JP2008191507A - Color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter which has a spacer of high accuracy for holding a cell gap uniform at a low cost. <P>SOLUTION: On a support, the color filter has a light shielding part, a colored pixel part of two or more colors having different spectral characteristics and a spacer constituted by laminating colored layers of two or more colors having different spectral characteristics on the light shielding part. The spacer satisfies all conditions:(a) a cross-sectional shape along a height direction is about a trapezoid, (b) height from the light shielding part is 2.0 to 4.0 μm, (c) a bottom area is 50 to 200 μm<SP>2</SP>and (d) a cross-sectional area when vertically cut at 2/3 height is 25 to 130 μm<SP>2</SP>. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a color filter used for a liquid crystal display element (LCD) or the like.

Conventionally, in order to make the thickness of the liquid crystal uniform when manufacturing liquid crystal panels, fine and uniform organic and inorganic particles called ball spacers such as plastic beads, ceramic beads, and glass beads are placed between the color filter substrate and the array substrate. The distance between the two substrates (also referred to as a cell gap) was controlled between them. In this method, since the liquid crystal after cell preparation is injected, if the size of the cell increases with an increase in the size of the screen, the liquid crystal injection process takes a lot of time, and the productivity in panel manufacturing is inferior. .
In addition, the process of spraying spacer particles needs to be isolated to contaminate the manufacturing process, and it is difficult to make the spray of spacer particles uniform, and the cell gap cannot be made constant throughout the display area. was there. Also, because of the ball spacers present in the colored pixel area, the panel transmittance and contrast are reduced, and color blurring occurs when the screen is touched with a finger, which is also preferable for image quality. There wasn't.

Therefore, it has been proposed to form columnar spacers on the color filter substrate and / or the array substrate by a photolithography method (see, for example, cited documents 1 and 2).
In the case of a photo spacer formed by this method, it is known that a liquid crystal dropping method (one drop filling: abbreviated as ODF) is applied instead of the time-consuming liquid crystal injection method, and the productivity is greatly improved. Specifically, a method is used in which a liquid crystal is dropped on a color filter substrate on which photo spacers are formed or an array substrate and leveled, and then the array substrate or the color filter substrate is bonded to produce a panel.

In addition, as a method of forming a spacer by photolithography, a colored pixel portion is formed on a color filter substrate and a colored layer formed from a colored photosensitive composition is laminated on a color filter substrate in order to improve productivity. A method of simultaneously forming spacers has been proposed (see, for example, Patent Documents 3, 4, and 5).
However, in the method of forming the spacer by laminating the colored layers, the coating of the colored photosensitive composition for forming the second and subsequent layers is performed on the previously formed spacer pattern with a small area. In addition, there is a problem that a colored layer having a thickness similar to that of the colored pixel portion cannot be obtained, and it is difficult to control the uniformity of the thickness. In particular, since the height of the spacer (cell gap) controls the thickness of the liquid crystal layer, if there is unevenness in the thickness of the spacer, unevenness in the alignment of the liquid crystal due to the thickness of the liquid crystal layer results in uneven display of the image. Become.
In particular, liquid crystal display devices using color filters, as typified by television, are developing liquid crystal materials themselves to improve the image quality of moving images = display response speed. Therefore, it is necessary to narrow the cell gap. For this purpose, even within a large screen, uniformity (height, shape, etc.) within and between spacer substrates is necessary and important.
JP 2002-20442 A JP-A-10-82909 JP 2003-15119 A JP 2003-84118 A JP 2006-184505 A

  The present invention has been made to improve the above-mentioned drawbacks of the prior art, and an object of the present invention is to provide a color filter having a highly accurate spacer for making the cell gap uniform at low cost. It is in.

Means for solving the above problems are as follows.
That is, the color filter of the present invention includes a light shielding part, a plurality of colored pixel parts having different spectral characteristics, and a colored layer of two or more colors having different spectral characteristics laminated on the light shielding part. And the spacer satisfies all of the following conditions (a) to (d).
(A) The cross-sectional shape along the height direction is substantially trapezoidal. (B) The height from the light shielding portion is 2.0 to 4.0 μm.
(C) The bottom area is 50 to 200 μm ²
(D) The cross-sectional area when cut horizontally at a height of 2/3 is 25 to 130 μm ^2.

In the color filter of the present invention, the optical density of the light shielding portion is 4.0 or more, the film thickness thereof is 0.1 μm or more and 1.2 μm or less, and the film thickness of the colored pixel portion is 1.2 μm or more and 2 It is a preferable aspect that it is 4 micrometers or less.
In the present invention, it is preferable that the spacer is formed by laminating two or more colored layers having different spectral characteristics in descending order of the sum of the transmittance at a wavelength of 365 nm and the transmittance at a wavelength of 405 nm.

  In the color filter of the present invention, the colored pixel portion and the spacer are (A) a colorant, (B) a compound represented by the following general formula (1), and a monomer represented by the following general formula (I). Selected from the group consisting of a polymer containing copolymer units derived from the above and a polymer containing a structural unit represented by the following general formula (a), having an acid value of 20 to 300 mg / g, and a weight average It is preferable to contain one or more polymer dispersants having a molecular weight in the range of 3,000 to 100,000.

[In General Formula (1), A ¹ represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a carbon number of 4 A monovalent organic group containing at least one site selected from the above hydrocarbon groups, alkoxysilyl groups, epoxy groups, isocyanate groups, and hydroxyl groups. n A ¹ and R ² may be the same or different independently. R ¹ represents an (m + n) -valent organic linking group, where m represents 1 to 8, n represents 2 to 9, and satisfies 3 <(m + n) <10. R ² represents a single bond or a divalent organic linking group. P ¹ represents a polymer skeleton. The m P ¹ may be the same or different. ]

[In the above general formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (═O ) Represents one selected from S-, -OC (= O)-, -OCONH-, and -NHCO-. Y represents any one selected from NR ⁰³ , O, and S, and R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. In the formula, N and Y are connected to each other to form a cyclic structure. m1 and n1 are each independently 0 or 1. ]

[In the general formula (a), R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure. ]

  Moreover, in this invention, in addition to said (A) coloring agent and (B) polymer dispersing agent, at least 1 selected from the compound group represented by the following general formula (A)-general formula (D). It is a more preferable aspect to contain the seed | species nonionic surfactant.

[The above general formula (A) ~ the general formula (D), (Styryl) represents ph-CH = CH- (benzyl) is ph-CH ₂ - represents a. Here, ph is a phenyl group. PO represents propylene oxide, and EO represents ethylene oxide. n is 1 to 3, m is 7 to 30, l is 0 to 10, a is 0 to 20, b is 0 to 20, c is 6 to 30, x is 5 to 100, and y is 20 to 100. Each represents an integer. X and y satisfy 0.1 ≦ x / y ≦ 2.0. The four x and y existing in the general formula (C) and the general formula (D) are the same or different integers, respectively. ]

  The color filter of the present invention includes a step of applying a colored curable composition on a support on which a light-shielding portion is formed to form a curable composition layer, and exposing and developing the curable composition layer. And forming the colored pixel portion, and at the same time, forming the colored layer and repeating the process a predetermined number of times.

The color filter of the present invention has a spacer formed by laminating two or more colored layers having different spectral characteristics on the light shielding portion, and the spacer needs to satisfy all the conditions (a) to (d).
In this way, by having the spacer having a tapered shape in the height direction from the light shielding portion, the spacer can be appropriately deformed when the color filter (substrate) is bonded to the array substrate. A uniform cell gap can be secured. Further, after the panel is manufactured, it can flexibly cope with deformation from the outside, and can be restored to its original shape when the external force applied with the deformation disappears.
In addition, the spacer in the present invention is a laminate of a colored layer having a tapered shape in the lower layer because all the conditions (a) to (d) are satisfied. Therefore, when forming the upper colored layer, there is an advantage that foaming due to air entrainment caused by an abrupt step when applying the coating liquid hardly occurs, and a colored layer with a uniform thickness is easily obtained. is there.

According to the present invention, a color filter having a highly accurate spacer for making the cell gap uniform can be provided at low cost.
As a result, by using this color filter, a display device having no color blur, high transmittance and contrast, and good image quality can be obtained at low cost.

Hereinafter, the color filter of the present invention will be described in detail.
The color filter of the present invention is a spacer formed by laminating a light shielding part, a plurality of colored pixel parts having different spectral characteristics, and a colored layer of two or more colors having different spectral characteristics on the light shielding part. And the spacer satisfies all of the following conditions (a) to (d).
(A) The cross-sectional shape along the height direction is substantially trapezoidal. (B) The height from the light shielding portion is 2.0 to 4.0 μm.
(C) The bottom area is 50 to 200 μm ²
(D) The cross-sectional area when cut horizontally at a height of 2/3 is 25 to 130 μm ^2.

As described above, the color filter of the present invention is characterized by having a spacer having a specific shape. Hereinafter, the conditions (a) to (d) regarding the shape of the spacer in the present invention will be described in detail.
The spacer in the present invention (a) requires that the cross-sectional shape along the height direction is a substantially trapezoid. Here, the “cross-sectional shape along the height direction” of the spacer is a cross-sectional profile of the pattern, and is usually observed using a transmission electron microscope from the lateral direction of the cut color filter. The “substantially trapezoidal shape” means a shape in which the cross-sectional area along the height direction of the spacer (columnar structure) decreases as the distance from the side (lower base) in contact with the light shielding portion on the support increases. Yes. The tip of the spacer (columnar structure) may be rounded.
In order to obtain the uniformity of the cell gap, it is preferable that the tip (upper bottom portion) of the spacer is small, and it is particularly preferable that the tip is spherical. A spherical tip of the spacer is preferable because it can be easily deformed by contact stress when bonded to the panel, and the non-uniformity of the spacer height can be absorbed.
Furthermore, the spacer support in the present invention and the cross-sectional shape in the horizontal direction are not particularly limited, and include a circle, an ellipse, an oval, a square, a rectangle, a triangle, and other polygons (including those with rounded corners). ) And the like.

The spacer in the present invention requires (b) a height from the light shielding portion of 2.0 to 4.0 μm, and preferably 2.5 to 3.5 μm.
When the spacer height is within this range, it is sufficient to shield the liquid crystal when applied to a liquid crystal display device, and the liquid crystal response speed can be secured, so that the liquid crystal thickness suitable for displaying a moving image can be secured. Is obtained.

The spacer in the present invention requires (c) a bottom area of 50 to 200 μm ² , and preferably 50 to 150 μm. Here, the “bottom area” of the spacer means the area of the region where the lowermost colored layer constituting one spacer covers the light shielding portion.
When the bottom area of the spacer is within this range, when the colored layer is laminated, application failure of the next liquid is unlikely to occur, pattern formation during development is good and there is no peeling, and an alignment film is applied in the next step In addition, failures in the alignment film rubbing process can be eliminated. In addition, since the area of the colored pixel portion can be increased, a bright image with a high aperture ratio can be provided.

The spacer in the present invention requires a cross-sectional area of 25 to 130 μm ² when cut vertically at (d) 2/3 height, and preferably 25 to 100 μm ² . Here, “a cross-sectional area when horizontally cut at a height of 2/3” means a cross-sectional area when the spacer is horizontally cut at a position corresponding to 2/3 of the height of the spacer. To do.
When the cross-sectional area is within the above range, the spacer taper shape (tapered shape in the height direction from the light-shielding portion) is ensured, and the taper is not steep. Since the deformation can be reduced, good image quality can be obtained. Further, as described above, it is possible to prevent failures in the subsequent liquid coating process, the alignment film coating process, and the alignment film rubbing process.

The condition (a) is confirmed by cutting the color filter and observing the cross section with a transmission electron microscope, or with a laser microscope.
Moreover, the said conditions (b)-(d) can be measured from the image obtained by the said observation.
In the present invention, the numerical values of the conditions (b) to (d) are measured by the above method for 5 (or more) spacers at each measurement point on the formed color filter, and the numerical values are averaged. Means things.

As described above, the color filter of the present invention has a spacer having a tapered shape in the height direction from the light shielding portion. This spacer has high accuracy for making the cell gap uniform and has the following effects.
That is, due to the shape of the spacer, the colored layer to be laminated is also tapered, so that the next colored curable composition liquid and the alignment film can be uniformly coated without generating bubbles.
In addition, since the transparent electrode film can be applied continuously, there is an effect that ITO disconnection does not occur.
Further, when a liquid crystal display device is obtained using the color filter of the present invention, a rubbing treatment is performed after the alignment film is applied. However, since the spacer in the present invention has a large surface in contact with the light shielding portion, the light shielding is performed. Since the rubbing process is carried out by scraping the rubbing bristles due to the high adhesive force to the part and the tapered shape in the height direction from the light shielding part, the orientation in the vicinity of the spacer becomes uniform, and the spacer It is also possible to prevent chipping and peeling.

  The spacer as described above is preferably provided in a range of 5 to 30% of the total number of colored pixel portions of the color filter of the present invention, and more preferably in a range of 10 to 25%. By providing the spacer in this range, it is possible to flexibly follow the deformation when an external force is applied to the panel, and to keep the cell gap uniform.

Further, the light shielding part of the color filter of the present invention preferably has an optical density (OD value) of 4.0 or more, more preferably 4.5 or more, and an upper limit value of preferably 6.0 or less. is there.
When the optical density of the light shielding portion is 4.0 or more, the backlight light is shielded, stray light from other adjacent colored pixel portions is shielded, and an image with high contrast can be obtained.
In addition, the optical density said here means the optical density (OD value) measured by the method as described in an Example.

The thickness of the light shielding part of the color filter of the present invention is preferably in the range of 0.1 to 1.2 μm, and more preferably in the range of 0.5 to 1.0 μm.
When the film thickness of the light shielding portion is in the range of 0.1 to 1.2 μm, the peripheral portion of the overlapping colored pixel portion becomes thicker than the upper surface of the colored pixel portion after development or after post-baking treatment (so-called Corner) phenomenon can be prevented. If the corners are formed, the alignment of the liquid crystal is disturbed and a preferable image cannot be obtained. In order to prevent this phenomenon, the light shielding layer is preferably a thin layer.

The thickness of the colored pixel portion of the color filter of the present invention is preferably in the range of 1.2 to 2.4 μm, and more preferably in the range of 1.5 to 2.4 μm.
When the thickness of the colored pixel portion is in the range of 1.2 to 2.4 μm, it is possible to easily apply a uniform film thickness, and the patterning property during development is good. Further, a colored pixel portion having no corners or small corners can be formed, and a panel with good image quality can be obtained.

In addition, the color purity of the colored pixel portion of the color filter of the present invention at the C light source is preferably in the range of 50 to 110 with respect to the area (100) of the three primary color chromaticity points of the NTSC system, and 60 to 85. More preferably, it is the range.
When the color purity of the colored pixel portion is in the above range, an image quality close to a natural color with good color reproducibility can be obtained, and a natural color image can be obtained in combination with a backlight light source. The color filter of the present invention is not limited to the above-described color purity, but the result is particularly preferable in the above-described color purity range.
Here, the color purity of the colored pixel portion is the size of the chromaticity (RGB color filter in this case) with respect to the area (100) of the NTSC three primary color chromaticity points in the CIE color system. Can be measured using a commercially available colorimetric colorimeter in accordance with JIS-Z-8701. In the present invention, the color pixel portion is measured with the C light source of the backlight.

In the present invention, it is preferable that the spacer is formed by laminating two or more colored layers having different spectral characteristics in the descending order of the sum of the transmittance at a wavelength of 365 nm and the transmittance at a wavelength of 405 nm. That is, it is preferable that the colored layer closer to the support is formed of a curable composition having a transmittance of a wavelength of 365 nm and a high sensitivity to a wavelength of 405 nm.
Here, the transmittance at a wavelength of 365 nm and the wavelength of 405 nm are wavelengths of a general light source, i-line (365 nm), and h-line (405 nm) used when forming a colored layer. A curable composition having a high sensitivity has good curability. Thus, when a colored layer is formed using a curable composition having a high sensitivity to the above-mentioned wavelength, it has excellent development resistance, and therefore has a columnar shape with a wide base (that is, a cross-sectional shape along the height direction). A colored layer having a trapezoidal shape that is tapered in the height direction is easily formed.

When a columnar colored layer with an expanded hem is formed, it becomes easy to apply the curable composition for forming the next colored layer, and the next coating liquid tends to remain on the colored layer, thereby causing uneven coating. It can be suppressed and the thickness of the colored layer can be easily controlled.
Moreover, when it exposes after apply | coating the curable composition for forming the next colored layer on the colored layer of the 1st color, exposure light permeate | transmits also to a lower layer (1st colored layer), The curing reaction will proceed. As a result, the spacers in the stacked state of two or three layers are trapezoidal as shown in the above-mentioned condition (a), so the height of the spacer (cell gap) is controlled. It becomes easy.

As described above, the color filter of the present invention includes a plurality of colored pixel portions having different spectral characteristics and a spacer formed by stacking two or more colored layers having different spectral characteristics. Each of the colored pixel portion and the spacer is formed using a plurality of curable compositions having different spectral characteristics. From the viewpoint of manufacturability, it is preferable that the spacer is formed of a curable composition used for forming the colored pixel portion. In other words, the curable composition of a plurality of colors having different spectral characteristics used for forming a plurality of colored pixel portions can be used at the same time when forming two or more colored layers constituting the spacer. Is preferred.
Hereinafter, the multi-color curable composition (colored curable composition) having different spectral characteristics used when forming the colored pixel portion and the spacer in the color filter of the present invention will be described.

[Colored curable composition]
The colored curable composition in the present invention is a radiation-sensitive composition and is particularly suitable for curing with light. (A-1) Colorant, (B-1) Polymer dispersant, (C-1) It preferably contains a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, and may further contain other components as desired.
Hereinafter, each component will be described.

<(A-1) Colorant>
The colored curable composition in the present invention contains (A-1) a colorant. By changing the type of the colorant, a multi-color curable composition having different spectral characteristics can be obtained.
As the colorant (A-1), a pigment is preferably used. The pigment used may be an inorganic pigment or an organic pigment, but considering that it is preferable to have a high transmittance, it is preferable to use a pigment having a particle size as small as possible, and the average primary particle size is 10 to 100 nm, more preferably. It is the range of 10-50 nm.
Even when the size of the colorant (pigment) is small, the use of a specific (B-1) polymer dispersant described later improves pigment dispersibility and dispersion stability, and even if it is thin. A colored pixel portion having excellent color purity can be formed.

  Examples of inorganic pigments that can be used in the colored curable composition include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium And metal oxides such as magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

Examples of organic pigments that can be used in the colored curable composition include:
C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;
C. I. Pigment violet 19, 23, 32, 37, 39;
C. I. Pigment blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1;
Alternatively, as green and blue pigments, phthalocyanines of metals other than copper described in JP-A Nos. 2001-133620 and 2003-161821, naphthalocyanines described in JP-A No. 2005-241928, and JP-A 2003-2003 Aluminum phthalocyanine disclosed in Japanese Patent No. 4930, subphthalocyanine pigments described in JP-A-2004-10838, and the like can be used.

Although it does not specifically limit in this invention, The following pigment is more preferable.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment violet 19, 23, 37,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment green 7, 36, 37;
Alternatively, as the green and blue pigments, there are phthalocyanines of metals other than copper described in JP-A Nos. 2001-133620 and 2003-161821, and aluminum phthalocyanine described in JP-A No. 2003-4930.

These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of combinations are shown below.
For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a bisazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment A mixture of these can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Mixing with CI Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50 from the viewpoint of obtaining sufficient color purity and suppressing deviation from the NTSC target hue. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

  In addition, as a green pigment, a halogenated phthalocyanine pigment may be used alone or in combination, or a mixture thereof with a bisazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, and an isoindoline yellow pigment. Two or more yellow pigments may be used in combination. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixture with CI Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150 from the viewpoint of obtaining sufficient color purity and suppressing deviation from the NTSC target hue. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment Blue 15: 6 and C.I. I. Mixing with Pigment Violet 23 is preferred. The mass ratio of the blue pigment and the purple pigment is preferably 100: 0 to 100: 50, more preferably 100: 5 to 100: 30.

  As content of (A-1) colorant (pigment) in the colored curable composition of this invention, 25-75 mass% is preferable with respect to the total solid (mass) of this composition, 32- 70 mass% is more preferable. (A-1) When the content of the colorant (pigment) is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

<(B-1) Polymer dispersant>
When a pigment is used as the colorant (A-1) in the colored curable composition of the present invention, it is preferable to use a polymer dispersant (B-1) shown below as the dispersant for the pigment.
The polymer dispersant (B-1) in the present invention is preferably a compound having an acid value of 20 to 300 mg / g and a weight average molecular weight in the range of 3,000 to 100,000.

(B-1) Since it is a preferable aspect that a polymer dispersing agent has a specific acid value as mentioned above, it is preferable that it is a polymer compound which has an acidic group.
Examples of the polymer skeleton of the polymer compound include polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and modified products thereof. Or a copolymer [for example, a polyether / polyurethane copolymer, a copolymer of a polyether / vinyl monomer polymer, etc. (any of a random copolymer, a block copolymer, and a graft copolymer) Good). At least one selected from the group consisting of vinyl monomers, selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferable, and a polymer or copolymer of vinyl monomers is particularly preferable.

Examples of a method for introducing an acidic group into the polymer skeleton as described above include, for example, a method of copolymerizing a monomer containing an acidic group when polymerizing the polymer skeleton, and the polymer described above. There is a method of introducing a skeleton by polymer reaction after polymerization.
Examples of the monomer containing an acidic group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, acrylic acid dimer, vinyl benzoic acid, styrene sulfonic acid, 2-acrylamide-2- It is obtained by reacting an alcoholic hydroxyl group-containing monomer such as methylpropanesulfonic acid, mono (meth) acryloylethyl phosphate, or 2-hydroxyethyl methacrylate with a cyclic acid anhydride such as maleic anhydride or phthalic anhydride. And monomers.
Among these, examples of preferable monomers are obtained by reacting an alcoholic hydroxyl group-containing monomer such as (meth) acrylic acid or 2-hydroxyethyl methacrylate with a cyclic acid anhydride such as maleic anhydride or phthalic anhydride. And the like. Examples of the cyclic acid anhydride used here include itaconic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, trimetic anhydride, etc., and particularly phthalic anhydride, succinic anhydride, etc. Is preferred.

Furthermore, the polymer compound having an acidic group may further be obtained by copolymerizing a vinyl monomer component.
Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides , Vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable.

Examples of such vinyl monomers include the following compounds.
Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.
Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

In addition to the above compounds, (meth) acrylonitrile, heterocyclic groups substituted with a vinyl group (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, Vinyl caprolactone can also be used.
Furthermore, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

Further, polymerizable oligomers as shown below may be used as vinyl monomers.
The polymerizable oligomer (hereinafter sometimes referred to as “macromonomer”) is an oligomer having a group having an ethylenically unsaturated double bond at the terminal. In the present invention, among the polymerizable oligomers, it is preferable to have a group having the ethylenically unsaturated double bond only at one of both ends of the oligomer.

  The molecular weight of the polymerizable oligomer is preferably a polystyrene-equivalent number average molecular weight (Mn) of 1000 to 20000, more preferably 2000 to 15000. If the number average molecular weight is less than 1000, the steric repulsion effect as a dispersant may not be sufficient, and if it exceeds 20000, it may take time to adsorb to the colorant (pigment) due to the steric effect. .

  The oligomer generally includes, for example, a homopolymer or copolymer formed from at least one monomer selected from alkyl (meth) acrylate, styrene, acrylonitrile, vinyl acetate and butadiene, Among these, alkyl (meth) acrylate homopolymers or copolymers, polystyrene, and the like are preferable. In the present invention, these oligomers may be substituted with a substituent, and the substituent is not particularly limited, and examples thereof include a hydroxyl group and a halogen atom.

The above vinyl monomers may be polymerized by only one kind, or may be copolymerized by using two or more kinds together. Such a radical polymer is prepared by a known method in accordance with a conventional method for each corresponding vinyl monomer. It is obtained by polymerizing.
For example, a method in which these vinyl monomer and chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto and polymerized in solution at about 50 ° C. to 220 ° C. (solution polymerization method) Can be obtained using

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer. For example, methanol, ethanol, propanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene Can be mentioned. These solvents may be used as a mixture of two or more.

  Examples of radical polymerization initiators include azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl par Peroxides such as oxides, and persulfates such as potassium persulfate and ammonium persulfate can be used.

As described above, the polymer dispersant (B-1) in the present invention preferably has an acid value in the range of 20 to 300 mg / g, more preferably in the range of 30 to 250 mg / g. Preferably, it is the range of 30-200 mg / g.
(B-1) When the acid value of the polymer dispersant is within this range, the dispersibility and dispersion stability of the pigment are excellent, and the alkali developability is also excellent.

The weight average molecular weight of the polymer dispersant (B-1) is preferably in the range of 3,000 to 100,000, more preferably in the range of 3,000 to 70,000, and still more preferably. Is in the range of 5,000 to 50,000.
(B-1) When the weight average molecular weight of the polymer dispersant is within this range, it is preferable from the viewpoint of shortening the dispersion time of the pigment and stability of the dispersion over time.

In the present invention, the polymer dispersant (B-1) is a polymer compound having 2 to 100 pigment-adsorptive groups at the polymer terminal, or a nitrogen-containing heterocyclic ring, and having an ethylenic defect. A polymer compound containing a monomer having a saturated group as a copolymer unit is preferable.
Hereinafter, these two polymer compounds will be specifically described.

(B-1) The polymer compound having 2 to 100 pigment-adsorptive groups as a polymer dispersant at the polymer terminal has a specific acid value and a weight average molecular weight as described above, and a pigment. Although it will not restrict | limit especially if it is a high molecular compound which has 2-100 adsorptive groups at the polymer terminal, It is preferable that it is the following.
That is, a polymer compound having 4 to 70 pigment adsorbing groups at the polymer terminal is preferable, and a polymer compound having 5 to 50 pigment adsorbing groups at the polymer terminal is more preferable. The pigment adsorbing group is preferably an organic dye structure, a heterocyclic structure, an acidic group, a basic group, or the like. Among these, a polymer compound represented by the general formula (1) described later is preferable.

(B-1) The polymer compound having a nitrogen-containing heterocyclic ring as a polymer dispersant and having a monomer having an ethylenically unsaturated group as a copolymer unit includes the specific acid as described above. The polymer compound is not particularly limited as long as it is a polymer compound having a valence and a weight average molecular weight, a nitrogen-containing heterocyclic ring, and a monomer having an ethylenically unsaturated group as a copolymerization unit. Those having a nitrogen heterocycle are preferred.
Preferred nitrogen-containing heterocycles include pyrrole, pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzo Examples include thiazole, succinimide, phthalimide, naphthalimide, hydantoin, and carbazole.
Especially, it is preferable that it is a polymer containing the copolymer unit derived from the monomer represented by general formula (I) mentioned later, or the polymer containing the structural unit represented by general formula (a).

  Hereinafter, (B-1) a polymer compound represented by formula (1), (B-1-2) formula (I), which is suitable as a polymer dispersant (B-1) in the present invention. And a polymer containing a copolymer unit derived from the monomer represented by formula (B) and a polymer containing a structural unit represented by formula (a).

[(B-1-1) Polymer Compound Represented by General Formula (1)]
First, a polymer compound represented by the following general formula (1) (hereinafter referred to as “(B-1-1) specific polymer dispersant” as appropriate) will be described.

In the general formula (1), A ¹ represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms. Represents a monovalent organic group containing at least one portion selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ¹ may be the same or different.

That is, the A ¹ has a structure capable of adsorbing to a pigment such as an organic dye structure or a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, or a coordinating oxygen atom. And a monovalent organic group containing at least one functional group capable of adsorbing to a pigment, such as a group, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group.
Hereinafter, the site having the ability to adsorb to the pigment (the above structure and functional group) will be collectively referred to as “adsorption site” as appropriate.

The adsorption sites are in one A ^1, it may be contained at least one, may contain two or more kinds.
Further, in the present invention, the “monovalent organic group containing at least one kind of adsorption site” means the above-mentioned adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to It is a monovalent organic group formed by bonding up to 100 oxygen atoms, 1 to 400 hydrogen atoms, and an organic linking group consisting of 0 to 40 sulfur atoms. In the case where adsorption sites themselves may constitute a monovalent organic group, adsorption sites itself may be a monovalent organic group represented by A ^1.
First, the adsorption site constituting A ¹ will be described below.

  Examples of the “organic dye structure” include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, anthanthrone, indanthrone, flavan. Examples of preferable dye structures of throne, perinone, perylene, and thioindigo are phthalocyanine, azo lake, anthraquinone, dioxazine, and diketopyrrolopyrrole, and phthalocyanine and anthraquinone. A diketopyrrolopyrrole dye structure is particularly preferred.

  Examples of the “heterocyclic structure” include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine. , Piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, Anthraquinone is mentioned as a preferred example, pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, Riazor, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, carbazole, acridine, acridone, anthraquinone are more preferable.

  The “organic dye structure” or “heterocyclic structure” may further have a substituent. Examples of the substituent include alkyl groups having 1 to 20 carbon atoms such as a methyl group and an ethyl group. An acyloxy group having 1 to 6 carbon atoms, such as an aryl group having 6 to 16 carbon atoms such as a hydroxyl group, a phenyl group or a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group or an acetoxy group. Alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group , A cyano group, a carbonate group such as t-butyl carbonate, and the like. Here, these substituents may be bonded to the organic dye structure or the heterocyclic ring through the following structural unit or a linking group constituted by combining the structural units.

  Preferred examples of the “acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and a boric acid group. Sulfuric acid ester groups, phosphoric acid groups, and monophosphoric acid ester groups are more preferable, and carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups are particularly preferable.

Examples of the “group having a basic nitrogen atom” include an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), Preferred examples include the amidinyl group represented by a2).

In formula (a1), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ each independently has 1 to 10 carbon atoms. An alkyl group, a phenyl group, and a benzyl group.), A guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms. Represents a phenyl group or a benzyl group. ] An amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. ] Is more preferable.
In particular, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. , A phenyl group and a benzyl group), a guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 5 carbon atoms, phenyl Represents a benzyl group. Amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group. Etc. are preferably used.

Examples of the “urea group” include —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number) Preferred examples include 6 or more aryl groups and an aralkyl group having 7 or more carbon atoms. —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom or 1 carbon atom) More preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms), -NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or 1 to 10 carbon atoms). An alkyl group, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are particularly preferable.

Examples of the “urethane group” include —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (wherein R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like. -NHCOOR ¹⁸ , -OCONHR ²¹ (here And R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like, more preferably —NHCOOR ¹⁸ , -OCONHR ^{21 (wherein,} R ^{18, R 21} each independently represents an alkyl group having from 1 to 10 carbon atoms, 6 or more arylene carbon Group, the number 7 or aralkyl group having a carbon.), Etc. are particularly preferred.

  Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether.

  Preferred examples of the “hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferred are an alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 4 to 15 carbon atoms (for example, an octyl group, a dodecyl group, etc.), and an aryl having 6 to 15 carbon atoms. A group (for example, phenyl group, naphthyl group, etc.), an aralkyl group having 7 to 15 carbon atoms (for example, benzyl group, etc.) and the like are particularly preferable.

  Examples of the “alkoxysilyl group” include a trimethoxysilyl group and a triethoxysilyl group.

The organic linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200. An organic linking group consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms is preferred, and this organic linking group may be unsubstituted or may further have a substituent.
Specific examples of the organic linking group include the following structural units or groups constituted by combining the structural units.

  When the organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. C1-C6 alkoxy such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide group, acetoxy group, etc., C1-C6 acyloxy group, methoxy group, ethoxy group, etc. Group, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, etc. Can be mentioned.

In the above, as A ¹ , at least one site selected from an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is used. It is preferable that it is a monovalent organic group to contain.

The A ¹ is more preferably a monovalent organic group represented by the following general formula (4).

In the general formula (4), B ¹ represents the adsorption site (that is, an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, or a group having a coordinating oxygen atom). , A moiety selected from a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group), and R ²⁴ represents a single bond or an (a + 1) -valent organic linking group. a represents an integer of 1 to 10, and a number of B ¹ may be the same or different.

Examples of the adsorption site represented by B ¹ include those similar to the adsorption site constituting A ¹ in the general formula (1) described above, and preferred examples are also the same.
Among these, a site selected from an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is preferable.

R ²⁴ represents a single bond or an (a + 1) -valent organic linking group, and a represents 1 to 10. Preferably, a is 1-7, more preferably, a is 1-5, and particularly preferably, a is 1-3.
(A + 1) valent organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, And a group consisting of 0 to 20 sulfur atoms, which may be unsubstituted or further substituted.

  Specific examples of the (a + 1) -valent organic linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).

R ²⁴ may be a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and An (a + 1) valent organic linking group consisting of 0 to 10 sulfur atoms is preferred, a single bond, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are (a + 1) valent organic linking groups consisting of up to 1 oxygen atom, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond, or 1 to 10 (A + 1) valence consisting of 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms The organic linking group is particularly preferred.

  Among the above, when the (a + 1) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, and the like. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl carbonate And the like, and the like.

In the general formula (1), R ² represents a single bond or a divalent organic linking group. n R ² may be the same or different.
Divalent organic linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 Groups comprising from 20 to 20 sulfur atoms are included and may be unsubstituted or further substituted.

  Specific examples of the divalent organic linking group include the following structural units or groups formed by combining the structural units.

R ² may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and A divalent organic linking group consisting of 0 to 10 sulfur atoms is preferred, a single bond, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 And more preferably a divalent organic linking group comprising 1 to 50 hydrogen atoms and 0 to 7 sulfur atoms, a single bond or 1 to 10 carbon atoms, A divalent organic linking group consisting of 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms, in particular preferable.

  Among the above, when the divalent organic linking group has a substituent, examples of the substituent include carbon having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a carbon such as a phenyl group and a naphthyl group. Carbon number such as acyloxy group having 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc., methoxy group, ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And carbonate ester groups.

In the general formula (1), R ¹ represents an (m + n) -valent organic linking group. Here, m represents 1 to 8, n represents 2 to 9, and satisfies 3 <(m + n) <10.
The (m + n) -valent organic linking group represented by R ¹ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups consisting of up to 200 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.

  Specific examples of the (m + n) -valent organic linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).

  (M + n) -valent organic linking group includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, And groups consisting of 0 to 10 sulfur atoms are preferred, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 More preferred are groups consisting of up to 5 hydrogen atoms and 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms. Particularly preferred are groups consisting of 1 to 80 hydrogen atoms and 0 to 5 sulfur atoms.

  Among the above, when the (m + n) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl carbonate And the like, and the like.

Specific examples (specific examples (1) to (17)) of the (m + n) -valent organic linking group represented by R ¹ are shown below. However, the present invention is not limited to these.

  Among the above specific examples, the most preferable (m + n) -valent organic linking group is the following group from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents.

In said general formula (1), m represents 1-8. As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.
Moreover, in said general formula (1), n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In the general formula (1), P ¹ represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. The m P ¹ may be the same or different.
Among polymers, in order to constitute a polymer skeleton, a polymer or copolymer of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and these Modified product or copolymer [for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer, etc. (any of random copolymer, block copolymer, graft copolymer) May be included). At least one selected from the group consisting of vinyl monomers, selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferable, and a polymer or copolymer of vinyl monomers is particularly preferable.
Furthermore, the polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, for example, when used as a pigment dispersant, the affinity with the dispersion medium is weakened, and it may not be possible to secure a sufficient adsorption layer for stabilizing the dispersion.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having an acidic group, and the like are preferable.
Hereinafter, preferable examples of these vinyl monomers will be described.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid acetoxyethyl, (meth) acrylic acid phenyl, (meth) 2-hydroxyethyl acrylate, (meth) acrylic acid-2-hydroxypropyl, (meth ) Acrylic acid-3-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid 2- (2- Methoxyethoxy) ethyl, 3-methoxy-2-hydroxypropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, (Meth) vinyl acrylate, (meth) acrylic acid-2-phenylvinyl, (meth) acrylic acid-1-propenyl, (meth) acrylic acid allyl, (meth) acrylic acid-2-allyloxyethyl, (meth) Propargyl acrylate, benzyl (meth) acrylate, diethylene glycol (meth) acrylate Methyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic Polyethylene glycol monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth ) Trifluoroethyl acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Meth) acrylic acid tribromophenyl, (meth) tribromophenyl oxyethyl acrylate, and (meth) acrylic acid -γ- butyrolactone.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.

  (Meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (for example, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, etc. are also used. it can.

  In addition to the above compounds, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

Examples of the vinyl monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and the like.

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  Furthermore, a vinyl monomer containing a phenolic hydroxyl group or a vinyl monomer containing a sulfonamide group can be used as the vinyl monomer having an acidic group.

  Among the polymer compounds represented by the general formula (1), the polymer compound represented by the following general formula (2) is preferable.

In the general formula (2), A ² represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms. Represents a monovalent organic group containing at least one portion selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ² may be the same or different.
Incidentally, A ² has the same meaning as the A ¹ in the general formula (1), a preferable embodiment thereof is also the same.

In the general formula (2), R ⁴ and R ⁵ each independently represents a single bond or a divalent organic linking group. The n R ^{4 s} may be the same or different. The m R ^{5 s} may be the same or different.
As the divalent organic linking group represented by R ⁴ and R ⁵ , the same ones as those mentioned as the divalent organic linking group represented by R ² in the general formula (1) are used, The preferred embodiment is also the same.

In the general formula (2), R ³ represents an (m + n) -valent organic linking group. Here, m represents 1 to 8, n represents 2 to 9, and 3 <(m + n) <10 is satisfied.
Examples of the (m + n) -valent organic linking group represented by R ³ include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups comprising up to 100 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.
Specifically, the (m + n) -valent organic linking group represented by R ³ is the same as the (m + n) -valent organic linking group represented by R ¹ in the general formula (1). The preferred embodiments are the same.

In said general formula (2), m represents 1-8. As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.
Moreover, in said general formula (2), n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

Further, P ² in the general formula (2) represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. the m P ² can be the same or different. The preferred embodiment of the polymer is the same as P ¹ in Formula (1).

Among the polymer compounds represented by the general formula (2), those satisfying all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below are most preferable.
R ³ : Specific examples (1), (2), (10), (11), (16), or (17)
R ⁴ : A single bond or the following structural unit or a combination of the structural units: “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygens” A divalent organic linking group comprising an atom, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms (which may have a substituent, for example, C1-C20 alkyl group such as methyl group and ethyl group, aryl group having 6 to 16 carbon atoms such as phenyl group and naphthyl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide Groups, acyloxy groups having 1 to 6 carbon atoms such as acetoxy groups, alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups, halogen atoms such as chlorine and bromine, methoxycarbonyl groups, etho Aryloxycarbonyl group, an alkoxycarbonyl group having from 2 to 7 carbon atoms such as cyclohexyl oxycarbonyl group, a cyano group, carbonate group, such as t- butyl carbonate, and the like.)

R ⁵ : single bond, ethylene group, propylene group, the following group (a), or the following group (b)
In the following groups, R ¹² represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : Polymer or copolymer of vinyl monomer, ester polymer, ether polymer, urethane polymer, and modified products thereof m: 1 to 3
n: 3-6

(Synthesis method)
The polymer compound represented by the general formula (1) (including those represented by the general formula (2)) is not particularly limited, but can be synthesized by the following method.
1. A polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group, or the like is introduced at the terminal; an acid halide having a plurality of the adsorption sites; an alkyl halide having a plurality of the adsorption sites; or a plurality of the adsorption sites. A method of polymerizing the isocyanate and the like.
2. A method in which a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having a plurality of the adsorption sites are subjected to a Michael addition reaction.
3. A method of reacting a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having the adsorption site in the presence of a radical generator.
4). A method in which a polymer having a plurality of mercaptans introduced at its terminal is reacted with a compound having a carbon-carbon double bond and the adsorption site in the presence of a radical generator.
5. A method of radical polymerizing a vinyl monomer in the presence of a mercaptan compound having a plurality of the adsorption sites.

  Among the above, the (B-1-1) specific polymer dispersant in the present invention is preferably a synthesis method of 2, 3, 4, 5 and preferably a synthesis method of 3, 4, 5 because of ease of synthesis. More preferred. In particular, when the (B-1-1) specific polymer dispersant has a structure represented by the general formula (2), it is most preferable to synthesize by the synthesis method 5 in view of ease of synthesis.

  More specifically, the synthesis method 5 is preferably a method in which a vinyl monomer is radically polymerized in the presence of a compound represented by the following general formula (3).

In the general formula (3), R ⁶ , R ⁷ , A ³ , m, and n have the same meanings as R ³ , R ⁴ , A ² , m, and n in the general formula (2), respectively. The preferred embodiment is also the same.

The compound represented by the general formula (3) can be synthesized by the following method or the like, but the following method 7 is more preferable because of ease of synthesis.
6). A method of converting a halide compound having a plurality of adsorption sites into a mercaptan compound (a method of reacting with thiourea and hydrolyzing, a method of reacting directly with NaSH, a method of reacting with CH ₃ COSNa and hydrolyzing, etc.) )
7). Method of addition reaction of a compound having 3 to 10 mercapto groups in one molecule and a compound having the adsorption site and having a functional group capable of reacting with a mercapto group

Preferable examples of the “functional group capable of reacting with a mercapto group” in the synthesis method 7 include acid halides, alkyl halides, isocyanates, and carbon-carbon double bonds.
It is particularly preferable that the “functional group capable of reacting with a mercapto group” is a carbon-carbon double bond, and the addition reaction is a radical addition reaction. The carbon-carbon double bond is more preferably a mono- or di-substituted vinyl group in terms of reactivity with the mercapto group.

  Specific examples of the compound having 3 to 10 mercapto groups in one molecule [specific examples (18) to (34)] include the following compounds.

  Among the above, the following compounds are particularly preferable from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents.

  A compound having the adsorption site and having a carbon-carbon double bond (specifically, an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a coordination group) A group having a coordinated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group; and a carbon-carbon double bond Although it does not restrict | limit especially as a compound which has, The following are mentioned.

  The radical addition reaction product of the “compound having 3 to 10 mercapto groups in one molecule” and the “compound having the adsorption site and having a carbon-carbon double bond” is, for example, The above-mentioned “compound having 3 to 10 mercapto groups in one molecule” and “compound having the adsorption site and having a carbon-carbon double bond” are dissolved in a suitable solvent, It is obtained using a method (thiol-ene reaction method) in which a radical generator is added and added at about 50 ° C. to 100 ° C.

Examples of suitable solvents used in the thiol-ene reaction method include “compound having 3 to 10 mercapto groups in one molecule”, “having the adsorption site, and carbon-carbon double. It can be arbitrarily selected according to the solubility of the “compound having a bond” and the “radical addition reaction product to be produced”.
For example, methanol, ethanol, propanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene Can be mentioned. These solvents may be used as a mixture of two or more.

  In addition, as radical generators, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate An azo compound such as benzoyl peroxide, a peroxide such as benzoyl peroxide, and a persulfate such as potassium persulfate and ammonium persulfate can be used.

The vinyl monomer used in the synthesis method of 5 is not particularly limited, for example, those similar to the vinyl monomers used in obtaining the polymer skeleton represented by P ¹ of the general formula (1) is used It is done.

The above vinyl monomers may be polymerized alone or in combination of two or more.
The (B-1-1) specific polymer dispersant is more preferably copolymerized with a vinyl monomer having one or more acidic groups and a vinyl monomer not having one or more acidic groups. .

[(B-1-2) Polymer containing copolymer units derived from the monomer represented by formula (I)]
Next, a polymer containing a copolymer unit derived from a monomer represented by the following general formula (I) (hereinafter, appropriately referred to as “(B-1-2) specific polymer dispersant”). explain.

In the general formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-. Y represents —NR ⁰³ —, —O—, —S—, or —N═, and is linked to an N atom via an adjacent atomic group to form a cyclic structure. R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. m1 and n1 each independently represents 0 or 1.

  Hereinafter, the monomer represented by the general formula (I), which is an essential copolymer unit of the specific polymer dispersant (B-1-2) in the present invention, will be described in detail.

In the general formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
The alkyl group represented by R ⁰¹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When the alkyl group represented by R ⁰¹ is a substituted alkyl group, examples of the substituent that can be introduced include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, and a halogen group.
Specifically, preferred examples of the alkyl group represented by R ⁰¹ include methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2-hydroxy group. Examples thereof include an ethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group.

R ⁰² represents an alkylene group.
The alkylene group represented by R ⁰² is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms.
The alkylene group represented by R ⁰² may have a substituent when it can be introduced, and examples of the substituent include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, and the like. It is done.
Specific examples of the preferable alkylene group represented by R ⁰² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.

  W represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and is —C (═O) O— or —CONH—. Is preferred.

Y represents —NR ⁰³ —, —O—, —S—, or —N═, and is linked to an N atom via an adjacent atomic group to form a cyclic structure.
R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably a hydrogen atom or a methyl group.
Y is particularly preferably -S-, -NH-, or -N =.

  Examples of the cyclic structure formed by linking Y with an N atom through an atomic group adjacent thereto include imidazole ring, pyrimidine ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, and the like, and , A condensed ring structure such as a benzimidazole ring, a benzthiazole ring, a benzoxazole ring, a purine ring, a quinazoline ring, and a perimidine ring, and a condensed ring structure is preferable from the viewpoint of affinity with a pigment. Of the condensed ring structures, a benzimidazole ring, a benzthiazole ring, and a benzoxazole ring are particularly preferred.

X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-.
X is particularly preferably —O—, —S—, —CONH—, —NHCONH—, and —NHC (═O) S—.

  m1 and n1 each independently represents 0 or 1, and it is particularly preferable that both m1 and n1 are 1.

  Preferred specific examples (monomer M-1 to monomer M-18) of the monomer represented by formula (I) are listed below, but the present invention is not limited thereto.

  The specific polymer dispersant (B-1-2) in the present invention, together with a copolymer unit derived from the monomer represented by the general formula (I), from the viewpoint of imparting dispersion stability of the pigment, A graft copolymer containing a copolymer unit derived from a polymerizable oligomer having an ethylenically unsaturated bond at the terminal is particularly preferred.

  Such a polymerizable oligomer having an ethylenically unsaturated bond at the terminal is also called a macromonomer because it is a compound having a predetermined molecular weight. In the following description, the “polymerizable oligomer having an ethylenically unsaturated bond at the terminal” in the present invention may be appropriately referred to as “polymerizable oligomer” or “macromonomer”.

  The polymerizable oligomer optionally used in the present invention comprises a polymer chain part and a part of a polymerizable functional group having an ethylenically unsaturated double bond at its terminal. It is preferable from the viewpoint of obtaining a desired graft polymer that such a group having an ethylenically unsaturated double bond is present only at one end of the polymer chain. As the group having an ethylenically unsaturated double bond, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Moreover, it is preferable that this macromonomer has the number average molecular weight (Mn) of polystyrene conversion in the range of 1000-10000, and the range of 2000-9000 is especially preferable.
The polymer chain portion is a homopolymer or copolymer formed from at least one monomer selected from the group consisting of alkyl (meth) acrylate, styrene and derivatives thereof, acrylonitrile, vinyl acetate and butadiene, or polyethylene oxide. Polypropylene oxide and polycaprolactone are generally used.

  The polymerizable oligomer is preferably an oligomer represented by the following general formula (II).

In general formula (II), R ¹¹ and R ¹³ each independently represent a hydrogen atom or a methyl group.
R ¹² represents a linking group containing an alkylene group having 1 to ¹² carbon atoms, and the linking group may be an alkylene group having 1 to 12 carbon atoms, or a plurality of the alkylene groups may be ester bonds or ethers. It may be linked via a bond, an amide bond or the like. R ¹² is preferably a group in which an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms is linked by breaking an ester bond. The alkylene group represented by R ¹² may further have a substituent (for example, a hydroxyl group).
Y ¹¹ represents a phenyl group having no substituent, a phenyl group having one alkyl group having 1 to 4 carbon atoms, or —COOR ¹⁴ . Here, R ¹⁴ represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms. Y is preferably a phenyl group or —COOR ¹⁴ where R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms.
q represents an integer of 20 to 200.

  Preferred examples of the polymerizable oligomer (macromonomer) that can be used for the synthesis of the (B-1-2) specific polymer dispersant in the present invention include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and Examples include poly-i-butyl (meth) acrylate and polymers in which a (meth) acryloyl group is bonded to one molecular end of polystyrene. As such polymerizable oligomers available on the market, one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toagosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer ( Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-terminal methacryloylated poly-n-butyl acrylate oligomer (Mn = 6000, trade name: AB-6, Toa Gosei Chemical Co., Ltd.) ) Made).

In order to obtain a specific acid value, the (B-1-2) specific polymer dispersant according to the present invention preferably further includes a copolymer unit derived from a monomer having an acid group.
Monomers having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) mono [2- (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monoacrylate Mono (meth) acrylates such as both terminal carboxy polymers methacrylate and the like.

The (B-1-2) specific polymer dispersant according to the present invention may further contain a copolymerizable vinyl monomer as a copolymer component as long as the effect is not impaired.
Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds.

  As a preferable aspect of the (B-1-2) specific polymer dispersant according to the present invention, the copolymer unit derived from the monomer represented by the general formula (1) is included at 2 to 50% by mass, Furthermore, 10 to 90% by mass of a copolymer unit derived from a polymerizable oligomer having an ethylenically unsaturated bond at the terminal, 1 to 30% by mass of a copolymer unit derived from a monomer having an acid group, and a vinyl monomer. The copolymer which contains 0-20 mass% of derived copolymer units can be mentioned preferably.

  Hereinafter, specific examples (Exemplary Compound 1 to Exemplified Compound 16) of the specific polymer dispersant (B-1-2) that can be suitably used for the colored pattern forming composition of the present invention will be given together with its weight average molecular weight. The present invention is not limited to these.

Exemplary compound (1): monomer M-2 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/25/65 mass%, weight average molecular weight 50000, acid value 163 mg / g)
Exemplary compound (2): Monomer M-2 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75% by mass, weight average molecular weight 35000, acid value 98 mg / g)
Exemplary compound (3): monomer M-3 / methacrylic acid / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (5/5/10/80 mass%, weight average molecular weight 40000, acid (Value 33 mg / g)
Illustrative compound (4): monomer M-3 / methacrylic acid / benzyl methacrylate copolymer / terminal methacryloylated polymethyl methacrylate copolymer (15/10/10/65 mass%, weight average molecular weight 60000, acid (Value 65 mg / g)
Exemplary compound (5): monomer M-4 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/30/60 mass%, weight average molecular weight 80000, acid value 195 mg / g)

Exemplary compound (6): monomer M-4 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 20000, acid value 98 mg / g)
Exemplary compound (7): Monomer M-5 / acrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (25/15/60 mass%, weight average molecular weight 60000, acid value 117 mg / g)
Exemplary compound (8): Monomer M-5 / acrylic acid / terminated methacryloylated polybutyl acrylate copolymer (15/5/80 mass%, weight average molecular weight 45000, acid value 39 mg / g)
Illustrative compound (9): monomer M-6 / acrylic acid / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (15/10/5/70 mass%, weight average molecular weight 80,000, acid (Value 78 mg / g)
Exemplary Compound (10): Monomer M-6 / Acrylic acid / Terminal methacryloylated polymethyl methacrylate copolymer (12/18/70 mass%, weight average molecular weight 50000, acid value 140 mg / g)

Exemplary compound (11): monomer M-7 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/18/72% by mass, weight average molecular weight 15000, acid value 117 mg / g)
Illustrative compound (12): monomer M-7 / methacrylic acid / benzyl methacrylate / methoxypolyethylene glycol methacrylate copolymer (10/10/50/30 mass%, weight average molecular weight 50000, acid value 65 mg / g)
Illustrative compound (13): monomer M-10 / acrylic acid / 2-hydroxyethyl methacrylate / terminal methacryloylated polystyrene copolymer (5/35/10/50 mass%, weight average molecular weight 20000, acid value 272 mg) / G)
Exemplary compound (14): monomer M-10 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/12/78 mass%, weight average molecular weight 10,000, acid value 78 mg / g)
Exemplary compound (15): monomer M-10 / acrylic acid / methoxypolyethylene glycol methacrylate copolymer (15/3/82 mass%, weight average molecular weight 15000, acid value 23 mg / g)
Exemplary compound (16): monomer M-13 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/25/65 mass%, weight average molecular weight 20000, acid value 163 mg / g)

[(B-1-3) Polymer containing structural unit represented by general formula (a)]
Subsequently, a polymer containing a structural unit represented by the following general formula (a) (hereinafter, appropriately referred to as “(B-1-3) specific polymer dispersant”) will be described.

In the general formula (a), R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure.
^Examples of the alkylene group represented by R ^2a include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a 2-hydroxypropylene group, a methyleneoxy group, an ethyleneoxy group, a methyleneoxycarbonyl group, a methylenethio group, Among them, a methylene group, a methyleneoxy group, a methyleneoxycarbonyl group, and a methylenethio group are preferable.

In the general formula (a), Z ¹ represents a nitrogen-containing heterocyclic structure, specifically, for example, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, Examples thereof include quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea structure, and cyclic imide structure.
Among these, the nitrogen-containing heterocyclic structure represented by Z ¹ is preferably a structure represented by the following general formula (b) or general formula (c).

In the general formula (b), X ¹ represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), —O—, —S—, —NR—, and , -C (= O)-. Here, R represents a hydrogen atom or an alkyl group, and examples of the alkyl group when R represents an alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. , T-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among these, X ¹ is preferably a single bond, a methylene group, —O— or —C (═O) —, and particularly preferably —C (═O) —.

  In the general formula (b) and the general formula (c), the ring A, the ring B, and the ring C each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring. Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

  Preferred specific examples of the structural unit represented by the general formula (a) [Exemplary structural units (M′-1) to (M′-7)] are listed below, but the present invention is not limited thereto. .

The structural unit represented by the general formula (a) is preferably contained in the specific polymer dispersant (B-1-3) in an amount of 2 to 50% by mass, and more preferably 4 to 30% by mass. 5 to 20% by mass is particularly preferable.
In addition to the structural unit represented by the general formula (a), the specific polymer dispersant (B-1-3) in the present invention is further copolymerized with a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal. Particularly preferred is a graft copolymer contained as a unit.
Examples of the polymerizable oligomer having an ethylenically unsaturated double bond at the terminal include those similar to the polymerizable oligomer used as a copolymerization component in the aforementioned (B-1-2) specific polymer dispersant. The preferred embodiments (oligomers represented by formula (II)) and preferred examples (specific examples) are also the same.

In order to obtain a specific acid value, the (B-1-3) specific polymer dispersant in the present invention preferably further contains a monomer (structural unit) having an acid group as a copolymerization component.
Examples of the monomer having an acid group include (meth) acrylic acid, p-vinylbenzoic acid, maleic acid, fumaric acid, itaconic acid, succinic anhydride adduct of 2-hydroxyethyl (meth) acrylate, (meth) And phthalic anhydride adduct of 2-hydroxyethyl acrylate.

The (B-1-3) specific polymer dispersant in the present invention may further contain a copolymerizable vinyl monomer as a copolymer component as long as the effect is not impaired.
Examples of the vinyl monomer that can be used here include those similar to the vinyl monomer used as a copolymerization component in the aforementioned (B-1-2) specific polymer dispersant, and preferred examples thereof are also the same.

  In addition, as a preferable aspect of the specific dispersion resin according to the present invention, polymerization containing 2 to 50% by mass of the structural unit represented by the general formula (a) and further having an ethylenically unsaturated double bond at the terminal Preferred examples include a copolymer containing 10 to 90% by mass of a functional oligomer, 1 to 30% by mass of a structural unit having an acid group, and 0 to 20% by mass of a vinyl monomer.

  Specific examples of the specific polymer dispersant (Exemplary compounds (I) to (XV)) that can be suitably used in the colored pattern forming composition of the present invention are shown below together with their weight average molecular weights. However, the present invention is not limited to these.

Exemplary Compound (I): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (Copolymerization Ratio = 10/4/86 Mass%, Weight) that can Form the Exemplary Structural Unit (M′-1) (Average molecular weight 50000, acid value 26 mg / g)
Exemplary Compound (II): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (10/33/57% by Mass, Weight Average Molecular Weight 30000, Forming the Exemplary Structural Unit (M′-1)) Acid value 214mg / g)
Exemplary Compound (III): Monomer / Methacrylic Acid / 2-Hydroxyethyl Methacrylate / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (5/28/10 /) that can Form the Exemplary Structural Unit (M′-1) 57 mass%, weight average molecular weight 40000, acid value 182 mg / g)
Exemplary compound (IV): monomer capable of forming the exemplary structural unit (M′-1) / methacrylic acid / benzyl methacrylate copolymer / terminal methacryloylated polymethyl methacrylate copolymer (15/5/10 / 70 mass%, weight average molecular weight 60000, acid value 33 mg / g)
Exemplary Compound (V): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (20/20/60% by Mass, Weight Average Molecular Weight 80000, Forming the Exemplary Structural Unit (M′-5) Acid value 130mg / g)

Exemplary Compound (VI): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (10/20/70% by Mass, Weight Average Molecular Weight 30000, Forming the Exemplary Structural Unit (M′-5) Acid value 130mg / g)
Exemplary compound (VII): monomer / acrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (25/20/55 mass%, weight average molecular weight 60000, which can form the exemplary structural unit (M′-5) Acid value 156 mg / g)
Exemplary compound (VIII): monomer / acrylic acid / terminated methacryloylated polybutyl acrylate copolymer (15/15/70% by mass, weight average molecular weight 40000, which can form the exemplary structural unit (M′-5) Acid value 117mg / g)
Exemplary Compound (IX): Monomer / Acrylic Acid / 2-Hydroxyethyl Methacrylate / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (15/5/5 /) capable of Forming the Exemplary Structural Unit (M′-5) 75% by mass, weight average molecular weight 80000, acid value 39 mg / g)
Exemplary Compound (X): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (12/17/71% by Mass, Weight Average Molecular Weight 50000, Forming the Exemplary Structural Unit (M′-6)) Acid value 110mg / g)

Exemplary Compound (XI): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (10/12/78% by Mass, Weight Average Molecular Weight 20000, which can Form Exemplary Structural Unit (M′-6)) Acid value 78 mg / g)
Exemplary Compound (XII): Monomer / Methacrylic Acid / Benzyl Methacrylate / Methoxypolyethylene Glycol Methacrylate Copolymer (10/10/50/30% by Weight, Can Form the Exemplary Structural Unit (M′-6)) (Average molecular weight 35000, acid value 65 mg / g)
Exemplary Compound (XIII): Monomer / Acrylic Acid / 2-Hydroxyethyl Methacrylate / Terminal Methacryloylated Polystyrene Copolymer (5/5/10/80 Mass) that can Form the Exemplary Structural Unit (M′-6) %, Weight average molecular weight 20000, acid value 39 mg / g)
Exemplary Compound (XIV): Monomer / Methacrylic Acid / Methyl Methacrylate / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (8/12/10/70% by Mass) that can Form the Exemplary Structural Unit (M′-7) , Weight average molecular weight 70000, acid value 78 mg / g)
Exemplary compound (XV): monomer / acrylic acid / methoxypolyethylene glycol methacrylate copolymer (15/20/65% by mass, weight average molecular weight 15000, acid value) capable of forming the exemplary structural unit (M′-7) 156 mg / g)

  The copolymer as described above, which is the specific polymer dispersant (B-1-3) in the present invention, is a monomer that can be a structural unit represented by the general formula (a), and is used in combination as desired. A polymerizable oligomer and other monomers can be obtained by radical polymerization in a solvent. In this radical polymerization, the same radical polymerization initiator and chain transfer agent as those used when the (B-1-2) specific polymer dispersant is synthesized are used.

  As content of (B-1) polymer dispersing agent in the colored curable composition of this invention, 5-35 mass% is preferable with respect to the total solid (mass) of this composition, 10-30 The mass% is more preferable. (B-1) When the content of the polymer dispersant is within the above range, (A-1) the dispersion time of the pigment used as the colorant can be shortened, and the stability after dispersion is long. It is preferable because it is maintained.

[Other dispersants]
The colored curable composition in the present invention may be used in combination with a conventionally known dispersant (pigment dispersant) shown below, in addition to the polymer dispersant (B-1).

Known dispersants (pigment dispersants) include polymer dispersants [for example, polyamidoamines and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic types. Copolymers], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of known dispersants (pigment dispersants) that can be used in the present invention include "Disperbyk-107 (carboxylic acid ester), 130 (polyamide), 161, 162, 163, 164, 165, 166" manufactured by BYK Chemie. , 170 (polymer copolymer) ”,“ EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide) manufactured by EFKA ), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," Ajisper PB821, PB822 "manufactured by Ajinomoto Fine Techno Co., Ltd.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd., Poly Low No. 50E, No. 300 (acrylic copolymer) ”,“ Dispalon # 7004 (polyetherester), DA-703-50, DA-705, DA-725 ”manufactured by Enomoto Kasei Co., Ltd.,“ “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)”, “acetamine 86 (stearylamine acetate)”, “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester) manufactured by Lubrizol Corporation Amine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate) "manufactured by Nikko Chemical Co., Ltd. , M YS-IEX (polyoxyethylene monostearate) ”and the like.

  In the present invention, when a known dispersant as described above is used, with respect to the compound having the acid value of 20 to 300 mg / g and the weight average molecular weight in the range of 3,000 to 100,000, It can be used in the range of 10 to 100% by mass, that is, 1/10 to 1/1 (equal amount).

<(C-1) polymerizable compound>
The colored curable composition of the present invention preferably contains (C-1) a polymerizable compound.
The polymerizable compound (C-1) that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, preferably 2 It is selected from compounds having at least one. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (V) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (V)
(However, R ⁴ and R ⁵ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these polymerizable compounds, the details of usage such as the structure, single use or combination, addition amount and the like can be arbitrarily set according to the performance design of the final composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether). A method of adjusting both sensitivity and strength by using a compound of a compound system) is also effective. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, it is preferable to contain an EO modified body from a viewpoint of hardening sensitivity and developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.
In addition, the selection and use method of the addition polymerization compound is important for the compatibility and dispersibility with other components in the composition (for example, binder polymer, polymerization initiator, colorant (pigment, dye, etc.)). For example, the compatibility may be improved by using a low-purity compound or a combination of two or more types, and for the purpose of improving the adhesion of the support and the overcoat layer described below, etc. It is possible to select a structure.

  From the above viewpoints, bisphenol A diacrylate, modified bisphenol A diacrylate EO, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha) are preferred.

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Examples of commercially available modified products such as pentaerythritol hexaacrylate EO include DPHA (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha). ) Is more preferable.

  (C-1) The content of the polymerizable compound is preferably 5 to 50% by mass, more preferably 7 to 40% by mass in the total solid content of the colored curable composition in the present invention. More preferably, it is 10-35 mass%.

<(D) Photopolymerization initiator>
The colored curable composition of the present invention preferably contains (D) a photopolymerization initiator.
The (D) photopolymerization initiator in the present invention is a compound that is decomposed by light and initiates and accelerates the polymerization of the (C-1) polymerizable compound, and has absorption in a wavelength region of 300 to 500 nm. It is preferable. Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

  Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaaryes. Examples include rubiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 4- (o-bromo-pN) , N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (Tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, etc. It is done.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl-1- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-mol Forinophenyl) -butanone-1,2,4,6 trimethylbenzoyl-diphenyl-phosphine oxide, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4 -Acetophenone derivatives such as morpholinobyrophenone, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, Examples thereof include benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl dimethyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate and the like.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188865, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like. Specific examples include Irgacure OXE-01 and OXE-02 manufactured by Ciba Specialty Chemicals.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  As the photopolymerization initiator (D) used in the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, phosphine Oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxa Compounds selected from the group consisting of diazole compounds and 3-aryl substituted coumarin compounds are preferred.

  More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  The content of the (D) photopolymerization initiator contained in the colored curable composition in the present invention is preferably 0.1 to 50% by mass, more preferably based on the total solid content of the composition. It is 0.5-30 mass%, Most preferably, it is 1-20 mass%. Within this range, good sensitivity and pattern formability can be obtained.

<(E) Solvent>
The colored curable composition of the present invention can generally be prepared using a solvent (E).
(E) Solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-oxypropionic acid 3-oxypropionic acid alkyl esters such as ethyl (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), methyl 2-oxypropionate 2-oxypropionic acid alkyl esters such as ethyl 2-oxypropionate and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxy Methyl propionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2- Methyl methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1,3-butanediol diacetate, etc. ;
Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol Ethyl ether acetate, propylene glycol propyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol diacetate, propylene glycol n-butyl ether acetate, propylene glycol phenyl ether, propylene glycol phenyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n- Butyl ether acetate, tripropylene glycol mono n-butyl ether, tripropylene glycol methyl ether acetate and the like;
Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Alcohols such as ethanol, isopropyl alcohol, propylene glycol methyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether;
Aromatic hydrocarbons such as toluene and xylene are exemplified.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using it independently.

  The colored pixel portion forming composition containing the components (A-1), (B-1), (C-1), (D), and (E) is (B-1) presence of a polymer dispersant. Therefore, the dispersibility of the pigment (colorant) is excellent, and the coating uniformity (particularly, coating uniformity in slit coating) is excellent. Therefore, it is possible to form a colored pixel portion having good color purity and color reproducibility and having high contrast, and even when forming a spacer by laminating colored layers, thickness unevenness hardly occurs. A spacer with good accuracy can be obtained.

Further, the present invention is characterized by a spacer that satisfies the conditions (a) to (d) described above. A problem in forming such a spacer is that the height of the spacer is not simply the sum of the thicknesses of the colored pixel portions formed at the same time. Specifically, since the colored layer of the second color overlaps the colored layer of the first color, the coating thickness becomes lower than the height of the first color due to leveling or the like, and further, the third color is lower than the height of the second color. Become.
Thus, for example, when the RGB colored pixel portion and the spacer are formed at the same time, the control of the height of the spacer (cell gap) is a matter necessary for the design of the colored curable composition. Specifically, it is preferable to adjust the solid content of the colored curable composition to control the thickness of the colored layer constituting the spacer and to design the desired spacer height. In addition, after setting the solid content, it is preferable to design the pigment concentration (= pigment content / total solid content) so that the required chromaticity can be obtained with the film thickness of the colored pixel portion. By these methods, it is possible to design the chromaticity of the colored pixel portion and design the height of the spacer (the size of the cell gap).
In particular, in the colored curable composition of the present invention, if a specific polymer dispersant (B-1-1) to (B-1-3) having a specific acid value is used, the development latitude of the composition spreads. (A-1) Since the formulation can be designed according to the colorant (pigment) concentration, the film thickness can be easily designed.

From the above, the colored pixel portion constituting the color filter of the present invention and the spacer are all the above-mentioned (A-1), (B-1), (C-1), (D), and (E) It is preferably formed using a composition for forming a colored pixel portion containing a component. Among them, a pigment is used as the component (A-1), and (B-1) as the component (B-1). -(B-1-3) The aspect using a specific polymer dispersing agent is preferable.
That is, both the colored pixel portion constituting the color filter of the present invention and the spacer contain a pigment and one of (B-1-1) to (B-1-3) specific polymer dispersant. It is preferable.

The light-shielding part (black matrix) in the color filter of the present invention may be formed of a curable composition containing a light-shielding agent as in the case of the colored pixel part and the spacer, or the metal thin film is etched to form a pattern. It may be formed in a shape.
For the metal thin film, a metal material such as a chromium compound such as metal chromium, chromium oxide or chromium nitride, or an alloy of nickel and tungsten is used. The metal thin film may be a single layer or a laminate of a plurality of layers.
Moreover, the curable composition for forming the light-shielding part in the color filter of this invention is explained in full detail below.

[Curable composition for light shielding part formation]
The curable composition for forming a light shielding part in the present invention comprises (A-2) a light shielding agent, (B-2) a dispersant, (C-2) a polymerizable compound, (D) a polymerization initiator, and (E) a solvent. It is preferable to contain, and it may further contain other components as desired.
Hereinafter, each component will be described.

<(A-2) Shading agent>
Here, as the (A-2) light-shielding agent, carbon black, titanium black, metal fine particles, metal oxides, metal sulfide fine particles and the like are preferably mentioned.
These are used singly or in combination as required. For example, carbon black alone, metal fine particles alone, a combination of both, or a mode in which other coloring pigments or titanium carbon are further used in combination with these.
Conventionally, two or more pigments have been used in combination as a black colorant so as to shield the visible light region. Examples of these pigments include those described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-17521 [0080] to [0088]. The formation of the used light shielding layer is disclosed in JP-A-7-271020. However, when the pigment was used for the light shielding layer, sufficient shielding properties could not be obtained.
In order to increase the light-shielding effect, JP-A-2000-147240, JP-A-2000-143985, JP-A-2005-338328, JP-A-2006-154849, etc. describe carbon black, titanium black, graphite, etc. Has been developed as a suitable shading material. In the present invention, carbon black is preferable as one of the light shielding materials from the viewpoint of light shielding properties and cost.

As an example of carbon black, pigment black 7 is preferable.
Specifically, as carbon black, carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850 manufactured by Mitsubishi Chemical Corporation, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44 , # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234 , Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N 39, diamond black SH, diamond black SHA, diamond black LH, diamond black H, diamond black HA, diamond black SF, diamond black N550M, diamond black E, diamond black G, diamond black R, diamond black N760M, diamond black LP; Degussa AG of carbon black Color black FW200, Color black FW2, Color black FW1, Color black FW18, Color black S170, Color black S160, Special Black6, Special Black5, Special Black4, Special Black4A, Printex U, PrintexV, Printex 140U, Printex 140 Carbon black REGAL 400, REGAL 400R, REGAL XC72, VULCAN XC72R, MOGUL L, MONARCH 1400, MONARCH 1000, BLACK PEARLS 1400; carbon black SUNBLACK900, 910, 930, 930 970 or the like.
Moreover, in order to increase electric resistance, those coated with a polymer compound are also preferable.
The preferred single particle size of these carbon blacks is 10 to 100 nm, more preferably 10 to 50 nm.

As an example of titanium black, TiO ₂ , TiO, TiN and a mixture thereof are preferable. Examples of commercially available products include (trade names) 12S and 13M manufactured by Mitsubishi Materials Corporation. The average particle size of titanium black is preferably 10 to 100 nm.
By using graphite having a major axis of 1 μm or less as the light shielding material for the color filter, the contour shape of the light shielding pattern becomes uniform and the sharpness is improved. The major axis is more preferably 20 nm or more and 500 nm or less. Moreover, it is preferable that the abundance ratio of particles having a particle diameter of 100 nm or less is 70% or more.

Although the above-described titanium black is also a metal-based fine particle, silver or the like described in JP-A-2005-17322, JP-A-2005-179632, JP-A-2005-263920, or the like can be used as a light-shielding property. Metal particles or metal-containing particles (hereinafter sometimes referred to as “metal-based fine particles”) have been developed.
Examples of preferred metals constituting these metal-based fine particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium. , Tantel, bismuth, antimony, and alloys thereof. Preferred metals include at least one selected from copper, silver, gold, platinum, palladium, tin, calcium, and alloys thereof. Particularly preferred metals include copper, silver, gold, platinum, tin, and these. At least one selected from these alloys.

As the metal-based fine particles in the present invention, a compound of the above metal and an element other than the metal is also preferable. Examples of the compound of metal and other elements include metal oxides, sulfides, sulfates, carbonates, and the like, and these particles are suitable as the metal-based fine particles. Of these, metal sulfide particles are preferred because of their color tone and ease of fine particle formation. Moreover, a metal, its alloy, and a metal compound may be used together, and may be used in combination of 2 or more types.
Among these, silver or an alloy thereof and a sulfide thereof are particularly preferable because of their high shielding effect. As an example of an alloy, a silver tin alloy is mentioned as a preferable example.

In addition, as the metal-based fine particles, composite particles in which a metal and a metal compound are combined into one particle are also suitable, for example, those having different compositions between the inside and the surface of the particle, The united thing etc. can be mentioned. As specific examples, composite fine particles of silver and silver sulfide, composite fine particles of silver and copper (II) oxide, and the like are suitable.
As the composite particles, core-shell type composite particles (core-shell particles) in which the surface of the core material is coated with a shell material are preferable, and specific examples thereof include paragraph numbers [ And the core / shell fine particles described in [0024] to [0027].

  These metal-based fine particles have a high black density, can exhibit excellent light-shielding performance in a small amount or in a thin film, and have high thermal stability. Therefore, at a high temperature (eg, 200 degrees or more) without impairing the black density. Heat treatment is possible, and a high degree of light-shielding property can be secured stably. Therefore, it is preferably applied to a light shielding portion (black matrix) for a color filter that requires a high degree of light shielding properties and is generally subjected to a baking process.

  The metal-based fine particles in the present invention can be commercially available, or can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like. For example, by using spherical silver fine particles as seed particles, then adding a silver salt, and using a reducing agent having a relatively low reducing power such as ascorbic acid in the presence of a surfactant such as cetyltrimethylammonium bromide, Wire-shaped silver fine particles are obtained. This is described in Advanced Materials 2002, 14, 80-82. Similar descriptions are made in Materials Chemistry and Physics 2004, 84, 197-204, Advanced Functional Materials 2004, 14, 183-189.

  In the present invention, the number average particle diameter of the metal-based fine particles is preferably 5 to 100 nm, more preferably 5 to 80 nm, and particularly preferably 5 to 50 nm. When the number average particle diameter of the particles is 100 nm or less, there is an advantage that the surface smoothness is good and the failure due to coarse particles is reduced.

(A-2) When metal-based fine particles are used as the light-shielding agent, the content thereof is, for example, in consideration of preventing the metal-based fine particles from being fused during post-baking when producing a color filter. On the other hand, considering the light shielding effect, it is preferable to adjust the total light content of the curable composition for forming a light shielding part to about 50 to 90% by mass, preferably 50 to 85% by mass.
In addition, the content of the metal-based fine particles is preferably performed in consideration of a change in optical density due to an average particle diameter. Depending on the metal-based fine particles used, the pigment, carbon black and the like can be used in combination for hue correction.

  In the curable composition for forming a light-shielding part in the present invention, 40 to 80% by mass of carbon black or 50 to 90% by mass of metal-based fine particles as a light-shielding agent (A-2) in the total solid content of the composition. % Content is preferable.

<(B-2) Dispersant>
When metal-based fine particles are used as the light-shielding part-forming curable composition in the present invention (A-2) as the light-shielding agent, the metal-based fine particles are preferably present in a stable dispersed state. More preferably, it is in a state. In the colloidal state, for example, it is preferable that the metal-based fine particles are dispersed in a substantially fine particle state. Here, “substantially dispersed” refers to a state in which primary particles are dispersed independently without being aggregated or softly aggregated.
Additives that may be added to the dispersant or composition (B-2) when dispersing the metal-based fine particles include those described in paragraphs [0027] to [0031] of JP-A-2005-17322. It is mentioned as preferable.

  The dispersing agent (B-2) used when dispersing the metal-based fine particles includes a carboxyl group, an OH group, a sulfonic acid group, a phosphoric acid group, an amino group, a carbonyl group, a thiol group, a polyoxyalkylene part, and the like. A compound having both a hydrophilic part and a phenyl group (including a naphthalene ring), an alicyclic ring, an alkyl group, and a lipophilic part such as a substituted group thereof is generally used as a dispersant. The compounds exemplified below can be used. However, it is not limited to these compounds.

That is, EFKA-1101, 1120, 1125, 4008, 4009, 4046, 4047, 4520, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 5070, 5207 (manufactured by EFKA ADDITIVES),
Anti-Terra-U, Anti-Terra-U100, Anti-Terra-204, Anti-Terra-205, Anti-Terra-P, Disperbyk-101, 102, 103, 106, 108, 109, 110, 111, 112, 151, P-104, P-104S, P105, 220S, 203, 204, 205, 9075, 9076, 9077 (manufactured by BYK),
Disparlon 7301, 325, 374, 234, 1220, 2100, 2200, KS260, KS273N, 1210, 2150, KS860, KS873N, 7004, 1813, 1860, 1401, 1200, 550, EDAPLAN 470, 472, 480, 482, K-SPERSE 131, 152,152MS (manufactured by Enomoto Kasei Co., Ltd.),

Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, etc. (manufactured by AVECIA),
Carribon B, L-400, Eleminor MBN-1, Sunspearl PS-2, PS-8, Ionette S-20 (manufactured by Sanyo Chemical)
Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco) and the like.

The light-shielding part-forming curable composition in the present invention is (B-1) a polymer dispersant (preferably an acid value of 20 to 300 mg / g) exemplified in the colored curable composition as (B-2) dispersant. And a polymer compound having a weight average molecular weight in the range of 3,000 to 100,000, more preferably (B-1-1) to (B-1-3) specific polymer dispersant). It can also be used.
Furthermore, a polymer dispersant can be used as required in addition to the polymer dispersant (B-1). Dispersion stability and storage stability are improved by using a polymer dispersant. Examples of the polymer dispersant that can be used include those described in “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000).

What is necessary is just to select these (B-2) dispersing agents suitably according to the kind of (A-2) light-shielding agent. Moreover, a dispersing agent may be used independently and may use 2 or more types together.
In this invention, the addition amount of (B-2) dispersing agent is 3-30 mass parts with respect to (A-2) light-shielding agent, Preferably it is 5-20 mass parts.

<(C-2) polymerizable compound>
As the (C-2) polymerizable compound used in the curable composition for forming a light shielding part in the present invention, the (C-1) polymerizable compound used in the colored curable composition is also preferable. However, the following are particularly preferable.

  (C-2) The polymerizable compound is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.

Moreover, as a (C-2) polymeric compound, an acidic polyfunctional photocurable compound is also mentioned as a preferable thing. Examples of the acidic polyfunctional photocurable compound include (1) those having a carboxyl group introduced by modifying a monomer or oligomer having a hydroxyl group and three or more photocurable functional groups with a dibasic acid anhydride, (2) Introducing a carboxyl group by adding a compound having both a glycidyl group or an isocyanate group and a COOH group to a monomer or oligomer having a hydroxyl group and three or more photocurable functional groups, or (3) three or more Those having a sulfonic acid group introduced by modifying an aromatic compound having a photocurable functional group with concentrated sulfuric acid or fuming sulfuric acid can be used.
Moreover, you may use the oligomer which contains the monomer which is an acidic polyfunctional photocurable compound itself as a repeating unit as an acidic polyfunctional photocurable compound.

  As an example of an acidic polyfunctional photocurable compound, the compound represented by the following general formula (i) and the compound represented by the following general formula (ii) are preferable.

In formula (i), R represents a (meth) acryloyloxy group, X represents -COOH, or -OPO ₃ H _2. T represents an oxyalkylene group, wherein the alkylene group has 1 to 4 carbon atoms. n is 0-20.
In general formula (ii), W represents R or X in general formula (i), and 3 or more Ws are R among 6 Ws. G has the same meaning as T in formula (i). Z represents —O— or —OC═ONH (CH ₂ ) qNHCOO—. p is 0-20 and q is 1-8.
A plurality of W, R, X, T, and G present in one molecule may be the same or different.
In general formula (i) and general formula (ii), the oxyalkylene group represented by T or G is bonded to R, X, and W adjacent to the carbon atom side end.

  As a commercial item of the compound represented by the said general formula (i), and the compound represented by general formula (ii), TO-756 which is a carboxyl group containing trifunctional acrylate by Toagosei Co., Ltd., and And TO-1382 which is a carboxyl group-containing pentafunctional acrylate.

  Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid it can. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, the above carboxyl group-containing pentafunctional acrylate, etc. Is preferred. In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.

  As content of the (C-2) polymeric compound in the curable composition for light-shielding part formation in this invention, it is preferable that it is 5-50 mass% with respect to the total solid of this composition, 7 More preferably, it is -40 mass%, and it is still more preferable that it is 10-35 mass%.

<(D) Polymerization initiator and (E) Solvent>
The (D) polymerization initiator, (E) solvent, and the like used in the curable composition for forming a light shielding part in the present invention are the same as those in the colored curable composition, and the preferred contents are also the same.

≪Other ingredients≫
Various known additives can be used in the colored curable composition and the curable composition for forming a light-shielding part in the present invention depending on the purpose.
Hereinafter, such additives will be described.

<Alkali-soluble resin (binder polymer)>
In the curable composition of the present invention, an alkali-soluble resin can be used as a binder polymer for the purpose of improving film properties.
The alkali-soluble resin used in the present invention is a linear organic polymer, and at least one molecule in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group that promotes alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, hydroxyl group, etc.).

More preferable as the alkali-soluble resin is a polymer having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-54-25957, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, maleic acid as described in JP-A-59-53836 and JP-A-59-71048 Copolymers, partially esterified maleic acid copolymers, etc., as well as those of acrylic copolymers such as acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group with an acid anhydride added. It is done.
The acid value is preferably in the range of 20 to 200 mgKOH / g, preferably 30 to 180 mgKOH / g, more preferably 50 to 150 mgKOH / g.

  As a specific configuration of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include CH ₂ = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² Represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (Meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl has 1 to 8 carbon atoms) Alkyl group), hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.

A resin having a polyalkylene oxide chain in the molecular side chain is also preferable. As the polyalkylene oxide chain, a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof can be used, and the terminal is a hydrogen atom or a linear or branched alkyl group.
1-20 are preferable and, as for the repeating unit of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable.
Examples of the acrylic copolymer having a polyalkylene oxide chain in the side chain include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, and the like. , And compounds in which these terminal OH groups are alkyl-blocked, such as methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol-propylene glycol) mono (meth) acrylate, etc. An acrylic copolymer as a component.

As the vinyl compound, CH ₂ = CR ¹ R ² [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. , R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. Specific examples include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, polymethylmethacrylate macromonomer, and the like.
Other monomers that can be copolymerized can be used singly or in combination of two or more. Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.

As described above, the acrylic resin preferably has an acid value in the range of 20 to 200 mgKOH / g. When the acid value exceeds 200, the acrylic resin becomes too soluble in alkali and the appropriate development range (development latitude) becomes narrow. On the other hand, if it is too small, such as less than 20, the solubility in alkali is so small that it takes too much time for development, which is not preferable.
In addition, the weight average molecular weight Mw of the acrylic resin (polystyrene conversion value measured by the GPC method) is used to realize a viscosity range that is easy to use in a process such as applying a color resist, and to secure film strength. It is preferable that it is 2,000-100,000, More preferably, it is 3,000-50,000.

Moreover, in order to improve the crosslinking efficiency of the curable composition in the present invention, an alkali-soluble resin having a polymerizable group may be used alone or in combination with an alkali-soluble resin having no polymerizable group.
As the alkali-soluble resin having a polymerizable group, a polymer having an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. The alkali-soluble resin having a polymerizable double bond can be developed with an alkali developer, and further has photocurability and thermosetting properties. Examples of polymers containing these polymerizable groups are shown below, but are not limited to the following as long as each molecule contains an alkali-soluble group such as a COOH group and an OH group and a carbon-carbon unsaturated bond. .

(1) Urethane modification obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group A polymerizable double bond-containing acrylic resin,
(2) an unsaturated group-containing acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule;
(3) Acid pendant type epoxy acrylate resin,
(4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
Of the above, the resins (1) and (2) are particularly preferable.

As a specific example, a copolymer of an OH group, for example, 2-hydroxyethyl acrylate, a COOH group, for example, methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable therewith. Further, a compound obtained by reacting an epoxy ring having reactivity with an OH group and a compound having an unsaturated bond group between carbon (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, in addition to the epoxy ring, a compound having an acid anhydride, an isocyanate group, or an acryloyl group can also be used.
Further, a compound obtained by reacting an unsaturated ring carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

  Examples of the compound having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing Polyurethane acrylic oligomer, Diamond Shamrock Co., Ltd.). Ltd .; Biscort R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel) And UCB Co., Ltd.).

  As addition amount of alkali-soluble resin, it is preferable that it is the range of 3-30 mass% in the total solid of both curable compositions of this invention, and 5-20 mass% is more preferable.

In preparing the resist, it is preferable to add the following epoxy resin in addition to the alkali-soluble resin. The epoxy resin is a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( As described above, manufactured by Tohto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103 etc. In addition, bisphenol F type and bisphenol S type epoxy resins similar to these can also be used.
Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used. As cresol novolak type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above made by Tohto Kasei), Denacol EM-125, etc. (above made by Nagase Kasei), biphenyl type Examples of cycloaliphatic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT. -401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100, etc. (manufactured by Toto Kasei), Epilon 430, 673, 695, 850S, 4032 (made by Dainippon Ink and Co., Ltd.) It is possible. Also 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester In addition, glycidyl esters such as Epototo YH-434 and YH-434L, which are amine-type epoxy resins, and glycidyl esters obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resins can also be used.

Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage at the time of curing is large, and if it is too large, the curability is insufficient and the reliability is poor or the flatness is poor.
Specific compounds include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3,5,3 ', 5'-tetramethyl- 4,4 'diglycidyl biphenyl, ceroxide 2021, 2081, epolide GT-302, GT-403, EHPE-3150, etc. are mentioned.

<Surfactant>
The curable composition in the present invention preferably contains an appropriate surfactant for improving coating properties and controlling leveling properties.
As the surfactant for improving the coating property, a nonionic surfactant, a fluorine-based surfactant, a silicone-based surfactant, or the like is used.

  As the nonionic surfactant in the present invention, it is preferable to use at least one selected from the group of compounds represented by the following general formulas (A) to (D).

In the above general formulas (A) to (D), PO represents propylene oxide, and EO represents ethylene oxide. In the propylene oxide, propylene includes both — (CH ₂ ) ₃ — and —CH ₂ CH (CH ₃ ) —.

In general formula (A) and general formula (B), (Style) represents ph-CH = CH-, and (benzyl) represents ph-CH _2- . Here, ph is a phenyl group.
N is an integer of 1 to 3, preferably 1. m is an integer of 7 to 30, preferably an integer of 8 to 20. l is an integer of 0 to 10, preferably an integer of 0 to 5. a is 0-20, b is 0-20, c is an integer of 6-30, Preferably, a is 0-10, b is 0-10, c is 10-20, respectively.

In general formula (C) and general formula (D), x is an integer of 5-100, Preferably it is an integer of 5-50. Moreover, y is an integer of 20-100. Note that x and y satisfy 0.1 ≦ x / y ≦ 2.0, preferably 0.2 ≦ x / y ≦ 1.0.
Here, four x and y which exist in general formula (C) and general formula (D) are respectively the same or different integers. That is, in the general formula (C) and the general formula (D), four ethylene oxide blocks exist, but the number of ethylene oxide units constituting each of the four blocks may be the same or different. . Moreover, although four propylene oxide blocks exist in General Formula (C) and General Formula (D), the number of propylene oxide units constituting each of the four blocks may be the same or different. .

In the present invention, among the compound groups represented by the general formulas (A) to (D), the compound represented by the general formula (A) and the compound represented by the general formula (B) are preferable. .
More specifically, in the general formula (A), n is 1, l is an integer of 0 to 5, and m is an integer of 8 to 20, and specific examples include addition of ethylene oxide 8 of styrylphenol. , 10 adducts, 12 adducts, 16 adducts, 20 adducts and the like.
In the general formula (B), a compound in which n is 1 to 3, a is 0 to 10, b is 0 to 10, and c is an integer of 10 to 20 is preferable. As a specific example, monostyrylbenzylphenyl is used. Is an addition compound in which a is 4, b is 2, and c is 10, an adduct in which a is 0, b is 0, and c is 16 in tristyrylbenzylphenyl, a is 6, b is 2, c Is an adduct of 10 and an adduct of tristyrylbenzylphenyl wherein a is 8, b is 6, and c is 18.

Moreover, in this invention, well-known surfactant other than the compound group represented by the said general formula (A)-general formula (D) may be used, and these may be used together.
As the surfactant to be used, surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600 are preferable.

  Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers. Polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters and the like are preferable.

  Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate , Polyoxyalkylene dialkyl esters such as polyoxyethylene distearate, sorbitan fatty acid ester There are nonionic surfactants such as stealth and polyoxyalkylene sorbitan fatty acid esters.

  Specific examples of these include, for example, Adeka Pluronic series, Adecanol series i, Tetronic series (above made by ADEKA), Emulgen series, Rheodor series (above made by Kao Corporation), Eleminor series, Nonipole series, The Octopole series, Dodecapol series, Newpole series (Sanyo Kasei Co., Ltd.), Pionein series (Takemoto Yushi Co., Ltd.), Nissan Nonion series (Nippon Yushi Co., Ltd.), etc. These commercially available products can be used as appropriate. A preferable HLB value is 8 to 20, more preferably 10 to 17.

As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used.
Specific commercial products include, for example, Megafax F142D, F172, F173, F176, F177, F183, F183, 780, 781, R30, R08 (Dai Nippon Ink Co., Ltd.), Fluorard FC-135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S -145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, and 802 (manufactured by JEMCO).

  Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF- 8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 ( As mentioned above, GE Toshiba Silicone Co., Ltd.) and the like can be mentioned.

  The total content of the surfactant in the curable composition in the present invention is preferably in the range of 0.01 to 3.0% by mass with respect to the total mass of the composition, 0.1 to 2 More preferably, it is in the range of 0.0 mass%. In particular, it is preferable to use a small amount (0.001 to 0.1% by mass) of a fluorosurfactant.

<Organic carboxylic acid>
In the curable composition of the present invention, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less, is added in order to promote alkali solubility of the uncured part and further improve the developability. can do.
Specific examples of organic carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid, etc. Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, and mesitylene acid; phthalic acid, isophthalic acid, Aromatic polymers such as terephthalic acid, trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid Rubonic acid; phenylacetic acid, phenoxyacetic acid, methoxyphenoxyacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, Other carboxylic acids such as umbelic acid can be mentioned.

<Alkoxysilane compound>
In the curable composition of the present invention, it is preferable to use an alkoxysilane compound, particularly a silane coupling agent, from the viewpoint of improving adhesion to a support (substrate).
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material, and (meth) acryloyl or phenyl that exhibits affinity by interacting or forming a bond with an organic resin. , Mercapto, and epoxysilane, and (meth) acryloylpropyltrimethoxysilane is more preferable among them.
The amount of addition in the case of using a silane coupling agent is preferably in the range of 0.2 to 5.0 mass% with respect to the total solid content of both curable compositions in the present invention, 0.5 to 3 0.0 mass% is more preferable.

<Co-sensitizer>
If desired, the curable composition of the present invention preferably contains a co-sensitizer.
This co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and the polymerization initiator to actinic radiation, or suppressing inhibition of polymerization of the polymerizable compound by oxygen.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

0001
Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is 0.1 to 30 mass with respect to the total solid content of both curable compositions in the present invention, from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. % Is preferable, a range of 1 to 25% by mass is more preferable, and a range of 0.5 to 20% by mass is further preferable.

<Polymerization inhibitor>
In the present invention, it is desirable to add a small amount of a thermal polymerization inhibitor as a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of both curable compositions.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition.
Also, if necessary, in order to prevent polymerization inhibition by oxygen, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added and unevenly distributed on the coating film surface in the drying process after coating. Good.
The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

<Other additives>
Furthermore, in this invention, in order to improve the physical property of a cured film, you may add well-known additives, such as an inorganic filler and a plasticizer.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. , 10% by mass or less can be added with respect to the total mass of the polymerizable compound and the binder polymer.

[Color filter and manufacturing method thereof]
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention has a light-shielding portion, a colored pixel portion, and a spacer having a specific shape as described above on a support.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method.

The color filter of the present invention is a process for forming a curable composition layer by applying the above-described curable composition for forming a light shielding part or the above-mentioned colored curable composition on a support (hereinafter referred to as “curing” as appropriate). Curable composition layer forming step ”), a step of exposing the curable composition layer through a mask (hereinafter abbreviated as“ exposure step ”as appropriate), and the curable property after exposure. And a step of developing the composition layer to form a colored pixel portion (hereinafter abbreviated as “development step” as appropriate).
The steps of the curable composition layer forming step, the exposure step, and the developing step are the same when the light shielding portion is formed and when the colored pixel portion is formed. In the present invention, first, a light shielding portion is formed, and then, for example, colored pixel portions of each hue of RGB are sequentially formed.
Hereafter, each process in the manufacturing method of this invention is demonstrated.

<Curable composition layer forming step>
In this step, the above-described curable composition for forming a light shielding part or the above-mentioned colored curable composition is applied on a support to form a curable composition layer.

Examples of the support that can be used in this step include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to them. . Furthermore, a plastic substrate is also possible.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface.

As a coating method of the curable composition on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing method can be applied.
Moreover, as a method of forming a curable composition layer on a support, in addition to the above-described application method, a method of transferring a coating film formed by applying the above method on a temporary support in advance onto a support is also provided. It can also be applied.
Regarding the transfer method, the production methods described in paragraph numbers [0023] and [0036] to [0051] of JP-A-2006-23696 and paragraph numbers [0096] to [0108] of JP-A-2006-47592 Can also be suitably used in the present invention.

  The coating thickness of the curable composition (the thickness of the curable composition layer) is appropriately adjusted depending on the design values of the thickness of the light-shielding portion and the colored pixel portion to be formed. 10 μm is preferred.

  Drying (prebaking) of the curable composition layer applied on the support can be performed at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, an oven or the like.

<Exposure process>
In the exposure step, the curable composition layer formed in the curable composition layer forming step is exposed through a mask having a predetermined mask pattern.
In this step, by performing pattern exposure on the curable composition layer, only the light-irradiated portion of the curable composition layer can be cured.
As radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferably used. Irradiation dose is more preferably preferably ^{10~1000mJ / cm 2 5~1500mJ / cm 2} , and most preferably 10 to 500 mJ / cm ^2.

If the color filter of the present invention is a liquid crystal display element is preferably 5 to 200 mJ / cm ² within the above range, more preferably 10~150mJ / cm ^2, and most preferably 10 to 100 mJ / cm ^2. The exposure machine can be a proximity type exposure machine, a mirror projection system or a stepper system.

<Development process>
Next, an alkali development treatment is performed to elute the curable composition layer in the light non-irradiated part in the exposure step into an alkaline aqueous solution. Thereby, only the photocured part of the curable composition layer remains on the support.
As the developer used in this step, an inorganic alkali developer is mainly used in the case of a color filter for a liquid crystal display device, but an organic alkali developer is also used.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the alkali agent used in the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxy. , Tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the like. These alkali agents have a concentration of 0.001 to 10% by mass, An alkaline aqueous solution diluted with pure water so as to be preferably 0.01 to 1% by mass is preferably used as the developer.
In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans (rinse) with a pure water after image development.

Next, after drying, heat treatment (post-bake) is performed.
The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 240 ° C. is performed. When the substrate is a glass substrate or a silicone substrate, 200 ° C. to 240 ° C. is preferable in the above temperature range.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so that the coating film after development is in the above-mentioned condition. be able to.

  In the production method of the present invention, after the curable composition layer forming step, the exposure step, and the development step described above are performed, the formed light shielding portion and the colored pixels are heated and / or exposed as necessary. A curing step for curing may be included.

  After performing the curable composition layer forming step, the exposure step, and the developing step (further, if necessary) described above, and first forming a light shielding portion such as a lattice so as to isolate each colored pixel portion A colored pixel portion is formed by repeating these steps for a desired number of hues (for example, three colors of RGB) in an empty portion of the lattice (exposed region of the support), and at the same time, 2 on the light shielding portion. By stacking colored layers of colors or more, a spacer is also formed, and a color filter including a light shielding portion, a colored pixel portion, and a spacer is manufactured.

Hereinafter, with reference to FIG. 1, the formation process of the colored pixel portion and the spacer in the present invention will be described in detail. Here, FIG. 1 is a process diagram showing an example of a method for producing a color filter of the present invention.
First, as shown in FIG. 1A, a red colored pixel portion forming composition is applied on a support 10 on which a light shielding portion 20 is formed to form a curable composition layer 30R (curing). Property composition layer forming step). Next, by performing an exposure process and a development process on the curable composition layer 30R, as shown in FIG. 1B, a red colored pixel portion 30R is formed on the support 10 again. A red colored layer 42 </ b> R constituting a spacer is formed on a part of the light shielding part 10.
Subsequently, as shown in FIG. 1C, a green colored pixel portion forming composition is applied on the colored pixel portion 30R and the colored layer 42R to form a curable composition layer 30G (curability). Composition layer forming step). Thereafter, by performing an exposure step and a development step on the curable composition layer 30G, as shown in FIG. 1D, the green colored pixel portion 30G is also formed on the support 10, A green colored layer 42G is formed on the red colored layer 42R.
Next, as shown in FIG. 1E, a blue colored pixel portion forming composition is applied from above the colored pixel portion 30R, the colored pixel portion 30G, and the colored layer 42G, and the curable composition layer 32B is applied. Form (curable composition layer forming step). Thereafter, by performing an exposure step and a development step on the curable composition layer 32B, a blue colored layer 42B is formed on the green colored layer 42G as shown in FIG. 1 (f). At the same time, a blue colored pixel portion 30 </ b> B (not shown) is formed on the support 10.
As described above, the spacer 40 formed by stacking the three color pixel portions 30R, 30G, and 30B and the three color layers 42R, 42G, and 42B is formed.
In the embodiment shown in FIG. 1, the colored pixel portion and the colored layer are formed in the order of red, green, and blue. However, the embodiment is not necessarily limited to this embodiment, and has a wavelength of 365 nm as described above. The colored pixel portion and the colored layer may be formed in descending order of the transmittance and the total transmittance at a wavelength of 405 nm.

  As described above, the spacer 40 shown in FIG. 1 is formed by laminating three colored layers 42R, 42G, and 42B. The spacer according to the present invention is formed by laminating two or more colored layers. Therefore, as long as all the conditions (a) to (d) are satisfied, a combination of the colored layer 42R and the colored layer 42G, a combination of the colored layer 42R and the colored layer 42B, You may be comprised from the coloring layer of 2 colors.

<Liquid crystal display device with color filter>
The color filter of the present invention is used for display devices such as liquid crystal display devices, plasma display devices, EL display devices, and CRT display devices. The definition of the display device and the description of each display device can be found in, for example, “Electronic Display Device (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Device (written by Junaki Ibuki, Heisei Sangyo Co., Ltd.) Issued in the first year).

Of the display devices to which the color filter of the present invention is applied, a liquid crystal display device is particularly preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Investigative Research Institute, Inc., 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”.
Among these, the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, IPS, OCS, FFS, and R-OCB. Is also applicable. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".

In addition to the color filter, the liquid crystal display device is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members.
Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., 2003) ”.

  Since the color filter of the present invention has a uniform spacer height, a liquid crystal display device using the spacer has a uniform cell gap, and can display with high transmittance without color blur.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.

<1. Preparation of colored pixel portion and spacer forming composition>
1-1. Preparation of red curable composition [Preparation of red curable composition CR-1]
The following composition R-1 was stirred for 1 hour using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads to obtain dispersion R-1.

(Composition R-1)
Pigment Red 254 (average particle size 20 nm) ... 11 parts Pigment Red 177 (average particle size 18 nm) ... 4 parts (B-1-2) Specific polymer dispersant: the exemplified compound (6)・ ・ ・ 5 parts ・ Dispersant: Trade name Disperbyk-161, 30% solution manufactured by Big Chemie ・ 3 parts ・ Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 75/25 [mass ratio] copolymer, Propylene glycol monomethyl ether acetate solution with a weight average molecular weight Mw of 5000 (solid content: 50% by mass) ... 4 parts, solvent: propylene glycol monomethyl ether acetate ... 73 parts

  Next, using the obtained dispersion R-1, the following composition CR-1 was mixed and stirred to obtain a red curable composition CR-1.

(Composition CR-1)
-Dispersion R-1 ... 100 parts-Epoxy resin (trade name EHPE3150, manufactured by Daicel Chemical) ... 2 parts-Polymerizable compound (dipentaerythritol penta-hexaacrylate) ... 8 parts-Polymerization initiator ( 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triane ... 1 part-polymerization initiator: 2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1 ... 1 part-Polymerization initiator: Diethylthioxanthone-0.5 part-Polymerization inhibitor: p-methoxyphenol ... 0.001 part ・ Fluorine-based surfactant: Trade name Megafac R30 manufactured by Dainippon Ink ・ 0.01 part ・ Nonionic surfactant: Trade name Pluronic TR702 ADEK Ltd. · 0.2 parts Solvent: 3-ethoxyethyl propionate ... 30 parts Solvent: propylene glycol monomethyl ether acetate ... 100 parts

[Preparation of Red Curable Composition CR-2]
A dispersion R-2 was obtained in the same manner as the dispersion R-1, except that the polymer dispersant in the composition R-1 was replaced with an alkali-soluble resin, that is, the following composition R-2 was used.

(Composition R-2)
Pigment Red 254 (average particle size 20 nm) ... 11 parts Pigment Red 177 (average particle size 18 nm) ... 4 parts Dispersant: Trade name Disperbyk-161, manufactured by BYK Chemie, propylene glycol monomethyl ether 30% solution: 3 parts Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid (Minute: 50% by mass) 14 parts propylene glycol monomethyl ether acetate 68 parts

  A red curable composition CR-2 was obtained in the same manner as the preparation method of the red curable composition CR-1, except that the obtained dispersion R-2 was used instead of the dispersion R-1. It was.

1-2. Preparation of green curable composition [Preparation of green curable composition CG-1]
A dispersion G-1 was obtained in the same manner as the dispersion R-1, except that the following composition G-1 was used.

(Composition G-1)
Pigment Green 36 (average particle size 19 nm) ... 11 parts Pigment Yellow 150 (average particle size 22 nm) ... 7 parts (B-1-3) Specific polymer dispersant: the exemplified compound (X)・ ・ 5 parts dispersant: trade name Disperbyk-163, 45% solution manufactured by Big Chemie ・ ・ 2 parts ・ Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 85/15 [mass ratio] copolymer, weight average Molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid content: 50% by mass) ... 4 parts, solvent: propylene glycol monomethyl ether acetate ... 71 parts

  Next, using the obtained dispersion G-1, the following composition CG-1 was mixed and stirred to obtain a green curable composition CG-1.

(Composition CG-1)
・ Dispersion G-1 ・ ・ ・ 100 parts ・ Epoxy resin: Trade name EHPE3150 manufactured by Daicel Chemical Industries, Ltd. ・ 2 parts ・ Polymerizable compound: dipentaerythritol pentahexaacrylate ・ ・ ・ 6 parts Of tetra (ethoxyacrylate) 2 parts polymerization initiator: 1,3-bistrihalomethyl-5-benzooxolantolyazine 2 parts polymerization initiator 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1 ... 1 part polymerization initiator: diethylthioxanthone 0.5 parts polymerization inhibitor: p-methoxyphenol 0.001 part fluorine-based surface activity Agent: Trade name Megafac R08 Made by Dainippon Ink ・ 0.02 part ・ Nonionic surfactant: Polyoxyethylene tristyryl Vinyl ether (the repeating unit of the polyoxyethylene 12) ... 0.5 parts Solvent: propylene glycol monomethyl ether acetate ... 120 parts Solvent: propylene glycol n- propyl ether acetate ... 30 parts

[Preparation of green curable composition CG-2]
A dispersion G-2 was obtained in the same manner as the preparation of the dispersion G-1, except that the polymer dispersant in the composition G-1 was replaced with an alkali-soluble resin, that is, the following composition G-2 was used.

(Composition G-2)
・ Pigment Green 36 (average particle size 19 nm) ・ ・ ・ 9 parts ・ Pigment Green 7 (average particle size 15 nm) ・ ・ ・ 2 parts ・ Pigment Yellow 138 (average particle size 18 nm) ・ ・ ・ 7 parts ・ Dispersant: Trade name Disperbyk-163, 45% solution manufactured by Big Chemie) 2 parts alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 85/15 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol Monomethyl ether acetate solution (solid content: 50% by mass) ... 14 parts ・ Solvent: Propylene glycol monomethyl ether acetate ... 69 parts

  A green curable composition CG-2 is obtained in the same manner as the method for preparing the green curable composition CG-1, except that the obtained dispersion G-2 is used instead of the dispersion G-1. It was.

1-3. Preparation of blue curable composition [Preparation of blue curable composition CB-1]
A dispersion B-1 was obtained in the same manner as the preparation of the dispersion R-1, except that the following composition B-1 was used.

(Composition B-1)
Pigment Blue 15: 6 (average particle diameter 15 nm) 14 parts Pigment Violet 23 (average particle diameter 23 nm) 1 part (B-1-1) specific polymer dispersant: in the following synthesis example Example compound B-1 obtained 5 parts Dispersant: Trade name SOLSPERS-20000, manufactured by ZENEKA Corporation 1 part Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 80/20 [mass Ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid content: 50% by mass) ... 4 parts, solvent: propylene glycol monomethyl ether acetate ... 75 parts

[Synthesis Example: Synthesis of Exemplary Compound B-1]
(1. Synthesis of chain transfer agent)
7.83 parts of dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd.] and the following compound having an adsorption site and having a carbon-carbon double bond ( m-6) 4.55 parts was dissolved in 28.90 parts of propylene glycol monomethyl ether and heated to 70 ° C. under a nitrogen stream. To this, 0.04 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Further, 0.04 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, a 30% solution of a mercaptan compound (chain transfer agent) shown below was obtained.

(2. Synthesis of specific polymer dispersant)
A mixed solution of 4.99 parts of a 30% solution of the chain transfer agent obtained as described above, 19.0 parts of methyl methacrylate, 1.0 part of methacrylic acid and 4.66 parts of propylene glycol monomethyl ether was added to nitrogen. It heated to 90 degreeC under airflow. While stirring this mixed solution, 0.139 part of dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.], 5.36 parts of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate 9 40 parts of the mixed solution was added dropwise over 2.5 hours. After the completion of the dropwise addition, the mixture was reacted at 90 ° C. for 2.5 hours, and then a mixed solution of 0.046 parts of dimethyl 2,2′-azobisisobutyrate and 4.00 parts of propylene glycol monomethyl ether acetate was added, and further 2 hours. Reacted. To the reaction solution, 1.52 parts of propylene glycol monomethyl ether and 21.7 parts of propylene glycol monomethyl ether acetate were added and cooled to room temperature. 130 mass%, propylene glycol monomethyl ether 21 mass%, propylene glycol monomethyl ether acetate 49 mass%).
The acid value of this exemplary compound B-1 was 48 mg / g. The structure of exemplary compound B-1 is shown below.

  Subsequently, using the obtained dispersion B-1, the following composition CB-1 was mixed and stirred to obtain a blue curable composition CB-1.

(Composition CB-1)
-Dispersion B-1 ... 100 parts-Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 80/20 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate Solution (solid content: 50% by mass) ··· 6 parts · Epoxy resin: Brand name Celoxide 2080 · Made by Daicel Chemical · · · 2 parts · UV curable resin: Product name Cyclomer P ACA-250 Made by Daicel Chemical A propylene glycol monomethyl ether acetate solution of an acrylic copolymer having an alicyclic ring, a COOH group, and an acryloyl group (solid content: 50% by mass) ... 4 parts; polymerizable compound: dipentaerythritol pentahexaacrylate ... 12 parts Polymerization initiator: 1- (9-ethyl-6- (2-methylbenzoyl) 9H-carbazol-3-yl) -1- (o-acetyloxime) ethanone 3 parts, polymerization inhibitor: p-methoxyphenol 0.001 part, fluorosurfactant: Trade name Megafac R08 Made by Dainippon Ink ・ 0.02 part ・ Nonionic surfactant: Polyoxyethylene polyoxypropylene distyryl benzyl phenyl ether (Polyoxyethylene repeat unit is 10, polyoxypropylene repeat unit is 2) ・ ・ ・ 1 .5 parts ・ Solvent: 1,3-butylene glycol diacetate ... 20 parts ・ Solvent: Propylene glycol monomethyl ether acetate ... 150 parts

[Preparation of Blue Curable Composition CB-2]
A dispersion B-2 was obtained in the same manner as the preparation of the dispersion B-1, except that the polymer dispersant in the composition B-1 was replaced with an alkali-soluble resin, that is, the following composition B-2 was used.

(Composition B-2)
Pigment Blue 15: 6 (average particle diameter 15 nm) 14 parts Pigment Violet 23 (average particle diameter 23 nm) 1 part Dispersant: Trade name Disperbyk-161, 30% solution manufactured by Big Chemie Corporation 3 Part / alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 80/20 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)・ ・ 14 parts ・ Solvent: Propylene glycol monomethyl ether acetate ・ ・ ・ 68 parts

  A blue curable composition CB-2 is obtained in the same manner as the preparation method of the blue curable composition CB-1, except that the obtained dispersion B-2 is used instead of the dispersion B-1. It was.

<1. Adjustment of curable composition for light shielding>
1-1. Preparation of Silver Sulfide Fine Particle Dispersion (Dispersion K-1) 25.2 g of silver acetate was dissolved in 100 ml of diethylaminoethanol (Solution 1). Separately, 25.8 g of ammonium sulfide was dissolved in 100 ml of ethanol (solution 2). Solution 2 was added thereto while vigorously stirring Solution 1 maintained at 25 ° C. Thereafter, the stirring was continued gently for 15 minutes. The liquid mixture turned black and silver sulfide was produced. Thereafter, the mixture was allowed to stand for 8 hours to precipitate silver sulfide, and the supernatant was discarded. Next, 100 ml of methyl ethyl ketone was added, stirred for 15 minutes, and then allowed to stand for 8 hours to precipitate silver sulfide, and the supernatant was discarded. This operation was repeated again. Methyl ethyl ketone was added to the silver sulfide slurry thus obtained to make a total volume of 50 ml.
This silver sulfide dispersion was placed in a glass bottle with a capacity of 100 ml together with 40 g of zirconia beads having a diameter of 0.3 mm and dispersed with a paint shaker for 6 hours. After the dispersion, the glass beads were removed to obtain a silver sulfide fine particle dispersion K-1. The obtained liquid volume was 47 mL and the amount of silver sulfide was 17.2 g. When the fine particles were observed with a transmission electron microscope, the average particle size was about 20 nm.

1-2. Preparation of carbon black dispersion (dispersion K-2) The following composition K-2 was stirred for 1 hour using a homogenizer at 3000 rpm. The obtained mixed solution was finely dispersed for 8 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads to obtain Dispersion K-1.

(Composition K-2)
Carbon black: Degussa Color Black FW2 26.7 parts Dispersant: Enomoto Kasei Disparon DA7500 Acid value 26 Amine value 40 3.3 parts Benzyl methacrylate / methacrylic acid (72/28 molar ratio) ) Copolymer, Mw 10,000, 50% by mass solution of propylene glycol monomethyl ether acetate 10 parts Solvent: propylene glycol monomethyl ether acetate 60 parts

1-4. Preparation of curable composition for light-shielding portion formation Using the obtained dispersions K-1 and K-2, curable compositions CK-1 and CK-2 were prepared according to the formulation shown in Table 1 below. The numbers in the table indicate the mass ratio.

Details of each compound used in Table 1 are as shown below.
Resin solution C-1: benzyl methacrylate / methacrylic acid (= 85/15 molar ratio) copolymer (Mw10000, 50 wt% solution of propylene glycol monomethyl ether acetate)
UV curable resin C-2: trade name Cyclomer P ACA-250, manufactured by Daicel Chemical Industries, Ltd. [Acrylic copolymer having alicyclic, COOH, and acryloyl groups in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)]
-Polymerizable compound C-3: Trade name TO-1382 manufactured by Toagosei Co., Ltd. The main component is a monomer having a pentafunctional acryloyl group in which part of the terminal OH group of dipentaerythritol pentaacrylate is substituted with a COOH group.
・ Polymerization initiator C-4: Trade name “OXE-02” Ciba Specialty Chemicals ・ Surfactant C-5: Trade name “Megafac R30” Made by Dainippon Ink ・ Solvent: PGMEA = propylene glycol monomethyl ether acetate EEP = 3-Ethoxyethyl propionate

<2-1. Formation of Black Matrix (BM)>
[Production of Black Matrix Substrates BM-1 and BM-2]
The obtained light-shielding part forming curable compositions CK-1 and CK-2 were provided with a slit head having a slit interval of 100 μm and an effective coating width of 540 mm on a glass substrate (Corning Millennium 0.7 mm thickness, 550 mm × 650 mm). The film was applied at a coating speed of 100 mm / second by adjusting the distance between the slit and the glass substrate and the discharge amount so that the film thickness after post-baking was 0.5 μm and 1.0 μm, respectively, with a slit coating device.
Next, after heating (pre-baking treatment) at 100 ° C. for 120 seconds using a hot plate, the proximity gap is set to 300 μm with a mask having a line width of 10 μm using a HITACHI exposure machine LE5565 (all wavelengths), and 100 mJ / Cm ² (illuminance: 20 mW / cm ² ).

  Thereafter, development was performed with a 1.0% developer (25 ° C.) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) and washed with pure water. Subsequently, a post baking process was performed for 30 minutes in a 220 ° C. clean oven to form a grid-like black matrix substrate having a light-shielding portion with a line width of about 13 μm so that the opening of the colored pixel portion forming region was 90 μm × 200 μm. The opposing part of the TFT electrode left 25 μm × 25 μm as a light shielding part. In this way, black matrix substrates BM-1 and BM-2 were obtained.

[Production of Black Matrix Substrate BM-3]
Further, as a metal light-shielding portion, a substrate having a chromium oxide two-layer vapor-deposited film (the substrate is Corning Millennium 0.7 mm thickness 550 mm × 650 mm) is shielded in the same shape as described above by a photolithography method using a positive resist by a conventional method. Then, a lattice-like black matrix substrate BM-3 was produced.

The light shielding property was measured by the optical density (OD value) in the visual mode using a transmission densitometer X-RITE 310T. Further, the film thickness was measured with a stylus-type film thickness meter DECTAC-3 manufactured by ULVAC, Inc. for the post-baked substrate.
The film thickness and optical density (OD value) of the black matrix are shown in Table 2 below.

[Example 1]
<Production of color filter>
On the black matrix substrate BM-3, the blue curable composition CB-1 prepared by the above-described method is applied to the black matrix substrate BM-3 by using the same slit coater used when the black matrix substrates BM-1 and BM-2 are produced. It was applied in the longitudinal direction of the opening. Then, after heating at 80 ° C. for 60 seconds (pre-bake treatment), exposure was performed at 100 mJ / cm ² with a proximity gap of 300 μm using a HITACHI exposure machine LE5565 (all wavelengths) (illuminance: 20 mW / cm ² ). As the mask, a colored pixel portion was exposed in a stripe shape having a width of 198 μm, and a spacer portion was exposed to an 8 μm square on the TFT electrode facing portion. Then, it developed with the 1.0% developing solution (25 degreeC) of CDK-1 developing solution (made by Fuji Film Electronics Materials Co., Ltd.), and wash | cleaned with the pure water. Subsequently, it was post-baked for 30 minutes in a 220 ° C. clean oven.
As a result, a blue pixel portion and a blue colored layer were formed.

Then, application | coating, a prebaking process, exposure, image development, rinse, and a post-baking process were performed like the case where the blue curable composition CB-1 was used using red curable composition CR-1. In the exposure, a colored pixel portion was exposed in a stripe shape having a width of 198 μm, and a spacer portion was exposed to a TFT electrode facing portion at a 7 μm square.
Thereby, a red pixel portion and a red colored layer were formed.
Subsequently, using the green curable composition CG-1, similarly to the case of using the blue curable composition CB-1, coating, pre-baking treatment, exposure, development, rinsing, and post-baking treatment were performed. . As the mask, a colored pixel portion was exposed in a stripe shape having a width of 198 μm, and a spacer portion was exposed to a 6 μm square on the TFT electrode facing portion.
Thereby, a green pixel portion and a green colored layer were formed.
The film thickness of each color pixel formed was 2.2 μm.
In this way, a color filter CF-1 of Example 1 was obtained.

[Comparative Example 1]
In the production of the color filter CF-1 of Example 1, the size of the exposed portion of the TFT facing portion when forming the spacer portion is 5 μm square for CB-1, 4 μm square for CR-1, and CG. In the case of -1, the color filter CF-2 of Comparative Example 1 was produced by changing to 3 μ square.
The film thickness of each color pixel formed was 2.2 μm.

[Comparative Example 2]
In the production of the color filter CF-1 of Example 1, a color filter CF-3 without a spacer (Comparative Example 2) was prepared in the same manner as in Example 1 except that the exposure for forming the spacer portion was not performed. Produced.
The film thickness of each color pixel formed was 2.2 μm.

[Examples 2 and 3]
In the production of the color filter CF-1 of the first embodiment, the color filter CF of the second embodiment is similar to the first embodiment except that the black matrix substrate BM-3 is replaced with BM-1 and BM-2. -4, Color filter CF-5 of Example 3 was produced.
The film thickness of each color pixel formed was 2.2 μm.

Example 4
In the production of the color filter CF-1 of Example 1, the order of blue, red, and green when forming the colored pixel portion and the colored layer was changed to the order of blue, green, and red in the same manner as Example 1. Thus, a color filter CF-6 of Example 4 was produced. At this time, the size of the mask opening for forming the spacer portion was blue: 8 μm square, green: 7 μm square, and last red: 6 μm square.
The film thickness of each color pixel formed was 2.2 μm.

Example 5
In preparation of the color filter CF-1 of Example 1, CR-2 instead of the red curable composition CR-1, CG-2 instead of the green curable composition CG-1, and blue curable composition A color filter CF-7 of Example 5 was produced in the same manner as in Example 1 except that CB-2 was used instead of CB-1.
The film thickness of each color pixel formed was 2.2 μm.

Example 6
In the production of the color filter CF-1 of Example 1, the same amount of polyethylene glycol nonylphenyl ether (polyethylene glycol) was added to the nonionic surfactant in each of the curable compositions CR-1, CG-1, and CB-1. In the same manner as in Example 1 except that this curable composition was used, a color filter CF-8 of Example 6 was produced. .
The film thickness of each color pixel formed was 2.2 μm.

Example 7
In the production of the color filter CF-1 in Example 1, the propylene glycol monomethyl ether acetate was changed to 190 parts in the composition of the blue curable composition CB-1, and the composition of the red curable composition CR-1 was propylene. The glycol monomethyl ether acetate was changed to 140 parts, and the propylene glycol monomethyl ether acetate was changed to 160 parts in the composition of the green curable composition CG-1, and each of the curable compositions CB-3 and CR-3 was changed. CG-3 was prepared. Using this curable composition, a colored pixel portion and a colored layer were formed in the order of blue, red, and green in the same manner as in Example 1 to produce a color filter CF-9 of Example 7. Here, the film thickness (after post-baking) of the colored pixel portion of each color was 1.5 μm.

<Evaluation method>
(Particle size)
The average particle size of the colorant in each curable composition described above was measured using a photograph obtained with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd., magnification: 100,000 times, acceleration voltage: 200 kV). This was performed as follows.
That is, 100 particles were selected, the diameter of a circle having the same area as each particle image was defined as the particle diameter, and the average value of the particle diameters of 100 particles was defined as the number average particle diameter.

(Transparency of colored layer)
Films after drying red curable compositions CR-1 to CR-3, green curable compositions CG-1 to CG-3, and blue curable compositions CB-1 to CB-3, respectively, on a quartz substrate A coating was prepared so as to have a thickness of 2.0 μm and prebaked at 80 ° C. for 2 minutes.
With respect to the red colored layer, the green colored layer, and the blue colored layer thus obtained, transmittance was measured in a wavelength region of 350 to 700 nm using a C light source with an Otsuka Electronics chromaticity meter MCPD2000. Table 3 below shows the transmittance at a wavelength of 365 nm and a wavelength of 405 nm.

(Spacer shape)
A total of 8 spacers in the vicinity of 4 locations 50 mm from 4 corners in the diagonal direction and 4 locations 50 mm in the diagonal direction from the center on the 550 × 650 mm square substrate. Each was observed and measured. The color filter was cut, and the cross section was observed with a transmission electron microscope at a magnification of 5000 from the lateral direction, and the height was measured on the image. The bottom area of the spacer was determined by squaring the length of the bottom side of the spacer in contact with the light shielding portion. Furthermore, the cross-sectional area when the spacer was cut horizontally at a height of 2/3 was calculated by cutting the spacer horizontally at a height of 2/3 and squaring one side of the spacer.
In the present invention, the numerical values of the conditions (b) to (d) mean the average value of the numerical values measured by the above method on the formed color filter.
The observation and measurement results are shown in Table 4 below.

(Uniformity of spacer height in substrate)
The uniformity of the spacer height within the substrate was measured with a laser interferometer manufactured by Zygo. The uniformity of the spacer height within the substrate is a spacer in the vicinity of 4 points from 4 corners to 50 mm diagonally and 4 points from the center to 50 mm diagonally from a 550 × 650 mm square substrate. A total of 8 points were measured and obtained. The height of the spacer portion is a height from the upper surface of the light shielding portion (black matrix).
The measurement results are shown in Table 4 below.

(Contrast of color filter)
As a backlight unit, a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) is used, and between two polarizing plates (Nitto Denko Corporation SEG1224DU), When the transmittance of the colored layer is measured, a substrate on which a red colored layer, a green colored layer, and a blue colored layer are respectively formed is installed, and the chromaticity of light that passes when the polarizing plate is installed in parallel Nicol Contrast was obtained by dividing the Yp value by the Yc value of the chromaticity of the light passing through when installed in crossed Nicols. For the measurement of chromaticity, a color luminance meter (BM-5 manufactured by Topcon Corporation) was used.
The contrast of the color filter CF-9 of Example 7 was not measured because the thickness of the colored pixel portion was different from Examples 1 to 6 and Comparative Examples 1 and 2, and could not be compared.
The measurement results are shown in Table 4 below.

(Panel visibility)
<Production of liquid crystal display device>
For the color filters CR-1, CR-2, CR-4 to CR-9 obtained as described above, ITO (Indium Tin Oxide) transparent electrodes are further formed on the R, G, B pixels and the black matrix by sputtering. did. Separately, a glass substrate is prepared as a counter substrate, and a PVA mode patterning is performed on the transparent electrode of the color filter substrate and the counter substrate, respectively, and a polyimide alignment film (Nissan Chemical's Sun Ever 7492 70 nm after baking) is formed thereon. And baked at 180 ° C. for 1 hour. After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and a liquid crystal for PVA mode is dropped, and a counter substrate and After bonding, the bonded substrate was irradiated with UV, and then heat treated to cure the sealant. A polarizing plate (NPF-SEG1224DU manufactured by Nitto Denko) was attached to both surfaces of the liquid crystal cell thus obtained. Next, a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) was placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device. .

  Since the color filter CR-3 does not have a spacer, before attaching to the TFT array substrate, Sekisui Fine Chemical's Micropearl SP-2035 (average particle size 3.5 μm) is applied with a spacer spraying device, and the color filter CF -3. After spraying and bonding with a sealing agent, liquid crystal for PVA mode was injected under vacuum, and the inlet was sealed. A polarizing plate (NPF-SEG1224DU manufactured by Nitto Denko) was attached to both surfaces of the liquid crystal cell thus obtained. Next, a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) was placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device. .

The panel of the liquid crystal display device using each of the color filters CR-1 to CR-9 obtained as described above was turned on, and the hue when a 50% luminance signal was input was visually evaluated as visibility. Further, the color blur when the display screen was lightly pressed with a finger was visually evaluated and the boundary of the colored pixels was observed with a microscope.
The observation and measurement results are shown in Table 4 below.

As is apparent from Table 4, it can be seen that the color filters of the examples are excellent in uniformity within the substrate. In addition, it was confirmed that the color filter of the example was excellent in contrast, and that the liquid crystal display device using the color filter could form an image with excellent visibility.
In the color filter of Comparative Example 1, it can be seen that the spacers are chipped and peeled off, and the uniformity within the substrate is extremely poor.

It is process drawing which shows an example of the manufacturing method of the color filter of this invention.

Explanation of symbols

10 Support 20 Light-shielding part (black matrix)
30 Colored Pixels 40 Spacers 42R, 42G, 42B Colored Layer

Claims (5)

A light-shielding portion on the support, a plurality of colored pixel portions having different spectral characteristics, and a spacer formed by laminating two or more colored layers having different spectral characteristics on the light-shielding portion, A color filter, wherein the spacer satisfies all of the following conditions (a) to (d):
(A) The cross-sectional shape along the height direction is substantially trapezoidal. (B) The height from the light shielding portion is 2.0 to 4.0 μm.
(C) The bottom area is 50 to 200 μm ²
(D) The cross-sectional area when cut horizontally at a height of 2/3 is 25 to 130 μm ^2.   The optical density of the light shielding part is 4.0 or more, the film thickness is 0.1 μm or more and 1.2 μm or less, and the film thickness of the colored pixel part is 1.2 μm or more and 2.4 μm or less. The color filter according to claim 1.   2. The color filter according to claim 1, wherein the spacer is formed by laminating two or more colored layers having different spectral characteristics in descending order of the sum of the transmittance at a wavelength of 365 nm and the transmittance at a wavelength of 405 nm. . The colored pixel portion and the spacer are copolymer units derived from (A) a colorant, (B) a compound represented by the following general formula (1), and a monomer represented by the following general formula (I). And an acid value of 20 to 300 mg / g, and a weight average molecular weight of 3,000 to 3,000, and a polymer containing a structural unit represented by the following general formula (a). The color filter according to claim 1, comprising one or more polymer dispersants in the range of 100,000.

[In General Formula (1), A ¹ represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a carbon number of 4 A monovalent organic group containing at least one site selected from the above hydrocarbon groups, alkoxysilyl groups, epoxy groups, isocyanate groups, and hydroxyl groups. n A ¹ and R ² may be the same or different independently. R ¹ represents an (m + n) -valent organic linking group, where m represents 1 to 8, n represents 2 to 9, and satisfies 3 <(m + n) <10. R ² represents a single bond or a divalent organic linking group. P ¹ represents a polymer skeleton. The m P ¹ may be the same or different. ]

[In the above general formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (═O ) Represents one selected from S-, -OC (= O)-, -OCONH-, and -NHCO-. Y represents any one selected from NR ⁰³ , O, and S, and R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. In the formula, N and Y are connected to each other to form a cyclic structure. m1 and n1 are each independently 0 or 1. ]

[In the general formula (a), R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure. ] The colored pixel portion and the spacer further contain at least one nonionic surfactant selected from a compound group represented by the following general formula (A) to general formula (D). Item 5. The color filter according to Item 4.

[The above general formula (A) ~ the general formula (D), (Styryl) represents ph-CH = CH- (benzyl) is ph-CH ₂ - represents a. Here, ph is a phenyl group. PO represents propylene oxide, and EO represents ethylene oxide. n is 1 to 3, m is 7 to 30, l is 0 to 10, a is 0 to 20, b is 0 to 20, c is 6 to 30, x is 5 to 100, and y is 20 to 100. Each represents an integer. X and y satisfy 0.1 ≦ x / y ≦ 2.0. The four x and y existing in the general formula (C) and the general formula (D) are the same or different integers, respectively. ]

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