JP3394148B2 - Color filter, method of manufacturing the same, and liquid crystal display - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a color filter and a method for manufacturing the same. More specifically, the present invention provides
The present invention relates to an inexpensive color filter having excellent display quality and flatness of pixels, and a simple manufacturing method thereof. further,
The present invention relates to a liquid crystal display device including such a color filter, which is excellent in color display performance and is inexpensive.

[0002]

2. Description of the Related Art A color filter for a display element such as a liquid crystal display element is an essential member for colorizing a display element and is manufactured by forming colored pixels on a glass or transparent plastic substrate. The colored pixel is configured by arranging pixels of three primary colors of red (R), blue (B), and green (G) in a line shape or a mosaic shape, and the size of each pixel is around 100 μm. For the pixel coloring method,
A method of patterning with light using each of the R, G, and B photosensitive coloring pastes, a method of ejecting and coloring a non-photosensitive ink at a predetermined position by an inkjet method, and a screen on a substrate using a printing device. A method of coloring by printing, a method of coloring on a substrate having a transparent electrode formed thereon by an electrodeposition method, and the like have been proposed.

Between each pixel (that is, the non-pixel portion),
A light-shielding coloring layer generally called a black matrix is formed in order to increase the contrast of pixels. The light-shielding colored layer is used, for example, in a TFT-driving type liquid crystal display element to shield the transistor and the wiring portion from light. The light-shielding colored layer has a width of several μm in a narrow place and a width of about 100 μm in a wide place. Conventionally, such a light-shielding coloring layer is formed by etching a vapor deposition film of metal chromium or a sputtering film.

When the conventional light-shielding colored layer is used, ink squeezes out on the light-shielding colored layer, and flat pixels cannot be obtained. This is because the conventional light-shielding colored layer has insufficient ink resilience. As a method for solving such a problem, for example, JP-A-4-123005, JP-A-4-123006, JP-A-4-123007, JP-A-4-15
JP-A No. 160 and JP-A-4-195102 describe a method for producing a color filter by an inkjet method or a printing method in which a silicone resin layer is formed on a photosensitive resin layer and the ink resilience of the silicone resin is used. ing. However, in such a method, the light-shielding coloring layer, the photosensitive resin layer and the silicone resin layer must be laminated. Further, such a method requires a step of developing the photosensitive resin. Therefore, the conventional color filter using the light-shielding colored layer and the manufacturing method thereof have many problems such as an increase in the thickness of the color filter (as a result, an increase in the thickness of the liquid crystal display device), a complicated manufacturing process, and an increase in cost. have.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems, and (1) to provide an inexpensive color filter which is excellent in display quality and pixel flatness; ) An object of the present invention is to provide a simple method for producing such a color filter, and (3) to provide an inexpensive liquid crystal display device having such a color filter, which is excellent in color display performance.

[0006]

The color filter of the present invention is a color filter having pixels and a light-shielding coloring layer on a transparent substrate, and the light-shielding coloring layer changes to hydrophobic by heating.
To be formed by using a hydrophilic light-shielding colored ink, the hydrophilic light-shielding colored ink comprises a resin having a monomer unit containing a quaternary ammonium salt moiety of the formula (I), is a color filter:

[0007]

[Chemical 19]

Where X ⁺ is represented by the formula (II):

[0009]

[Chemical 20]

Wherein R ¹ , R ² , R ³ and R ⁴ are independently hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or Two
A substituted or unsubstituted linear or branched alkenyl group having -8 carbon atoms.

In a preferred embodiment, R ¹ above,
R ² , R ³ and R ⁴ are independently hydrogen, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, an allyl group and a methallyl group. Selected, more preferably R ¹ , R ² ,
One of R ³ and R ⁴ is hydrogen and the other three are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl and butyl groups.

In another preferred embodiment, the monomeric unit containing the quaternary ammonium salt moiety has the formula (III)
A monomer unit represented by formula (IV), a monomer unit represented by formula (IV), a monomer unit represented by formula (V), and a formula (V
At least one monomer unit selected from the group consisting of monomer units represented by I):

[0013]

[Chemical 21]

Wherein R ⁵ is hydrogen, a methyl group, or a trifluoromethyl group; R ⁶ , R ⁷ and R ⁸ are each hydrogen, a substituted or unsubstituted having 1 to 12 carbon atoms. Linear or branched alkyl group, substituted or unsubstituted linear or branched alkenyl group having 2 to 8 carbon atoms, substituted or unsubstituted aralkyl group, substituted or unsubstituted phenyl group, heterocycle A group, a linear or branched fluorine-substituted alkyl group having 1 to 12 carbon atoms, and a fluorine-substituted alkylaryl group.

In still another preferred embodiment, the resin contained in the hydrophilic light-shielding colored ink further has a fluorine-containing monomer unit, and preferably the fluorine-containing monomer unit is represented by the formula (VII). The monomer units represented are:

[0016]

[Chemical formula 22]

Here, R ^A is hydrogen, a methyl group, or a trifluoromethyl group, and R ^B is a linear or branched fluorine-substituted alkyl group having 1 to 22 carbon atoms, or fluorine. It is a substituted alkylaryl group.

Preferably, the fluorine-containing monomer unit is contained in the resin in a ratio of 2 mol% to 90 mol%. Preferably, the monomer unit having a quaternary ammonium salt moiety is contained in the resin in a ratio of 10 mol% to 70 mol%.

In another preferred embodiment, the resin contained in the hydrophilic light-shielding colored ink is an acrylate monomer unit, a methacrylate monomer unit, a styrene monomer unit, a vinyl acetate monomer unit, and an isobutylene monomer unit. It further has at least one monomer unit selected from the group consisting of: Preferably, the styrenic monomer unit is represented by formula (VIII):

[0020]

[Chemical formula 23]

Here, R ²¹ is hydrogen or a methyl group, and R ²² is hydrogen, an alkyl group having 1 to 12 carbon atoms, a nitro group or halogen.

In another preferred embodiment, the hydrophilic light-shielding colored ink further contains a fluorine-containing compound. Preferably the fluorine containing compound is represented by formula (IX):

[0023]

[Chemical formula 24]

Here, R ³¹ is a fluorine-substituted alkyl group having 1 to 12 carbon atoms, and Y is —COO—, —OC.
O-, -CONH-, -CO-, -O-, -S-, phenylene group, -SO ₂ -,-
SO ₃ -or -SO ₂ NH-, and Z is -COOH, -OH, -CONH
₂ , -SO ₂ NH ₂ , -NH ₂ , -SO ₃ ^- NH ₄ ⁺ , -COO ^- NH ₄ ⁺ , -COO ^- NH ⁺ (C
₂ H _{5) 3} or -NH ₃ ⁺ · B, ^- (wherein B ^- is an anion residue), m and n are independently an integer of 0 to 6,
p is 0 or 1.

In still another preferred embodiment, the hydrophilic light-shielding colored ink has a monomer unit represented by the above formula (III), a monomer unit represented by the above formula (IV), and the above formula ( V) comprising a resin having a monomer unit containing at least one quaternary ammonium salt moiety selected from the group consisting of monomer units represented by:
R ⁵ is hydrogen or a methyl group; R ⁶ is hydrogen, 1 to
Substituted or unsubstituted linear or branched alkyl group having 12 carbon atoms, substituted or unsubstituted linear or branched group having 2 to 8 carbon atoms, substituted or unsubstituted aralkyl group A substituted or unsubstituted phenyl group,
And a heterocyclic group. Preferably, the resin contained in the hydrophilic light-shielding colored ink is at least selected from the group consisting of acrylate-based monomer units, methacrylate-based monomer units, styrene-based monomer units, vinyl acetate monomer units, and isobutylene monomer units. It further has one monomer unit. Further, preferably, the hydrophilic light-shielding colored ink further contains a fluorine-containing compound.

In another preferred embodiment, the hydrophilic light-shielding colored ink has a monomer unit represented by the above formula (III), a monomer unit represented by the above formula (IV), and the above formula (V ) A resin having a monomer unit containing at least one quaternary ammonium salt moiety selected from the group consisting of monomer units and a fluorine-containing monomer unit, wherein R ⁵ is hydrogen or a methyl group. Or a trifluoromethyl group; R ⁶ is hydrogen, 1 to 12
Substituted or unsubstituted linear or branched alkyl group having 4 carbon atoms, substituted or unsubstituted linear or branched group having 2 to 8 carbon atoms, substituted or unsubstituted aralkyl group, It is selected from the group consisting of substituted or unsubstituted phenyl groups, as well as heterocyclic groups. Preferably, the fluorine-containing monomer unit is contained in the resin in a ratio of 2 mol% to 90 mol%, and preferably, the monomer unit having a quaternary ammonium salt moiety is 10 mol%.
It is contained in the resin in a ratio of mol% to 70 mol%.
Preferably, the resin contained in the hydrophilic light-shielding colored ink is at least 1 selected from the group consisting of an acrylate monomer unit, a methacrylate monomer unit, a styrene monomer unit, a vinyl acetate monomer unit, and an isobutylene monomer unit. It further has a monomer unit of the species. Furthermore, preferably, the hydrophilic light-shielding colored ink further contains a fluorine-containing compound.

In another preferred embodiment, the hydrophilic light-shielding colored ink is selected from the group consisting of a monomer unit represented by the above formula (V) and a monomer unit represented by the above formula (VI). A resin having a monomer unit containing at least one quaternary ammonium salt moiety, wherein R ⁶ is a linear or branched fluorine-substituted alkyl group having 1 to 12 carbon atoms, and a fluorine-substituted alkyl group. Selected from the group consisting of alkylaryl groups; R ⁷ and R ⁸ are each hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, 2 to 8
Substituted or unsubstituted linear or branched alkenyl group having 1 carbon atom, substituted or unsubstituted aralkyl group, substituted or unsubstituted phenyl group, heterocyclic group, 1 to 1
Selected from the group consisting of linear or branched fluorine-substituted alkyl groups having 2 carbon atoms, and fluorine-substituted alkylaryl groups, provided that at least one of R ⁷ and R ⁸ is 1-12 Selected from the group consisting of linear or branched fluorine-substituted alkyl groups having carbon atoms of, and fluorine-substituted alkylaryl groups. Preferably, the resin contained in the hydrophilic light-shielding colored ink is at least 1 selected from the group consisting of an acrylate monomer unit, a methacrylate monomer unit, a styrene monomer unit, a vinyl acetate monomer unit, and an isobutylene monomer unit. It further has a monomer unit of the species. Preferably, the hydrophilic light-shielding colored ink further contains a fluorine-containing compound.

[0028] In still another preferred embodiment, the hydrophilic light-shielding colored ink further contains at least one polyamino compound. This polyamino compound is preferably a diamino compound of formula (X):

[0029]

[Chemical 25]

Where A is a divalent hydrocarbon residue; and R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are independently hydrogen, substituted with 1 to 12 carbon atoms. Or an unsubstituted linear or branched alkyl group, a substituted or unsubstituted cycloalkyl group having 5 to 6 carbon atoms, or a substituted or unsubstituted linear group having 2 to 8 carbon atoms, or It is a branched alkenyl group.

In another preferred embodiment, the light-shielding coloring layer contains a coloring agent, and the coloring agent is a pigment-based coloring agent. Preferably, the pigment-based colorant is carbon black having --COOM groups on its surface, where M is hydrogen,
It is one selected from ammonium and alkali metals.

In another preferred embodiment, an undercoat layer having adhesiveness to the light-shielding colored layer is provided on the surface of the transparent substrate. Preferably, the subbing layer is gelatin, or the subbing layer comprises a polymer having monomer units of formula (XI):

[0033]

[Chemical formula 26]

Where R ⁵¹ is hydrogen or a methyl group; and R ⁵² is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkyl group. It is an unsubstituted linear or branched aralkyl group, a substituted or unsubstituted phenyl group, or a heterocyclic group.

The method of manufacturing a color filter of the present invention comprises a step of adhering a hydrophilic light-shielding colored ink, which changes into hydrophobicity by heating on a transparent substrate, in a predetermined pattern, and the hydrophilic light-shielding colored ink is made hydrophobic. To form a water-repellent light-shielding coloring layer, and a step of forming a pixel by attaching a hydrophilic pixel color ink to a portion of the transparent substrate where the water-repellent light-shielding coloring layer is not formed. Include.

In a preferred embodiment, the hydrophilic light-shielding colored ink comprises a resin having a monomer unit containing a quaternary ammonium salt moiety of formula (I):

[0037]

[Chemical 27]

Where X ⁺ is represented by the formula (II):

[0039]

[Chemical 28]

Wherein R ¹ , R ² , R ³ and R ⁴ are independently hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or Two
A substituted or unsubstituted linear or branched alkenyl group having -8 carbon atoms.

In a preferred embodiment, the monomer unit containing a quaternary ammonium salt moiety is a monomer unit represented by the formula (III), a monomer unit represented by the formula (IV) or a formula (V). Monomer units, and formula (VI)
Is at least one monomer unit selected from the group consisting of monomer units represented by:

[0042]

[Chemical 29]

Wherein R ⁵ is hydrogen, a methyl group or a trifluoromethyl group; R ⁶ , R ⁷ and R ⁸ are each hydrogen, a substituted or unsubstituted having 1 to 12 carbon atoms. Linear or branched alkyl group, substituted or unsubstituted linear or branched alkenyl group having 2 to 8 carbon atoms, substituted or unsubstituted aralkyl group, substituted or unsubstituted phenyl group, heterocycle A group, a linear or branched fluorine-substituted alkyl group having 1 to 12 carbon atoms, and a fluorine-substituted alkylaryl group.

In another preferred embodiment, the hydrophilic light-shielding colored ink has a monomer unit represented by the above formula (III), a monomer unit represented by the above formula (IV), and the above formula (V ) a resin having a monomer unit containing at least one quaternary ammonium salt moiety is selected from the group consisting of monomer units represented by wherein, R ⁵ is
Hydrogen or a methyl group; R ⁶ is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkyl group having 2 to 8 carbon atoms It is selected from the group consisting of linear or branched groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted phenyl groups, and heterocyclic groups.

In still another preferred embodiment, the hydrophilic light-shielding colored ink has a monomer unit represented by the above formula (III), a monomer unit represented by the above formula (IV), and the above formula (IV). V) including a resin having a monomer unit containing at least one quaternary ammonium salt moiety selected from the group consisting of monomer units represented by V) and a fluorine-containing monomer unit, wherein R ⁵ is hydrogen, methyl A group or a trifluoromethyl group; R ⁶ is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkyl group having 2 to 8 carbon atoms or It is selected from the group consisting of an unsubstituted linear or branched group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, and a heterocyclic group.

In another preferred embodiment, the hydrophilic light-shielding colored ink is selected from the group consisting of a monomer unit represented by the above formula (V) and a monomer unit represented by the above formula (VI). A resin having a monomer unit containing at least one quaternary ammonium salt moiety, wherein R ⁶ is a linear or branched fluorine-substituted alkyl group having 1 to 12 carbon atoms, and fluorine. Selected from the group consisting of substituted alkylaryl groups; R ⁷ and R ⁸ are each hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, 2 to 8
Substituted or unsubstituted linear or branched alkenyl group having 1 carbon atom, substituted or unsubstituted aralkyl group, substituted or unsubstituted phenyl group, heterocyclic group, 1 to 1
Selected from the group consisting of linear or branched fluorine-substituted alkyl groups having 2 carbon atoms, and fluorine-substituted alkylaryl groups, provided that at least one of R ⁷ and R ⁸ is 1-12 Selected from the group consisting of linear or branched fluorine-substituted alkyl groups having carbon atoms of, and fluorine-substituted alkylaryl groups.

In a preferred embodiment, the light-shielding colored layer is formed so as to match the pattern of the non-pixel portion of the liquid crystal display device.

In another preferred embodiment, the light-shielding colored ink is applied to the transparent substrate by an ink jet method, a dispenser method, a stencil printing method, a screen printing method, or an offset printing method.

In still another preferred embodiment, the hydrophilic light-shielding colored ink further contains at least one polyamino compound, and the light-shielding colored ink is attached to the transparent substrate by a screen printing method or an offset printing method. Let Preferably the polyamino compound is a diamino compound of formula (X):

[0050]

[Chemical 30]

Where A is a divalent hydrocarbon residue; and R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are independently hydrogen, substituted with 1 to 12 carbon atoms. Or an unsubstituted linear or branched alkyl group, a substituted or unsubstituted cycloalkyl group having 5 to 6 carbon atoms, or a substituted or unsubstituted linear group having 2 to 8 carbon atoms, or It is a branched alkenyl group.

In another preferred embodiment, the hydrophilic pixel color ink is deposited on the transparent substrate by an inkjet method.

The liquid crystal display device of the present invention is a liquid crystal display device in which a liquid crystal is sealed between a pair of substrates, and the color filter of the present invention is provided on at least one of the substrates. .

The operation will be described below. According to the present invention, the hydrophilic light-shielding colored ink forming the light-shielding colored layer contains a resin having a monomer unit containing a quaternary ammonium salt moiety. The quaternary ammonium salt portion in the water or alcohol-based solution or dispersion (that is, in the hydrophilic light-shielding colored ink) has a cation portion that easily undergoes ammonia or amine (primary amine, secondary amine) by ordinary heat treatment.
Primary amine, tertiary amine). This ammonia or amine is easily vaporized by heating. By utilizing such characteristics of the ammonium salt moiety,
The hydrophilic portion (ie, salt portion) of the resin in the light-shielding colored ink is very easily removed. Therefore, since the resin in the light-shielding color ink easily changes from hydrophilic to hydrophobic by heating, the light-shielding color ink used in the color filter of the present invention has good adhesion (hydrophilicity) when attached to the substrate. In addition, the water-repellent light-shielding colored layer can be easily obtained by heating.

Preferably, the light-shielding colored ink contains fluorine functionality in addition to the resin containing quaternary ammonium monomer units. As a result, the water-repellent color layer (black matrix) obtained has extremely excellent water repellency. Therefore, the adhesion of the R, G, and B pixel color inks to the light-shielding colored layer can be prevented very well. As a result, the light-shielding colored layer prevents color mixing of the color inks for each pixel very well, so that a color filter having high accuracy and stability can be obtained. Fluorine functionality can be shielded from light by various methods, as described above, such as by using a quaternary ammonium monomer containing a fluorine containing moiety; by using a fluorine containing monomer; and / or by using a fluorine containing compound. Can be incorporated into the color ink. In particular, when a quaternary ammonium monomer containing a fluorine-containing moiety is used or when a fluorine-containing monomer is used, since fluorine functionality is present in the resin molecule, compared to the case where the fluorine-containing compound is simply added to the light-shielding colored ink. The resulting light-shielding colored layer is particularly excellent in water repellency. Furthermore, since there is no concern about bleeding out of the fluorine-containing low molecular weight substance, the adhesion of the ink to the substrate is not impaired. Therefore, such a resin having fluorine functionality has both excellent adhesion of the ink to the substrate and excellent water repellency of the light-shielding colored layer.

Furthermore, when the light-shielding colored ink uses a polyamino compound, the thickening effect of ionic crosslinking causes
Since the viscosity of the ink increases, such a light-shielding colored ink is particularly suitable for a printing method such as screen printing and offset printing in which the viscosity of the ink is required.

[0057]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, the "monomer unit" means a repeating unit constituting a resin (that is, a polymer) contained in the light-shielding colored ink used in the color filter of the present invention. Further, "quaternary ammonium monomer unit" means a monomer unit having a quaternary ammonium salt moiety; "fluorine-containing monomer unit"
Means a monomer unit having no quaternary ammonium salt moiety and containing fluorine.

The color filter of the present invention has pixels and light-shielding colored layers on a transparent substrate. This light-shielding coloring layer is formed by using a hydrophilic light-shielding coloring ink. As will be described in detail later, this hydrophilic light-shielding coloring ink can be changed to hydrophobic by a simple treatment such as heating after being applied on a transparent substrate, and provides a water-repellent light-shielding coloring layer.

The hydrophilic light-shielding colored ink used in the present invention will be described below.

A. Quaternary Ammonium Monomer Unit The hydrophilic light-shielding colored ink used in the color filter of the invention comprises a monomer unit containing a quaternary ammonium salt moiety represented by the formula (I) (hereinafter referred to as a quaternary ammonium monomer unit). Including resin with:

[0061]

[Chemical 31]

Here, the cation moiety X ⁺ of the quaternary ammonium salt moiety is any cation which gives ammonia or amine which can be easily volatilized by heating. Preferably, X ⁺ is represented by formula (II):

[0063]

[Chemical 32]

Wherein R ¹ , R ² , R ³ and R ⁴ independently have hydrogen, 1 to 12, preferably 1 to 6, more preferably 1 to 4 carbon atoms. A substituted or unsubstituted linear or branched alkyl group, or 2 to 8
A substituted or unsubstituted linear or branched alkenyl group having 1, preferably 3 to 6, more preferably 3 to 4 carbon atoms. Unless impairing the advantages of the present invention,
The alkyl group or alkenyl group may be substituted with any substituent. Representative examples of such a substituent include a hydroxyl group, a halogen, an alkoxy group and the like.
Hydroxyl groups are preferred.

Preferably, in the formula (II), R ¹ , R ² and
R ³ and R ⁴ are independently selected from the group consisting of hydrogen, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, an allyl group and a methallyl group. . More preferably, R ¹ , R ² , R ³ ,
R ⁴ is independently selected from the group consisting of hydrogen, alkyl groups having 1 to 4 carbon atoms, and allyl groups.
Particularly preferably, ^one of R ¹ , R ² , R ³ and R ⁴ is hydrogen and the other three are independently hydrogen, a methyl group,
It is selected from the group consisting of ethyl, propyl, and butyl groups. Most preferably, ^one of R ¹ , R ² , R ³ , R ⁴ is hydrogen and the other three are independently selected from the group consisting of hydrogen, methyl and ethyl groups. Since such a cation portion is easily vaporized by heating,
This is because it is easy to make the light-shielding colored ink hydrophobic.

Specific examples of such a cation moiety include NH ₄ ⁺ , NH ₃ (CH ₃ ) ⁺ , NH ₂ (CH ₃ ) ₂ ⁺ , NH (nC ₃ H ₇ ) ₃ ⁺ , NH
^{_{(CH 3) 3 +, N}} (C 2 H 5) 4 +, NH (C 2 H 5) 3 +, NH 2 (C 2 H 5) 2 +, NH 3 (C
₂ H ₅ ) ⁺ , NH (C ₂ H ₅ ) ₂ (CH ₃ ) ⁺ , NH (CH ₃ ) ₂ (nC ₃ H ₇ ) ⁺ , NH (CH ₃ ).
₂ (nC ₄ H ₉ ) ⁺ , NH (iso-C ₃ H ₇ ) ₃ ⁺ , NH ₃ (iso-C ₃ H ₇ ) ⁺ , NH ₂ (n-
^{_{C 4 H 9) 2 +,}} NH 3 (nC 4 H 9) +, NH (CH 2 CH = CH 2) 3 +, NH 2 (CH 2 CH =
^{_{CH 2) 2 +, NH (}} C (CH 3) HCH = CH 2) 3 +, NH (CH 2 C (CH 3) = CH 2) 3 +,
NH ₃ (nC ₆ H ₁₃ ) ⁺ , NH ₃ (nC ₁₂ H ₂₅ ) ⁺ , NH ₃ (nC ₈ H ₁₇ ) ⁺ , N (CH
^{_{3) 4 +, N (CH}} 3) (C 2 H 5) 3 +, N (CH 3) 2 (C 2 H 5) 2 +, N (CH 3) 3 (CH 2
CH = CH ₂ ) ⁺ , NH ₂ (C ₂ H ₄ OH) ₂ ⁺ , NH ₃ (C ₂ H ₄ OH) ⁺ , NH ₃ (CH ₂ O
H) ⁺ , NH ₂ (CH ₂ OH) ₂ ⁺ , NH (C ₂ H ₄ OH) ₃ ⁺ , and NH (CH ₂ OH) ₃ ⁺ . ^{_{NH 4 +, NH 3 (CH}} 3) +, NH 2 (CH 3) 2 +, NH (CH 3) 3 +, NH
^{_{3 (C 2 H 5) +}} , NH 2 (C 2 H 5) 2 +, NH (C 2 H 5) 3 + are preferred.

When a resin having such a quaternary ammonium monomer unit is heated, the cation portion of the quaternary ammonium salt has ammonia or amine (primary amine,
It is easily vaporized as a secondary amine or a tertiary amine, and as a result, the quaternary ammonium salt is easily converted into a carboxylic acid or a carboxylic acid ester. That is, such a resin exhibits good adhesion to the substrate (that is, hydrophilicity) because the quaternary ammonium salt portion is present in the resin when it is attached to the substrate, and after formation of the light-shielding colored layer, , The hydrophilic portion (that is, the salt portion) is removed from the resin, and thus exhibits good water repellency.

The change from hydrophilicity to hydrophobicity is as follows.
It can be achieved by the following reaction:

[0069]

[Chemical 33]

The liberated amine compounds are shown in Table 1 below.

[0071]

[Table 1]

Specific examples of free amine compounds are as follows: ammonia; primary amines: methylamine, ethylamine, n-butylamine, n-propylamine, iso-propylamine, n-hexylamine, n -Stearylamine, n-octylamine, ethanolamine, methanolamine, benzylamine, 4-methylbenzylamine, 4-chlorobenzylamine; secondary amine: dimethylamine, diethylamine, dimethanolamine, diethanolamine, N-ethyl- N-ethanolamine, dipropylamine, N-methylbenzylamine, diallylamine, dimethallylamine, dibutylamine, N-methyl-N-ethylamine; tertiary amine: trimethylamine, triethylamine,
Tripropylamine, N, N-diethylethanolamine,
N, N-dimethyl-N-ethylamine, N, N-diethyl-N-methylamine, N, N-dimethyl-N-propylamine, trimethanolamine, triethanolamine, triallylamine, N, N-dimethyl-N -Allylamine, trimetaallylamine, N, N-diethyl-N-butylamine, N, N-dimethylbenzylamine.

Therefore, the cation moiety X of formula (I) above
^{The +} may be ammonia or any cation that can give an amine that readily volatilizes upon heating as described above.

Preferred quaternary ammonium monomer units are represented by the following formulas (III) to (VI):

[0075]

[Chemical 34]

Here, R ⁵ is hydrogen, a methyl group, or a trifluoromethyl group; R ⁶ , R ⁷ and R ⁸ are each hydrogen, 1 to 12, preferably 1 to 6, more preferably Is a substituted or unsubstituted linear or branched alkyl group having 2 to 4 carbon atoms, substituted or unsubstituted having 2 to 8, preferably 3 to 6, and more preferably 3 to 4 carbon atoms. Unsubstituted linear or branched group, substituted or unsubstituted linear or branched aralkyl group, substituted or unsubstituted phenyl group, heterocyclic group, 1 to 12, preferably 1 to 8 It is preferably selected from the group consisting of linear or branched fluorine-substituted alkyl groups having 1 to 4 carbon atoms, as well as fluorine-substituted alkylaryl groups. An alkyl group, an alkenyl group, an aralkyl group or a phenyl group may be substituted with any substituent as long as the advantages of the present invention are not impaired. Representative examples of such a substituent include a hydroxyl group, a nitro group, a sulfonic acid group, halogen and the like. Hydroxyl groups are preferred.

The alkyl group is preferably a methyl group or an ethyl group. The alkenyl group is preferably
An allyl group and a methallyl group. The aralkyl group is preferably a benzyl group. The above heterocyclic group is
A nitrogen-containing 5-membered ring or an oxygen-containing 5-membered ring is preferable.

The above-mentioned fluorine-substituted alkyl group and fluorine-substituted alkylaryl group may be perfluoro-substituted or partially fluorine-substituted. The fluorine-substituted alkylaryl group is preferably a phenyl group substituted with a fluorine-substituted alkyl.

It is preferable to use, as the quaternary ammonium monomer unit, a monomer unit containing a fluorine-containing portion in addition to the quaternary ammonium salt portion in the monomer unit because the water repellency of the obtained light-shielding colored layer is further improved. is there. Examples of such a quaternary ammonium monomer unit containing a fluorine-containing moiety include a quaternary ammonium monomer unit represented by the above formula (V), wherein R ⁶ is a straight chain or branched chain having 1 to 12 carbon atoms. A fluorine-substituted alkyl group, and a monomer unit selected from the group consisting of fluorine-substituted alkylaryl groups; and a quaternary ammonium monomer unit represented by the above formula (VI), R ⁷
And R ⁸ includes at least one monomer unit selected from the group consisting of a linear or branched fluorine-substituted alkyl group having 1 to 12 carbon atoms, and a fluorine-substituted alkylaryl group.

Examples of the quaternary ammonium monomer unit containing a fluorine-containing moiety include the following (Example-1) to (Example-
The monomer units of 21) are mentioned:

[0081]

[Chemical 35]

[0082]

[Chemical 36]

Particularly, in terms of excellent water repellency, (Example-6), (Example-7), (Example-8), (Example-14), (Example-)
The monomer units of 15) and (Example-18) are preferred.

The above quaternary ammonium-containing monomer units may be used alone or in combination.

B. Fluorine-Containing Monomer Preferably, the resin contained in the hydrophilic light-shielding colored ink further has a fluorine-containing monomer unit in addition to the quaternary ammonium monomer unit. When the resin contained in the light-shielding colored ink contains a fluorine-containing monomer unit,
The water repellency of the obtained light-shielding colored layer is further improved. In particular,
When a monomer unit containing no fluorine-containing moiety is used as the quaternary ammonium monomer unit, the resin preferably further contains a fluorine-containing monomer unit. Therefore, when the quaternary ammonium monomer unit represented by the above formula (III) or (IV) is used, or in the quaternary ammonium monomer unit represented by the above formula (V) or (VI), the substituent R ⁶ , When R ⁷ and R ⁸ use a monomer unit which is not a fluorine-containing substituent, it is preferable to further use a fluorine-containing monomer unit.

The preferred fluorine-containing monomer unit is copolymerizable with the monomer capable of forming the above quaternary ammonium monomer unit, and can be formed from any fluorine-containing monomer. Preferred fluorine-containing monomer units include, for example, vinylidene fluoride monomer units, vinyl fluoride monomer units, ethylene trifluoride monomer units, tetrafluoroethylene monomer units, and monomer units represented by the formula (VII). :

[0087]

[Chemical 37]

Here, R ^A is hydrogen, a methyl group, or a trifluoromethyl group, and R ^B is a linear or branched fluorine-substituted alkyl group having 1 to 22 carbon atoms, or fluorine. It is a substituted alkylaryl group. R
^B is more preferably a linear or branched fluorine-substituted alkyl group having 1 to 18 carbon atoms, particularly α, α,
An α-trifluoromethyl group-containing substituted alkyl group, for example, CF ₃ (CH ₂ ) _n- (n = 0 to 8).

Preferably, the fluorine-containing monomer unit is
It is a monomer unit represented by the formula (VII). An expression like this
The monomer capable of forming the fluorine-containing monomer unit represented by (VII) is, for example, acryloyl chloride (forming a monomer unit in which R ^A is hydrogen in the formula (VII)) or methacryloyl chloride (R in the formula (VII)). ^A forms a monomer unit in which ^M is a methyl group) and a fluorine-containing alcohol such as R ^B OH (R ^B is as described above), in a solvent (eg, methyl ethyl ketone) using a basic catalyst. It can be easily synthesized. Some of such compounds are available as industrial chemicals.

Specific examples of the monomer capable of forming the fluorine-containing monomer unit include 3,3,3-trifluoropropyl acrylate, 3,3,3-trifluoropropyl methacrylate and 2,2,2-trifluoroethyl acrylate. , 4,4,4-Trifluorobutyl methacrylate, α, α, α, 2,2,2-hexafluoroethyl methacrylate, α, α, α, 3,3,3-
Hexafluoropropyl methacrylate, 3,3,4,4,4-pentafluorobutyl methacrylate, etc. may be mentioned.

The content of the fluorine-containing monomer unit in the resin having the quaternary ammonium monomer unit and the fluorine-containing monomer unit may vary depending on the use, but it is preferably about 2 to about 90 mol%, more preferably about 10 to about 70 mol%. When the content is less than about 2 mol%, the water repellency of the obtained light-shielding colored layer is often insufficient. If the content exceeds about 90 mol%, the adhesion of the light-shielding colored ink to the substrate is often insufficient.

The content of the quaternary ammonium monomer unit in the resin having the quaternary ammonium monomer unit and the fluorine-containing monomer unit may vary depending on the use, but is preferably about 10 to about 70 mol%, more preferably About 30 ~
It is about 60 mol%. If the content is less than about 10 mol%,
In many cases, the adhesion of the light-shielding colored ink to the substrate is insufficient. Further, the dispersibility (solubility) in a polar solvent (for example, water, alcohol and a mixture thereof) is insufficient,
It is often difficult to prepare stable aqueous suspensions, that is, hydrophilic light-shielding colored inks. About 70
When it exceeds mol%, the water repellency of the obtained light-shielding colored layer is often insufficient.

The above-mentioned fluorine-containing monomer unit is
Or they can be used in combination.

C. The resin having a comonomer quaternary ammonium monomer unit and optionally a fluorine-containing monomer unit may further have another monomer unit (hereinafter referred to as a comonomer unit) if necessary. By having such a comonomer unit, the following properties can be further improved depending on the purpose: viscosity of the light-shielding colored ink, binder properties of the resin, dispersibility (solubility) of the resin in water or alcohol, Coating properties (eg, water repellency, blocking resistance, cracking resistance) and heat resistance of the light-shielding colored layer.

As a monomer capable of forming such a comonomer unit (hereinafter referred to as a comonomer), a radically polymerizable ethylenically unsaturated monomer is usually used. Representative examples of ethylenically unsaturated monomers include acrylates, methacrylates, styrene derivatives, vinyl acetate, isobutylene and the like. Acrylate, methacrylate, and vinyl acetate are preferable in that a uniform light-shielding colored ink can be obtained and a light-shielding colored layer having excellent water repellency can be obtained.

Examples of acrylates include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dimethylaminoethyl acrylate, 2-ethoxy acrylate, and t.
-Butyl acrylate, iso-butyl acrylate,
Cyclohexyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, n-lauryl acrylate,
Examples include n-stearyl acrylate, dimethylaminoethyl acrylate, and diethylaminoethyl acrylate. An alkyl acrylate having 1 to 12 carbon atoms is preferable in that a uniform light-shielding colored ink can be obtained and a light-shielding coloring layer having excellent water repellency can be obtained.
Alkyl acrylates having 1 to 8 carbon atoms are more preferred.

Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxy methacrylate, n-octyl methacrylate, n-lauryl methacrylate, glycidyl methacrylate and 2-ethylhexyl. Methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, n-stearyl methacrylate, tetrahydrofurfuryl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate may be mentioned. An alkyl methacrylate having 1 to 12 carbon atoms is preferable, and an alkyl methacrylate having 1 to 8 carbon atoms is preferable in that a uniform light shielding colored ink can be obtained and a light shielding colored layer having excellent water repellency can be obtained. Is more preferable.

Preferably, the styrenic monomer unit (formed from the styrene derivative) is represented by formula (VIII):

[0099]

[Chemical 38]

Here, R ²¹ is hydrogen or a methyl group, and R ²² is hydrogen, an alkyl group having 1 to 12 carbon atoms, a nitro group or halogen. Examples of the styrene derivative include styrene, α-methylstyrene, x-methylstyrene, x-nitrostyrene (x: meta, para, ortho), and parachlorostyrene. Styrene, in that a uniform ink composition is obtained, and the resulting light-shielding colored layer is excellent in water repellency,
α-Methylstyrene is preferred.

In addition to the above monomers, any monomer such as a maleic acid diester derivative can be used as a comonomer. Examples of the maleic acid diester derivative include maleic acid di (2-ethylhexyl) ester, maleic acid diethyl ester, maleic acid di (n-butyl) ester, maleic acid dioctyl ester and the like.
Maleic acid di (2-ethylhexyl) ester and maleic acid diethyl ester are preferable in that a uniform ink composition can be obtained and the resulting light-shielding colored layer is excellent in water repellency.

The above comonomer units may be used alone or in combination.

D. Combination of Monomer Units In a preferred embodiment, the hydrophilic light-shielding colored ink has a monomer unit represented by formula (III), a monomer unit represented by formula (IV), and a formula (V). A resin having a monomer unit containing at least one quaternary ammonium salt moiety selected from the group consisting of monomer units,

[0104]

[Chemical Formula 39]

Wherein R ⁵ is hydrogen or a methyl group; R ⁶ is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, 2 to 8
Selected from the group consisting of a substituted or unsubstituted linear or branched group having 4 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, and a heterocyclic group.

In another preferred embodiment, the hydrophilic light-shielding colored ink comprises a monomer unit represented by the formula (III), a monomer unit represented by the formula (IV), and a formula (V).
A resin having a monomer unit containing at least one quaternary ammonium salt moiety selected from the group consisting of monomer units represented by and a fluorine-containing monomer unit,

[0107]

[Chemical 40]

Here, R ⁵ is hydrogen, a methyl group or a trifluoromethyl group; R ⁶ is hydrogen, 1 to 12
Substituted or unsubstituted linear or branched alkyl group having 4 carbon atoms, substituted or unsubstituted linear or branched group having 2 to 8 carbon atoms, substituted or unsubstituted aralkyl group, It is selected from the group consisting of substituted or unsubstituted phenyl groups, as well as heterocyclic groups. Preferably, the fluorine-containing monomer unit is contained in the resin in a ratio of 2 mol% to 90 mol%, and the monomer unit having a quaternary ammonium salt moiety is 10 mol% to 70 mol%.
It is contained in the resin in a ratio of mol%.

In still another preferred embodiment, the hydrophilic light-shielding colored ink has at least one selected from the group consisting of a monomer unit represented by the formula (V) and a monomer unit represented by the formula (VI). A resin having a monomer unit containing four quaternary ammonium salt moieties,

[0110]

[Chemical 41]

Where R ⁶ is selected from the group consisting of linear or branched fluorine-substituted alkyl groups having 1 to 12 carbon atoms, and fluorine-substituted alkylaryl groups; R ⁷ and R ⁸ are Hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted linear or branched alkenyl group having 2 to 8 carbon atoms, respectively. A group consisting of a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, a heterocyclic group, a linear or branched fluorine-substituted alkyl group having 1 to 12 carbon atoms, and a fluorine-substituted alkylaryl group. At least one of R ⁷ and R ⁸ is a linear or branched fluorine-substituted alkyl group having 1 to 12 carbon atoms,
And a fluorine-substituted alkylaryl group.

In any of the above embodiments, the resin contained in the hydrophilic light-shielding colored ink is composed of an acrylate monomer unit, a methacrylate monomer unit, a styrene monomer unit, a vinyl acetate monomer unit, and an isobutylene monomer unit. It may further have at least one ethylenically unsaturated monomer unit selected from the group consisting of:

When the above fluorine-containing monomer units and / or comonomer units are used in combination with the above quaternary ammonium monomer units, the resin containing these monomer units may be a copolymer having a plurality of monomer units, or It may be a blend of homopolymers. Copolymers are preferred. This is because the obtained light-shielding colored layer is excellent in uniformity, and as a result, the strength and stability of the light-shielding colored layer are improved.

E. Method for Preparing Resin Hereinafter, a method for preparing a resin having a quaternary ammonium monomer unit contained in the hydrophilic light-shielding colored ink used in the color filter of the present invention will be described.

Formula (I):

[0116]

[Chemical 42]

The resin containing a monomer unit containing a quaternary ammonium salt moiety represented by can be prepared by any known method from a monomer capable of forming a quaternary ammonium monomer unit. The monomer capable of forming the quaternary ammonium monomer unit may be a carboxyl group-containing monomer. In the present specification, the carboxyl group-containing monomer also includes a carboxyl group-containing monomer and its acid anhydride. Similarly, with a carboxyl group-containing polymer,
It includes a carboxyl group-containing polymer and its anhydride. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, maleic acid and maleic acid monoester.

The resin containing a quaternary ammonium monomer unit is obtained by, for example, polymerizing (or copolymerizing) a carboxyl group-containing monomer and, if necessary, another monomer, and then adding the obtained carboxyl group-containing polymer to an ammonia or amine compound. Can be obtained by treating with. Alternatively, it can be obtained by reacting a carboxyl group-containing monomer with ammonia or amine to form a monomer having a quaternary ammonium salt moiety, and then polymerizing this monomer. Usually, a resin containing a quaternary ammonium monomer unit is obtained by polymerizing a carboxyl group-containing monomer and then treating the resulting polymer with ammonia or an amine compound. This is because, since the polymerization is easy, a resin having desired properties (for example, molecular weight and viscosity) can be easily obtained. In this case, for example, a solution obtained by dissolving the carboxyl group-containing polymer obtained by an arbitrary method in a suitable organic solvent at a predetermined concentration is mixed with ammonia water or an amine (an amine aqueous solution, if necessary) and heated and stirred. A resin containing a quaternary ammonium monomer unit can be obtained by pouring. The heating temperature may vary depending on the type of ammonia or amine used, but is preferably room temperature to about 8
The temperature is 0 ° C, more preferably about 60 to about 80 ° C. The heating time may vary depending on the heating temperature, stirring speed, etc.,
It is typically 1 hour to several days.

For example, the formula (III):

[0120]

[Chemical 43]

The quaternary ammonium monomer unit represented by (wherein R ⁵ and X ⁺ are as defined above) is
For example, it can be obtained by polymerizing a carboxyl group-containing monomer such as acrylic acid and methacrylic acid together with other monomers as necessary, and treating the resulting polymer with ammonia or a predetermined amine compound.

Further, for example, formula (IV), (V) or (VI):

[0123]

[Chemical 44]

The quaternary ammonium monomer unit represented by (wherein R ⁶ , R ⁷ , R ⁸ and X ⁺ are as defined above) may be derived from maleic acid or a derivative thereof. The resin having a quaternary ammonium monomer unit represented by the formula (IV) is obtained by, for example, polymerizing maleic anhydride together with other monomer as necessary, and treating the resulting polymer with ammonia or a predetermined amine compound. Can be obtained by doing. The resin having a quaternary ammonium monomer unit represented by the formula (V) is obtained by, for example, polymerizing a maleic acid monoester together with other monomers as necessary, and treating the resulting polymer with ammonia or a predetermined amine compound. Can be obtained by doing. Alternatively, maleic anhydride is optionally polymerized with other monomers and the resulting polymer is partially esterified by reacting with a compound such as R ⁶ OH and further treated with ammonia or the amine compound of interest. Can be obtained. When R ⁶ is a fluorine-containing substituent, the latter method is particularly suitable. The resin having a quaternary ammonium monomer unit represented by the formula (VI) is obtained, for example, by polymerizing maleic anhydride together with another monomer, if necessary, and polymerizing the resulting polymer with R ⁷ R ⁸
It can be obtained by reacting with NH, partially amidating and further treating with ammonia or certain amine compounds.

The resin having a fluorine-containing monomer unit and / or a comonomer unit in addition to the quaternary ammonium monomer unit has a monomer and / or a comonomer which can form a fluorine-containing monomer unit together with a monomer which can form a quaternary ammonium monomer unit. It may be obtained by copolymerization and optionally treatment with ammonia or amine as described above. Alternatively, it can be obtained by blending a resin having a quaternary ammonium monomer unit with a resin having a fluorine-containing monomer unit and / or a resin having a comonomer unit by any known method.

The monomer capable of forming the fluorine-containing monomer unit may be a fluorine-containing monomer, or may be a monomer capable of forming the fluorine-containing monomer unit by a treatment after polymerization. For example, formula (VII):

[0127]

[Chemical formula 45]

The fluorine-containing monomer unit represented by (wherein R ^A and R ^B are as defined above) is obtained by polymerizing acrylic acid or methacrylic acid and then adding the resulting polymer to R ^B OH or the like. It can also be obtained by esterification with the compound of

Specific examples of particularly preferred combinations of monomers capable of forming quaternary ammonium monomer units and (optionally) fluorine-containing monomer units and / or comonomers are as follows: styrene and Acrylic acid (molar ratio 5: 1); n-butyl methacrylate and methacrylic acid (molar ratio 7: 1);
Styrene, ethyl acrylate and acrylic acid (molar ratio 4: 4: 1); α-methylstyrene and methacrylic acid (molar ratio 2: 1); ethylhexyl methacrylate and methacrylic acid (molar ratio 10: 1); cyclohexyl methacrylate and methacrylic acid. (Molar ratio 2: 1); 2-ethoxyacrylate and acrylic acid (molar ratio 1: 1); styrene and maleic anhydride (molar ratio 3: 1); styrene and maleic acid monobutyl ester (molar ratio 2: 1). N-butyl acrylate and maleic acid monoethyl ester (molar ratio 2:
1); styrene and maleic acid monoethyl ester (molar ratio 3: 1); styrene, maleic anhydride and n-butyl methacrylate (molar ratio 3: 1: 1); vinyl acetate and maleic anhydride (molar ratio 3: 1). ); 2-Ethylhexyl methacrylate and maleic acid mono (2-ethylhexyl) ester (molar ratio 3: 1); Cyclohexyl methacrylate and maleic acid monoethyl ester (molar ratio 3: 1);
3,3,3, -Trifluoropropyl acrylate and acrylic acid (molar ratio 1:10); 3,3,4,4,4, -pentafluorobutyl methacrylate, methacrylic acid and n-butyl methacrylate (molar ratio 4: 4: 3); α, α, α-trifluoromethyl-2,2,2-trifluoroethyl acrylate, methacrylic acid and styrene (molar ratio 4: 2: 4); 3,3,3-trifluoropropyl acrylate And acrylic acid (molar ratio 3: 8); 3,3,3-trifluoropropyl acrylate and acrylic acid (molar ratio 5: 5); 3,3,3-trifluoropropyl acrylate and acrylic acid (molar ratio 8: 3); vinyl acetate, maleic acid monohexyl ester and 3,3,3-trifluoropropyl acrylate (molar ratio 4: 4: 2);
n-butyl methacrylate, maleic anhydride, α, α,
α, 3,3,3-hexafluoropropyl methacrylate (molar ratio 2: 4: 4); styrene, maleic acid monoethyl ester and 3,3,4,4,4-pentafluorobutyl acrylate (molar ratio 4: 5) 1); styrene and maleic acid monoethyl ester and 3,3,4,4,4-pentafluorobutyl acrylate (molar ratio 4: 4: 2); styrene and maleic acid monoethyl ester and 3,3,4, 4,4-pentafluorobutyl acrylate (molar ratio 4: 2: 4); maleic acid monobenzyl ester and 3,3,3-trifluoropropyl acrylate (molar ratio 4: 1).

F. Fluorine-containing compound Preferably, the hydrophilic light-shielding colored ink further contains an arbitrary fluorine-containing compound. The fluorine-containing compound is preferably any fluorine-based surfactant. The fluorine-containing compound is particularly useful when the resin contained in the light-shielding colored ink does not contain a quaternary ammonium monomer having a fluorine-containing portion in the quaternary ammonium monomer unit and the resin does not have a fluorine-containing monomer unit. Is. This is because by using the fluorine-containing compound, the water repellency of the obtained light-shielding colored layer can be improved. The content of the fluorine-containing compound in the light-shielding colored ink may vary depending on its type, but is preferably in the range of about 1 to about 30 parts by weight, more preferably about 1 to about 30 parts by weight with respect to 100 parts by weight of the ink solid content. 1
It may be contained in the range of 0 parts by weight.

Preferred fluorine-containing compounds have the formula (IX):

[0132]

[Chemical formula 46]

Here, R ³¹ is a fluorine-substituted alkyl group having 1 to 12 carbon atoms, and Y is —COO—, —OC.
O-, -CONH-, -CO-, -O-, -S-, phenylene group, -SO ₂ -,-
SO ₃ -or -SO ₂ NH-, and Z is -COOH, -OH, -CONH
₂ , -SO ₂ NH ₂ , -NH ₂ , -SO ₃ ^- NH ₄ ⁺ , -COO ^- NH ₄ ⁺ , -COO ^- NH ⁺ (C
₂ H _{5) 3} or _{^{-NH 3 + · B, - (}} B - is an anion residue),
m and n are each independently an integer of 0 to 6, and p is 0.
Or 1.

The fluorine-containing compound may be added at the time of polymerizing the above-mentioned monomer, or may be added at any stage of preparation of the light-shielding colored ink.

G. Polyamino compound Preferably, the hydrophilic light-shielding colored ink comprises at least 1
Further contains a polyamino compound of the species. Here, the polyamino compound means a compound having two or more amino groups. The polyamino compound can be a diamino compound, a triamino compound and the like. Preferred are diamino compounds. By containing such a polyamino compound, the viscosity of the light-shielding colored ink can be increased. This is because the carboxyl group in the resin contained in the light-shielding colored ink is
It is considered that this is because of ionic crosslinking through the polyamino compound. The carboxyl group in the resin can be derived from the anion portion of the quaternary ammonium monomer unit in the resin, or it can be a free carboxyl group that has not formed a quaternary ammonium salt. As a result of the increased viscosity of the ink in this manner, the flow of the ink when attached to the substrate can be significantly prevented. Therefore, it is preferable when the light-shielding colored layer is formed by a printing method (in particular, offset printing or screen printing method). In fact, in screen printing, offset printing, etc., ink viscosity of about 1000 cp or more is often required. The relationship between the degree of crosslinking and the viscosity of the ink may change depending on the acid value of the resin, the type of amino compound, the type of colorant (pigment type or dye type) that can be contained in the ink, but it is almost proportional. It is a relationship. That is,
As the degree of crosslinking increases, the ink viscosity also increases.

Typical examples of such polyamino compounds include ethylenediamine (ie, 1,2-diaminopropane), m-xylenediamine, p-xylenediamine, p-phenylenediamine, 1,4-diaminobutane, 1,5 -Diaminopentane, 1,6-diaminohexane, 1,2-diaminoethane, 2,2-dimethyl-1,3-diaminopropane, N, N, N ', N'-
Tetramethyl-1,2-diaminoethane, piperazine, N, N'-
Diethylpiperazine, 1,4-diaminocyclohexane, 4,
4'-diamino-2,2'-disulfostilbene, 1,3-diamino-
2-propanol ((H ₂ NCH ₂ ) ₂ CHOH), 3,3′-diaminodipropylamine, 2,4-diamino-6-methyl-5-triazine,
N, N'-diallyl-1,2-diaminopropane, N, N'-dimethyl-
1,2-diaminoethane, 1,3-diamino-cyclopentane,
N, N'-dibutyl-1,2-diaminoethane may be mentioned.

The diamino compound represented by the formula (X) is preferable in terms of excellent thickening property and low cost:

[0138]

[Chemical 47]

Where A is a divalent hydrocarbon residue; and R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are independently hydrogen, substituted with 1 to 12 carbon atoms. Or an unsubstituted linear or branched alkyl group, a substituted or unsubstituted cycloalkyl group having 5 to 6 carbon atoms, or a substituted or unsubstituted linear group having 2 to 8 carbon atoms, or It is a branched alkenyl group. Preferably,
The alkyl group is a methyl group or an ethyl group. Preferably, the alkenyl group is an allyl group or a methallyl group. An alkyl or alkenyl group may be substituted with any substituent, provided that the benefits of this invention are not impaired. Representative examples of such a substituent include a hydroxyl group, a halogen, a methoxy group and the like. Hydroxyl groups are preferred.

More preferably, A is a linear alkyl group having 2 to 12 carbon atoms, R ⁴¹ , R ⁴² ,
R ⁴³ and R ⁴⁴ are independently a compound selected from the group consisting of hydrogen, a methyl group, and an ethyl group. Particularly preferred diamino compounds are ethylenediamine, N, N'-diethylethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl-
It is 1,3-diaminobutane. This is because it has excellent ionic cross-linking property, and since it has high volatility at the time of heating as described later, the obtained light-shielding colored ink changes from hydrophilic to hydrophobic quickly and easily, and at a low cost.

Such a polyamino compound may be added at the time of polymerizing the above-mentioned monomer, or may be added at any stage of preparation of the light-shielding colored ink.

The content of the polyamino compound in the light-shielding colored ink may vary depending on its type, but it is preferably in the range of about 0.1 to about 30 parts by weight, more preferably 100 parts by weight of the ink solid content. It can be included in the range of about 1 to about 5 parts by weight. If the content is less than about 0.1 part by weight, the thickening effect is often insufficient. If the content exceeds about 30 parts by weight, the light-shielding colored ink may gel.

Further, it is preferable that the ionically crosslinked polyamino compound is released by heating after the light-shielding colored ink is attached to the substrate and easily volatilizes.

The ionic cross-linking of the carboxyl group-containing resin with the polyamino compound and the liberation of the polyamino compound by heating may be the following reactions, for example.

[0145]

[Chemical 48]

As is clear from the above reaction formula, the polyamino compound can also have the same action as the above-mentioned quaternary ammonium salt moiety in the hydrophilic light-shielding colored ink used in the color filter of the present invention. That is, the polyamino compound may have a function of imparting hydrophilicity to the light-shielding colored ink and making the hydrophilic ink hydrophobic by heating. Therefore, the polyamino compound can be used in combination with a resin having a quaternary ammonium monomer unit,
It can be used with any carboxyl group-containing resin that does not contain a quaternary ammonium salt moiety, and as a result can form a light-shielding colored ink that changes from hydrophilic to hydrophobic by heating. Hereinafter, the carboxyl group-containing resin is intended to include a resin containing the above quaternary ammonium monomer unit.

The carboxyl group-containing resin that can be used with the polyamino compound is not particularly limited, but is typically a condensation polymerization resin, a radical polymerization resin, an addition polymerization resin or the like. A resin having a large acid value is suitable for increasing the ionic crosslinkability. The acid value of the carboxyl group-containing resin is preferably 20 or more, more preferably 30.
That is all. When the acid value is less than 20, ionic crosslinking is insufficient and a light-shielding colored ink having desired viscosity cannot be obtained in many cases. The radical polymerization type resin is preferable because a resin having a large acid value can be obtained relatively easily.
Preferably, the radical polymerization resin is methacrylic acid, acrylic acid, crotonic acid, maleic anhydride, maleic acid,
And a copolymer resin having at least one monomer unit selected from the group consisting of maleic acid monoester.

Alternatively, by incorporating the monoamino compound together with the polyamino compound into the light-shielding colored ink,
The light-shielding colored ink can be adjusted to a desired viscosity, and the solubility of the resin in water, that is, the hydrophilicity can be improved.
This monoamino compound can form a quaternary ammonium salt moiety in the carboxyl group-containing resin.

Preferably, the monoamino compound is a compound in which each of the substituents bonded to the nitrogen is hydrogen or an alkyl group or a hydroxyalkyl group having 1 to 6 carbon atoms. Particularly preferred monoamino compounds are triethylamine, ammonia, n-butylamine and diethylamine. This is because the obtained light-shielding colored ink changes from hydrophilicity to hydrophobicity quickly and easily.

The monoamino compound is contained in the light-shielding colored ink in an amount of preferably about 1 to about 40 parts by weight, more preferably about 3 to about 30 parts by weight, based on 100 parts by weight of the carboxyl group-containing resin.

H. Colorant The hydrophilic light-shielding colored ink contains a colorant (that is, a light-shielding colorant). The light-shielding colorant contained in the light-shielding color ink may be a pigment-type colorant or a dye-type colorant. These colorants may be a soluble type dissolved in the ink or a dispersed type dispersed in the ink. These colorants are water, hydroalcoholic,
It can be used by dispersing or dissolving it in alcohols, water-containing ketones and the like. The colorant is preferably a black pigment-based colorant such as carbon black from the viewpoint of light shielding properties. Specific examples of the pigment-based colorant (organic black pigment) include CI
-Acid Black 1, Same 2, Same 3, Same 24, Same 26,
Same 30, Same 31, Same 33, Same 48, Same 50, Same 60, Same 110, Same 112, Same 207, CI-Direct Black 5, Same 7, Same 19, Same 22, Same 51, Same 62, Same 11
2, ibid 117, ibid 118, ibid 122, ibid 154, ibid 15
9, 169, and 173. Carbon black has a smaller particle size (for example, 0.01 to 0.
1 μm) preferred. Further, carbon black having a —COOM group (M is one selected from hydrogen, ammonium, and alkali metals) on the surface is preferable. Surface -C
The OOM group can be formed by a conventional acid treatment. Such carbon black has ink properties (dispersion stability,
Viscosity, stability over time), heat resistance, oxidation resistance, optical density, etc. are excellent.

When the colorant is a dispersion type, the content ratio of the colorant and the resin in the ink is in the range of about 2 to about 200 parts by weight of the resin with respect to 10 parts by weight of the colorant. preferable. When the colorant is of the soluble type, the content of the colorant may be smaller than that of the dispersed type.

I. Method of Preparing Ink The light-shielding colored ink used in the color filter of the present invention can be prepared by dissolving or dispersing each of the above components in water or an alcohol solvent by a usual method. Preferred solvents are ethyl alcohol, isopropyl alcohol, water, hydrous alcohol and the like. For example,
The light-shielding colored ink is prepared by adding a carboxyl group-containing polymer to water or an alcohol solvent containing an organic solvent such as acetone or methyl ethyl ketone as necessary, and further adding an ammonia or amine compound and / or polyamine compound to disperse the polymer. Can be obtained. Components such as colorants and fluorine-containing compounds can be added at any stage. The organic solvent such as acetone and methyl ethyl ketone added as necessary can be removed by vacuum distillation or the like after the dispersion.

J. Substrate The transparent substrate used for the color filter of the present invention may be any known transparent substrate for color filters. Specific examples include a glass substrate and a plastic substrate. The thickness of the transparent substrate may vary depending on the application, but it is preferably about 1 to about 3 mm.

K. Undercoat layer Preferably, the transparent substrate may be subjected to a hydrophilic treatment. For example, an undercoat layer having adhesiveness to the light-shielding colored ink may be formed in order to improve the adhesion of the light-shielding colored ink to the glass substrate. The undercoat layer is not particularly limited as long as it is a hydrophilic transparent thin film. Such an undercoat layer includes, for example, natural resins such as gelatin and casein; polyvinyl alcohol, partially saponified vinyl acetate resin, polyethyleneimine, polyhydroxyethyl methacrylate (for example, poly (2-hydroxyethyl) methacrylate). Resins), hydroxyethyl cellulose, polyacrylamide and its derivatives, polymethacrylamide and its derivatives (for example, methylolated polyacrylamide), aminoalkylalkoxysilane derivatives (for example, (N-trimethoxysilylpropyl) polyethylene), and other synthetic resins. Can be used. Gelatin, polyacrylamide and its derivatives, polymethacrylamide and its derivatives are preferred. These are
Or they can be used in combination.

Polyacrylamide and its derivatives, and polymethacrylamide and its derivatives have the formula (X
Having a monomer unit represented by I):

[0157]

[Chemical 49]

Wherein R ⁵¹ is hydrogen or a methyl group; and R ⁵² is hydrogen, 1 to 12, preferably 1
A substituted or unsubstituted linear or branched alkyl group having 8 to 8 carbon atoms, a substituted or unsubstituted linear or branched aralkyl group, a substituted or unsubstituted phenyl group, or a heterocyclic group. . Preferably the substituted alkyl group is a hydroxyalkyl group. Preferably the aralkyl group is a benzyl group. Preferred polyacrylamides, polymethacrylamides and their derivatives are poly (N-methylolacrylamide), poly (N-ethanolacrylamide), poly (N-ethanolmethacrylamide) and the like.

The undercoat layer can be formed by applying and drying a solution containing these resins on a substrate. The thickness of the undercoat layer is preferably about 0.5 to about 5.0 μm.

L. Color Filter Manufacturing Method A preferred example of the color filter manufacturing method of the present invention using the hydrophilic light-shielding colored ink will be described below.

FIG. 1 is a flow chart of a preferred example of the method for manufacturing a color filter of the present invention. First, the hydrophilic light-shielding colored ink is attached to a desired position on the transparent substrate (steps 1 and 2). Examples of the method of attaching the light-shielding colored ink to a desired position on the transparent substrate include an inkjet method, a screen printing method, an offset printing method, a dispenser method, and a stencil printing method.
When the color filter is used in the liquid crystal display device, it is preferable to form the light-shielding colored layer in conformity with the pattern of the non-pixel portion of the liquid crystal display device.

Next, the light-shielding colored ink attached on the transparent substrate is heated (step 3). By heating, the light-shielding colored ink changes from hydrophilic to hydrophobic (step 4). The heating temperature may vary depending on the type of resin contained in the hydrophilic light-shielding colored ink, but is preferably about 50 ° C to about 250 ° C.
C., more preferably about 60.degree. C. to about 150.degree. C., most preferably about 80.degree. C. to about 120.degree. The heating time may vary depending on the heating temperature and the like, but preferably 1 to 30 minutes,
More preferably, it is 5 to 15 minutes.

As described above, the quaternary ammonium salt portion contained in the resin in the light-shielding colored ink has its cation portion heated by ammonia or amine (primary amine,
It is easily vaporized as a secondary amine or a tertiary amine, and the hydrophilic portion (that is, salt portion) is removed from the resin.
Therefore, the resin in the light-shielding colored ink changes from hydrophilic to hydrophobic. As described above, a water-repellent light-shielding colored layer is obtained (step 5).

The light-shielding colored layer (that is, the black matrix) thus obtained has a thickness of preferably about 0.8 to about 10 μm, more preferably about 1.0 to about 5.0 μm, and its optical property. The concentration (OD) is preferably about 1.5 to about 5.0, more preferably about 2.
0 to about 4.5.

Next, a hydrophilic pixel color ink is adhered to a portion (preferably a pixel portion) where the water-repellent light-shielding colored layer is not formed on the transparent substrate, and red (R) and blue (B) are applied. , Green (G) pixels of three primary colors are formed (steps 6 and 7). In this way, the color filter is completed (step 8).

The color ink for pixels is not particularly limited, and any ink usually used for color filters can be used. Typically, color inks are aqueous dispersions containing pigments, binder resins (eg, melamine resins), hardeners, and surfactants.

Examples of the method of attaching the color ink for pixels include a printing method and an inkjet method. The inkjet method is preferred. This is for the following reasons:
The hydrophilic color ink for pixels ejected by the inkjet is less likely to adhere to the water-repellent light-shielding colored layer due to the offset effect. Therefore, each color (R, G,
The color mixture of B) is satisfactorily prevented, and as a result, accuracy, stability and convenience can be significantly improved in the production of color filters. The inkjet method is particularly preferable in the production of color filters for displays, which have become larger in size in recent years.

The following method is effective as a method for adhering the color ink for pixels by using the ink jet device: heads for three colors of R, G, B are prepared,
A minute ink droplet is ejected from each head to color the pixel portion on the transparent substrate. As a coloring method in this case,
The dyeable medium may be dyed with a dyeing ink, and the resin may be heat-cured or photo-cured after ink-jetting an ink including a resin, a dye or a pigment, and an ink solvent. When dyeing a dyeable medium with ink, it is effective to first form a dyeable film on a transparent substrate and then form an ink repellent (water repellent) light-shielding colored layer. When coloring the pixel portion on the transparent substrate by such a method, it is important that the contact angle between the light-shielding colored layer and the ink ejected from the inkjet device is large.
As is well known, the contact angle includes an advancing contact angle and a receding contact angle, but the receding contact angle is particularly important in the present invention. When the contact angle (particularly the receding contact angle) is small, the ink adheres to the light-shielding colored layer, and the amount of ink adhered to the pixel portion fluctuates. As a result, color unevenness often occurs in the obtained color filter. Specifically, the contact angle (receding contact angle) is preferably about 20 degrees or more, more preferably about 40 degrees or more.

Even when the pixel color ink is applied by using a printing method (for example, a lithographic printing machine using a waterless lithographic plate), it is very effective that the receding contact angle between the light-shielding colored layer and the ink is large. Is.

As described above, the light-shielding colored ink having the viscosity increased by adding the polyamino compound is suitable for the screen printing method or the offset printing method.

Preferably, the top coat can be formed after the pixel portion on the transparent substrate is colored to produce a color filter. The top coat is a transparent resin thin film that covers the upper surface of the color filter. The material for forming the top coat and the method for forming the top coat are not particularly limited, and known materials and methods can be adopted. By forming the top coat, (1) the color filter is protected from impact and the like, (2) the flatness of the color filter is improved, and (3) when a liquid crystal display device is manufactured using the color filter. Inflow of impurities from the color filter to the liquid crystal layer can be prevented.

The color filter manufactured as described above has excellent display quality and pixel flatness.

M. Liquid crystal display element Such a color filter can be suitably applied to all liquid crystal display devices such as an active drive type transmissive liquid crystal display device, a simple multiplex drive type liquid crystal display device, and a reflective display type liquid crystal display device. Further, such a color filter is used in a color plasma display (PDP),
It can be widely applied to devices that use color filters, such as electroluminescent displays (EL).

As a preferable application example of the color filter,
FIG. 2A shows an active drive type transmissive liquid crystal display device.
And with reference to FIG. 2B.

FIG. 2A is a schematic sectional view of the liquid crystal display panel 21 used in the liquid crystal display device, and FIG. 2B is a perspective view of the liquid crystal display panel 21.

In the liquid crystal display panel 21, a TFT substrate 22 made of a transparent insulating substrate and a counter substrate 23 are arranged so as to face each other.
The structure is such that the liquid crystal is sealed by adhering it through the sealing material 24 to form the liquid crystal layer 33, that is, the structure in which the liquid crystal layer 33 is sandwiched between the TFT substrate 22 and the counter substrate 23.

On the TFT substrate 22, pixel electrodes 25 are formed in a matrix, and signal electrodes (source electrodes) 26 and scanning electrodes (gate electrodes) 27 are formed. A thin film transistor (TFT) 28 is provided near the intersection of the signal electrode 26 and the scanning electrode 27, and the pixel electrode 25 is connected to the TFT 28.

On the other hand, the common electrode 29 is formed on the counter substrate 23.
And the R corresponding to each pixel electrode 25 is formed.
(Red), G (green), B (blue) color filters 30,
A black matrix 31 for separating each pixel portion is formed. The black matrix 31 is provided to block light from entering the gap between the pixel electrodes 25 and the TFT area.

In addition, the TFT substrate 22 and the counter substrate 23
An alignment film 34 for orienting liquid crystal molecules in a predetermined direction is formed on the surface of each of the opposing surfaces that is in contact with the liquid crystal layer 33. Furthermore, the alignment films 34 of both substrates 22 and 23,
On the surface opposite to the surface on which 34 is formed, the polarizing plate 3
5, 35 are provided.

The pixel electrodes 25 correspond to the R, G, and B color filters 30, respectively, and the pixel electrode 25r for displaying red and the pixel electrode 25 for displaying green, respectively.
One pixel 32 is formed with the pixel electrode 25b for displaying g and blue.

Each pixel 32 has a pixel electrode 25.
It is driven by the TFT 28 connected to. That is, the gate of each TFT 28 is connected to the scan electrode 27,
Each pixel electrode 25 is connected to the signal electrode 26 via the drain and source of the TFT 28. As a result, each TFT 28 controls the supply of the image signal to the pixel electrode 25 and drives the pixel electrode 25 independently.

In the liquid crystal display device having the liquid crystal display panel 21, the transmittance of the liquid crystal changes in accordance with the image signal supplied to each pixel electrode 25, thereby modulating the light incident from the backlight not shown. A color image is displayed by transmitting the light.

[0183]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" are based on weight unless otherwise specified.

First, the preparation of the light-shielding colored ink used in the light-shielding colored layer of the color filter of the present invention will be specifically described with reference to production examples.

(Production Example 1) 40% methyl ethyl ketone solution 1 of styrene: acrylic acid copolymer (molar ratio 5: 1)
Carbon black (Mitsubishi Carbon Co., MA
-100) 10 g was added. This mixture was vibrated for 30 minutes using a paint conditioner to carry out a fine dispersion treatment of carbon black to obtain a dispersion liquid. Pure water 250
The obtained dispersion was gradually added to a solution of 3.0 g of triethylamine dissolved therein with stirring. Then
The solution to which the dispersion liquid was added was heated to 80 ° C. and reacted for about 1 hour. After completion of the reaction, methyl ethyl ketone was removed by distillation under reduced pressure to obtain an aqueous dispersion type black ink.
The viscosity of the obtained black ink is 400 cp (30
℃).

(Production Example 2) n-butyl methacrylate:
120 g of a 30% acetone solution of a methacrylic acid copolymer (molar ratio 7: 1) was added to CI-Acid Black (No. 2).
6) To 200 g of an aqueous solution containing 5 g and 10 cc of 30% aqueous ammonia was gradually added with stirring. Next, this mixed solution was heated to 40 ° C. and reacted until the smell of ammonia disappeared. After the reaction was completed, acetone was removed by distillation under reduced pressure to obtain an aqueous homogeneous black ink.

(Production Example 3) 10% of styrene: ethyl acrylate: acrylic acid copolymer (molar ratio 4: 4: 1)
To 100 g of the isopropyl alcohol solution, a modified azine dye (CI-Direct Black No. 7 analog) of 0.
6 g was added to prepare a black uniform solution. This black uniform solution was added to a solution in which n-butylamine (2.0 g) was dissolved in isopropyl alcohol (100 g), and after sufficient stirring, the mixture was left for 3 days. After standing, n-butylamine was removed by distillation under reduced pressure to obtain a uniform alcohol black ink.

(Production Examples 4 to 6) 100 g of a solution of the copolymer shown in Table 2 below was added to CI-Acid Black (N
o. 31) 1 g and 2.0 g of diethylamine were added to 50 g of an aqueous solution, and the reaction was continued until the smell of diethylamine disappeared. After completion of the reaction, acetone and the like were removed by vacuum distillation to obtain an aqueous homogeneous black ink.

[0189]

[Table 2]

(Production Example 7) 50 g of a 30% solution of α-methylstyrene: methacrylic acid copolymer (molar ratio 2: 1) in n-butyl alcohol was treated with acid to obtain carbon black (manufactured by Orient Chemical Co., Micro Zet) 3 g was added. This mixture is mixed with a paint conditioner 3 times.
It was vibrated for 0 minutes to obtain a carbon black dispersion. This dispersion was added to 100 g of an aqueous solution in which 5 g of monoethanolamine was dissolved, heated to 80 ° C., and stirred. As the mixture was stirred, n-butyl alcohol was gradually phase-separated into an oil layer, and the copolymer and carbon black were phase-separated into an aqueous layer. After the n-butyl alcohol is completely separated,
The n-butanol was removed to obtain an aqueous dispersion type black ink. The viscosity of the obtained black ink is 5300c.
It was p (30 degreeC).

(Production Example 8) 8 g of carbon black (MA-100 manufactured by Mitsubishi Carbon Co., Ltd.) was added to 100 g of a 40% acetone solution of a styrene: maleic acid monoethyl ester copolymer (molar ratio 3: 1). This mixture was vibrated for 30 minutes using a paint conditioner to carry out a fine dispersion treatment of carbon black to obtain a dispersion liquid. Thirty
% Ammonia water 15 cc and pure water 185 cc were gradually added to the solution with stirring. Then, this mixed solution was heated to 40 to 45 ° C. and reacted until the smell of ammonia disappeared. After completion of the reaction, acetone was removed by distillation under reduced pressure to obtain about 200 g of a water-based homogeneous black ink. The viscosity of the obtained black ink is 4500 cp
(30 ° C.).

(Production Example 9) 3 g of CI-Acid Black (No. 2) was added to 75 g of a 40% methyl ethyl ketone solution of a styrene: maleic anhydride copolymer (molar ratio 2: 1).
And 4.0 g of monoethanolamine were added, heated to 60 ° C. and stirred for about 1 hour. Next, 150 cc of water was added to this mixed solution, and the mixture was vibrated for about 1 hour using a paint conditioner. Next, the phase-separated methyl ethyl ketone was removed at the top, and the remaining methyl ethyl ketone was removed by vacuum distillation to obtain about 190 g of an aqueous homogeneous black ink.

(Production Example 10) Styrene: maleic anhydride: n-butyl methacrylate copolymer (molar ratio 3:
50 g of a 40% tetrahydrofuran solution of 1: 1) was added to C
I-acid black (No. 33) 2 g and 30%
To 150 g of an aqueous solution containing 10 cc of ammonia water was gradually added with stirring. Then, this mixed solution is
The mixture was heated to 40 ° C. and reacted until the smell of ammonia disappeared. In this way, 200 g of a water-tetrahydrofuran mixed solvent system homogeneous black ink was obtained.

(Production Example 11) 50% ethanol solution of vinyl acetate: maleic anhydride copolymer (molar ratio 3: 1) 6
To 0 g, 3 g of acid-treated carbon black (Microjet, manufactured by Orient Chemical Co., Ltd.) was added. The mixture was vibrated for 30 minutes using a paint conditioner to obtain a carbon black dispersion liquid. This dispersion is
6 g of n-hexylamine was added to 140 g of an aqueous solution in which the mixture was heated to 70 ° C. and stirred. The initially cloudy solution became a transparent and uniform solution. In this way, 200 g of a water-ethanol mixed solvent system dispersion type black ink was obtained. The viscosity of the obtained black ink is
It was 250 cp (30 ° C.).

Production Example 12 100 g of a 50% solution of 2-ethylhexyl methacrylate / maleic acid mono (2-ethylhexyl) ester copolymer (molar ratio 1: 1) in 50% n-butyl alcohol and the following structural formula (XII) A solution of 2 g of amide black (10B) having 10 g in 200 g of water was mixed with 10 cc of aqueous ammonia. The mixture was reacted at 60 ° C. with stirring for about 2 hours. As the reaction proceeded, the ammonia changed to a quaternary ammonium salt, and accordingly, n-butyl alcohol separated into layers.
The layer-separated n-butyl alcohol was removed to obtain 220 g of an aqueous black ink.

[0196]

[Chemical 50]

(Production Example 13) 200 g of a 30% acetone solution of a cyclohexyl methacrylate / maleic acid monoethyl ester copolymer (molar ratio 2: 1) and the following structural formula
200 g of a modified azine dye (CI-Direct Black No. 19) aqueous solution containing (XIII) and 7.5 cc of isopropylamine were mixed. This mixture is heated to 50 ° C.
And stirred for about 2 hours. Next, acetone was removed by vacuum distillation to obtain 200 g of black ink. The viscosity of the obtained black ink was 5000 cp (30 ° C.).

[0198]

[Chemical 51]

(Production Example 14) 3,3,3, -trifluoropropyl acrylate (formula (XIV); hereinafter referred to as TFA)
And acrylic acid (hereinafter, AA) copolymer (molar ratio 1:
To 100 g of 30% acetone solution of 10), 3 g of carbon black (MA-100 manufactured by Mitsubishi Carbon Co., Ltd.) was added,
Further, 3 g of glycerin was added as a viscosity modifier.

[0200]

[Chemical 52]

This mixture was vibrated for 30 minutes using a paint conditioner to finely disperse carbon black to obtain a dispersion liquid. During the vibration of the mixture, 30 g of glass beads having a diameter of 2 mm were added to promote dispersion. After the dispersion treatment, the glass beads were removed and 30 ml of 30% aqueous ammonia was added. The dispersion liquid to which aqueous ammonia was added was gently stirred at 40 to 45 ° C overnight.
The resulting dispersion was gradually added to 100 g of pure water while stirring. Next, acetone and ammonia were removed from the solution to which the dispersion was added by vacuum distillation to obtain about 140 g of an aqueous dispersion black ink. The viscosity of the obtained black ink was 100 cp (30 ° C.).
The solution obtained without adding carbon black was uniformly transparent at 30 ° C. These results are listed in Table 3 below together with the results of Production Examples 15 to 17.

[0202]

[Table 3]

(Preparation Examples 15 to 17) The same manner as in Preparation Example 14 except that the TFA / AA copolymers having the molar ratios shown in Table 3 were used and the amount of aqueous ammonia shown in Table 3 was used. As a result, an aqueous dispersion black ink was obtained. The viscosity of the obtained black ink is shown in Table 3. Further, Table 3 shows the state of the solution obtained without adding carbon black.

(Production Example 18) Copolymer of 3,3,4,4,4, -pentafluorobutylmethacrylate (formula (XV)) and methacrylic acid and n-butylmethacrylate (molar ratio 4:
100 g of a 30% tetrahydrofuran solution of 4: 3) was added to 300 g of pure water, and the mixture was stirred with a homogenizer to obtain a white turbid liquid.

[0205]

[Chemical 53]

The cloudy liquid was heated to 50 ° C., and triethylamine was gradually added dropwise until the cloudy liquid became transparent. The amount of triethylamine added was 25 g. Then, tetrahydrofuran and excess triethylamine were removed by vacuum distillation to obtain 315 g of a transparent solution. To the resulting solution, 0.5 g of urea, 20 g of ethylene glycol and 100 g of isopropyl alcohol were added, and finally, CI
340 g of black ink was obtained by adding 5 g of direct black (No. 19). The viscosity of the obtained black ink was 40 cp (30 ° C.).

(Production Example 19) α, α, α-trifluoromethyl- was prepared by a solution polymerization method in a methyl ethyl ketone using benzoyl peroxide as an initiator under a stream of N _2.
2,2,2-Trifluoroethyl acrylate (Formula (XVI))
And a copolymer of methacrylic acid and styrene (molar ratio 4:
2: 4) was obtained.

[0208]

[Chemical 54]

When excess n-butylamine was added to this reaction system and the mixture was heated under reflux for 2 hours, the reaction system became cloudy. Then, ion-exchanged distilled water was added, and the mixture was shaken with a shaker for about 10 minutes to phase-separate the quaternary chlorinated copolymer into an aqueous layer. Next, upper layer (oil layer)
The methyl ethyl ketone separated into the above was removed, and the residual methyl ethyl ketone, n-butylamine and the like were further removed by distillation under reduced pressure to obtain a dispersion liquid having a solid content of about 5%. To 100 parts by weight of this dispersion liquid, 10 parts by weight of diethylene glycol monoethyl ester was added, and further, carbon black whose surface was subjected to an acid treatment (Microzet manufactured by Orient Chemical Co., Ltd.) was added to 100 parts by weight of the solid content of the dispersion liquid. To 20
Added by weight. This mixture was dispersed by a ball mill to obtain a black ink having a concentration of about 6%. The viscosity of the obtained black ink was 15 cp (30 ° C.).

(Production Comparative Example 1) A concentration of about 6 was obtained in the same manner as in Production Example 19 except that n-butylamine was not added.
% Black ink was obtained. The viscosity of the obtained black ink was 35 cp (30 ° C.).

(Production Example 20) 100 g of a 50% acetone solution of vinyl acetate: maleic acid monohexyl ester: 3,3,3, -trifluoropropyl acrylate copolymer (molar ratio 4: 4: 2) was added to carbon black. (Mitsubishi Carbon Co., MA-100) 6 g was added. This mixture was vibrated for 30 minutes using a paint conditioner to carry out a fine dispersion treatment of carbon black to obtain a black dispersion liquid. This dispersion was gradually added to a solution prepared by dissolving 20 ml of 30% ammonia water in 200 g of ion-exchanged water. Then, the solution to which the dispersion liquid was added was heated to 45 ° C. and reacted until the smell of ammonia disappeared. During this reaction,
The solution changed from a cloudy state to a transparent state.

After completion of the reaction, acetone, ammonia and the like were removed by vacuum distillation to obtain 270 g of an aqueous dispersion type black ink. The viscosity of the obtained black ink is
It was 150 cp (30 ° C.).

(Production Example 21) n-Butylmethacrylate: maleic anhydride: α, α, α, 3,3,3-hexafluoropropylmethacrylate (the following formula (XVII)) copolymer (molar ratio 2: 4: 4) Methyl ethyl ketone solution 100
To g, 2 g of CI-Direct Black (No. 19) was added, further an aqueous solution of diethylamine was added, and the mixture was shaken at room temperature for one day using a shaker (Eight-W manufactured by Yayoi Co., Ltd.).

[0214]

[Chemical 55]

Upon completion of shaking, the solution was separated into an aqueous layer and an oil layer. Take out the black solution in the lower layer (water layer),
Residual diethylamine was removed by vacuum distillation. Glycerin monoester was added as a viscosity modifier to obtain a uniform black ink. The viscosity of the obtained black ink was 8000 cp (30 ° C.).

(Production Example 22) Styrene: maleic acid monoethyl ester: 3,3,4,4,4-pentafluorobutyl acrylate copolymer (molar ratio 4: 5) was obtained by dispersion polymerization in n-butyl alcohol. 1) was obtained. The copolymer was quaternary ammonium chloride with triethylamine.
This quaternary ammonium chloride copolymer was dissolved in n-butyl alcohol. 2 to 100 parts of copolymer
A uniform dispersion black ink was obtained by adding 0 part of acid-treated surface-treated carbon black (average particle diameter of 0.05 μm) and 2 parts of oxalic acid and stirring with a homogenizer. Further, 1 part of butyral resin (Sekisui Chemical Co., Ltd., S-lex M) was added to 2 parts of the copolymer in order to adjust the viscosity to 5000 cp or more. The viscosity of the obtained black ink was 6500 cp. The molar ratio of the copolymer, the amount of butyral resin added, and the viscosity of the obtained black ink are shown in Table 4 together with the results of Production Examples 23 and 24 described later.

[0217]

[Table 4]

(Preparation Examples 23 and 24) A black ink was prepared in the same manner as in Preparation Example 22 except that the copolymers having the molar ratios shown in Table 4 were used and the butyral resin was added at the ratio shown in Table 4. Got The viscosity of the resulting ink is also shown in Table 4.

(Production Example 25) Maleic acid monobenzyl ester (the following formula (XVIII)): 3,3,3-trifluoropropyl acrylate copolymer (molar ratio 4: 1) was added to a 50% ethyl acetate solution to give n. 300 ml of an aqueous solution in which 30 g of butylamine was dissolved was added. This solution was shaken overnight at room temperature using a shaker (Eight-W, manufactured by Yayoi Co., Ltd.).

[0220]

[Chemical 56]

Upon completion of shaking, the solution separated into an aqueous layer and an oil layer. Take out the black solution in the lower layer (water layer),
Residual ethyl acetate and n-butylamine were removed by vacuum distillation. Furthermore, CI-Acid Black (10
B) Add 50 ml of an aqueous solution containing 5 g, and add 410 ml.
Got black ink.

(Production Example 26) Styrene: maleic anhydride copolymer (molar ratio 1: 1) (manufactured by Elef Atchem Co., S
100 g of MA 1000A) was dissolved in 1 liter of dioxane. To this solution, 80 g of 2,2,2-trifluoroethyl alcohol was added, and the mixture was heated and stirred in an oil bath (bath temperature 100 ° C.) for about 2 hours using argon oxychloride as a catalyst to obtain the compound of formula (XIX) 156 g of a partially esterified terpolymer represented by

[0223]

[Chemical 57]

In the formula (XX), N: M: L = 34: 1.
It is 00:66. The degree of esterification was determined from the amount of residual carboxyl groups in the neutralization titration using phenolphthalein as an indicator.

The obtained terpolymer was pulverized with n-hexane, dispersed in ethanol, and aqueous ammonia was added to carry out quaternary ammonium chloride. As the reaction proceeded, the solution became transparent and uniform. The resulting solution had a solid content of 35% and a viscosity of 8600 cp (25 ° C.).

To 60 g of this solution was added 3 g of carbon black whose surface was treated with an acid (Microjet, manufactured by Orient Chemical Co.). This mixture was vibrated for 30 minutes using a paint conditioner to obtain a dispersed black ink. The viscosity of the obtained black ink is 8600c.
It was p (25 degreeC).

(Production Example 27) A black ink was obtained in the same manner as in Production Example 26 except that 0.5 g of ethylenediamine was added to the above solution in addition to carbon black. The viscosity of the obtained black ink is 10200 cp
(25 ° C).

(Production Example 28) Carbon black whose surface is treated with an acid (Microjet, manufactured by Orient Chemical Co.) 3
CI-Acid Black (No. 33) instead of g
A black ink was obtained in the same manner as in Production Example 26 except that 2 g was used. The viscosity of the obtained black ink is
It was 8600 cp (25 ° C).

(Production Example 29) 50 g of vinyl acetate: maleic anhydride copolymer (molar ratio 1: 1) was dissolved in 1 liter of dioxane. To this solution, N, N-bis (2,2,2-
Trifluoroethyl) amine (18 g) was added, and the mixture was heated and stirred in an oil bath (bath temperature 80 ° C.) for about 2 hours in an argon gas to give a partially amidated terpolymer 61 represented by the formula (XX).
g was obtained.

[0230]

[Chemical 58]

In the formula (XXI), N: M: L = 5:
It is 7: 2. The degree of amidation was determined from the amount of residual carboxyl groups in a neutralization titration using phenolphthalein as an indicator.

The obtained terpolymer was pulverized with n-hexane, dispersed in ethanol, triethylamine was added, and the mixture was heated at 80 ° C. for about 1 hour to obtain a uniform solution. The obtained solution has a solid content of 38% and a viscosity of 1400.
It was 0 cp (25 ° C).

To 55 g of this solution was added 3 g of carbon black whose surface was treated with an acid (Microjet, manufactured by Orient Chemical Co.). This mixture was vibrated for 30 minutes using a paint conditioner to obtain a dispersed black ink. The viscosity of the obtained black ink is 14200.
It was cp (25 ° C).

(Production Example 30) CI-Direct Black (No. 19) was added to 55 g of the solution obtained in Production Example 29.
1.5 g was added and ultrasonic treatment was performed at room temperature for about 1 hour to obtain a solution-type black ink. The viscosity of the obtained black ink was 13000 cp (25 ° C.).

(Production Example 31) 100 g of a 40% acetone solution of a styrene: maleic acid monoethyl ester copolymer (molar ratio 3: 1) was treated with nitric acid on the surface of carbon black (MA-100 manufactured by Mitsubishi Carbon Co., Ltd.). ) 8 g was added. This mixture is mixed with a paint conditioner 3 times.
The dispersion was obtained by vibrating for 0 minutes to finely disperse the carbon black. Add ethylenediamine 5 to this dispersion.
100 g of distilled water in which g was dissolved was added, and the mixture was heated and stirred at 60 ° C. With vigorous stirring, the viscous solution that was cloudy turned transparent. Next, acetone and the like were removed by vacuum distillation to obtain 150 g of a dispersion black ink. The viscosity of the obtained black ink was 15000 cp (30 ° C.).

(Production Example 32) 1 g of ethylenediamine was used instead of 100 g of distilled water in which 5 g of ethylenediamine was dissolved.
100g of distilled water in which 4g and 4g of triethylamine are dissolved
150 g of a dispersion black ink was obtained in the same manner as in Production Example 31 except that the above was used. The viscosity of the obtained black ink was 8000 cp (30 ° C.).

(Production Example 33) n-Butyl acrylate:
100 g of a 30% methyl ethyl ketone solution of 3,3,3-trifluoropropyl acrylate: acrylic acid copolymer (molar ratio 2: 2: 1) was dissolved in 3 g of amide black (10B) represented by the formula (XXI). It was added to 100 g of distilled water.

[0238]

[Chemical 59]

Next, 5 g of 30% aqueous ammonia and 0.6 g of N, N'-diethylethylenediamine were added to the solution obtained as described above. This solution was used at about 70 ° C. for about 1 using a shaker (Eight-W, manufactured by Yayoi Co.).
Shake for time. When shaking was completed, the solution separated into an aqueous layer and an oil layer. Methyl ethyl ketone in the upper layer portion (oil layer) was removed to obtain 141 g of a solution-type black ink.
The viscosity of the obtained black ink was measured with an R-type viscometer. The measurement results are shown in Table 5 together with the results of Production Examples 34 to 36 described later.

[0240]

[Table 5]

(Production Examples 34 to 36) The amount of 30 shown in Table 5 was used.
% Aqueous ammonia and N, N′-diethylethylenediamine were used to obtain a black ink in the same manner as in Production Example 33. The yield and viscosity of black ink are shown in Table 5. The viscosity of the black ink when N, N'-diethylethylenediamine was not added was 680 cp.
Met.

(Production Example 37) 5 g of vinyl acetate: crotonic acid copolymer (molar ratio 1: 1), 2-ethylhexyl methacrylate: mono (2-ethylhexyl maleate)
100 g of a solution prepared by dissolving 5 g of the ester (molar ratio 3: 1) in n-butyl alcohol was prepared. In this solution, n
A solution obtained by dissolving 5 g of -butylamine and 1 g of N, N, N ', N'-tetramethylethylenediamine in 10 g of n-butyl alcohol was added, and the mixture was heated at 80 ° C for about 1 hour. Upon heating, the solution viscosity increased significantly. Then, 5 g of a derivative of direct black (No. 4) represented by the formula (XXII)
Was added to 50 g of n-butyl alcohol and dispersed at room temperature using a paint conditioner to obtain 170 g of a partially dissolved black ink. The average particle size of the dispersion was 0.1 μm. Furthermore, the viscosity of the obtained black ink is 8400 cp.
(30 ° C.).

[0243]

[Chemical 60]

(Production Example 38) 1.5 g of N, N, N ', N'-tetramethyl-1,3-diaminobutane was used instead of 1 g of N, N, N', N'-tetramethylethylenediamine. Except that
170 g of black ink was obtained in the same manner as in Production Example 37. The viscosity of the obtained black ink is 7600 cp
(30 ° C.).

(Production Example 39) 170 g of black ink was obtained in the same manner as in Production Example 37, except that 5 g of diethylamine was used instead of 5 g of n-butylamine. The viscosity of the obtained black ink is 8900 cp (30
℃).

(Example 1) A 0.3% ethanol solution of an aminosilane coupling agent (PS076, manufactured by Chisso Corporation) was applied on a glass substrate having a thickness of 1.2 mm by a dip method to give a hydrophilicity of 0.2 μm. An undercoat layer was formed. Then, the light-shielding colored ink (solid content concentration: 25.0%) obtained in Production Example 7 was printed on the undercoat layer by a screen printing method, and the light-shielding colored ink was applied on a substrate in a grid pattern with a width of 15 μm and an interval of 100 μm. Attached. Immediately after the light-shading colored ink adheres
Approximately 1 on the side of the glass substrate where the light-shielding colored ink is not attached
The shading colored ink was changed from hydrophilic to hydrophobic by heating at 00 ° C. for about 5 minutes. The light-shielding colored layer thus formed had a thickness of 2.0 μm and an optical density of 3.1.

On the other hand, the red, green, and blue inks (that is,
A pixel color ink) was prepared as follows: (A) 5 parts of a red pigment (PR177), 5 parts of a surfactant (Nippon Emulsifier, Newcol 710F), melamine resin (Sumitomo Chemical Co., Ltd., Sumitex resin M-3) 10
Part, a curing agent (Sumitex Accelerator ACX manufactured by Sumitomo Chemical Co., Ltd.), and 89 parts of water are mixed, and this mixture is vibrated at room temperature for 1 hour using a paint conditioner to finely disperse the pigment. The red ink was prepared by performing (B) Instead of the red pigment (PR177), a green pigment (P
A green ink was prepared in the same manner as in the above (A) except that G-36) was used. (C) Instead of the red pigment (PR177), a blue pigment (P
A blue ink was prepared in the same manner as in the above (A) except that B-15) was used.

Next, an inkjet device (our prototype)
Each of the red, green and blue inks prepared as described above was adhered to a predetermined position on a portion of the glass substrate where the water repellent light shielding colored layer was not formed. In this way, red, green and blue pixels were formed at predetermined positions on the glass substrate. Each of the formed pixels was thermoset at 120 ° C. for 15 minutes to produce a color filter. The thickness of each pixel after curing was 1.8 μm.

The color filter manufactured as described above was observed with an optical microscope to examine the adhesion of the color ink for pixels to the light-shielding colored layer. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. In this color filter, uneven color difference was not observed at all.
Further, since this color filter does not require the development exposure process of each pattern of R, G, and B at the time of manufacturing, the manufacturing cost is remarkably reduced.

Example 2 A color filter was produced in the same manner as in Example 1 except that the light-shielding colored layer was formed by stencil printing. The obtained color filter was observed with an optical microscope in the same manner as in Example 1 to examine the adhesion of the pixel color ink to the light-shielding colored layer. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. In this color filter, uneven color difference was not observed at all. Furthermore, this color filter is
Since the development exposure process for each of the G and B patterns is not required,
Manufacturing costs have been significantly reduced.

Example 3 To 100 parts of the resin component of the light-shielding colored ink obtained in Production Example 5, 5 parts of the fluorine-containing surfactant represented by the chemical formula (XXIII) was added, and the mixture was thoroughly sonicated. It was stirred.

[0252]

[Chemical formula 61]

This light-shielding colored ink was printed on a glass substrate using an inkjet printer (piezo system), and the light-shielding colored ink was adhered to the substrate in a grid pattern with a width of 20 μm and an interval of 100 μm. Immediately after the light-shielding color ink was attached, the side of the glass substrate to which the light-shielding color ink was not attached was heated at about 80 ° C. for about 5 minutes to change the light-shielding color ink from hydrophilic to hydrophobic. The light-shielding colored layer thus formed had a thickness of 1.2 μm and an optical density of 2.3.

A color filter was produced in the same manner as in Example 1 with the following procedure. The obtained color filter was observed with an optical microscope in the same manner as in Example 1 to examine the adhesion of the pixel color ink to the light-shielding colored layer. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. No color mixture was observed in each pixel. In this color filter, uneven color difference was not observed at all. Further, since this color filter does not require the development exposure process of each pattern of R, G, and B at the time of manufacturing, the manufacturing cost is remarkably reduced.

Example 4 A liquid crystal display device as shown in FIG. 2 was produced using the color filter produced in Example 1. When the color display performance of this liquid crystal display device was measured by a colorimeter, it was possible to obtain sufficient performance as shown in FIG. 3, and it was a performance that was sufficiently satisfactory as a color display device for both OA and AV. I confirmed that there is. further,
Since the color filter is inexpensive, this liquid crystal display device can be manufactured at a lower cost than the conventional one.

Example 5 A liquid crystal display device as shown in FIG. 2 was produced using the color filter produced in Example 3. The color display performance of this liquid crystal display device was also sufficiently satisfactory as in Example 4, and could be manufactured at low cost.

(Example 6) A 0.5% ethanol solution of an aminosilane coupling agent (PS076 manufactured by Chisso Corporation) was applied on a glass substrate having a thickness of 1.2 mm by a dip method to give a hydrophilicity of 0.3 μm. An undercoat layer was formed. Then, on the undercoat layer, a mixture of the light-shielding colored ink (solid content concentration: 25.0%) obtained in Production Example 8 and a fluorine-based surfactant represented by the chemical formula (XXIII) was applied by a screen printing method. Printed and shaded colored ink 15 μm wide, 100 μm spacing
It was adhered to the substrate in a grid pattern with m. At this time, 5 parts of the fluorine-based surfactant was added to 100 parts of the solid content of the light-shielding colored ink. Immediately after the light-shielding color ink was attached, the side of the glass substrate on which the light-shielding color ink was not attached was heated at about 90 ° C. until the ammonia odor disappeared, and the light-shielding color ink was changed from hydrophilic to hydrophobic. The light-shielding colored layer thus formed had a thickness of 2.5 μm and an optical density of 3.4.

[0258]

[Chemical formula 62]

The following procedure was carried out in the same manner as in Example 1 to produce a color filter. The resulting color filter was observed with an optical microscope to examine the adhesion of the pixel color ink to the light-shielding colored layer. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. In this color filter, uneven color difference was not observed at all. The receding contact angles of the light-shielding colored layer and the color inks for pixels (R, G, B) each exceeded 25 degrees, which were favorable. Further, since this color filter does not require the development exposure process of each pattern of R, G, and B at the time of manufacturing, the manufacturing cost is remarkably reduced.

(Example 7) A color filter was produced in the same manner as in Example 6 except that the light-shielding colored layer was formed by stencil printing. The obtained color filter was observed with an optical microscope in the same manner as in Example 6 to examine the adhesion of the pixel color ink to the light-shielding colored layer. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. In this color filter, uneven color difference was not observed at all. Furthermore, this color filter is
Since the development exposure process for each of the G and B patterns is not required,
Manufacturing costs have been significantly reduced.

Example 8 A liquid crystal display device as shown in FIG. 2 was produced using the color filter produced in Example 6. When the color display performance of this liquid crystal display device was measured with a colorimeter, it was confirmed that the performance was sufficiently satisfactory as a color display device for both OA and AV. Further, this liquid crystal display device can be manufactured at a lower cost than the conventional one because the color filter is inexpensive.

(Example 9) Example 6 was repeated except that the light-shielding colored layer was formed by ink jet (piezo system).
A color filter was produced in the same manner as in. The obtained color filter was observed with an optical microscope in the same manner as in Example 6 to examine the adhesion of the pixel color ink to the light-shielding colored layer. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. This color filter is
No uneven color difference was observed. Further, since this color filter does not require the development exposure process of each pattern of R, G, and B at the time of manufacturing, the manufacturing cost is remarkably reduced.

Example 10 Using the color filter produced in Example 9, a liquid crystal display device as shown in FIG. 2 was produced. When the color display performance of this liquid crystal display device was measured with a colorimeter, it was confirmed that the performance was sufficiently satisfactory as a color display device for both OA and AV.
Further, this liquid crystal display device can be manufactured at a lower cost than the conventional one because the color filter is inexpensive.

Example 11 A 1.0% aqueous solution of a copolymer of acrylamide and acrylic acid (molar ratio 4: 1) was added,
The surface is washed with acetone by the dip method, and the thickness is 1.2 m.
m glass substrate to form a hydrophilic subbing layer having a thickness of 0.2 μm. On the other hand, 0.5 parts of the surfactant represented by the formula (XXIV) was added to 10 parts of the black ink obtained in Production Example 14.
Parts were added to prepare a light-shielding colored ink (solid content concentration about 25%).

[0265]

[Chemical formula 63]

Then, this light-shielding colored ink is printed on the undercoat layer by a dispenser method to form a light-shielding colored ink with a width of 2.
It was adhered to the substrate in a grid pattern at 5 μm and a spacing of 100 μm.
Immediately after the light-shielding color ink was attached, the side of the glass substrate on which the light-shielding color ink was not attached was heated at about 80 ° C. until the smell of ammonia disappeared, and the light-shielding color ink was changed from hydrophilic to water repellent. The light-shielding colored layer thus formed had a thickness d of 1.3 μm and an optical density OD of 2.4. Further, the receding contact angle θ _R was automatically measured by an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). These results are listed in Table 6 together with the results of Examples 12 to 14 described later.

[0267]

[Table 6]

On the other hand, the red, green, and blue inks (that is,
A pixel color ink) was prepared as follows: (A) 5 parts of a red pigment (PR177), 5 parts of a surfactant (Nippon Emulsifier, Newcol 710F), melamine resin (Sumitomo Chemical Co., Ltd., Sumitex resin M-3) 10
Part, a curing agent (Sumitex Accelerator ACX manufactured by Sumitomo Chemical Co., Ltd.), and 89 parts of water are mixed, and this mixture is vibrated at room temperature for 1 hour using a paint conditioner to finely disperse the pigment. The red ink was prepared by performing (B) Instead of the red pigment (PR177), a green pigment (P
A green ink was prepared in the same manner as in the above (A) except that G-36) was used. (C) Instead of the red pigment (PR177), a blue pigment (P
A blue ink was prepared in the same manner as in the above (A) except that B-15) was used.

Next, an inkjet device (our prototype)
Each of the red, green and blue inks prepared as described above was adhered to a predetermined position on a portion of the glass substrate where the water repellent light shielding colored layer was not formed. In this way, red, green and blue pixels were formed at predetermined positions on the glass substrate. Each of the formed pixels was thermally cured at 120 ° C. for 10 minutes to produce a color filter. The thickness of each pixel after curing was 2.4 μm.

The color filter produced as described above was observed with an optical microscope to examine the adhesion of the pixel color ink to the light-shielding colored layer. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. In this color filter, uneven color difference was not observed at all.
Further, since this color filter does not require the development exposure process of each pattern of R, G, and B at the time of manufacturing, the manufacturing cost is remarkably reduced.

Example 12 A color filter was produced in the same manner as in Example 11 except that a light-shielding colored ink was prepared using the black ink obtained in Production Example 15. Table 6 shows the thickness d, the optical density OD, and the receding contact angle θ _R of the light-shielding colored layer. Further, the obtained color filter was observed with an optical microscope in the same manner as in Example 11 to examine the adhesion of the pixel color ink to the light-shielding colored layer. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. In this color filter, uneven color difference was not observed at all. Further, since this color filter does not require the development exposure process of each pattern of R, G, and B at the time of manufacturing, the manufacturing cost is remarkably reduced.

Example 13 A color filter was produced in the same manner as in Example 11 except that a light-shielding colored ink was prepared using the black ink obtained in Production Example 16. Table 6 shows the thickness d, the optical density OD, and the receding contact angle θ _R of the light-shielding colored layer. Further, the obtained color filter was observed with an optical microscope in the same manner as in Example 11 to examine the adhesion of the pixel color ink to the light-shielding colored layer. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. In this color filter, uneven color difference was not observed at all. Further, since this color filter does not require the development exposure process of each pattern of R, G, and B at the time of manufacturing, the manufacturing cost is remarkably reduced.

Example 14 A color filter was produced in the same manner as in Example 11 except that a light-shielding colored ink was prepared using the black ink obtained in Production Example 17. Table 6 shows the thickness d, the optical density OD, and the receding contact angle θ _R of the light-shielding colored layer. Further, the obtained color filter was observed with an optical microscope in the same manner as in Example 11 to examine the adhesion of the pixel color ink to the light-shielding colored layer. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. In this color filter, uneven color difference was not observed at all. Further, since this color filter does not require the development exposure process of each pattern of R, G, and B at the time of manufacturing, the manufacturing cost is remarkably reduced.

Example 15 A 1.0% aqueous solution of gelatin was applied by dipping onto a glass substrate having a thickness of 1.5 mm at 45 ° C. to form a hydrophilic subbing layer having a thickness of 0.4 μm. Next, this glass substrate is heated to a surface temperature of 60 ° C., and the black ink (light-shielding coloring ink) obtained in Production Example 18 is printed on the undercoat layer by an inkjet method to form a light-shielding coloring layer. , Thickness 1.5 μm,
It was formed in a grid pattern with a width of 35 μm and a spacing of 100 μm. Example 1 except that the pixel thickness was 1.4 μm
A color filter was produced in the same manner as in 1. The obtained color filter was observed with an optical microscope in the same manner as in Example 11, and the adhesion of the color ink for pixels to the light-shielding colored layer was examined. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. In this color filter, uneven color difference was not observed at all. Further, since this color filter does not require the development exposure process of each pattern of R, G, and B at the time of manufacturing, the manufacturing cost is remarkably reduced.

(Comparative Example 1) Production An attempt was made to form a light-shielding colored layer in the same manner as in Example 15 except that the black ink of Comparative Example 1 was used. However, the ink did not adhere uniformly to the glass substrate, and it was impossible to form the light-shielding colored layer.

Example 16 Using the color filter produced in Example 11, a liquid crystal display device as shown in FIG. 2 was produced. When the color display performance of this liquid crystal display device was measured by a colorimeter, it was possible to obtain sufficient performance as shown in FIG. 3, and it was a performance that was sufficiently satisfactory as a color display device for both OA and AV. I confirmed that there is. Further, this liquid crystal display device can be manufactured at a lower cost than the conventional one because the color filter is inexpensive.

Example 17 A liquid crystal display device as shown in FIG. 2 was produced using the color filter produced in Example 15. The color display performance of this liquid crystal display device is also
It was sufficiently satisfactory as in Example 16 and could be manufactured at low cost.

(Example 18) A 2% aqueous solution of a copolymer of acrylamide and acrylic acid (molar ratio 4: 1) was applied on a glass substrate having a thickness of 1.5 mm by a dip method,
A hydrophilic subbing layer having a thickness of 0.5 μm was formed. On the other hand, 10 parts of the black ink obtained in Production Example 23 was mixed with the formula (XXIII)
0.5 part of the surfactant represented by the formula (3) was added, and the mixture was sufficiently stirred by ultrasonic waves to prepare a light-shielding colored ink.

[0279]

[Chemical 64]

Next, this light-shielding colored ink is printed on the undercoat layer by a dispenser method, and the light-shielding colored ink is printed with a width of 2.
It was adhered to the substrate in a grid pattern with 0 μm and an interval of 100 μm.
Immediately after the light-shielding color ink was attached, the side of the glass substrate on which the light-shielding color ink was not attached was heated at about 90 ° C. until the odor of triethylamine disappeared, and the light-shielding color ink was changed from hydrophilic to hydrophobic. The light-shielding colored layer thus formed had a thickness d of 3.0 μm and an optical density OD of 3.1.

On the other hand, the red, green, and blue inks (that is,
Pixel color ink) was prepared in the same manner as in Example 11: The red, green and blue inks prepared as described above were then mixed with glass using an inkjet device (our prototype). It was made to adhere to a predetermined position on the portion where the above-mentioned hydrophobic light-shielding colored layer was not formed on the substrate. In this way, red, green and blue pixels were formed at predetermined positions on the glass substrate. Each of the formed pixels was thermally cured at 120 ° C. for 10 minutes to produce a color filter. The thickness of each pixel after curing was 2.4 μm.

The color filter produced as described above was observed with an optical microscope to examine the adhesion of the pixel color ink to the light-shielding colored layer. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. In this color filter, uneven color difference was not observed at all.
Further, since this color filter does not require the development exposure process of each pattern of R, G, and B at the time of manufacturing, the manufacturing cost is remarkably reduced. The receding contact angle between the pixel color ink of each pixel and the light-shielding colored layer was more than 30 °.

Example 19 Using the color filter produced in Example 18, a liquid crystal display device as shown in FIG. 2 was produced. When the color display performance of this liquid crystal display device was measured by a colorimeter, it was possible to obtain sufficient performance as shown in FIG. 3, and it was a performance that was sufficiently satisfactory as a color display device for both OA and AV. I confirmed that there is. Furthermore, this liquid crystal display device can be manufactured at a lower cost than the conventional one because the color filter is inexpensive.

Example 20 A gelatin solution containing formalin was applied onto a glass substrate having a thickness of 1.4 mm by a squeezing doctor method, and dried by heating at 80 ° C. for about 10 minutes to give a hydrophilic undercoat layer having a thickness of 0.8 μm. Was formed. On the other hand, the formula (XXV) was added to 10 parts of the black ink obtained in Production Example 27.
0.5 part of a fluorine-containing compound represented by was added to prepare a light-shielding colored ink.

[0285]

[Chemical 65]

Next, this light-shielding colored ink is printed on the undercoat layer by a screen printing method, and the light-shielding colored ink is printed in a width of 2
It was adhered to the substrate in a grid pattern with 0 μm and an interval of 100 μm.
Immediately after the light-shielding color ink was attached, the side of the glass substrate on which the light-shielding color ink was not attached was heated at about 100 ° C. until the smell of ammonia disappeared, and the light-shielding color ink was changed from hydrophilic to hydrophobic. The light-shielding colored layer thus formed had a thickness of 2.8 μm and an optical density of 3.8.

On the other hand, the red, green, and blue inks (that is,
Pixel color ink) was prepared in the same manner as in Example 11: The red, green and blue inks prepared as described above were then mixed with glass using an inkjet device (our prototype). It was made to adhere to a predetermined position on the portion where the above-mentioned hydrophobic light-shielding colored layer was not formed on the substrate. In this way, red, green and blue pixels were formed at predetermined positions on the glass substrate. Each of the formed pixels was thermally cured at 120 ° C. for 10 minutes to produce a color filter. The thickness of each pixel after curing was 2.4 μm.

The color filter produced as described above was observed with an optical microscope to examine the adhesion of the pixel color ink to the light-shielding colored layer. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. In this color filter, uneven color difference was not observed at all.
Further, since this color filter does not require the development exposure process of each pattern of R, G, and B at the time of manufacturing, the manufacturing cost is remarkably reduced. The receding contact angle between the pixel color ink of each pixel and the light-shielding colored layer was more than 25 °.

Example 21 Using the color filter produced in Example 20, a liquid crystal display device as shown in FIG. 2 was produced. When the color display performance of this liquid crystal display device was measured by a colorimeter, it was possible to obtain sufficient performance as shown in FIG. 3, and it was a performance that was sufficiently satisfactory as a color display device for both OA and AV. I confirmed that there is. Further, this liquid crystal display device can be manufactured at a lower cost than the conventional one because the color filter is inexpensive.

Example 22 A 1% ethanol solution of a partially saponified vinyl acetate resin (saponification degree 40%) was applied on a glass substrate having a thickness of 1.2 mm by a dip method to give a hydrophilicity of 0.3 μm. An undercoat layer was formed. On the other hand, Production Example 3
Bis (acrylamide) represented by the formula (XXVI) was added to the black ink (solid concentration 22%) obtained in Example 5 to prepare a light-shielding colored ink.

[0291]

[Chemical formula 66]

Next, the above-mentioned light-shielding colored ink is printed on the undercoat layer by a screen printing method, and the light-shielding colored ink is applied in a width of 2
It was adhered to the substrate in a grid pattern with 0 μm and an interval of 100 μm.
Immediately after the light-shielding color ink was attached, the side of the glass substrate on which the light-shielding color ink was not attached was heated at about 90 ° C. until the smell of ethylenediamine disappeared, and the light-shielding color ink was changed from hydrophilic to hydrophobic. The light-shielding colored layer thus formed had a thickness of 3.0 μm and an optical density of 3.2.

On the other hand, the red, green, and blue inks (that is,
Pixel color ink) was prepared in the same manner as in Example 11: The red, green and blue inks prepared as described above were then mixed with glass using an inkjet device (our prototype). It was made to adhere to a predetermined position on the portion where the above-mentioned hydrophobic light-shielding colored layer was not formed on the substrate. In this way, red, green and blue pixels were formed at predetermined positions on the glass substrate. Each of the formed pixels was thermally cured at 120 ° C. for 10 minutes to produce a color filter. The thickness of each pixel after curing was 2.4 μm.

The color filter produced as described above was observed with an optical microscope to examine the adhesion of the pixel color ink to the light-shielding colored layer. As a result, adhesion of the pixel color ink to the light-shielding colored layer was not observed at all. In this color filter, uneven color difference was not observed at all.
Further, since this color filter does not require the development exposure process of each pattern of R, G, and B at the time of manufacturing, the manufacturing cost is remarkably reduced. The receding contact angle between the pixel color ink of each pixel and the light-shielding coloring layer was more than 25 °.

Example 23 A liquid crystal display device as shown in FIG. 2 was produced using the color filter produced in Example 22. When the color display performance of this liquid crystal display device was measured by a colorimeter, it was possible to obtain sufficient performance as shown in FIG. 3, and it was a performance that was sufficiently satisfactory as a color display device for both OA and AV. I confirmed that there is. Further, this liquid crystal display device can be manufactured at a lower cost than the conventional one because the color filter is inexpensive.

[0296]

As described above, according to the present invention, the light-shielding colored ink easily changes from hydrophilic to hydrophobic only by ordinary heating. Therefore, the light-shielding colored ink used in the color filter of the present invention is Has a good adhesive property (hydrophilicity) when attached to the substrate, and a water-repellent light-shielding colored layer can be easily obtained by heating. That is, unlike a conventional color filter having a light-shielding colored layer, it is not necessary to form an ink repellent layer such as a silicone resin. Further, since the light-shielding colored ink used in the present invention can easily form a pattern by a normal printing method, it is necessary to use a photomask or develop unlike the case where a conventional photosensitive resin is used. Absent. Moreover, the patterned light-shielding colored ink surely changes from hydrophilic to hydrophobic without changing its size or shape, and as a result, forms a water-repellent light-shielding colored layer. Therefore, (1) the manufacturing process is remarkably simplified; (2) the manufacturing is possible at a low cost; (3) it is not necessary to laminate the light-shielding colored layer and the ink repellent layer, so that the color filter , And the thickness of the liquid crystal display device) can be reduced; and (4) since the pattern of the ink repulsion portion is formed with high precision, the pixels of the color filter are formed with high precision,
As a result, a color filter having excellent display quality can be obtained.

Such a color filter can be preferably used in a liquid crystal display device, and an inexpensive liquid crystal display device having excellent color display performance is provided.

[Brief description of drawings]

FIG. 1 is a flowchart of a preferred example of a method for manufacturing a color filter of the present invention.

FIG. 2A is a schematic cross-sectional view of a liquid crystal display panel used in the liquid crystal display device of the present invention. 3B is a perspective view of the liquid crystal display panel of A. FIG.

FIG. 3 is a graph of a chromaticity diagram showing color display performance of the liquid crystal display device of the present invention.

[Explanation of symbols]

21 Liquid crystal display panel 22 TFT substrate 23 Counter substrate 24 Seal material 25 pixel electrodes 26 signal electrode (source electrode) 27 Scan electrodes (gate electrodes) 28 Thin film transistor (TFT) 29 common electrode 30 color filters 31 Black Matrix 32 pixels 33 Liquid crystal layer 34 Alignment film 35 Polarizer

Continuation of front page (31) Priority claim number Japanese Patent Application No. 8-68804 (32) Priority date March 25, 1996 (March 25, 1996) (33) Country of priority claim Japan (JP) (31) Priority claim number Japanese Patent Application No. 8-68806 (32) Priority date March 25, 1996 (March 25, 1996) (33) Country of priority claim Japan (JP) Preliminary examination (56) References 7-35917 (JP, A) JP 7-84122 (JP, A) JP 7-49416 (JP, A) JP 6-67421 (JP, A) JP 9-90115 (JP , A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) G02B 5/20-5/28

Claims (41)

(57) [Claims] 1. A color filter having a pixel and a light-shielding coloring layer on a transparent substrate, wherein the light-shielding coloring layer is formed by using a hydrophilic light-shielding coloring ink that changes to hydrophobic by heating, The light-shielding colored ink of is represented by the formula (III).
Nomer unit, monomer unit represented by formula (IV), formula
A monomer unit represented by (V) and a unit represented by formula (VI)
At least 1 selected from the group consisting of monomer units
A color filter comprising a resin having a monomer unit containing four quaternary ammonium salt moieties: Here, R ⁵ is hydrogen, a methyl group, or trifluoro
A methyl group; R ⁶ , R ⁷ and R ⁸ are each hydrogen, 1
~ Substituted or unsubstituted straight chain having 12 carbon atoms
Or a branched alkyl group, having 2-8 carbon atoms
A substituted or unsubstituted linear or branched alkenyl group,
A substituted or unsubstituted aralkyl group, a substituted or unsubstituted
Having a phenyl group, a heterocyclic group, 1 to 12 carbon atoms
A linear or branched fluorine-substituted alkyl group, and
Selected from the group consisting of fluorine-substituted alkylaryl groups, wherein X ⁺ is represented by formula (II): Here, one of R ¹ , R ² , R ³ and R ⁴ is hydrogen,
The other three are independently hydrogen, methyl, ethyl, and
It is selected from the group consisting of a ropyl group and a butyl group . 2. The color filter according to claim 1, wherein the resin contained in the hydrophilic light-shielding colored ink further has a fluorine-containing monomer unit. 3. The fluorine-containing monomer unit has the formula (VI
The color filter according to claim 2 , which is a monomer unit represented by I): Here, R ^A is hydrogen, a methyl group, or a trifluoromethyl group, and R ^B is a linear or branched fluorine-substituted alkyl group having 1 to 22 carbon atoms, or a fluorine-substituted alkylaryl. It is a base. 4. The color filter according to claim 2 , wherein the fluorine-containing monomer unit is contained in the resin in a ratio of 2 mol% to 90 mol%. 5. The color filter according to claim 2 , wherein the monomer unit having a quaternary ammonium salt moiety is contained in the resin in a ratio of 10 mol% to 70 mol%. 6. The resin contained in the hydrophilic light-shielding colored ink is selected from the group consisting of an acrylate monomer unit, a methacrylate monomer unit, a styrene monomer unit, a vinyl acetate monomer unit, and an isobutylene monomer unit. The color filter according to claim 1, further comprising at least one kind of monomer unit. 7. The styrenic monomer unit has the formula (VI
The color filter according to claim 6 , represented by II): Where R ²¹ is hydrogen or a methyl group, and
R ²² is hydrogen, an alkyl group having 1 to 12 carbon atoms, a nitro group or halogen. 8. The color filter according to claim 1, wherein the hydrophilic light-shielding colored ink further contains a fluorine-containing compound. 9. The color filter according to claim 8 , wherein the fluorine-containing compound is represented by the formula (IX): Here, R ³¹ is a fluorine-substituted alkyl group having 1 to 12 carbon atoms, Y is —COO—, —OCO—, —CONH—,
-CO-, -O-, -S-, phenylene group, -SO _2- , -SO _3- , or
-SO ₂ NH-, Z is -COOH, -OH, -CONH ₂ , -SO ₂ NH ₂ ,
_{^{-NH 2, -SO 3 - NH 4}} +, -COO - NH 4 +, -COO - NH + (C 2 H 5) 3 or -NH ₃ ⁺ · B, ^- (wherein B ^- is an anion residue) And m and n are each independently an integer of 0 to 6, and p is 0 or 1. 10. A group of the hydrophilic light-shielding colored ink, which comprises a monomer unit represented by the formula (III), a monomer unit represented by the formula (IV), and a monomer unit represented by the formula (V). A color filter according to claim 1 , comprising a resin having a monomer unit containing at least one quaternary ammonium salt moiety selected from: Wherein R ⁵ is hydrogen or a methyl group; R ⁶ is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, 2 to 8 carbon atoms Selected from the group consisting of a substituted or unsubstituted linear or branched group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, and a heterocyclic group. 11. The resin contained in the hydrophilic light-shielding colored ink is selected from the group consisting of an acrylate monomer unit, a methacrylate monomer unit, a styrene monomer unit, a vinyl acetate monomer unit, and an isobutylene monomer unit. The color filter according to claim 10 , further comprising at least one monomer unit. 12. The color filter according to claim 10 , wherein the hydrophilic light-shielding colored ink further contains a fluorine-containing compound. 13. A group of the hydrophilic light-shielding colored ink, comprising a monomer unit represented by the formula (III), a monomer unit represented by the formula (IV), and a monomer unit represented by the formula (V). The color filter according to claim 1 , comprising a resin having a monomer unit containing at least one quaternary ammonium salt moiety selected from: and a fluorine-containing monomer unit: Wherein R ⁵ is hydrogen, a methyl group, or a trifluoromethyl group; R ⁶ is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, 2 It is selected from the group consisting of a substituted or unsubstituted linear or branched group having ˜8 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, and a heterocyclic group. 14. The color filter according to claim 13 , wherein the fluorine-containing monomer unit is contained in the resin in a ratio of 2 mol% to 90 mol%. 15. The color filter according to claim 13 , wherein the monomer unit having a quaternary ammonium salt moiety is contained in the resin in a ratio of 10 mol% to 70 mol%. 16. The resin contained in the hydrophilic light-shielding colored ink is selected from the group consisting of an acrylate monomer unit, a methacrylate monomer unit, a styrene monomer unit, a vinyl acetate monomer unit, and an isobutylene monomer unit. The color filter according to claim 13 , further comprising at least one monomer unit. 17. The color filter according to claim 13 , wherein the hydrophilic light-shielding colored ink further contains a fluorine-containing compound. 18. The hydrophilic light-shielding colored ink has at least one quaternary ammonium salt moiety selected from the group consisting of a monomer unit represented by the formula (V) and a monomer unit represented by the formula (VI). A color filter according to claim 1 , comprising a resin having a monomer unit comprising: Wherein R ⁶ is selected from the group consisting of linear or branched fluorine-substituted alkyl groups having 1 to 12 carbon atoms, and fluorine-substituted alkylaryl groups; R ⁷ and R ⁸ are each hydrogen. A substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, 2
A substituted or unsubstituted linear or branched alkenyl group having 8 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, a heterocyclic group, 1 to
Selected from the group consisting of linear or branched fluorine-substituted alkyl groups having 12 carbon atoms, and fluorine-substituted alkylaryl groups, provided that at least one of R ⁷ and R ⁸ is 1-12 Selected from the group consisting of linear or branched fluorine-substituted alkyl groups having carbon atoms of, and fluorine-substituted alkylaryl groups. 19. The resin contained in the hydrophilic light-shielding colored ink is selected from the group consisting of an acrylate-based monomer unit, a methacrylate-based monomer unit, a styrene-based monomer unit, a vinyl acetate monomer unit, and an isobutylene monomer unit. The color filter according to claim 18 , further comprising at least one monomer unit. 20. The color filter according to claim 18 , wherein the hydrophilic light-shielding colored ink further contains a fluorine-containing compound. 21. The color filter according to claim 1, wherein the hydrophilic light-shielding colored ink further contains at least one polyamino compound. 22. The color filter according to claim 21 , wherein the polyamino compound is a diamino compound represented by the formula (X): Where A is a divalent hydrocarbon residue; and R
⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are independently hydrogen, 1 to 1
Substituted or unsubstituted linear or branched alkyl group having 2 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 6 carbon atoms, or substituted having 2 to 8 carbon atoms Alternatively, it is an unsubstituted linear or branched alkenyl group. 23. The color filter according to claim 1, wherein the light-shielding colored layer contains a coloring agent, and the coloring agent is a pigment-based coloring agent. 24. The pigment-based colorant is carbon black having a —COOM group on its surface, wherein M is hydrogen,
The color filter according to claim 23 , which is one kind selected from ammonium and alkali metals. 25. The color filter according to claim 1, wherein an undercoat layer having adhesiveness to the light-shielding colored layer is provided on the surface of the transparent substrate. 26. The subbing layer is gelatin.
25. The color filter according to item 25 . 27. The color filter according to claim 25 , wherein the undercoat layer contains a polymer having a monomer unit represented by the formula (XI): Where R ⁵¹ is hydrogen or a methyl group; and
R ⁵² is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted linear or branched aralkyl group, a substituted or unsubstituted phenyl group , Or a heterocyclic group. 28. A step of adhering a hydrophilic light-shielding colored ink, which is changed to hydrophobic by heating on a transparent substrate, in a predetermined pattern, and a step of changing the hydrophilic light-shielding colored ink to hydrophobic to give water-repellent light-shielding. A color filter comprising: a step of forming a colored layer; and a step of forming a pixel by attaching a hydrophilic pixel color ink to a portion of the transparent substrate where the water-repellent light-shielding colored layer is not formed. Manufacturing method : Here, the hydrophilic light-shielding colored ink is represented by the formula (III).
Monomer unit represented by the formula (IV)
Position, a monomer unit represented by formula (V), and formula (VI)
Less selected from the group consisting of monomer units represented by
And a monomer unit containing one quaternary ammonium salt moiety
Including a resin having Here, R ⁵ is hydrogen, a methyl group, or trifluoro
A methyl group; R ⁶ , R ⁷ and R ⁸ are each hydrogen, 1
~ Substituted or unsubstituted straight chain having 12 carbon atoms
Or a branched alkyl group, having 2-8 carbon atoms
A substituted or unsubstituted linear or branched alkenyl group,
A substituted or unsubstituted aralkyl group, a substituted or unsubstituted
Having a phenyl group, a heterocyclic group, 1 to 12 carbon atoms
A linear or branched fluorine-substituted alkyl group, and
Selected from the group consisting of fluorine-substituted alkylaryl groups, where X ⁺ is represented by formula (II): Here, one of R ¹ , R ² , R ³ and R ⁴ is hydrogen,
The other three are independently hydrogen, methyl, ethyl, and
It is selected from the group consisting of a ropyl group and a butyl group. 29. A group of the hydrophilic light-shielding colored ink, which comprises monomer units represented by formula (III), monomer units represented by formula (IV), and monomer units represented by formula (V). The method for producing a color filter according to claim 28 , comprising a resin having a monomer unit containing at least one quaternary ammonium salt moiety selected from: Wherein R ⁵ is hydrogen or a methyl group; R ⁶ is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, 2 to 8 carbon atoms Selected from the group consisting of a substituted or unsubstituted linear or branched group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, and a heterocyclic group. 30. A group in which the hydrophilic light-shielding colored ink comprises a monomer unit represented by the formula (III), a monomer unit represented by the formula (IV), and a monomer unit represented by the formula (V). 29. The method for producing a color filter according to claim 28 , comprising a resin having a monomer unit containing at least one quaternary ammonium salt moiety selected from the group: and a fluorine-containing monomer unit: Wherein R ⁵ is hydrogen, a methyl group, or a trifluoromethyl group; R ⁶ is hydrogen, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, 2 It is selected from the group consisting of a substituted or unsubstituted linear or branched group having ˜8 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, and a heterocyclic group. 31. The hydrophilic light-shielding colored ink has at least one quaternary ammonium salt moiety selected from the group consisting of a monomer unit represented by the formula (V) and a monomer unit represented by the formula (VI). The method for producing a color filter according to claim 28 , comprising a resin having a monomer unit containing: Wherein R ⁶ is selected from the group consisting of linear or branched fluorine-substituted alkyl groups having 1 to 12 carbon atoms, and fluorine-substituted alkylaryl groups; R ⁷ and R ⁸ are each hydrogen. A substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, 2
A substituted or unsubstituted linear or branched alkenyl group having 8 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, a heterocyclic group, 1 to
Selected from the group consisting of linear or branched fluorine-substituted alkyl groups having 12 carbon atoms, and fluorine-substituted alkylaryl groups, provided that at least one of R ⁷ and R ⁸ is 1-12 Selected from the group consisting of linear or branched fluorine-substituted alkyl groups having carbon atoms of, and fluorine-substituted alkylaryl groups. 32. The method of manufacturing a color filter according to claim 28 , wherein the light-shielding colored layer is formed so as to match the pattern of the non-pixel portion of the liquid crystal display device. 33. The method of manufacturing a color filter according to claim 28 , wherein the light-shielding colored ink is attached to the transparent substrate by an inkjet method. 34. The method of manufacturing a color filter according to claim 28 , wherein the light-shielding colored ink is attached to the transparent substrate by a dispenser method. 35. The method of manufacturing a color filter according to claim 28 , wherein the light-shielding colored ink is attached to the transparent substrate by a stencil printing method. 36. The method of manufacturing a color filter according to claim 28 , wherein the light-shielding colored ink is attached to the transparent substrate by a screen printing method. 37. The method of manufacturing a color filter according to claim 28 , wherein the light-shielding colored ink is attached to the transparent substrate by an offset printing method. 38. further contains a hydrophilic light-shielding colored ink of at least one polyamino compound, is deposited on the transparent substrate by screen printing method or offset printing method a light shielding color ink, according to claim 28 Color filter manufacturing method. 39. The method for producing a color filter according to claim 38 , wherein the polyamino compound is a diamino compound represented by the formula (X): embedded image Where A is a divalent hydrocarbon residue; and R
⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are independently hydrogen, 1 to 1
Substituted or unsubstituted linear or branched alkyl group having 2 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 6 carbon atoms, or substituted having 2 to 8 carbon atoms Alternatively, it is an unsubstituted linear or branched alkenyl group. 40. The hydrophilic color ink for pixels,
29. The method of manufacturing a color filter according to claim 28 , wherein the color filter is attached onto the transparent substrate by an inkjet method. 41. A liquid crystal display device in which liquid crystal is sealed between a pair of substrates, wherein the liquid crystal display device is provided on at least one of the substrates.
A liquid crystal display device, comprising the color filter according to claim 1.