, and can also be performed by selecting a solvent to be used.

<About the color filter of the present invention>
The liquid crystal composition of the present invention can be used for forming a retardation layer for adjusting a viewing angle in a liquid crystal display device, and the retardation layer can be provided, for example, in a color filter of a liquid crystal display device. Hereinafter, a color filter provided with a retardation layer will be exemplarily described based on the drawings.

FIG. 1 is a color filter 1 showing an embodiment of the present invention. In order to form the color filter 1, first, the alignment film 5 is provided on the transparent substrate 2, and then the liquid crystal composition solution of the present invention is applied on the alignment film 5, and the crosslinking contained in the liquid crystal composition solution. The retardation layer 3 is formed by aligning and curing the liquid crystal molecules. Furthermore, after providing the protective layer 10 on the upper surface of the retardation layer 3, the colored layer 4 is formed. And after providing the protective layer 10 also on the upper surface of the colored layer 4, the several spacer 11 comprised with the hardened | cured material of the ionizing radiation curable resin composition is arranged at arbitrary space | intervals, and the color filter 1 of this invention. Is formed. In addition, although the protective layer 10 was formed before and after the colored layer 4 in the color filter 1 shown in FIG. 1, formation of a protective layer does not necessarily need to be performed in this invention, and either one or both shown by drawing are carried out. Can be omitted. The spacer 11 may be omitted.
It is important that the color filter of the present invention includes a colored layer and a retardation layer formed using the liquid crystal composition of the present invention on a transparent substrate. As a result, the retardation layer provides a color filter having a retardation layer that exhibits good adhesion to the base material surface (that is, the surface of the transparent substrate or the colored layer surface) and that is well-prevented by the unevenness. be able to.

<About transparent substrates>
The transparent substrate 2 has optical transparency and is preferably optically isotropic, but a region having optical anisotropy or light shielding properties can be locally provided as necessary. The light transmittance can be appropriately selected according to the use of the color filter. Specifically, it consists of an inorganic base material such as glass, silicon, or quartz, or an organic base material as listed below. Examples of organic base materials include acrylics such as polymethyl methacrylate, polyamide, polyacetal, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, or syndiotactic polystyrene, polyphenylene sulfide, polyether ketone, polyether ether Ketone, fluororesin, polyether nitrile, etc., polycarbonate, modified polyphenylene ether, polycyclohexene, polynorbornene resin, etc., or polysulfone, polyethersulfone, polypropylene, polyarylate, polyamideimide, polyetherimide, polyether Examples of such materials include ketones and thermoplastic polyimide. Made of a tick can also be used. Also about the thickness of the transparent substrate 2, the thing of about 5 micrometers-3 mm is used according to a use, for example.

<About alignment film>
Prior to forming the retardation layer 3 on the transparent substrate 2 using the liquid crystal composition of the present invention, the alignment film 5 is provided on the transparent substrate 2. Although the alignment film 5 is not necessarily essential, the alignment film 5 is preferably provided because the alignment film 5 facilitates control of the alignment direction of the liquid crystal molecules. The alignment film 5 can be formed by applying and drying an alignment resin such as polyimide on the transparent substrate 2 and then performing a rubbing process or a photo-alignment process, but the rubbing process or the photo-alignment process is not necessarily performed. Also good. The alignment film 5 can also be formed by obliquely depositing silicon oxide on the transparent substrate 2. A commercially available alignment film material can be used as the alignment film material used in the present invention. Specifically, alignment film material (Sunever) manufactured by Nissan Chemical Co., Ltd., alignment film material (QL, LX series) manufactured by Hitachi Chemical DuPont Microsystems Co., Ltd., alignment film material (AL series) manufactured by JSR Co., Ltd. ), An orientation agent (Rixon Aligner) manufactured by Chisso Corporation can be used.

<About retardation layer>
The retardation layer 3 can be formed by applying a solution of the liquid crystal composition of the present invention on the alignment film 5 provided as necessary to form a coating film, and drying and curing the coating film. .
Examples of the method for applying the liquid crystal composition solution on the substrate include various printing methods such as gravure printing, offset printing, letterpress printing, screen printing, transfer printing, electrostatic printing, and plateless printing. , 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 Can be used as appropriate.
After a liquid crystal coating film is formed on the alignment film 5, a predetermined orientation is imparted to the crosslinkable liquid crystal molecules contained in the liquid crystal coating film to crosslink and polymerize the crosslinkable liquid crystal molecules.

  In particular, by fixing the crosslinkable liquid crystal molecules by vertical alignment (homeotropic alignment), the optical axis of the liquid crystal molecules faces the normal direction of the retardation layer and an extraordinary ray refractive index larger than the ordinary ray refractive index. A so-called positive C plate having a normal direction of the retardation layer can be formed. In this case, a vertical alignment film may be formed in advance on the application surface of the liquid crystal composition, or a vertical alignment aid may be mixed with the liquid crystal composition.

  Examples of vertical alignment aids include surface coupling agents having vertically aligned alkyl or fluorocarbon chains such as lecithin and quaternary ammonium surfactants, HTAB (hexadecyl-trimethylammonium bromide), DMOAP (N, N-dimethyl-N-octadecyl-3-aminopropyltrimethoxysilyl chloride), N-perfluorooctylsulfonyl-3-aminopropyltrimethylammonium iodide, long-chain alkyl alcohol or silane polymer.

Further, as a retardation layer exhibiting another orientation, the so-called negative C, in which the optical axis of liquid crystal molecules is parallel to the retardation layer and has an extraordinary ray refractive index smaller than the ordinary ray refractive index in the normal direction of the retardation layer. When the plate is formed, a chiral nematic liquid crystal having cholesteric regularity obtained by further adding the above-described chiral agent to the liquid crystal composition can be suitably used as the crosslinkable nematic liquid crystal.

  Further, when forming a so-called positive A plate in which the optical axis of liquid crystal molecules is parallel to the retardation layer and has an extraordinary ray refractive index larger than the ordinary ray refractive index in the in-plane direction of the retardation layer, rubbing treatment, etc. The cross-linkable liquid crystal molecules are loaded with the alignment regulating force by the horizontal alignment film subjected to the above, or the molecules are horizontally aligned by adding a leveling agent for suppressing the surface free energy of the cross-linkable liquid crystal molecules against the air interface. be able to.

After the liquid crystal composition is applied, the solvent is removed by heating. The crosslinkable liquid crystal molecules in the liquid crystal composition can be aligned in a certain direction by using the heat at this time. Although heating temperature changes with differences in each raw material contained in a liquid crystal composition, it is 70-120 degreeC normally, and heating time is about 2 to 30 minutes. For example, homeotropic alignment is imparted to crosslinkable liquid crystal molecules by heating the liquid crystal coating film by means of heating with infrared rays, etc., and the temperature of the liquid crystal coating film is changed to the crosslinkable liquid crystal material contained therein. Can be carried out by setting the temperature to be the liquid crystal phase (liquid crystal phase transition temperature) or higher and lower than the temperature (isotropic phase transition temperature) at which the crosslinkable liquid crystal is isotropic (liquid phase).

Another method for vaporizing the solvent in the liquid crystal composition solution and simultaneously homeotropically aligning the crosslinkable liquid crystal molecules contained in the liquid crystal composition is a pressure of about 1.5 × 10 ^{−1 in a} sealed container. There is a method in which the solvent in the liquid crystal composition solution is vaporized by reducing the pressure to less than Torr and drying under reduced pressure.
In the vacuum drying treatment, the coating film can be brought into a supercooled state by bringing the coating film into a reduced pressure state, and the crosslinkable liquid crystal molecules contained in the coating film can be homeotropically aligned. Next, the substrate having the coating film is brought to about room temperature while maintaining the homeotropic alignment state. Thereby, the crosslinkable liquid crystal molecules can be efficiently maintained in a homeotropic alignment state until a crosslinking reaction is performed in the subsequent steps. Furthermore, the coated substrate may be baked in order to remove the remaining solvent and to ensure the orientation of the crosslinkable liquid crystal molecules contained in the coated layer. Although a baking method is not specifically limited, For example, a coating board | substrate is installed on a hotplate and it can bake at the temperature of 70 to 120 degreeC for 2 to 30 minutes.

Next, by irradiating the liquid crystal coating film with light having a photosensitive wavelength such as a cross-linked liquid crystal molecule or a photopolymerization initiator contained in the liquid crystal composition, polymerization of the cross-linkable liquid crystal molecules provided with alignment in the liquid crystal coating film ( Cross-linking polymerization) can proceed. At this time, the wavelength of light applied to the liquid crystal coating film is appropriately selected according to the type of crosslinkable liquid crystal molecules contained in the liquid crystal composition and the type of photopolymerization initiator added. The light applied to the liquid crystal coating film is not limited to monochromatic light, and may be light having a certain wavelength range including the photosensitive wavelength of the liquid crystal composition. More specifically, it is appropriately selected according to the absorption wavelength of the photopolymerization initiator contained in the liquid crystal composition. For example, the crosslinkable liquid crystal molecules can be crosslinked and cured by irradiation with active radiation such as ultraviolet rays. Ultraviolet rays having a wavelength of about 200 to 500 nm are irradiated, and high-pressure mercury lamps, xenon lamps, metal halide lamps and the like are used as ultraviolet ray sources. The amount of irradiation light varies depending on the type and composition of the crosslinkable liquid crystal molecules and the type and amount of the photopolymerization initiator, but is usually about 10 to 3000 mJ / cm ² . After the ultraviolet irradiation, further heat treatment is performed to crosslink unreacted cross-linkable liquid crystal molecules that could not be cured by photopolymerization, and polymerized into a three-dimensional structure in a state of being arranged in a certain direction to form the retardation layer 3. . The temperature and time for the heat treatment after the ultraviolet irradiation depend on the type and composition of the crosslinkable liquid crystal, but are usually 150 ° C. to 260 ° C. for 10 minutes to 60 minutes. The thickness of the retardation layer 3 obtained by crosslinking and curing the applied liquid crystal composition is not particularly limited as long as a desired retardation amount can be obtained. About 5-10 micrometers is preferable.

<About the colored layer>
Next, the colored layer 4 will be described. The colored layer 4 forms a black matrix 6 that blocks visible light in a predetermined wavelength region on the transparent substrate 2, and then a red (R) sub-pixel 7 that is a colored pixel that transmits visible light in the predetermined wavelength region, green A (G) sub-pixel 8 and a blue (B) sub-pixel 9 are sequentially provided.
The black matrix 6 is also referred to as red (R) sub-pixel 7, green (G) sub-pixel 8, and blue (B) sub-pixel 9 (hereinafter simply referred to as “colored pixels 7, 8, 9”) that are colored pixels. ) Prevents overlapping of each other and fills the gaps between the colored pixels to suppress leakage of light from adjacent colored pixels (leakage light). Therefore, the black matrix 6 is formed on the transparent substrate 2 so as to partition the area corresponding to the position where the colored pixels 7, 8, 9 are planned to be arranged in a plan view for each colored pixel. The colored pixels 7, 8, and 9 are arranged so as to cover the areas partitioned by the black matrix 6 in plan view.
The black matrix 6 can be formed, for example, by patterning a light-shielding or light-absorbing metal thin film such as a metal chromium thin film or a tungsten thin film on the surface of the transparent substrate 2 in a predetermined shape. The black matrix 6 can also be formed by printing an organic material such as a black resin in a predetermined shape by an inkjet method or the like.

The colored pixels 7, 8, and 9 formed after the black matrix 6 are formed by arranging colored pixels that transmit light of each color wavelength band in a predetermined pattern for each of red, green, and blue. As arrangement forms of the red (R) sub-pixel 7, the green (G) sub-pixel 8, and the blue (B) sub-pixel 9 constituting the coloring pixel, various arrangement patterns such as a stripe type, a mosaic type, and a triangle type are provided. Can be selected. More specifically, each colored pixel 7, 8, 9 is formed by patterning a coating film of a coloring material dispersion in which a coloring material is dispersed in a solvent into a predetermined shape by, for example, a photolithography method. be able to. As another method, it can be formed by applying a coloring material dispersion in a predetermined shape for each of the colored pixels 7, 8, and 9 by an ink jet method or the like. In addition, instead of the red (R) sub-pixel 7, the green (G) sub-pixel 8, and the blue (B) sub-pixel 9, a colored pixel that transmits light in the complementary wavelength band of each color is used. Is also possible.
The colored layer 4 in the present invention is not limited to the case where the three-color sub-pixels exemplified above are provided. For example, it may be configured using colored pixels of four or more colors, or may be configured with a single color or two colors. In accordance with this, the black matrix 6 can be omitted.

<About protective layer>
Moreover, the protective layer 10 can be provided before forming the colored layer 4 if necessary. The protective layer 10 is made of a transparent resin material made of a material such as an acrylic, amide or ester polymer containing a polyfunctional acrylate, or a material such as an acrylic, amide or ester polymer containing a polyfunctional epoxy. It can be formed by applying a transparent resin paint to the surface of the substrate, and further drying and curing it. For the curing of the protective layer, for example, a method of irradiating with UV light can be employed according to the properties of the transparent resin material. The protective layer 10 can be further provided on the surface of the colored layer 4 as necessary.

<About spacer>
A spacer 11 is further provided on the upper surface of the colored layer 4 or the protective layer 10 to obtain the color filter 1. The spacer 11 is formed by applying a photocurable photosensitive paint made of an acrylic, amide or ester polymer containing a polyfunctional acrylate on the retardation layer 3, the colored layer 4 or the protective layer 10. The coating is dried, and the paint is exposed and cured through a mask pattern corresponding to the position where the spacer 11 is to be formed. Then, the uncured portion is removed by etching, and the whole is baked.

  FIG. 2 shows a different embodiment of the color filter 1 of the present invention. The color filter 1 shown in FIG. 2 has a black matrix 6 formed on a transparent substrate 2, and then a red (R) sub-pixel 7, a green (G) sub-pixel 8, and a blue (B) sub-pixel 9 are sequentially provided. After forming the colored layer 4 and providing the alignment layer 5 on the surface of the colored layer 4 as necessary, the retardation layer 3 is provided with a liquid crystal composition, and further a protective layer 10 and a spacer 11 are provided on the surface as necessary. Are sequentially provided. As apparent from FIGS. 1 and 2, in the color filter of the present invention, the retardation layer and the colored layer provided on the transparent substrate may be formed in the order of the transparent substrate, the retardation layer, and the colored layer. Alternatively, a transparent substrate, a colored layer, and a retardation layer may be formed in this order. When the retardation layer is formed using the liquid crystal composition of the present invention, when formed on a transparent substrate, adhesion to the transparent substrate is improved, and when formed on a colored layer The adhesion to the colored layer is improved. In addition, when an alignment film is provided before the retardation layer is formed, the adhesion between the alignment film and the retardation layer is improved.

As in the color filter 1 of the present invention shown in FIG. 1 or FIG. 2, a liquid crystal composition is applied on a transparent substrate 2 or a colored layer 4, and the crosslinkable liquid crystal molecules in the composition are aligned and fixed to obtain a retardation. By forming the layer 3, it is possible to obtain a so-called in-cell type retardation layer 3 formed on the inside of the two substrates sandwiching the driving liquid crystal cell. Thereby, compared to the conventional method of attaching a retardation film externally formed into a sheet shape to a transparent substrate with an adhesive or the like, the entire color filter 1 can be made thinner, and light scattering by the adhesive can be prevented, Since the retardation layer 3 is protected by the transparent substrate 2, effects such as improvement of heat resistance and suppression of moisture absorption deformation can be obtained.

<Regarding Adhesion Evaluation Method of Retardation Layer>
Further, in the present invention that can improve the adhesion between the substrate and the retardation layer, when the retardation layer is formed on the substrate surface using the liquid crystal composition of the present invention, The peel strength of the retardation layer is particularly preferably 1 or less based on the evaluation standard of JISK5600-5-6. If the evaluation standard is a retardation layer of 1 or less, when the retardation layer is used in a liquid crystal display device or the like, the adhesiveness with the base material is high and sufficient adhesion reliability can be obtained over a long period of time. is there. Therefore, in the color filter 1 of this invention, it is preferable that the peeling strength of the phase difference layer 3 after an accelerated life test is 1 or less by the evaluation criteria of JISK5600-5-6.

The heating life test is performed for 1 hour at 100 ° C. and 100% RH using an accelerated life tester EHS-411M manufactured by Tabai. A specific peel test was performed in a grid pattern in each direction on a sample substrate coated with the retardation layer 3 in an environment of a temperature of about 23 ± 2 ° C. and a humidity of about 50 ± 5% after the accelerated life test. Cut 6 times at 1 mm intervals to provide 5 × 5 grids. Next, a tape having an adhesive force of 10 ± 1 N per width of 25 mm and a width of about 25 mm is used. The tape is pasted on the grid so that the longitudinal direction of the tape is parallel to any side of the grid, and is rubbed with a finger. . Further, the edge of the tape is picked up, and the state of the lattice after being peeled off for 0.5 to 1 second at an angle of about 60 ° with respect to the non-adhesive surface of the tape is evaluated in the following six stages.

Evaluation criteria 0: A state in which the edge of the cut is completely smooth and there is no peeling of any lattice.
Evaluation criteria 1: Although there is a small peeling of the coating film at the intersection of cuts, it is less than 5% that is affected by the crosscut part.
Evaluation criteria 2: The coating film is peeled along the edge of the cut and / or at the intersection. The cross cut part is clearly affected by more than 5%, but not more than 15%.
Evaluation criteria 3: The coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eyes are partially or completely peeled off. The cross-cut part is clearly affected by more than 15% but not more than 35%.
Evaluation criteria 4: The coating film is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely peeled off. The cross-cut portion is clearly affected by more than 35% but not more than 65%.
Evaluation Criteria 5: Any degree of peeling that cannot be classified even by classification 4 (including a state where the entire surface of the lattice is peeled).

In order to set the peel strength of the retardation layer 3 after an accelerated life test of 1 hour at a temperature of 100 ° C. and a humidity of 100% to 1 or less according to the evaluation standard of JISK5600-5-6,
(1) The retardation layer is composed of 99.89 to 70% by weight (vs. compound equivalent) (meth) acryloyl group-containing crosslinkable liquid crystal and 0.1 to 10% by weight (vs. compound equivalent) light. (2) A retardation layer formed by photocuring and baking a liquid crystal composition containing a polymerization initiator and an amino group-containing silane coupling agent in an amount of 0.01 to 20% by weight (compared to the formulation). 98.9 to 70% by weight (vs. compound equivalent) (meth) acryloyl group-containing crosslinkable liquid crystal, 0.1 to 10% by weight (vs. compound equivalent) photopolymerization initiator, and 1 to 20 (3) A retardation layer is formed by photocuring and baking a liquid crystal composition containing a sulfide group-containing silane coupling agent in an amount of wt. (Meth) acryloyl group-containing crosslinkable liquid crystal and 0.1 to 10% by weight (compared to compound) (4), a liquid crystal composition containing a photopolymerization initiator of (product equivalent value) and 1 to 20% by weight (vs. compound equivalent value) of a mercapto group-containing silane coupling agent is photocured and baked. The retardation layer is composed of 98.9 to 70% by weight (vs. compound equivalent) (meth) acryloyl group-containing crosslinkable liquid crystal and 0.1 to 10% by weight (vs. compound equivalent) photopolymerization initiator. And (5) retardation layer formed by photocuring and baking a liquid crystal composition containing 1 to 20% by weight (vs. compound equivalent value) (meth) acryloyl group-containing silane coupling agent. 89-70% by weight (vs. compound equivalent) (meth) acryloyl group-containing crosslinkable liquid crystal, 0.1-10% by weight (vs. compound equivalent) photopolymerization initiator, and amino group-containing silane Coupling agent, sulfide group-containing silane coupling agent, mercapto group-containing A liquid crystal composition comprising 0.01 to 20% by weight (based on a compound) of two or more silane coupling agents selected from a silane coupling agent and a (meth) acryloyl group-containing silane coupling agent. Examples of the method include photocuring and baking.
However, from the viewpoint of moyamura, it is preferable that the amount of the silane coupling agent added is 5% by weight or less.

<About the evaluation method of occurrence of haze on the surface of the retardation layer>
In addition, when the liquid crystal composition of the present invention is used to form a retardation layer, the occurrence of haze on the surface of the retardation layer is prevented. The presence or absence of the above-mentioned moire unevenness can be evaluated by a surface unevenness inspection described below. That is, in the surface unevenness inspection, when the S / N ratio of the light intensity is 2 or less, it is preferable because the occurrence of fog unevenness on the surface of the retardation layer is well prevented. The surface unevenness inspection can be performed according to the description in Japanese Patent No. 3631856.

The surface unevenness inspection will be described more specifically. In the inspection, in the retardation layer formed on the base material, by measuring the thickness of the retardation layer with monochromatic light as inspection light, a portion where there is no unevenness. Can be detected as a noise level (N), a spot where unevenness occurs is detected as a signal level (S), and the presence / absence of unevenness can be evaluated as an S / N ratio.

For the detection of the thickness, an inspection apparatus 101 shown in FIG. 8 was used. The inspection apparatus 101 includes a transport unit 102 for transporting a test body 110 having a retardation layer formed on a base material, and monochromatic light, which is inspection light, to the test body 110 transported on the transport unit 102. From the monochromatic light source 103 for irradiating at the incident angle θ ₁ , the photodetector 104 for detecting the light reflected at the reflection angle θ ₂ out of the reflected light reflected by the test body 110, and the photodetector 104. Are provided with an inspection processing unit 105 that electrically processes the image signal to detect unevenness of the transparent film, and an image display unit 106 for displaying an image processed by the inspection processing unit 105.

The conveyance part 102 is for conveying the test body 110 at a fixed speed.

The monochromatic light source 103 is for irradiating the test body 110 with monochromatic light as inspection light at a predetermined incident angle θ _1. For example, a sodium lamp (589 nm), a laser light transmission type high-pressure mercury lamp, a gas discharge For example, light that has been converted to a single wavelength by an optical filter can be used. The optical tester 104 is for detecting the reflected light reflected by the test body 110, and for example, a CCD line sensor, a CCD area sensor, or the like can be used.

When the reflected light (1) reflected on the surface of the retardation layer in the test body 110 and the reflected light (2) reflected on the back side interface of the retardation layer in the test body 110 are measured using the inspection apparatus, Interference occurs between the reflected light (1) and the reflected light (2). Such interference varies between a portion where unevenness occurs in the retardation layer and a portion where unevenness does not occur. This change in interference can be detected as a change in the intensity of reflected light received by the optical inspection device 104. Therefore, the image signal from the light detector 104 is electrically processed by the inspection processing unit 105 to obtain the intensity distribution of the reflected light, and a portion of the specimen 110 where the thickness of the retardation layer is uneven is detected by a predetermined amount or more of light. It can be detected as a region of the retardation layer in which an intensity change occurs. In addition, this apparatus scans the whole upper surface of the test pair 110, and measures and evaluates the light intensity ratio in the whole retardation layer surface in the test body 110.

The S / N ratio shown in the present invention was measured under the following measurement conditions using the following inspection apparatus and method.
Inspection condition Monochromatic light source: Sodium lamp (98% of radiation is 589 nm) (Sox manufactured by PHILIPS Co., Ltd.)
Photodetector: CCD line sensor (FH1024B manufactured by NED)
Glass substrate transport speed: 2.4 m / min Inspection light incident angle θ ₁ : 60 ° (photodetector installation angle)
Inspection light reflection angle θ ₂ : 45 ° (detector installation angle)

<About the liquid crystal display device of the present invention>
The color filter 1 of the present invention can be used as a display side substrate of a liquid crystal display device. The liquid crystal display device 12 shown in FIG. 3 uses the color filter 1 of the present invention for the display side substrate 13 installed on the viewer side (corresponding to the upper part in the figure), and the display side substrate 13 and the liquid crystal drive side substrate 14 are separated from each other. The liquid crystal cell 16 is configured by facing a spacer 11 and enclosing a driving liquid crystal material 15 therebetween. Here, the retardation layer 3 is disposed so as to be sandwiched between the transparent substrate 2 of the color filter 1 and the transparent substrate 31 constituting the liquid crystal driving side substrate 14, and forms a so-called in-cell type.
A functional layer 20 in which a transparent conductive film 21 and a positive A plate 22 are sequentially laminated is formed on the side of the transparent substrate 2 opposite to the colored layer 3. A linear polarizing plate 23 is laminated on the outer surface of the display side substrate 13, and a linear polarizing plate 32 is laminated on the outer surface of the liquid crystal driving side substrate 14.

  When the liquid crystal display device 12 is in the IPS mode, the linearly polarizing plate 23 of the display side substrate 13 and the linearly polarizing plate 32 of the liquid crystal driving side substrate 14 are arranged so that their transmission axes are orthogonal to each other.

  The liquid crystal driving side substrate 14 is provided with a driving circuit 33 on the in-cell side of the transparent substrate 31 (side where the driving liquid crystal material 15 is sealed), and a driving electrode 34 by which the voltage load is controlled. ing.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1
Using the compounds (a) to (d) shown in the following chemical formula 7, a composition A having the following composition was prepared. Composition A was prepared by mixing the materials listed below according to the description in JP-T-2004-524385. In addition, the weight ratio of each substance in the composition A shown below is the weight ratio of each substance to the total weight of the composition A.

(Composition A)
Compound (a) 32.67% by weight
Compound (b) 18.67% by weight
Compound (c) 21.00% by weight
Compound (d) 21.00% by weight
Dodecanol 1.02% by weight
BHT 0.04% by weight
Irgacure 907 5.60% by weight

Next, after adding 1% by weight (based on the equivalent of the compound) of 3-mercaptopropylmethyldimethoxysilane (KBM-802 manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent to the composition A, the concentration is 20%. The resulting solution was dissolved in 3-methoxybutyl acetate (specific evaporation rate 14) to obtain a liquid crystal composition solution of the present invention.
Next, a glass substrate (Corning 1737 glass) having a thickness of 100 × 100 mm and a thickness of 0.7 mm was prepared as a suitable transparent substrate.
The glass substrate was set on a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), and the liquid crystal composition was spin-coated on the glass substrate, and then dried under reduced pressure. Next, ultraviolet light having a wavelength of 365 nm is irradiated at 20 mW / cm ² for 10 seconds with an ultraviolet irradiation device having an ultrahigh pressure mercury lamp (manufactured by Harrison Toshiba Lighting Co., Ltd., “trade name TOSCURE 751”) to crosslink the crosslinkable liquid crystal. The retardation layer of the present invention having a thickness of 1.0 μm was formed by baking for 30 minutes using an oven.

(Evaluation 1)
The alignment state of the crosslinkable liquid crystal molecules constituting the retardation layer was evaluated by measuring the retardation generated when light having a wavelength of 589 nm was transmitted through the retardation layer as follows. For measurement of the phase difference, RETS-1250AV manufactured by Otsuka Electronics Co., Ltd. was used.

  In measuring the phase difference, as shown in FIG. 4, the phase difference assumed an x axis and a y axis perpendicular to each other on the surface of the phase difference layer, and a z axis perpendicular to the x axis and the y axis. And the phase difference of the optical element was measured about the z-axis direction and the direction inclined in the x-axis direction and the y-axis direction with respect to the z-axis.

  The measurement result of the phase difference in Example 1 is shown in FIG. When measured in the direction tilted in the x-axis direction, when measured in the direction tilted in the y-axis direction, in any case, the phase difference generated in the optical element shows symmetry with respect to the z-axis. Thus, it was possible to evaluate that the crosslinkable liquid crystal molecules contained in the retardation layer of the optical element were homeotropically aligned.

(Evaluation 2)
Using the above-described six-step evaluation, the retardation of the retardation layer in the color filter of Example 1 after an accelerated life test of 1 hour at a temperature of 100 ° C. and a humidity of 100% was determined according to JISK5600-5-6. The evaluation was as follows.
Evaluation criteria 0 or 1
Evaluation criteria 2 or 3 △
Evaluation criteria 4 or 5

In Example 1, the evaluation of the substrate adhesion in the evaluation 2 was “good”. That is, it can be said that good results were obtained for the adhesion of the retardation layer to the glass substrate.

(Evaluation 3)
The surface unevenness inspection of Example 1 was performed in accordance with the method for evaluating the occurrence of mottle unevenness on the upper surface of the retardation layer. The results were evaluated as follows.
S / N ratio is less than 2.0 ...
S / N ratio is 2.0 or more and 2.8 or less ... △
S / N ratio exceeds 2.8

Evaluation of S / N ratio calculated | required from the intensity | strength change of the reflected light of Example 1 was (circle).
From the above, in the phase difference layer with homeotropic alignment of Example 1, both the substrate adhesion force and the evaluation of occurrence of unevenness are good, the adhesion to the substrate is good, and the occurrence of unevenness on the upper surface of the retardation is well prevented. It was confirmed that

Example 2
A retardation layer was produced in the same manner as in Example 1 except that cyclohexanone (specific evaporation rate 23) was used as a solvent. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

Evaluation in evaluation 2 of Example 2 was ○. Moreover, the evaluation in evaluation 3 was also (circle). Therefore, in the phase difference layer with homeotropic alignment of Example 2, both the substrate adhesion force and the evaluation of occurrence of unevenness are good, the adhesion to the substrate is good, and the occurrence of unevenness on the upper surface of the retardation is well prevented. Was confirmed.

Example 3
A retardation layer was produced in the same manner as in Example 1 except that ethyl 3-ethoxypropionate (specific evaporation rate 12) was used as a solvent. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

The evaluation in evaluation 2 of Example 3 was ○. Moreover, the evaluation in evaluation 3 was also (circle). Therefore, in the homeotropically aligned retardation layer of Example 3, both the substrate adhesion force and the evaluation of occurrence of mottle are good, the adhesiveness to the substrate is good, and the occurrence of mottle on the upper surface of the retardation is well prevented. Was confirmed.

Example 4
A retardation layer was produced in the same manner as in Example 1 except that 1% by weight of bis (triethoxysilylpropyl) tetrasulfide (KBE-846 manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a silane coupling agent. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

  The evaluation in evaluation 2 of Example 4 was ○. Moreover, the evaluation in evaluation 3 was also (circle). Therefore, in the homeotropically aligned retardation layer of Example 4, both the substrate adhesion and the evaluation of occurrence of unevenness are good, the adhesion to the substrate is good, and the occurrence of unevenness on the upper surface of the retardation is well prevented. Was confirmed.

Example 5
A retardation layer was produced in the same manner as in Example 4 except that cyclohexanone (specific evaporation rate 23) was used as a solvent. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

The evaluation in evaluation 2 of Example 5 was ○. Moreover, the evaluation in evaluation 3 was also (circle). Therefore, in the homeotropically aligned retardation layer of Example 5, both the substrate adhesion and the evaluation of occurrence of unevenness are good, the adhesion to the substrate is good, and the occurrence of unevenness on the upper surface of the retardation is well prevented. Was confirmed.

Example 6
A retardation layer was produced in the same manner as in Example 4 except that ethyl 3-ethoxypropionate (specific evaporation rate 12) was used as a solvent. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

  The evaluation in evaluation 2 of Example 6 was ○. Moreover, the evaluation in evaluation 3 was also (circle). Therefore, in the homeotropically aligned retardation layer of Example 6, both the substrate adhesion and the evaluation of the occurrence of unevenness are good, the adhesiveness to the substrate is good, and the occurrence of unevenness on the upper surface of the retardation is well prevented. Was confirmed.

Example 7
Example 1 was used except that 0.01% by weight of 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (KBE-9103 manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a silane coupling agent. A retardation layer was produced. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

The evaluation in Evaluation 2 of Example 7 was ○. Moreover, the evaluation in evaluation 3 was also (circle). Therefore, in the homeotropically aligned retardation layer of Example 7, both the substrate adhesion and the evaluation of occurrence of unevenness are good, the adhesion to the substrate is good, and the occurrence of unevenness on the upper surface of the retardation is well prevented. Was confirmed.

Example 8
A retardation layer was produced in the same manner as in Example 7 except that cyclohexanone (specific evaporation rate 23) was used as a solvent. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

The evaluation in evaluation 2 of Example 8 was ○. Moreover, the evaluation in evaluation 3 was also (circle). Therefore, in the homeotropically aligned retardation layer of Example 8, both the substrate adhesion and the evaluation of occurrence of mottle are good, the adhesion to the substrate is good, and the occurrence of mottle on the upper surface of the retardation is well prevented. Was confirmed.

Example 9
A retardation layer was produced in the same manner as in Example 7 except that ethyl 3-ethoxypropionate (specific evaporation rate 12) was used as a solvent. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

  The evaluation in evaluation 2 of Example 9 was ○. Moreover, the evaluation in evaluation 3 was also (circle). Therefore, in the homeotropically aligned retardation layer of Example 9, both the substrate adhesion and the evaluation of occurrence of unevenness are good, the adhesion to the substrate is good, and the occurrence of unevenness on the upper surface of the retardation is well prevented. Was confirmed.

Example 10
A retardation layer was produced in the same manner as in Example 1 except that 1% by weight of 3-methacryloxypropylmethyldiethoxysilane (KBE-502 manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a silane coupling agent. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

Evaluation in evaluation 2 of Example 10 was ○. Moreover, the evaluation in evaluation 3 was also (circle). Therefore, in the homeotropically aligned retardation layer of Example 10, both the substrate adhesion and the evaluation of occurrence of mottle are good, the adhesion to the substrate is good, and the occurrence of mottle on the upper surface of the retardation is well prevented. Was confirmed.

Example 11
A retardation layer was produced in the same manner as in Example 10 except that cyclohexanone (specific evaporation rate 23) was used as a solvent. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

The evaluation in the evaluation 2 of Example 11 was (circle). Moreover, the evaluation in evaluation 3 was also (circle). Therefore, in the phase difference layer with homeotropic alignment in Example 11, both the substrate adhesion force and the evaluation of occurrence of unevenness are good, the adhesion to the substrate is good, and the occurrence of unevenness on the upper surface of the retardation is well prevented. Was confirmed.

Example 12
A retardation layer was produced in the same manner as in Example 10 except that ethyl 3-ethoxypropionate (specific evaporation rate 12) was used as a solvent. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

  The evaluation in evaluation 2 of Example 12 was ○. Moreover, the evaluation in evaluation 3 was also (circle). Therefore, in the homeotropically aligned retardation layer of Example 12, both the substrate adhesion and the evaluation of occurrence of mottle are good, the adhesion to the substrate is good, and the occurrence of mottle on the upper surface of the retardation is well prevented. Was confirmed.

Example 13
A retardation layer was produced in the same manner as in Example 1 except that a colored layer (thickness: 2.0 μm) was formed between the glass substrate and the retardation layer using the following colored resist. The colored layer is formed by applying the following red colored resist to the glass substrate surface by spin coating, prebaking at 90 ° C. for 3 minutes, alignment exposure (100 mJ / cm ² ), 230 ° C., Post-baking was performed for 30 minutes to form a red colored layer. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

  The evaluation in evaluation 2 of Example 13 was ○. Moreover, the evaluation in evaluation 3 was also (circle). Therefore, the homeotropically aligned retardation layer disposed on the colored layer of Example 13 has both a substrate adhesion force and an evaluation of occurrence of unevenness, good adhesion to the colored layer, and occurrence of unevenness on the upper surface of the retardation. It was confirmed that it was well prevented.

Photoresist composition for red (R) colored pixels, red pigment: 5.0 parts by weight (CIPR254 (Cibamorph DPP Red BP, manufactured by Ciba Specialty Chemicals))
・ Yellow pigment: 1.0 part by weight (CI PY139 (manufactured by BASF, Paliotor Yellow D1819))
・ Dispersant: 3.0 parts by weight (manufactured by Zeneca Corporation, Solsperse 24000)
・ Polyfunctional acrylate monomer: 4.0 parts by weight (Sartomer Co., Ltd., SR399)
-Polymer: 5.0 parts by weight (VR60 manufactured by Showa Polymer Co., Ltd.)
Initiator 1: 1.4 parts by weight (Ciba Geigy, Irgacure 907)
Initiator 2: 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

Comparative Example 1
A retardation layer was produced in the same manner as in Example 1 except that a silane coupling agent was not used and propylene glycol monomethyl ether acetate (PGMEA) (specific evaporation rate 34) was used as a solvent. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

  Evaluation in evaluation 2 of comparative example 1 was x. The evaluation in evaluation 3 was Δ. Therefore, it was confirmed that the homeotropically aligned retardation layer of Comparative Example 1 has poor adhesion to the transparent substrate and that some unevenness has occurred.

Comparative Example 2
Other than using 10% by weight of 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) as the silane coupling agent and using propylene glycol monomethyl ether acetate (PGMEA) (specific evaporation rate 34) as the solvent Produced a retardation layer in the same manner as in Example 1. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

  Evaluation in evaluation 2 of comparative example 2 was x. Moreover, the evaluation in evaluation 3 was also x. Therefore, it was confirmed that the phase difference layer with homeotropic orientation in Comparative Example 2 has poor adhesion to the transparent substrate and that moire is generated.

Comparative Example 3
A retardation layer was formed in the same manner as in Comparative Example 1 except that a colored layer (thickness: 2.0 μm) was formed on a glass substrate using the same colored resist as used in Example 13. According to Evaluation 1, the retardation of the obtained retardation layer at a wavelength of 589 nm was evaluated using RETS-1250AV manufactured by Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

  The evaluation in Evaluation 2 of Comparative Example 3 was x. Moreover, the evaluation in evaluation 3 was also x. Therefore, it was confirmed that the homeotropically oriented retardation layer disposed on the colored layer of Comparative Example 3 had poor adhesion to the colored layer and caused unevenness.

Comparative Example 4
A retardation layer was formed in the same manner as in Comparative Example 2 except that a colored layer (thickness: 2.0 μm) was formed on a glass substrate using the same colored resist as used in Example 13. According to the retardation evaluation 1 of wavelength 589nm of the obtained retardation layer, it evaluated using RETS-1250AV made from Otsuka Electronics. As a result, the tilt measurement from any measurement direction showed symmetry with respect to the z-axis, indicating that the retardation layer was homeotropically oriented (not shown).

  Evaluation in evaluation 2 of comparative example 4 was x. Moreover, the evaluation in evaluation 3 was also x. Therefore, it was confirmed that the homeotropically oriented retardation layer disposed on the colored layer of Comparative Example 4 had poor adhesion to the colored layer and caused unevenness.

As described above, a retardation layer that has good adhesion to the substrate surface and that does not have any unevenness on the surface of the retardation layer was achieved only in Examples 1-13.

It is a longitudinal cross-sectional view which shows one Example of the color filter of this invention. It is a longitudinal cross-sectional view which shows the other Example of the color filter of this invention. It is a longitudinal cross-sectional view which shows an example of the liquid crystal display device using the color filter of this invention. It is the figure which showed the phase difference measurement direction of the sample. 3 is a graph showing the relationship between the measurement angle of the retardation layer of Example 1 and the phase difference. It is the schematic of a bubble pressure dynamic surface tension meter. It is the schematic of a double cylinder system rheometer. It is an inspection apparatus for measuring the S / N ratio in the color filter of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Color filter 2 Transparent substrate 3 Phase difference layer 4 Colored layer 12 Liquid crystal display device 13 Display side substrate 14 Liquid crystal drive side substrate 15 Drive liquid crystal cell

Claims (16)

N-acetic acid at 25 ° C. at least one or two or more kinds of crosslinkable liquid crystal molecules and a silane coupling agent having at least one selected from a sulfide group, a mercapto group, an amino group, and a (meth) acryloyl group A liquid crystal composition, which is dissolved in a solvent having a specific evaporation rate of 5 to 30 when the evaporation rate of butyl is 100. 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. 1 to 10% by weight in total (one or more) of one or more of a silane coupling agent containing a sulfide group, a silane coupling agent containing a mercapto group, and a silane coupling agent having a (meth) acryloyl group 3. The liquid crystal composition according to claim 1 or 2, comprising: 3. The liquid crystal composition according to claim 1, comprising 0.01 to 5% by weight (based on a compound equivalent) of a silane coupling agent containing an amino group. As a silane coupling agent, a silane coupling agent containing an amino group, a silane coupling agent containing a sulfide group, a silane coupling agent containing a mercapto group, or a silane coupling agent having a (meth) acryloyl group The liquid crystal composition according to claim 1 or 2, comprising a total of 0.01 to 5% by weight (vs. compound equivalent value) of seeds or two or more kinds. The liquid crystal composition according to claim 1, further comprising a vertical alignment aid. The liquid crystal composition according to claim 1, wherein the liquid crystal composition is used for forming a retardation layer that is homeotropically aligned. A retardation layer and a colored layer are provided on a transparent substrate, and the retardation layer is applied to the substrate with the liquid crystal composition according to any one of claims 1 to 7 to form a coating film. A color filter formed by curing crosslinkable liquid crystal molecules contained in the coating film. Retardation layer is at least 98.9 to 70% by weight (vs. compound equivalent) (meth) acryloyl group-containing crosslinkable liquid crystal molecules, 0.1 to 10% by weight (vs. compound equivalent) photopolymerization start A coating film is formed by applying a liquid crystal composition containing an agent and a sulfide group-containing silane coupling agent in an amount of 1 to 5% by weight (compared to the compound) to form a coating film. The liquid crystal molecules are formed by photocuring and baking, and the peel strength of the retardation layer after an accelerated life test of 1 hour at a temperature of 100 ° C. and a humidity of 100% is 1 or less based on the evaluation standard of JISK5600-5-6. The color filter according to claim 8, wherein Retardation layer is at least 98.9 to 70% by weight (vs. compound equivalent) (meth) acryloyl group-containing crosslinkable liquid crystal molecules, 0.1 to 10% by weight (vs. compound equivalent) photopolymerization start The coating composition is formed by applying a liquid crystal composition containing an agent and a mercapto group-containing silane coupling agent in an amount of 1 to 5% by weight (compared to the equivalent of the formulation) to the upper surface of the substrate, and the crosslinking contained in the coating film The liquid crystal molecules are formed by photocuring and baking, and the peel strength of the retardation layer after an accelerated life test of 1 hour at a temperature of 100 ° C. and a humidity of 100% is 1 or less based on the evaluation standard of JISK5600-5-6. The color filter according to claim 8, wherein The retardation layer is at least 99.89 to 70% by weight (vs. compound equivalent) (meth) acryloyl group-containing crosslinkable liquid crystal molecules, 0.1 to 10% by weight (vs. compound equivalent) photopolymerization start A coating film is formed by applying a liquid crystal composition containing an agent and an amino group-containing silane coupling agent in an amount of 0.01 to 5% by weight (vs. the compound equivalent) to the upper surface of the substrate, and included in the coating film It is formed by photocuring and baking crosslinkable liquid crystal molecules, and the peel strength of the retardation layer after an accelerated life test of 1 hour at a temperature of 100 ° C. and a humidity of 100% is based on the evaluation standard of JISK5600-5-6. The color filter according to claim 8, wherein the color filter is 1 or less. Retardation layer is at least 98.9 to 70% by weight (vs. compound equivalent) (meth) acryloyl group-containing crosslinkable liquid crystal molecules, 0.1 to 10% by weight (vs. compound equivalent) photopolymerization start A liquid crystal composition containing an agent and a 1 to 5% by weight (vs. compound equivalent value) (meth) acryloyl group-containing silane coupling agent is applied to the upper surface of the substrate to form a coating film. The crosslinkable liquid crystal molecules contained are formed by photocuring and baking, and the peel strength of the retardation layer after an accelerated life test at a temperature of 100 ° C. and a humidity of 100% for 1 hour is evaluated according to JISK5600-5-6. The color filter according to claim 8, wherein the color filter is 1 or less. The phase difference layer is at least 99.89 to 70% by weight (vs. compound equivalent) (meth) acryloyl group-containing crosslinkable liquid crystal molecules and 0.1 to 10% by weight (vs. compound equivalent) photopolymerization. 2 of a silane coupling agent selected from an initiator, an amino group-containing silane coupling agent, a sulfide group-containing silane coupling agent, a mercapto group-containing silane coupling agent, and a (meth) acryloyl group-containing silane coupling agent A liquid crystal composition containing a total of 0.01 to 5% by weight (relative to the formulation) is applied to the upper surface of the base material to form a coating film, and the crosslinkable liquid crystal molecules contained in the coating film are exposed to light. It is formed by curing and baking, and the peel strength of the retardation layer after an accelerated life test of 1 hour at a temperature of 100 ° C. and a humidity of 100% is 1 or less according to the evaluation standard of JISK5600-5-6. 8 The color filter according. 14. The color filter according to claim 8, wherein the S / N ratio of the light intensity when the surface unevenness inspection of the retardation layer is performed is 2 or less. The color filter according to claim 8, wherein the retardation layer is homeotropically aligned. 16. A liquid crystal display device in which a display side substrate and a liquid crystal driving side substrate are opposed to each other, and a liquid crystal is sealed therebetween, wherein the display side substrate is the color according to any one of claims 8 to 15. A liquid crystal display device characterized by being a filter.

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