JP2010044276A - Composition for producing color filter having aligning ability - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for producing a color filter having aligning ability, and to provide a composition for producing a color filter capable of generating uniform aligning ability on the surface even when a color filter having ruggedness on the surface is produced. <P>SOLUTION: The composition for producing a color filter contains a pigment or a dye, and a photoreactive compound. A substrate for a liquid crystal display is provided, comprising a substrate, a color filter layer formed of the above composition on the substrate, and an optical anisotropic layer directly layered on the color filter layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a composition for producing a color filter having orientation ability. More specifically, the present invention relates to a composition for producing a color filter capable of imparting alignment ability by a photoreaction, a color filter produced from the composition, a substrate for a liquid crystal display device including the color filter, and the substrate. The present invention relates to a liquid crystal display device.

The liquid crystal display device usually includes an alignment film in order to align liquid crystal molecules used for polymerization in a liquid crystal cell for driving a liquid crystal cell or an optically anisotropic layer for viewing angle compensation, Patent Documents 1 to 4 disclose attempts to share the function of the alignment film with a color filter. In any of the techniques described in these documents, the color filter is provided with the alignment ability for the liquid crystal molecules for driving the liquid crystal cell using a rubbing technique.
However, in the case where the color filter layer has a black matrix for separating the colored layer and the surface has irregularities, the rubbing is insufficient at the partition wall portion, and the surface orientation ability becomes uneven. there is a possibility.
In addition, as a method for imparting the function of the alignment film to the resin layer, there is a photo-alignment film (Patent Documents 5 and 6) that is aligned by photoreaction, but there is no example in which this is applied to the color filter layer.
JP-A-8-76106 JP-A-8-122791 JP-A-9-274105 JP-A-10-104606 JP 2007-25203 A JP 2007-71952 A

  An object of the present invention is to provide a composition for producing a color filter having orientation ability. An object of the present invention is to provide a composition for producing a color filter capable of producing a uniform alignment ability on the surface even when a color filter having irregularities on the surface is produced. It is an object to provide a color filter manufactured using the composition, a substrate for a liquid crystal display device including the color filter, and a liquid crystal display device.

That is, the present invention provides the following (1) to (15).
(1) A composition for producing a color filter comprising a pigment or dye and a photoreactive compound.
(2) A substrate for a liquid crystal display device comprising a substrate, a color filter layer formed from the composition according to (1), and an optically anisotropic layer directly laminated on the color filter layer in this order.
(3) The liquid crystal display device according to (2), wherein the color filter layer includes a part of a partition formed on the substrate, and the partition divides the color filter layer into a plurality of regions. substrate.
(4) The substrate for a liquid crystal display device according to (3), wherein the optically anisotropic layer is divided into a plurality of regions by the partition walls.
(5) The substrate for a liquid crystal display device according to (3) or (4), wherein the partition walls are formed in a matrix.

(6) The optically anisotropic layer is formed by forming a liquid crystal phase from a composition containing a liquid crystal compound having at least one reactive group, and then fixing the liquid crystal phase by heat or light irradiation. The substrate for a liquid crystal display device according to any one of (2) to (5).
(7) The substrate for a liquid crystal display device according to (6), wherein the light irradiation is ultraviolet irradiation.
(8) The substrate for a liquid crystal display device according to (6) or (7), wherein the reactive group is an ethylenically unsaturated group.
(9) The substrate for a liquid crystal display device according to any one of (6) to (8), wherein the composition further contains at least one radical polymerization initiator.
(10) The substrate for a liquid crystal display device according to any one of (6) to (9), wherein the liquid crystal compound is a rod-like liquid crystal.

(11) A liquid crystal display device comprising the substrate for a liquid crystal display device according to any one of (2) to (10).
(12) The substrate for a liquid crystal display device according to any one of (2) to (10), wherein the optically anisotropic layer is a positive A plate.
(13) A liquid crystal display device comprising the liquid crystal display device substrate according to (12).
(14) A second optically anisotropic layer is included separately from the optically anisotropic layer,
The second optically anisotropic layer is a negative C plate;
The liquid crystal display device according to (13), wherein the display mode is a VA mode.

(15) Manufacturing method of substrate for liquid crystal display device including at least the following steps [1] to [4] in this order:
[1] A step of preparing a substrate having a partition wall and a fine region formed by the partition wall on the surface;
[2] A step of discharging and drying an ink liquid containing a pigment or dye and a photoreactive compound to the fine region by an inkjet method;
[3] A step of irradiating the substrate obtained after step [2] with polarized light; and [4] a fluid containing at least one liquid crystalline compound in the fine region and exhibiting a predetermined optical anisotropy. Forming an optically anisotropic layer by discharging the ink from an ink jet type discharge head and drying to form a liquid crystal phase and then exposing to light.

  According to the present invention, a composition for producing a color filter having orientation ability is provided. By using the composition of the present invention, an optically anisotropic layer composed of polymerizable liquid crystal molecules can be easily provided on the color filter layer without the need to provide an additional alignment film. Further, by using the composition of the present invention, it is possible to easily produce a fine structure in which a color filter layer and an optically anisotropic layer are laminated, so that the liquid crystal cell is optically compensated for each color. It is possible to design a liquid crystal display device that can be used more easily.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

In the present specification, Re (λ) and Rth (λ) represent in-plane retardation and retardation in the thickness direction at the wavelength λ, respectively. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments). When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rth (λ) is Re (λ), with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (if there is no slow axis, any in-plane film The light of wavelength λ nm is incident from each of the inclined directions in steps of 10 degrees from the normal direction to 50 degrees on one side with respect to the film normal direction (with the direction of the rotation axis as the rotation axis). KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value. In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, retardation at a tilt angle larger than the tilt angle. The value is calculated by KOBRA 21ADH or WR after changing its sign to negative. In addition, the retardation value is measured from the two inclined directions, with the slow axis as the tilt axis (rotation axis) (in the absence of the slow axis, the arbitrary direction in the film plane is the rotation axis), Based on the value, the assumed value of the average refractive index, and the input film thickness value, Rth can also be calculated from the following equations (1) and (2).

Rth = ((nx + ny) / 2−nz) x d −−− Formula (2)
Note:
The above Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction.
In the formula, nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction orthogonal to nx in the plane, and nz represents the refractive index in the direction orthogonal to nx and ny. d represents a film thickness.

In the case where the film to be measured cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film having no so-called optical axis, Rth (λ) is calculated by the following method.
Rth (λ) is from −50 degrees to +50 degrees with respect to the normal direction of the film, with Re (λ) being the in-plane slow axis (determined by KOBRA 21ADH or WR) and the tilt axis (rotating axis). In each of the 10 degree steps, light of wavelength λ nm is incident from the inclined direction and measured at 11 points. Based on the measured retardation value, the assumed average refractive index, and the input film thickness value, KOBRA 21ADH or WR is calculated. In the above measurement, the assumed value of the average refractive index may be a value in a polymer handbook (John Wiley & Sons, Inc.) or a catalog of various optical films. Those whose average refractive index is not known can be measured with an Abbe refractometer. Examples of the average refractive index values of main optical films are given below:

Cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), and polystyrene (1.59).
The KOBRA 21ADH or WR calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

Also, the sign of Rth is when the phase difference measured by injecting light having a wavelength of 550 nm from the direction inclined + 20 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis) exceeds Re Is positive and negative is below Re. However, in the sample with | Rth / Re | of 9 or more, it was tilted by + 40 ° with respect to the film normal direction with the in-plane fast axis as the tilt axis (rotation axis) using a polarizing microscope with a free rotation base. In the state, the case where the slow axis of the sample which can be determined using the polarizing plate inspection plate is parallel to the film plane is positive, and the case where the slow axis is in the thickness direction of the film is negative.
In the present specification, λ refers to 611 ± 5 nm, 545 ± 5 nm, 435 ± 5 nm for R, G, and B, respectively, and refers to 545 ± 5 nm or 590 ± 5 nm unless otherwise specified.

  In this specification, “substantially” for the angle means that the error from the exact angle is within a range of less than ± 5 °. Furthermore, the error from the exact angle is preferably less than 4 °, more preferably less than 3 °. With regard to retardation, “substantially” means that the retardation is within ± 5%. Further, “Re is not 0” means that the absolute value of Re is 5 nm or more. In addition, the measurement wavelength of the refractive index indicates an arbitrary wavelength in the visible light region unless otherwise specified. In the present specification, “visible light” refers to light having a wavelength of 400 to 700 nm.

[Composition for color filter preparation]
The composition for producing a color filter of the present invention is characterized by containing a photoreactive compound. By using a composition containing a photoreactive compound as the composition for producing a color filter and irradiating the layer formed from such a composition with light, anisotropy is formed on the surface of this layer, It becomes possible to orient the liquid crystal of the layer provided in.
Examples of the photoreactive compound include compounds that cause at least one of a photoisomerization reaction, a photodimerization reaction, and a photolysis reaction. In the present invention, it is preferable to use a compound causing a photoisomerization reaction or a compound causing a photodimerization reaction.

The compound causing the photoisomerization reaction may be a compound having a photoisomerization group. Moreover, the compound which causes a photodimerization reaction should just be a compound which has a photodimerization group. The composition for producing a color filter of the present invention may contain both a compound that undergoes a photoisomerization reaction and a compound that undergoes a photodimerization reaction, but preferably contains either one, and causes a photodimerization reaction. It is particularly preferred that it contains a compound.
The compound causing the photoisomerization reaction or the compound causing the photodimerization reaction may be either a low molecular compound or a high molecular compound, but in the case of a low molecular compound, it preferably has liquid crystallinity.

  A compound that undergoes a photoisomerization reaction refers to a compound that undergoes stereoisomerization or structural isomerization by the action of light. Photoisomerized compounds include azobenzene compounds (K. Ichimura et al., Langmuir, vol. 4, page 1214 (1988); K. Aoki et al., Langmuir, vol. 8, page 1007 (1992); Suzuki et al., Langmuir, vol. 8, page 2601 (1992); K. Ichimuraet al., Appl. Phys. Lett., Vol. 63, No. 4, page 449 (1993); N. Ishizuki, Langmuir, vol. 9, page 3298 (1993); N. Ishizuki, Langmuir, vol. 9, page 857 (1993)), hydrazono-β-ketoester compounds (S. Yamamura et al., Liquid Crystals, vol. 13, No. 2, page 189 (1993)), stilbene compounds (Kunihiro Ichimura et al., Polymer Journal, Vol. 47, No. 10, p. 771 (1990)) and spiropyran compounds (K. Ichimura et al., Chemistry Letters, page 1063 (1992); K. Ichimura et al., Thin Solid Films, vol. 235, page 101 (1993)), and low molecular weight compounds of these compounds have their residues in the main chain or side chain Polymer is included. Among them, a photoisomerization compound containing a double bond structure consisting of C = C or N = N is preferred, and an azobenzene compound containing a double bond structure consisting of N = N is particularly preferred.

  The compound that causes a photodimerization reaction refers to a compound that undergoes an addition reaction between two groups upon irradiation with light to cyclize. Photodimerized compounds include cinnamic acid derivatives (M. Schadt et al., J. Appl. Phys., Vol. 31, No. 7, page 2155 (1992)) and coumarin derivatives (M. Schadt et al., Nature , vol. 381, page 212 (1996)), chalcone derivatives (Toshihiro Ogawa et al., Proceedings of Liquid Crystal Panel Discussion, 2AB03 (1997)), benzophenone derivatives (YK Jang et al., SID Int. Symposium Digest, P -53 (1997).), And compounds having residues of these derivatives in the main chain or side chain. Among these, cinnamic acid derivatives, coumarin derivatives, and polymers having these residues in the side chain are preferable, and cinnamic acid derivatives and polymers having these residues in the side chain are more preferable.

As the photoreactive compound used in the composition for producing a color filter of the present invention, a polymer having at least one repeating unit represented by the following general formula (1) is particularly preferable.

In formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent; L is a divalent linking group selected from the following linking group group or 2 represents a divalent linking group formed by combining two or more selected from the group of linking groups, n1 represents an integer of 0 to 4, and n2 represents an integer of 0 to 5.
(Linked group group)
Single bond, —O—, —CO—, —NR ⁶ — (R ⁶ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), —S—, —SO ² —, —P (═O) (OR ⁷ ) — (R ⁷ represents an alkyl group, an aryl group, or an aralkyl group), an alkylene group, and an arylene group.

More specifically, in the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a substituent selected from the substituent group exemplified below.
(Substituent group)
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like, alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, Particularly preferred are alkenyl groups having 2 to 8 carbon atoms, such as vinyl group, aryl group, 2-butenyl group and 3-pentenyl group), alkynyl groups (preferably having 2 to 20 carbon atoms, more preferred). Is an alkynyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as propargyl group and 3-pentynyl group. An aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenyl group, a p-methylphenyl group, and a naphthyl group. Aralkyl groups (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as benzyl group, phenethyl group, 3- Phenylpropyl group and the like), a substituted or unsubstituted amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, Unsubstituted amino group, methylamino group, dimethylamino group, diethylamino group, anilino group, etc.),

An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group). An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group), acyloxy A group (preferably an acyloxy group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as an acetoxy group and a benzoyloxy group), an acylamino group (preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, particularly preferably 2-10 carbon atoms. A silamino group, for example, an acetylamino group, a benzoylamino group, and the like, an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms). An alkoxycarbonylamino group, for example, a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 12 carbon atoms). Aryloxycarbonylamino group, for example, phenyloxycarbonylamino group and the like, sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms). 12 sulfonylamino groups such as methanesulfonyl And sulfamoyl groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, such as sulfamoyl group). Group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group and the like), carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably carbon number). 1 to 12 carbamoyl groups, for example, unsubstituted carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group and the like),

An alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably an alkylthio group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a methylthio group and an ethylthio group), an arylthio group ( Preferably it is C6-C20, More preferably, it is C6-C16, Most preferably, it is C6-C12 arylthio group, for example, a phenylthio group etc. are mentioned, A sulfonyl group (preferably C1-C1). 20, more preferably a sulfonyl group having 1 to 16 carbon atoms, particularly preferably a sulfonyl group having 1 to 12 carbon atoms, such as a mesyl group and a tosyl group, and a sulfinyl group (preferably having a carbon number of 1 to 20, more A sulfinyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms is preferable. Zensulfinyl groups, etc.), ureido groups (preferably ureido groups having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as unsubstituted ureido groups. , Methylureido group, phenylureido group, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms). Yes, for example, diethyl phosphoric acid amide group, phenyl phosphoric acid amide group, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, Carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having a carbon number of 1 to 0, more preferably a heterocyclic group of 1 to 12, for example, a heterocyclic group having a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, such as an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group , Piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably A silyl group having 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group). These substituents may be further substituted with these substituents. Moreover, when it has two or more substituents, they may be the same or different. If possible, they may be bonded to each other to form a ring.

R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), or a group represented by -LQ described later. It is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a chlorine atom, or a group represented by -LQ, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, it is particularly preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, most preferably R2 and R3 are hydrogen atoms and R1 is a hydrogen atom or a methyl group. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group and the like. The alkyl group may have a suitable substituent. Examples of the substituent include a halogen atom, aryl group, heterocyclic group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxyl group, acyloxy group, amino group, alkoxycarbonyl group, acylamino group, oxycarbonyl Group, carbamoyl group, sulfonyl group, sulfamoyl group, sulfonamido group, sulfolyl group, carboxyl group and the like. The carbon number of the alkyl group does not include the carbon atom of the substituent. The same applies to the carbon number of other groups.

R ⁴ and R ⁵ are each independently preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) Particularly preferred are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a heterocyclic group having 1 to 12 carbon atoms, and a chlorine atom. Most preferably, ⁴ is a hydrogen atom and R ⁵ is a phenyl group.
When n1 and n2 represent an integer of 2 or more, a plurality of R ⁴ and R ⁵ may be the same or different.

L represents a divalent linking group selected from the above linking group group, or a divalent linking group formed by combining two or more thereof. In the above linking group group, R ^{6 in} —NR ⁶ — represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom or an alkyl group. R ⁷ in —PO (OR ⁷ ) — represents an alkyl group, an aryl group or an aralkyl group, and preferably an alkyl group. When R ⁶ and R ⁷ represent an alkyl group, an aryl group, or an aralkyl group, the number of carbon atoms is the same as that described in the “substituent group”. L preferably contains a single bond, —O—, —CO—, —NR ⁶ —, —S—, —SO ₂ —, an alkylene group or an arylene group, and is a single bond, —CO—, —O—. , -NR ⁶ -, it is particularly preferred that contain an alkylene group or an arylene group, -CO -, - O -, - NR 6 - or most preferably containing an alkylene group. When L contains an alkylene group, the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Specific examples of particularly preferred alkylene groups include methylene, ethylene, trimethylene, tetrabutylene, hexamethylene groups and the like. When L contains an arylene group, the carbon number of the arylene group is preferably 6 to 24, more preferably 6 to 18, and particularly preferably 6 to 12. Specific examples of particularly preferred arylene groups include phenylene and naphthalene groups. When L contains a divalent linking group (that is, an aralkylene group) obtained by combining an alkylene group and an arylene group, the carbon number of the aralkylene group is preferably 7 to 34, more preferably 7 to 26, and particularly preferably. 7-16. Specific examples of particularly preferred aralkylene groups include a phenylenemethylene group, a phenyleneethylene group, and a methylenephenylene group. The group listed as L may have a suitable substituent. Examples of such a substituent include the same substituents as those described above as the substituents for R ^{1 to} R ⁵ .
Although the specific structure of L is illustrated below, this invention is not limited to these specific examples.

The photoreactive compound may contain one type of repeating unit represented by the general formula (1), or may contain two or more types. The photoreactive compound may have one or more repeating units other than the above repeating units. The other repeating units are not particularly limited, and preferred examples thereof include repeating units derived from ordinary radical polymerizable monomers. Hereinafter, specific examples of monomers for deriving other repeating units will be given. The photoreactive compound may contain a repeating unit derived from one or more monomers selected from the following monomer group.

Monomer group (1) Alkenes ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-dodecene, 1-octadecene, 1-eicocene, hexafluoropropene, vinylidene fluoride, chlorotrifluoroethylene, 3, 3, 3-trifluoropropylene, tetrafluoroethylene, vinyl chloride, vinylidene chloride, etc .;
(2) Dienes 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2-n-propyl-1,3-butadiene, 2,3-dimethyl-1,3 -Butadiene, 2-methyl-1,3-pentadiene, 1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3-butadiene, 2-chloro -1,3-butadiene, 1-bromo-1,3-butadiene, 1-chlorobutadiene, 2-fluoro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1,1,2- Trichloro-1,3-butadiene and 2-cyano-1,3-butadiene, 1,4-divinylcyclohexane and the like;

(3) Derivatives of α, β-unsaturated carboxylic acid (3a) Alkyl acrylates methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate , Amyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, tert-octyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, 2-cyanoethyl acrylate, 2-acetoxyethyl acrylate, methoxybenzyl ester Chryrate, 2-chlorocyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 2-methoxyethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of added polyoxyethylene: n = 2 to 100), 3-methoxy Butyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, glycidyl acrylate Such);

(3b) alkyl methacrylates methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2 -Ethylhexyl methacrylate, n-octyl methacrylate, stearyl methacrylate, benzyl methacrylate, phenyl methacrylate, allyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, ω Methoxypolyethylene glycol methacrylate (number of added polyoxyethylene: n = 2 to 100), 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate Glycidyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, 2-isocyanatoethyl methacrylate, etc .;

(3c) Unsaturated polycarboxylic acid diesters dimethyl maleate, dibutyl maleate, dimethyl itaconate, dibutyl taconate, dibutyl crotonate, dihexyl crotonate, diethyl fumarate, dimethyl fumarate, etc .;

(3d) Amides of α, β-unsaturated carboxylic acids N, N-dimethylacrylamide, N, N-diethylacrylamide, Nn-propylacrylamide, N-tertbutylacrylamide, N-tertoctylmethacrylamide, N- Cyclohexylacrylamide, N-phenylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, N-benzylacrylamide, N-acryloylmorpholine, diacetone acrylamide, N-methylmaleimide and the like;

(4) Unsaturated nitriles acrylonitrile, methacrylonitrile, etc .;
(5) Styrene and its derivatives Styrene, vinyl toluene, ethyl styrene, p-tert butyl styrene, methyl p-vinyl benzoate, α-methyl styrene, p-chloromethyl styrene, vinyl naphthalene, p-methoxy styrene, p-hydroxy Methyl styrene, p-acetoxy styrene, etc .;
(6) Vinyl esters Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl benzoate, vinyl salicylate, vinyl chloroacetate, vinyl methoxyacetate, vinyl vinyl acetate, etc .;

(7) Vinyl ethers methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl Vinyl ether, n-eicosyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, fluorobutyl vinyl ether, fluorobutoxyethyl vinyl ether and the like; and (8) other polymerizable monomers N-vinylpyrrolidone, methyl vinyl ketone, phenyl vinyl ketone, Methoxyethyl vinyl ketone, 2-vinyl oxazoline, 2-isopropenyl oxazoline, etc.

In the photoreactive compound, the amount of the repeating unit represented by the general formula (1) is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total amount of constituent monomers of the polymer. It is particularly preferably 70% by mass or more.

Regarding the production method of the polymer having the repeating unit represented by the general formula (1), the description of [0046] to [0051] of JP-A-2007-25203 can be referred to.

Specific examples of the polymer having the repeating unit represented by the general formula (1) are shown below, but the present invention is not limited to these specific examples. Here, the numerical value in the formula is a mass percentage indicating the composition ratio of each monomer, and Mw is a mass average molecular weight in terms of PS measured by GPC. The numerical values of a and b represent mass ratios.

  The addition amount of the photoreactive compound is preferably 0.5% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass with respect to the composition for preparing a color filter (including a solvent). Moreover, it is preferable that the addition amount of a photoreactive compound is 20 mass%-70 mass% with respect to the mass of the coloring agent in the composition for color filter preparation, and it is 30 mass%-60 mass%. Further preferred.

The composition for producing a color filter of the present invention further contains a colorant such as a dye or a pigment. The colorant may be a known colorant (dye or pigment). In the case of using a pigment among the known colorants, it is desirable that the pigment is uniformly dispersed in the colored resin composition. Therefore, the particle diameter is preferably 0.1 μm or less, particularly preferably 0.08 μm or less. .
Examples of the known dyes or pigments include those described in paragraph numbers “0107” to “0109” of JP-A-2007-233376.

  As the colorant in the present invention, among the above-mentioned colorants, (i) R (red) colored resin composition is C.I. I. Pigment Red 254 is C.I. in (ii) G (green) colored resin composition. I. In the colored resin composition of (iii) B (blue), CI Pigment Green 36 is C.I. I. Pigment Blue 15: 6 is a preferable example. Furthermore, the above pigments may be used in combination.

  In the present invention, the combination of the above-described pigments preferably used in combination is C.I. I. In pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment yellow 139 or C.I. I. A combination with Pigment Violet 23; I. In Pigment Green 36, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 138 or C.I. I. A combination with CI Pigment Yellow 180, and C.I. I. In Pigment Blue 15: 6, C.I. I. Pigment violet 23 or C.I. I. A combination with Pigment Blue 60 is mentioned.

  C. in the pigment when used together in this way. I. Pigment red 254, C.I. I. Pigment green 36, C.I. I. The content of Pigment Blue 15: 6 is C.I. I. The pigment red 254 is preferably 80% by mass or more, particularly preferably 90% by mass or more. C. I. The pigment green 36 is preferably 50% by mass or more, particularly preferably 60% by mass or more. C. I. Pigment Blue 15: 6 is preferably 80% by mass or more, and particularly preferably 90% by mass or more.

  The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid portion that binds to the pigment and hardens the coating film (binder), and a component that dissolves and dilutes the portion. (Organic solvent). The disperser used when dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, First Edition, Asakura Shoten, 2000, 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described in Item 310 of the document.

  The colorant (pigment) used in the present invention preferably has a number average particle diameter of 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm. When the number average particle diameter of the pigment is less than 0.001 μm, the particle surface energy is increased and the particles are easily aggregated, so that it is difficult to disperse the pigment and it is difficult to keep the dispersion state stable. On the other hand, if the number average particle diameter of the pigment exceeds 0.1 μm, the polarization is canceled by the pigment, and the contrast is lowered. In the present specification, “particle size” means the diameter when the electron micrograph image of the particle is a circle of the same area, and “number average particle size” means the above-mentioned particle size for many particles. This means the average value of 100 obtained.

  The contrast of the colored pixels can be improved by reducing the particle size of the dispersed pigment. Reduction of the particle size can be achieved by adjusting the dispersion time of the pigment dispersion. For dispersion, the known disperser described above can be used. The dispersion time is preferably 10 to 30 hours, more preferably 18 to 30 hours, and most preferably 24 to 30 hours. When the dispersion time is less than 10 hours, the pigment particle size is large, the polarization due to the pigment is canceled, and the contrast may be lowered. On the other hand, if it exceeds 30 hours, the viscosity of the dispersion liquid increases and application may be difficult. Further, in order to make the difference in contrast between two or more colored pixels within 600, the pigment particle diameter is adjusted to obtain a desired contrast.

  The contrast of each colored pixel of the color filter formed from the color filter layer is preferably 2000 or more, more preferably 2800 or more, still more preferably 3000 or more, and most preferably 3400 or more. When the contrast of each colored pixel constituting the color filter is 2000 or less, when an image of a liquid crystal display device having the color pixel is observed, an overall whitish impression is obtained, which is not preferable. Further, the difference in contrast between the colored pixels is preferably within 600, more preferably within 410, still more preferably within 350, and most preferably within 200. If the difference in contrast between the colored pixels is within 600, the amount of light leakage from each colored pixel portion at the time of black display does not differ greatly.

  The composition for producing a color filter of the present invention may further contain a monomer or an oligomer. The radically polymerizable monomer or oligomer used is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.
These monomers or oligomers may be used alone or in admixture of two or more. The content of the colored resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred.

  Examples of the cationic polymerizable monomer or oligomer used in the color filter layer include cyclic ethers, cyclic formals, acetals, vinyl alkyl ethers, compounds containing thiirane groups, bisphenol type epoxy resins, novolac type epoxy resins, and alicyclic epoxy resins. And epoxy compounds such as epoxidized unsaturated fatty acid and epoxidized polybutadiene. Examples of such monomers or oligomers include compounds described in Hiroaki Kakiuchi's “New Epoxy Resin” Shoshodo (published in 1985), “Epoxy Resin” published by Kuniyuki Hashimoto, Nikkan Kogyo Shimbun (1969), etc. Other trifunctional glycidyl ethers (trimethylol ethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc.), tetra- or higher functional glycidyl ethers (sorbitol tetraglycidyl ether, Pentaerythritol tetraglycyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin, etc.) trifunctional or higher cycloaliphatic epoxy (Epolide GT-) 01, Epolede GT-401, EHPE (manufactured by Daicel Chemical Industries, Ltd.), phenol novolac resin polycyclohexyl epoxy methyl ether, etc., trifunctional or more oxetanes (OX-SQ, PNOX-1009 (above, Tojo) Synthetic Co., Ltd.) and the like.

  In addition, the monomer or oligomer demonstrated above may be contained in the optically anisotropic layer.

When the composition for producing a color filter of the present invention is cured with light or the like, it may further contain a photopolymerization initiator. Examples of the photopolymerization initiator or photopolymerization initiator system used in the color filter layer include a vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660 and US Pat. No. 2,448,828. Acyloin ether compounds, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, polynuclear quinones described in US Pat. Nos. 3,046,127 and 2,951,758 Compound, a combination of a triarylimidazole dimer and a p-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound and a trihalomethyl-s-triazine compound described in Japanese Patent Publication No. 51-48516, Trihalomethyl described in US Pat. No. 4,239,850 Triazine compound include a trihalomethyl oxadiazole compounds described in U.S. Pat. No. 4,212,976. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.
In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example. The content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

  Cationic polymerization initiators include aryl diazonium salts of Lewis acids such as etrafluoroborate and hexafluorophosphenol, double salts such as diaryl iodonium salts and triarylsulfonium luster, benzyl silyl ether, o-nitrobenzyl silyl ether, triphenyl ( Examples thereof include a mixed system of a silanol-generating silane compound such as (t-butyl) peroxysilane and an aluminum complex such as tris (ethylacetoacetate) aluminum. The content of the cationic polymerization initiator based on the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

  In the present invention, these photopolymerization initiators may be used in combination with two or more different photoreaction mechanisms.

The composition for producing a color filter of the present invention may further contain a binder in order to control film properties. As the binder, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-53836. As disclosed in JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. Can be mentioned.
Moreover, the cellulose derivative which has a carboxylic acid group in a side chain is also mentioned. Furthermore, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably.
As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid, and other monomers can be used. Mention may be made of multi-component copolymers. These binders having a polar group may be used singly or may be used in the state of a composition used in combination with an ordinary film-forming polymer.
As content in the dark color composition of a binder, 20-50 mass% is preferable with respect to the total solid (mass) of a layer or a composition, and 24-45 mass% is more preferable.

  In the present specification, “contrast of colored pixels” means a contrast that is individually evaluated for each color of R, G, and B constituting the color filter. The contrast measurement method is as follows. In the state where the polarizing plates are overlapped on both sides of the object to be measured and the polarizing directions of the polarizing plates are parallel to each other, the backlight Y is applied from the side of one polarizing plate, and the luminance Y1 of the light passing through the other polarizing plate is obtained. taking measurement. Next, in a state where the polarizing plates are orthogonal to each other, a backlight is applied from the side of one polarizing plate, and the luminance Y2 of the light passing through the other polarizing plate is measured. The contrast is calculated by Y1 / Y2 using the obtained measurement value. Note that the polarizing plate used for contrast measurement is the same as the polarizing plate used for the liquid crystal display device using the color filter.

  In the composition for producing a color filter of the present invention, it is preferable to contain an appropriate surfactant from the viewpoint of effectively preventing display unevenness (color unevenness due to film thickness variation). As the surfactant, reference can be made to the descriptions of [0095] to [0105] of JP-A-2007-121986.

The composition of the present invention can also contain a solvent. As the solvent, water, alcohols, ketones, etc., the solvents described in “New Edition Solvent Pocketbook (edited by Organic Synthetic Science Association, published by Ohm)” The mass in the composition is preferably 50% or less, more preferably 30% or less.
The composition of the present invention in a solution state is applied to a substrate or the like by a known method (eg, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method), or As will be described in detail, the layer can be formed by discharging to a substrate or the like by an ink jet method and then removing (drying) water or a polar organic solvent.

The dried layer can be cured by light irradiation in the step of imparting alignment ability to the color filter described later. Moreover, it is also preferable to carry out a heat treatment after the light irradiation for curing. The heat treatment may be performed by heating at about 120 ° C. to 260 ° C., preferably 150 ° C. to 250 ° C., more preferably 180 ° C. to 230 ° C. The heat treatment time is not particularly limited, but is preferably 1 minute to 5 hours, more preferably 3 minutes to 3 hours, and particularly preferably 5 minutes to 2 hours.
The thickness of the formed layer is preferably 1 to 8 μm, and particularly preferably 2 to 6 μm.

[Give alignment ability to color filter]
As described above, the layer formed from the composition for producing a color filter of the present invention can align liquid crystal molecules in the layer on the surface by irradiating the surface with light.
The liquid crystal molecules may be liquid crystal molecules for driving in a liquid crystal cell, but are preferably liquid crystal molecules for polymerization and fixation from the viewpoint of the stability of the alignment ability of the color filter by light irradiation. That is, it is preferable to provide an optically anisotropic layer formed by polymerizing a liquid crystalline compound on a color filter layer formed from the composition for producing a color filter of the present invention.

X-rays, electron beams, ultraviolet rays, visible rays or infrared rays (heat rays) are used as the irradiation light in the light irradiation, and it is particularly preferable to use ultraviolet rays. The wavelength of the ultraviolet light is preferably 400 nm or less, and more preferably 180 to 360 nm. As the light source, a low-pressure mercury lamp, a high-pressure discharge lamp, or a short arc discharge lamp is preferably used. It is preferable to irradiate the layer with light aligned in a single direction as much as possible. This “single direction” means a single direction in the film plane (direction in which the direction of light is projected onto the film plane), and includes a direction horizontal or perpendicular to the film plane.

When the color filter layer formed from the composition for producing a color filter of the present invention is used for alignment of liquid crystal molecules for driving a liquid crystal cell, light irradiation may be carried out after the liquid crystal layer is provided. When used for alignment of liquid crystalline molecules for layer formation, it is preferable to carry out light irradiation before producing the optically anisotropic layer (before applying the composition for producing an optically anisotropic layer to the surface). Therefore, light irradiation can be performed directly on the color filter layer, not from the substrate (support) side. The light irradiation may be polarized light irradiation or non-polarized light irradiation, preferably linearly polarized light irradiation. Irradiation dose is preferably ^{10mJ / cm 2 ~30000mJ / cm 2} , and most preferably ^{20mJ / cm 2 ~6000mJ / cm 2} .

[Partition wall]
An embodiment in which the composition for producing a color filter of the present invention can be preferably used includes a case where a color filter layer and an optically anisotropic layer are provided using a substrate having a partition wall.
The partition only needs to form a fine region (for example, each pixel region). It is preferable that the partition walls have a light-shielding property because they can be used as a black matrix (hereinafter, the partition walls that also function as a black matrix are referred to as “light-shielding partition walls”), and the configuration and manufacturing method can be simplified.
Regarding the formation of the partition wall, reference can be made to the description of [0133] to [0176] of JP-A-2007-233376.

[Liquid crystal display substrate]
The substrate for a liquid crystal display device produced using the composition for producing a color filter of the present invention preferably has a laminate of a color filter layer and an optically anisotropic layer for compensating the viewing angle of the liquid crystal cell. . The optically anisotropic layer may be a solid layer having the same composition throughout the entire layer without including another configuration such as a partition wall, and the region divided by the partition wall as described in detail below. The patterning optically anisotropic layer may be included. For example, depending on the hue of the color filter layer disposed below (substrate side) (for example, for each of R, G, and B colors), the optical characteristics are optimal for compensating the viewing angle of the liquid crystal cell. It is preferable. Such a substrate for a liquid crystal display device may be used for either one of a pair of substrates of a liquid crystal cell, or may be used for both.

[Method of manufacturing substrate for liquid crystal display device]
An example of a method for manufacturing a substrate for a liquid crystal display device is an example of using a substrate on which a partition wall is formed, in which a part of a color filter layer and an optically anisotropic layer are formed in a portion (fine region) formed from the partition wall. An example in which a laminated structure including partial regions is formed will be described with reference to FIG.

  First, partition walls are formed on the substrate 11. The partition is not particularly limited, but typically a black matrix formed from a negative black matrix resist material can be used. A black matrix 12 (partition) of a dot pattern may be formed by photolithography using a negative black matrix resist material, and a plurality of fine regions a separated by the partition 12 may be formed (FIG. 1A). In the formation of the black matrix 12, there is no particular limitation on the forming material and the forming process, and any method other than a method using a photolithography method using a resist material may be used as long as a matrix pattern can be formed. Further, the pattern of the black matrix 12 is not limited to a dot pattern, and the arrangement of the color filters to be formed is not particularly limited. For example, any of dot arrangement, stripe arrangement, mosaic arrangement, delta arrangement, and the like may be used.

The black matrix 12 is preferably subjected to plasma treatment with a gas containing F atoms (CF ₄ or the like) after pattern formation, and its surface is subjected to ink repellent treatment. In addition to the plasma treatment, the black matrix 12 may be made to contain an ink repellant in the black matrix material, or the black matrix may be formed from a material that exhibits ink repellency with respect to the glass substrate 11. May be.

  Next, the ink is discharged for the first time with the color filter ink liquid 13 'to the fine region a separated by the black matrix 12 subjected to the ink repellent treatment if desired (FIG. 1B), and this is dried. By performing processing such as exposure and polarization exposure as necessary, a partial region 13 of the color filter is formed (FIG. 1C).

  A fluid 14 ′ such as a solution exhibiting a predetermined optical anisotropy is ejected onto the partial region 13 of the color filter formed in this manner using an ink jet device, and the fluid 14 ′ is ejected into the fine region a. A layer made of fluid is formed (FIG. 1 (d)). The fluid preferably contains at least one liquid crystalline compound, and is preferably prepared so as to form a liquid crystal phase after drying. A dispersion liquid in which a part or all of a material such as a liquid crystal compound is dispersed may be used as long as it can be ejected by ink jetting, but a solution is preferable. After the discharge of the solution is completed, the solution layer is dried to form a liquid crystal phase and exposed to form a partial region 14 of the optically anisotropic layer (FIG. 1E). In order to form the liquid crystal phase, heating may be performed as necessary, and in that case, a heating device may be used.

  There are no particular restrictions on the ejection conditions of the ink or the like when forming the partial region 13 of the color filter and the partial region 14 of the optically anisotropic layer. In the case where the viscosity of the ink is high, it is preferable from the viewpoint of ejection stability that the ink is ejected at a lower temperature at room temperature or under heating (for example, 20 to 70 ° C.). It is preferable to keep the temperature of the ink or the like as constant as possible because the viscosity variation of the ink or the like greatly affects the droplet size and the droplet ejection speed as it is and causes image quality degradation.

  The inkjet head (hereinafter also simply referred to as a head) used in the method for manufacturing a substrate for a liquid crystal display device is not particularly limited, and various known ones can be used. Continuous type and dot on demand type can be used. Among the dot-on-demand types, the thermal head is preferably a type having an operation valve as described in JP-A-9-323420 for discharging. As the piezo head, for example, the heads described in European Patent A277,703, European Patent A278,590 and the like can be used. The head preferably has a temperature control function so that the temperature of the composition can be controlled. It is preferable to set the injection temperature so that the viscosity at the time of injection is 5 to 25 mPa · s, and to control the composition temperature so that the fluctuation range of the viscosity is within ± 5%. Moreover, as a drive frequency, it is preferable to operate | move at 1-500 kHz.

  Each region 14 in the optically anisotropic layer may be formed using fluids such as the same type of solution, and each has an optimal optical anisotropy, for example, depending on the hue of the color filter layer 13. It may be formed using fluids such as solutions containing different materials and / or different blending amounts so as to express. When using a different solution or the like depending on the hue of the color filter layer when forming the partial region 14 of the optically anisotropic layer, the respective solutions may be discharged and then dried simultaneously. You may perform the process of discharge and drying for every seed | species. Also, when forming the partial region 13 of the color filter layer, for example, after all ink liquids for forming the R layer, the G layer, and the B layer are discharged, drying may be performed simultaneously. You may perform the process of discharge and drying for every seed | species. Further, the color of the color filter is not necessarily limited to the three colors of red, green, and blue, and may be a multi-primary color filter.

  In this manner, for example, R, G, and B ink liquids are ejected and dried for each region corresponding to each pixel of the substrate and separated by the black matrix 12, and then a predetermined optical anisotropic property is further formed thereon. The fluid prepared so as to exhibit the property can be discharged and dried to form a pattern layer including a color filter pattern and an optically anisotropic layer pattern in each region. A color filter layer is formed by the plurality of color filter patterns and a part of the partition walls, and an optical anisotropic layer is formed by the plurality of optical anisotropic layer patterns and a part of the partition walls. A transparent electrode layer and / or an alignment layer may be formed on the optically anisotropic layer. For example, as described in JP-A Nos. 11-248921 and 3255107, a base is formed by overlapping colored resin compositions forming a color filter, a transparent electrode is formed thereon, and further required Accordingly, it is preferable from the viewpoint of cost reduction that the spacers are formed by overlapping the protrusions for split orientation.

  A liquid crystal device substrate manufactured as described above and another liquid crystal display device substrate as a counter substrate are prepared and bonded together. Furthermore, a liquid crystal layer can be formed by injecting a liquid crystal material into the vacant wall between these opposing surfaces to form a liquid crystal cell. The first substrate is preferably disposed with the surface on which the optically anisotropic layer and the color filter layer are formed facing inward, that is, with the opposing surface. Thereafter, a polarizing plate, an optical compensation film, and the like can be attached to the outer surfaces of both substrates, respectively, to produce a liquid crystal display device.

  By manufacturing the substrate for a liquid crystal device of the present invention by an inkjet method, the substrate can be manufactured with a small number of steps without complicating the structure. That is, when the ink liquid for forming the color filter layer and the fluid for forming the optically anisotropic layer, and the black matrix as the partition walls are first formed at the predetermined positions, the first matrix on the first substrate is formed. An optically anisotropic layer and a color filter layer can be accurately formed in a predetermined region.

  In the method of the present invention, an example in which an optically anisotropic layer and a color filter layer are formed in each fine region by using ink ejection by an ink jet method has been described. Of course, the invention is not limited to the produced embodiment, and the production method of the optically anisotropic layer and / or the color filter layer is also included in the present invention, for example, using an printing method other than the inkjet method. .

FIG. 2 shows a schematic cross-sectional view of an example of a substrate that can be used in the liquid crystal display device of the present invention.
The liquid crystal cell substrate shown in FIG. 2A has a pattern-like shape in which a black matrix 22 is formed as a partition on a transparent substrate 21 and is discharged by an inkjet method into a fine region separated by the partition. A color filter layer 23 and an optically anisotropic layer 27 are formed. Furthermore, the transparent electrode layer 25 and the alignment layer 26 are provided thereon. FIG. 2 shows an embodiment in which the color filter layers 23 of R, G, and B are formed. As is often seen recently, a color filter layer composed of layers of R, G, B, and W (white) is formed. May be. The first optical anisotropic layer 27 is divided into r, g, and b regions, and has optimum retardation characteristics for the hues of the R, G, and B filter layers 23, respectively.

  Furthermore, as shown in FIG. 2B, the optically anisotropic layer may be divided into a second optically anisotropic layer 24 and a patterned optically anisotropic layer 27. In the case of dividing into two, the solid optical anisotropic layer 24 may be formed on the same color filter side substrate side as the patterned optical anisotropic layer 27, or it is formed on the counter substrate side although not shown. May be. In general, a drive electrode such as a TFT array is generally arranged on the counter substrate side, and may be formed at any position on the counter substrate. However, in the case of an active drive type having a TFT, optical anisotropy is provided. The heat resistance of the conductive layer is preferably higher than that of the silicon layer.

[Liquid Crystal Display]
FIG. 3 is a schematic sectional view of an example of the liquid crystal display device of the present invention.
3 (a) and 3 (b) use the substrates of FIGS. 2 (a) and 2 (b) as upper substrates, respectively, and a glass substrate 21 having a transparent electrode layer 25 with TFT 32 and an alignment layer 26 thereon. Is a liquid crystal display device having a liquid crystal cell 37 with a liquid crystal 31 interposed therebetween. On both sides of the liquid crystal cell 37, a polarizing plate 36 made of a polarizing layer 33 sandwiched between protective layers 34 and 35 made of a cellulose acetate (TAC) film or the like is disposed. The protective layer 35 on the liquid crystal cell side may be a polymer film such as a TAC film that satisfies optical characteristics as an optical compensation sheet, or may be made of the same polymer film as the protective layer 34. Although not shown in the drawing, in the aspect of the reflective liquid crystal display device, only one polarizing plate is required on the observation side, and a reflective film is provided on the back surface of the liquid crystal cell or on the inner surface of the lower substrate of the liquid crystal cell. Of course, a front light can be provided on the liquid crystal cell observation side. Further, a transflective type in which a transmissive portion and a reflective portion are provided in one pixel of the display device is also possible. The display mode of the present liquid crystal display device is not particularly limited, and can be used for all transmissive and reflective liquid crystal display devices. In particular, the present invention is effective for the VA mode where color viewing angle characteristics are desired to be improved.

  Hereinafter, although this aspect demonstrates in detail about the material used for preparation, a preparation method, etc., this invention is not limited to this aspect. Other embodiments can also be produced with reference to the following description and conventionally known methods.

[substrate]
In the liquid crystal display device, the substrate on which the color filter layer and the optically anisotropic layer are provided is not particularly limited, and substrates made of various materials conventionally used as substrates for liquid crystal cells can be used. For example, a metallic support, a metal bonded support, glass, ceramic, synthetic resin film, or the like can be used. Particularly preferred are transparent glass and synthetic resin film having good dimensional stability.

[Optically anisotropic layer]
The optically anisotropic layer (which may be referred to as the first optically anisotropic layer in the present specification) provided on the color filter layer formed from the composition for producing a color filter of the present invention is at least one kind of liquid crystallinity. It is desirable that the composition containing the compound is an optically anisotropic layer formed by forming a liquid crystal phase and then curing it by irradiating with ultraviolet rays. Moreover, in order to harden | cure by ultraviolet irradiation, it is preferable that the said composition contains a radical polymerization initiator and / or a cationic polymerization initiator. The compound containing a polymerizable group having reactivity with the polymerization initiator itself has liquid crystallinity, or does not impair the liquid crystallinity of the liquid crystalline compound that forms an optically anisotropic layer upon addition. It is preferable that it is an added amount that is not impaired. The addition amount is preferably 0.1 to 50% by mass, more preferably 1.0 to 30% by mass, based on the solid content of the coating solution.

  As described above, the optically anisotropic layer functions as an optically anisotropic layer that compensates the viewing angle of the liquid crystal cell. Of course, the optically anisotropic layer alone may have sufficient viewing angle compensation ability, or may be an embodiment satisfying optical characteristics required for viewing angle compensation in combination with other layers. The birefringence of the first optically anisotropic layer is not particularly limited, but preferably functions as the optically anisotropic layer of the A-plate.

  In general, liquid crystal compounds can be classified into a rod-shaped type and a disk-shaped type based on their shapes. In addition, there are low and high molecular types, respectively. Polymer generally refers to a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, 2 pages, Iwanami Shoten, 1992). In this embodiment, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a disk-like liquid crystal compound is preferably used. Two or more kinds of rod-like liquid crystalline compounds, two or more kinds of disc-like liquid crystalline compounds, or a mixture of a rod-like liquid crystalline compound and a disk-like liquid crystalline compound may be used. It is more preferable to use a rod-like liquid crystal compound or a disk-like liquid crystal compound having a reactive group, since at least one of the reactive groups in one liquid crystal molecule can be formed. Is more preferably 2 or more. The liquid crystalline compound may be a mixture of two or more, and in that case, at least one preferably has two or more reactive groups. The thickness of the optically anisotropic layer is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, and further preferably 1 to 4 μm.

  Examples of rod-like liquid crystalline compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Not only the above low-molecular liquid crystalline compounds but also high-molecular liquid crystalline compounds can be used. The polymer liquid crystalline compound is a polymer compound obtained by polymerizing a rod-like liquid crystalline compound having a low molecular reactive group. The rod-like liquid crystal compound having a low-molecular reactive group that is particularly preferably used is a rod-like liquid crystal compound represented by the following general formula (I).

Formula (I): Q ¹ -L ¹ -A ¹ -L ³ -ML ⁴ -A ² -L ² -Q ²
Wherein, Q ¹ and Q ² respectively represent a reactive group, the L ^1, L ^2, L ³ and L ⁴ respectively represent a single bond or a divalent linking group, L ³ and At least one of L ⁴ is preferably —O— or O—CO—O—. A ¹ and A ² each independently represent a spacer group having 2 to 20 carbon atoms. M represents a mesogenic group.

Hereinafter, the rod-like liquid crystal compound having a reactive group represented by the general formula (I) will be described in more detail. In the formula, Q ¹ and Q ² are each independently a reactive group. The polymerization reaction of the reactive group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the reactive group is preferably a reactive group capable of an addition polymerization reaction or a condensation polymerization reaction. Examples of reactive groups are shown below.

Examples of the divalent linking group represented by L ¹ , L ² , L ³ and L ⁴ include —O—, —S—, —CO—, —NR ² —, —CO—O—, and —O—CO. —O—, —CO—NR ² —, —NR ² —CO—, —O—CO—, —O—CO—NR ² —, —NR ² —CO—O—, and NR ² —CO—NR ^2. A divalent linking group selected from the group consisting of-is preferred. R ² is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. In this case, at least one of L ³ and L ⁴ is preferably —O— or O—CO—O— (carbonate group). In the formula (I), Q ¹ -L ¹ and Q ² -L ² -are CH ₂ ═CH—CO—O—, CH ₂ ═C (CH ₃ ) —CO—O—, and CH ₂ ═C ( Cl) -CO-O-CO- O- are _{preferable, CH 2 = CH-CO-} O- is most preferable.

A ¹ and A ² represent spacer groups having 2 to 20 carbon atoms. An aliphatic group having 2 to 12 carbon atoms is preferable, and an alkylene group is particularly preferable. The spacer group is preferably chain-like and may contain oxygen atoms or sulfur atoms that are not adjacent to each other. The spacer group may have a substituent and may be substituted with a halogen atom (fluorine, chlorine, bromine), a cyano group, a methyl group, or an ethyl group.

Examples of the mesogenic group represented by M include all known mesogenic groups. In particular, a group represented by the following general formula (II) is preferable.
Formula (II): - (- W 1 -L 5) n-W 2 -
In the formula, W ¹ and W ² each independently represent a divalent cycloaliphatic group, a divalent aromatic group or a divalent heterocyclic group, L ⁵ represents a single bond or a linking group, and Specific examples of the group include specific examples of groups represented by L ^{1 to} L ⁴ in the formula (I), —CH ₂ —O—, and O—CH ₂ —. n represents 1, 2 or 3.

W ¹ and W ² include 1,4-cyclohexanediyl, 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5diyl, 1,3,4-thiadiazole-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,5-diyl, thiophene-2,5-diyl, pyridazine-3,6-diyl . In the case of 1,4-cyclohexanediyl, there are trans isomers and cis isomers, but either isomer may be used, and a mixture in any proportion may be used. More preferably, it is a trans form. W ¹ and W ² may each have a substituent. Examples of the substituent include a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, etc.), and an alkoxy group having 1 to 10 carbon atoms. (Methoxy group, ethoxy group, etc.), C1-10 acyl group (formyl group, acetyl group, etc.), C1-10 alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), carbon atom Examples thereof include an acyloxy group having 1 to 10 (acetyloxy group, propionyloxy group, etc.), nitro group, trifluoromethyl group, difluoromethyl group and the like.

  Preferred examples of the basic skeleton of the mesogenic group represented by the general formula (II) are shown below. These may be substituted with the above substituents.

  Examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto. The compound represented by the general formula (I) can be synthesized by the method described in JP-T-11-513019.

  The optically anisotropic layer is formed by applying a fluid containing a liquid crystal compound (for example, a solution of a liquid crystal compound) in an area separated by a black matrix by an ink jet method to obtain an alignment state exhibiting a desired liquid crystal phase. Thereafter, the layer is preferably a layer prepared by fixing the alignment state by irradiation with heat or ionizing radiation.

  When a rod-like liquid crystal compound having a reactive group is used as the liquid crystal compound, it may be fixed in any alignment state of horizontal alignment, tilt alignment, hybrid alignment, and twist alignment. In this specification, the horizontal orientation means an orientation having an inclination angle with a horizontal plane of less than 10 degrees.

  In the case of laminating two or more optically anisotropic layers made of a liquid crystalline compound, the combination of liquid crystalline compounds is not particularly limited, and a laminate of layers made of all discotic liquid crystalline compounds, all made of rod-like liquid crystalline compounds. It may be a laminate of layers composed of a layer, a layer composed of a discotic liquid crystalline compound and a layer composed of a rod-shaped liquid crystalline compound. The combination of the alignment states of the layers is not particularly limited, and optically anisotropic layers having the same alignment state may be stacked, or optically anisotropic layers having different alignment states may be stacked.

[A-Plate]
As described above, the first optically anisotropic layer is preferably a positive A plate. A uniaxial birefringent layer having an optical axis in the plane and having a refractive index of the slow axis larger than the refractive index in the thickness direction is referred to as a positive A plate. The positive A plate can be realized by horizontal alignment of rod-like liquid crystals.

  The first optically anisotropic layer is preferably formed by applying a coating liquid containing a liquid crystalline compound and the following polymerization initiator and other additives by an inkjet method. As a solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

[Fixation of alignment state of liquid crystalline composition]
The aligned liquid crystalline composition is fixed while maintaining the alignment state. The immobilization is preferably carried out by a polymerization reaction of a reactive group introduced into the liquid crystalline composition. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator, and a photopolymerization reaction is more preferable. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics. Group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents) No. 3549367), acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (described in U.S. Pat. No. 4,221,970).

The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution. Light irradiation for the polymerization of the liquid crystalline compound is preferably performed using ultraviolet rays. The irradiation energy is preferably ^{20mJ / cm 2 ~10J / cm 2} , further preferably 100 to 800 mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under a nitrogen atmosphere or under heating conditions.

  The optical characteristics of the first optically anisotropic layer are preferably adjusted to optical characteristics that are optimal for viewing angle compensation when R light, G light, and B light are incident. That is, when the color filter layer is colored red and used for forming the R layer of the color filter, the optical characteristics of the optical anisotropic layer are optimally adjusted for viewing angle compensation when R light is incident, When colored green, the optical properties of the optically anisotropic layer are optimally adjusted for viewing angle compensation when G light is incident, and when colored blue, the optical properties of the optically anisotropic layer Is preferably optimally adjusted for viewing angle compensation when B light is incident. The optical characteristics of the optically anisotropic layer are preferably in a preferable range depending on, for example, the type of liquid crystal compound, the type or addition amount of the alignment control agent, the type of alignment film, the rubbing treatment conditions of the alignment film, the film thickness, or the polarization irradiation conditions. Can be adjusted.

[Horizontal alignment control agent]
In the composition for forming the optically anisotropic layer, compounds represented by general formulas (1) to (3) described in [0068] to [0072] of JP-A-2007-121986 and the following general formula By containing at least one fluorine-containing homopolymer or copolymer using the monomer (4), the molecules of the liquid crystal compound can be substantially horizontally aligned.

In the formula, R represents a hydrogen atom or a methyl group, X represents an oxygen atom or a sulfur atom, Z represents a hydrogen atom or a fluorine atom, m is an integer of 1 to 6, and n is an integer of 1 to 12. Represents. In addition to the fluorine-containing polymer containing the general formula (4), the compounds described in JP-A-2005-206638 and JP-A-2006-91205 can be used as the unevenness improving polymer in coating as a horizontal alignment agent. Are also described in the specification.
The addition amount of the horizontal alignment agent is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.02 to 1% by mass of the mass of the liquid crystal compound. In addition, the compounds represented by the general formulas (1) to (4) may be used alone or in combination of two or more.

[Second optically anisotropic layer]
The liquid crystal display device may have a second optical anisotropic layer inside or outside the cell in addition to the first optical anisotropic layer on the color filter layer formed from the composition of the present invention. Good. In the case where the first optical anisotropic layer is a patterned optical anisotropic layer, the second optical anisotropic layer is preferably an unpatterned optical anisotropic layer. For example, it is possible to use various wave plates or liquid crystal layers for the purpose of coloring due to birefringence or compensation of viewing angle, etc., and two or more kinds of optical materials having appropriate optical anisotropy according to the purpose of use. Optical characteristics such as retardation can be controlled by laminating isotropic films. As such an optically anisotropic film, a film made of an appropriate polymer such as polycarbonate, norbornene resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polypropylene, other polyolefins, polyarylate, or polyamide is stretched. Examples thereof include an alignment film made of a liquid crystal compound such as a birefringent film and a liquid crystal polymer, and an alignment layer of a liquid crystal material supported by the film. In addition, a birefringent film or a birefringent film such as a tilted orientation film that has been biaxially stretched or stretched in two orthogonal directions is used. Examples of the inclined alignment film include a film obtained by bonding a heat shrink film to a polymer film and stretching or / and shrinking the polymer film under the action of the contraction force by heating, and a film obtained by obliquely aligning a liquid crystal polymer. Can be mentioned.

  As long as the second optically anisotropic layer region has the optical characteristics, the material and form thereof are basically not particularly limited. For example, a retardation film made of a birefringent polymer film, a film obtained by applying a high molecular compound on a transparent support and then heated and salted, and a low molecular weight or high molecular liquid crystalline compound applied or transferred onto the transparent support Any of the retardation films having the retardation layer formed can be used. Moreover, each can also be laminated | stacked and used.

  The birefringent polymer film is preferably a film having excellent controllability of birefringence characteristics, transparency and heat resistance. In this case, the polymer material to be used is not particularly limited as long as it is a polymer capable of achieving uniform biaxial orientation, but is preferably a conventionally known material that can be formed by a solution casting method or an extrusion method, and is preferably a norbornene-based material. Polymers, polycarbonate polymers, polyarylate polymers, polyester polymers, aromatic polymers such as polysulfone, cellulose acylate, or polymers in which two or more of these polymers are mixed It is done.

The biaxial orientation of the film is a film made of the thermoplastic resin produced by an appropriate method such as an extrusion molding method or a casting film forming method, for example, a longitudinal stretching method using a roll, a transverse stretching method using a tenter, or a biaxial stretching method. It can be obtained by stretching. In the longitudinal stretching method using the roll, an appropriate heating method such as a method using a heating roll, a method of heating an atmosphere, or a method of using them together can be adopted. In the biaxial stretching method using a tenter, an appropriate method such as a simultaneous biaxial stretching method using an all tenter method or a sequential biaxial stretching method using a roll tenter method can be employed.
Moreover, a thing with little orientation nonuniformity and phase difference nonuniformity is preferable. The thickness can be appropriately determined depending on the phase difference or the like, but is generally preferably 1 to 300 μm, more preferably 10 to 200 μm, particularly preferably 20 to 150 μm from the viewpoint of thinning.

  As a method for forming the transparent resin into a sheet or film, for example, either a hot melt molding method or a solution casting method can be used. The heat-melt molding method can be further classified into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch molding method, etc. Among these methods, mechanical strength, surface In order to obtain a film excellent in accuracy and the like, the extrusion molding method, the inflation molding method, and the press molding method are preferable, and the extrusion molding method is most preferable. The molding conditions are appropriately selected depending on the purpose of use and the molding method. In the case of the heat-melt molding method, the cylinder temperature is preferably set in the range of preferably 100 to 400 ° C, more preferably 150 to 350 ° C. The thickness of the sheet or film is preferably 10 to 300 μm, more preferably 30 to 200 μm.

  The sheet or film may be stretched. When the glass transition temperature of the transparent resin is Tg, the stretching of the sheet or film is preferably in a temperature range of Tg-30 ° C to Tg + 60 ° C, more preferably in a temperature range of Tg-10 ° C to Tg + 50 ° C. In at least one direction, the stretching ratio is preferably 1.01 to 2 times. The stretching direction may be at least one direction, but when the sheet is obtained by extrusion, the direction is preferably the mechanical flow direction (extrusion direction) of the resin. A free shrink uniaxial stretching method, a fixed width uniaxial stretching method, a biaxial stretching method, and the like are preferable. The optical characteristics can be controlled by controlling the draw ratio and the heating temperature.

[Liquid Crystal Display]
By using the patterned first optically anisotropic layer and the second optically anisotropic layer that is not patterned as desired, a liquid crystal display device having a wide viewing angle can be provided. . TN mode liquid crystal cell retardation plates (optical compensation sheets) are described in JP-A-6-214116, US Pat. Nos. 5,583,679, 5,646,703, and German Patent 3,911,620A1. A retardation plate (optical compensation sheet) for liquid crystal cells in IPS mode or FLC mode is described in JP-A-10-54982. Furthermore, a retardation plate (optical compensation sheet) for an OCB mode or HAN mode liquid crystal cell is described in US Pat. No. 5,805,253 and International Publication WO96 / 37804. Furthermore, a retardation plate (optical compensation sheet) for a liquid crystal cell in STN mode is described in JP-A-9-26572. A VA mode liquid crystal cell retardation plate (optical compensation sheet) is described in Japanese Patent No. 2866372.

  The present invention can be used for liquid crystal display devices in various display modes such as TN, IPS, FLC, OCB, STN, VA and HAN modes. Among them, it is suitable for a VA mode liquid crystal display device.

[VA mode]
In the VA mode liquid crystal display device, from the viewpoint of improving the viewing angle, as the first optical anisotropic layer, a positive A-plate having a forward dispersion of Re in the visible light region is used, and the second optical anisotropy is used. It is preferred to use a negative C-plate as the layer. A uniaxial birefringent layer having a refractive index in the thickness direction smaller than the in-plane refractive index is referred to as a negative C plate.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

Example 1
(Production method of black photosensitive composition for barrier rib preparation)
The black photosensitive composition K1 is first weighed in the amount of K pigment dispersion 1 and propylene glycol monomethyl ether acetate listed in Table 1, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 RPM for 10 minutes, Next, methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-diethoxycarbonylmethylamino) -3 in the amounts shown in Table 1 '-Bromophenyl] -s-triazine and surfactant 1 are weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) for 150 RPM for 30 minutes. . In addition, the quantity of Table 1 is a mass part, and has the following composition in detail.

<K pigment dispersion 1>
・ Carbon black (Nippex 35 manufactured by Degussa) 13.1%
・ Dispersant (Compound 1 below) 0.65%
-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72%
Propylene glycol monomethyl ether acetate 79.53%

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%
<DPHA solution>
Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76%
・ Propylene glycol monomethyl ether acetate 24%
<Surfactant 1>
・ The following structure 1 30%
・ Methyl ethyl ketone 70%

(Formation of light-shielding barrier)
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the glass substrate coater (manufactured by FAS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle has the composition described in Table 1 above. A black photosensitive composition K1 was applied. Subsequently, a portion of the solvent was dried for 30 seconds with a VCD (vacuum drying device, manufactured by Tokyo Ohka Kogyo Co., Ltd.) to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a black photosensitive film having a thickness of 10 μm. Layer K1 was obtained.

In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the black photosensitive layer K1 The distance was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² in a nitrogen atmosphere.

  Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the black photosensitive layer K1, and then a KOH-based developer (KOH, containing nonionic surfactant, trade names: CDK-1, Fuji Film) (Electronic Materials Co., Ltd.) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure washing nozzle to remove the residue, and post exposure was performed at an exposure amount of 2000 mJ / cm 2 in the atmosphere to obtain a black having an optical density of 3.9. A partition was obtained. A fine region separated by the black partition was formed on the surface of the glass substrate.

Color Filter Composition Table 2 shows the composition of each RGB pixel composition.

The composition of the composition in Table 2 is as follows.
[R pigment dispersion-1 composition]
────────────────────────────────── ――――――
R pigment dispersion-1 composition (%)
────────────────────────────────── ――――――
C. I. Pigment Red 254 8.0
5- [3-oxo-2- [4- [3,5-bis (3-diethylaminopropylaminocarbonyl) phenyl] aminocarbonyl] phenylazo] -butyroylaminobenzimidazolone 0.8
Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, (weight average molecular weight 37,000) 4.0
Compound P-2 4.0
Propylene glycol monomethyl ether acetate 83.2
────────────────────────────────────────

[R pigment dispersion-2 composition]
──────────────────────────────────――
R pigment dispersion-2 composition (%)
──────────────────────────────────――
C. I. Pigment Red 177 18.0
Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio,
(Weight average molecular weight 37,000) 6.0
Compound P-2 6.0
Propylene glycol monomethyl ether acetate 70.0
──────────────────────────────────――

[G pigment dispersion composition]
──────────────────────────────────――
G pigment dispersion composition (%)
──────────────────────────────────――
C. I. Pigment Green 36 18.0
Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio,
(Weight average molecular weight 37,000) 4.0
Compound P-2 8.0
Cyclohexanone 35.0
Propylene glycol monomethyl ether acetate 35.0
──────────────────────────────────――

[Binder 1 composition]
──────────────────────────────────――
Binder 1 composition (%)
──────────────────────────────────――
Random copolymer of benzyl methacrylate / methacrylic acid = 78/22 molar ratio (weight average molecular weight 40,000) 27.0
Propylene glycol monomethyl ether acetate 73.0
──────────────────────────────────――

[Binder 2 composition]
──────────────────────────────────――
Binder 2 composition (%)
──────────────────────────────────――
Benzyl methacrylate / methacrylic acid / methyl methacrylate =
Random copolymer with a 38/25/37 molar ratio (weight average molecular weight 30,000) 27.0
Propylene glycol monomethyl ether acetate 73.0
──────────────────────────────────――

[Binder 3 composition]
──────────────────────────────────――
Binder 3 composition (%)
──────────────────────────────────――
Benzyl methacrylate / methacrylic acid / methyl methacrylate =
Random copolymer of 36/22/42 molar ratio (weight average molecular weight 30,000) 4.0
Compound P-2 23.0
Propylene glycol monomethyl ether acetate 73.0
──────────────────────────────────――

[DPHA composition]
──────────────────────────────────――
DPHA solution composition (%)
──────────────────────────────────――
KAYARAD DPHA (Nippon Kayaku Co., Ltd.) 76.0
Propylene glycol monomethyl ether acetate 24.0
──────────────────────────────────――

(Preparation of R-layer forming solution PP-R1)
The R layer forming liquid PP-R1 is first weighed in the amounts of R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate shown in Table 2 and mixed at a temperature of 24 ° C. (± 2 ° C.). And then stirred for 10 minutes at 150 rpm, then the amounts of methyl ethyl ketone, binder 2, DPHA solution, 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxadiazole, 2 , 4-Bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine and phenothiazine were weighed and this was measured at a temperature of 24 ° C. (± 2 ° C.). Add in order and stir at 150 rpm for 10 minutes, then weigh out the amount of ED152 listed in Table 2, mix at a temperature of 24 ° C. (± 2 ° C.) and stir at 150 rpm for 20 minutes Further weighed amount of Megafac F-176PF according to Table 2, and stirred 30rpm30 minutes was added at a temperature 24 ° C. (± 2 ° C.), it was obtained by filtering with a nylon mesh # 200.

(Preparation of G-layer forming solution PP-G1)
G-layer forming liquid PP-G1 was first weighed in the amounts of G pigment dispersion, CF yellow EX3393, and propylene glycol monomethyl ether acetate listed in Table 2, mixed at a temperature of 24 ° C. (± 2 ° C.), and 150 rpm for 10 minutes. Stirring and then the amounts of methyl ethyl ketone, cyclohexanone, binder 1, DPHA solution, 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxadiazole, 2,4- Bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine and phenothiazine are weighed out and added in this order at a temperature of 24 ° C. (± 2 ° C.). And stirred at 150 rpm for 30 minutes, and then weighed out the amount of Megafac F-176PF shown in Table 2 to a temperature of 24 ° C. (± 2 ) Was added with stirring 30rpm5 minutes, and filtering the mixture through a nylon mesh # 200.

(Preparation of B-layer forming solution PP-B1)
The B-layer forming solution PP-B1 is first weighed in the amounts of CF Blue EX3357, CF Blue EX3383 and propylene glycol monomethyl ether acetate listed in Table 2, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. Then, the amounts of methyl ethyl ketone, binder 3, DPHA solution, 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxadiazole, and phenothiazine in the amounts shown in Table 2 were weighed, and the temperature was 25 At a temperature of 40 ° C. (± 2 ° C.) and stirred at 150 rpm for 30 minutes, and the amount of Megafac F-176PF shown in Table 2 was weighed out to a temperature of 24 ° C. (± 2 rpm) and stirred at 30 rpm for 5 minutes and filtered through nylon mesh # 200.

(Preparation of coating solution for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating solution for the optically anisotropic layer.
LC-1-1 was obtained from Tetrahedron Lett. Synthesized according to the method described in Journal, Vol. 43, page 6793 (2002).
──────────────────────────────────――
Coating composition for optically anisotropic layer (%)
──────────────────────────────────――
Polymerizable liquid crystal Illustrative compound I-2 20.0% by mass
1.4-butanediol diacetate 79.28% by mass
-0.02 mass% of horizontal alignment agent (LC-1-1) represented by the following structural formula
・ Irg-907 (Ciba Specialty Chemicals) 0.5% by mass
・ DETX (Nippon Kayaku Co., Ltd.) 0.2% by mass
──────────────────────────────────――

(Preparation of color filter layer)
The PP-R1, PP-G1, and PP-B1, which are liquids for forming the R, G, and B layers obtained above, are placed in a recess surrounded by a light-shielding partition using a piezo head as follows. The droplet was ejected.
The head has a nozzle density of 150 per 25.4 mm, and has 318 nozzles. By fixing these two nozzles in the nozzle row direction with a shift of 1/2 the nozzle interval, 25 heads are arranged on the substrate in the nozzle array direction. . 300 drops per 4 mm. The head and ink are controlled so that the vicinity of the ejection portion is 40 ± 0.5 ° C. by circulating hot water in the head.

  Ink ejection from the head is controlled by a piezo drive signal applied to the head, and ejection of 6 to 42 pl per drop is possible. In this embodiment, the head is moved while the glass substrate is conveyed at a position 1 mm below the head. More drops. The conveyance speed can be set in the range of 50 to 200 mm / s. The piezo drive frequency can be up to 4.6 KHz, and the droplet ejection amount can be controlled by these settings.

In the present embodiment, the parts corresponding to the R, G, and B pixels are conveyed so that the pigment coating amounts are 1.1, 1.8, and 0.75 g / m ² for R, G, and B, respectively. The speed and driving frequency were controlled, and each of the R, G, and B layer forming liquids PP-R1, PP-G1, and PP-B1 was ejected into the recesses corresponding to the desired R, G, and B.
Then, it was dried at 100 ° C., irradiated with polarized light, and further heat-treated at 200 ° C. for 1 hour to form a color filter pixel.

(Preparation of optically anisotropic layer)
A color filter in which the optically anisotropic layer coating liquid obtained above is surrounded by a light-shielding partition wall using a piezo-type head as an optically anisotropic layer (optically anisotropic layer pattern) R-2 for R A droplet was deposited on the layer and heat-dried and aged at 95 ° C. for 2 minutes to form a layer having a uniform liquid crystal phase. Further, immediately after aging, this layer was irradiated with UV (illuminance 200 mW / cm ² , irradiation amount 200 mJ / cm ² ) to fix the optically anisotropic layer, and an optically anisotropic layer having a thickness of 2.8 μm was formed. Formed.
Similarly, G and B optically anisotropic layers (optically anisotropic layer patterns) G-2 and B-2 were formed. The optically anisotropic layers of G-2 and B-2 were 2.75 μm and 2.3 μm, respectively.

(Phase difference measurement)
Retardation Re (40) when the sample is tilted by ± 40 degrees with the front axis Re (0) at the arbitrary wavelength λ and the slow axis as the rotation axis by the parallel Nicol method using a fiber type spectrometer. (-40) was measured. For R, G, and B, λ was measured for retardation of 611 nm, 545 nm, and 435 nm, respectively. For the retardation of the optically anisotropic layer of the present invention, only the retardation of the optically anisotropic layer was obtained by calibrating with the transmittance data of the substrate without the optically anisotropic layer measured in advance. Table 3 shows the phase difference measurement results.

(Formation of transparent electrode)
A transparent electrode film (film thickness of 2000 mm) was formed on the color filter produced above by ITO sputtering.

(Formation of alignment layer and liquid crystal cell formation)
Further, a polyimide alignment film was provided thereon. Next, glass beads having a particle diameter of 5 μm were sprayed. Further, an epoxy resin sealant containing spacer particles is printed at a position corresponding to the outer frame of the black matrix provided around the pixel group of the color filter, and the color filter substrate is applied to the counter substrate at a pressure of 10 kg / cm. Pasted together. Next, the bonded glass substrate was heat-treated at 150 ° C. for 90 minutes to cure the sealing agent, thereby obtaining a laminate of two glass substrates. This glass substrate laminate was degassed under vacuum, then returned to atmospheric pressure, and liquid crystal was injected into the gap between the two glass substrates to obtain a liquid crystal cell.
As the upper polarizing plate (observer side) of this liquid crystal cell, a polarizing plate with a negative C-plate produced according to the method described in JP-A-2005-173567 was used. A polarizing plate HLC2-2518 made by Sanritz was attached to the lower polarizing plate (backlight side). The negative C-plate had Re of 0 nm and Rth of 200 nm.

(Production of VA-LCD)
As a cold-cathode tube backlight for a color liquid crystal display device, a phosphor obtained by mixing BaMg2Al16O27: Eu, Mn and LaPO4: Ce, Tb at a weight ratio of 50:50 is green (G), and Y2O3: Eu is red (R ), BaMgAl10O17: Eu was blue (B), and a white three-wavelength fluorescent lamp having an arbitrary color tone was produced. A liquid crystal cell provided with the above polarizing plate was placed on this backlight to produce a VA-LCD.

(Production of VA-LCD of Comparative Example 1)
(Preparation of coating liquid AL-1 for alignment layer)
The following composition was prepared, filtered through a polypropylene filter having a pore size of 30 μm, and used as an alignment layer coating liquid AL-1.
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Coating liquid composition for alignment layer (%)
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Polyvinyl alcohol (PVA205, manufactured by Kuraray Co., Ltd.) 3.21
Polyvinylpyrrolidone (Luvitec K30, manufactured by BASF) 1.48
Distilled water 52.1
Methanol 43.21
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  After the polarized light irradiation step in Example 1, before the heat treatment step, the alignment layer coating solution AL-1 obtained above is formed on the upper part of the color filter layer surrounded by the light-shielding partition using a piezo head. And then rubbed. Other than that was carried out similarly to Example 1, and produced the VA-LCD of the comparative example 1. FIG.

(Evaluation of VA-LCD)
The viewing angle characteristics of the manufactured liquid crystal display device were measured with a viewing angle measuring device (EZ Contrast 160D, manufactured by ELDIM). Table 4 shows the results of visual evaluation of the examples and comparative examples.

It is a schematic diagram which shows an example of the flow of the manufacturing method of the board | substrate for liquid crystal display devices. It is a schematic sectional drawing of an example of the board | substrate for liquid crystal display devices. It is a schematic sectional drawing of an example of a liquid crystal display device.

Explanation of symbols

11 Transparent substrate 12 Black matrix
13 Partial region of color filter layer 14 Partial region of optically anisotropic layer 21 Substrate 22 Black matrix (partition)
23 Color filter layer 24 Solid optically anisotropic layer (second optically anisotropic layer)
25 Transparent electrode layer 26 Alignment layer 27 Patterning optical anisotropic layer (first optical anisotropic layer)
31 Liquid crystal 32 TFT
33 Polarizing layer 34 Cellulose acetate film (polarizing plate protective film)
35 Cellulose acetate film or optical compensation sheet 36 Polarizing plate 37 Liquid crystal cell

Claims (15)

A composition for producing a color filter comprising a pigment or dye and a photoreactive compound. substrate,
A substrate for a liquid crystal display device comprising a color filter layer formed from the composition according to claim 1 and an optically anisotropic layer directly laminated on the color filter layer in this order. The liquid crystal display device substrate according to claim 2, wherein the color filter layer includes a part of a partition formed on the substrate, and the partition divides the color filter layer into a plurality of regions. The liquid crystal display substrate according to claim 3, wherein the optically anisotropic layer is divided into a plurality of regions by the partition walls. The substrate for a liquid crystal display device according to claim 3 or 4, wherein the partition walls are formed in a matrix. The optically anisotropic layer is a layer formed by forming a liquid crystal phase from a composition containing a liquid crystal compound having at least one reactive group, and then fixing the liquid crystal phase by heat or light irradiation. Item 6. The substrate for a liquid crystal display device according to any one of Items 2 to 5. The liquid crystal display substrate according to claim 6, wherein the light irradiation is ultraviolet irradiation. The substrate for a liquid crystal display device according to claim 6, wherein the reactive group is an ethylenically unsaturated group. The liquid crystal display substrate according to claim 6, wherein the composition further contains at least one radical polymerization initiator. The substrate for a liquid crystal display device according to claim 6, wherein the liquid crystal compound is a rod-like liquid crystal. The liquid crystal display device containing the board | substrate for liquid crystal display devices as described in any one of Claims 2-10. The substrate for a liquid crystal display device according to claim 2, wherein the optically anisotropic layer is a positive A plate. A liquid crystal display device comprising the substrate for a liquid crystal display device according to claim 12. In addition to the optically anisotropic layer, a second optically anisotropic layer is included,
The second optically anisotropic layer is a negative C plate;
The liquid crystal display device according to claim 13, wherein the display mode is a VA mode. A manufacturing method of a substrate for a liquid crystal display device including at least the following steps [1] to [4] in this order:
[1] A step of preparing a substrate having a partition wall and a fine region formed by the partition wall on the surface;
[2] A step of discharging and drying an ink liquid containing a pigment or dye and a photoreactive compound to the fine region by an inkjet method;
[3] A step of irradiating the substrate obtained after step [2] with polarized light; and [4] a fluid containing at least one liquid crystalline compound in the fine region and exhibiting a predetermined optical anisotropy. Forming an optically anisotropic layer by discharging the ink from an ink jet type discharge head and drying to form a liquid crystal phase and then exposing to light.

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