KR100776561B1 - Curable resin composition, color filter and liquid crystal display - Google Patents

Abstract

In the manufacture of color filters, it is an object to provide a highly rheological performance curable resin composition suitable for resist coating according to the die coat method. In a specific power law, in the application of the relationship of the shear stress (τ) to the shear rate (D), a curable resin composition is provided wherein the power index (n) at a shear rate (D) of 10 ³ s ⁻¹ or more is 0.6 or more. do. According to the curable resin composition having a power index of 0.6 or more at a shear rate (D) of 10 ³ s ⁻¹ or more, any deterioration in the discharge flow rate distribution due to slit nonuniformity can be suppressed.

Description

Curable resin composition, color filter and liquid crystal display device {CURABLE RESIN COMPOSITION, COLOR FILTER AND LIQUID CRYSTAL DISPLAY}

The present invention relates to a curable resin composition, a color filter, and a liquid crystal display device mechanism. More specifically, the present invention relates to a curable resin composition having a high rheological property suitable for coating by a die coat method in the manufacture of color filters; A color filter manufactured using the curable resin composition; And a liquid crystal display device manufactured by arranging the color filters.

As a color filter manufacturing method for liquid crystal display devices, the pigment dispersion method, the dyeing method, the electrodeposition method, and the printing method are known, for example. Among these, the pigment dispersion method which has an average outstanding profile from the viewpoint of spectral characteristics, durability, pattern shape, and precision is most widely used.

The outline of the pigment dispersion method is described below. In general, the black matrix is first prepared from a light shielding film of a metal such as chromium and chromium oxide on a transparent support such as a glass substrate; Subsequently, for exposure through a mask, for example, a photosensitive resin composition (color resist) in which a red pigment is dispersed is applied to the entire surface thereof by a spin coating method. When developed after exposure, a red pixel is obtained. Blue and green pixels are also manufactured in the same manner, and three-color pixels are produced. Since the black matrix portion forms a concave portion with respect to the individual pixels, the surface is smoothed by applying with a protective film of a transparent resin such as an epoxy resin and an acrylic resin. However, the protective film may not often be disposed. In addition, a transparent conductive film such as an ITO film is formed on the protective film by, for example, sputtering or vacuum deposition. In recent years, furthermore, the pigment dispersion method seems to be frequently used for producing the black matrix. Specifically, photosensitive resin (black resist) which disperse | distributed a black pigment is apply | coated, exposed, and developed, and is manufactured.

Following the recent trend of technological innovation, the performance required for liquid crystal display devices has been diversified and advanced. Especially for color filters, a wide range of color reproducibility and high transparency that have not been achieved are required. In order to satisfy the above diverse needs with the pigment dispersion method, a wide variety of new pigments have been developed, and photosensitive resin compositions (color resists) incorporating the new pigments therein at higher concentrations are increasingly employed in the mainstream. In addition, black resist as well as color resist is required to have a high light shielding profile with a thin coated film. Thus, resists with higher pigment concentrations tend to be selected.

On the other hand, various new technologies have been developed for the color filter manufacturing method. In the resist coating step of the pixel forming step, for example, a method of dropping the resist in the center of the substrate and flattening the resist by spin coating is mainly selected. However, as the size of the substrate increases, more coatings have to be used in the spin coating method, and due to the limitation of the spin coater (for example, motor capability), a coating technique by the die coating method has been practically developed in recent years. It became.

However, when the die coating method is selected, even if the resist can be uniformly applied without a non-uniform coating by the spin coating method, due to the non-uniformity of the discharge flow rate and the non-uniform shape of the die blade tip, the resist is die coated. When used in law, stripes provide a non-uniform thickness. That is, a resist having excellent rheological properties by the spin coating method does not overcome the problem of non-uniform coating due to the die coating method.

For example, in Patent Literature 1, in a resist using a spin coat method, s = μD ^x (where s represents shear stress; D represents shear rate; μ represents Newtonian viscosity coefficient; x is ratio -Newton's viscosity coefficient), the power exponent x is preferably 0.9 or more and 1 or less. However, the shear rate range for coating of the spin coat method in the art is about 70 to 380 s ^- considered low as ^1, that the power factor with respect to shear rate by the die coating method that requires the rheological properties of the highly significant Never been.

Alternatively, Patent Document 2 discloses a method of improving the uniformity of coating in the width direction by forming a plurality of protrusions in a shim portion integrated into a slit nozzle for die coat, Means for solving the striped film thickness non-uniformity are not described.

[Patent Document 1]

Japanese Patent No. 3275520

[Patent Document 2]

JP-A-11-188301

Disclosure of the Invention

It is an object of the present invention to eliminate coating non-uniformity in the application of the die coat method, in particular the non-uniformity of streaks caused by non-uniform discharge in the slit nozzle width direction due to the large number of protrusions on the shim part. It is providing the curable resin composition which can be solved, the high quality color filter and liquid crystal display device mechanism which use the said curable resin composition.

The present inventors found that the curable resin composition having a power index of 0.6 or more when the shear rate is 10 ³ s ^{−1 or} more can suppress the nonuniform defect in the striped width direction caused by nonuniform discharge in the slit nozzle width direction. Found that. In addition, the present inventors have made the curable resin composition have a normal viscosity of 5 mPa · s or less, or a surface tension of 25 dyne / cm or more, so that the nonuniformity of streaks which are naturally weakened by the above-mentioned improvement is a leveling action. It has been found that by leveling action it can be made more uniform and solved. The present invention has been accomplished based on this finding.

The curable resin composition of the present invention has a shear of 10 ³ s ⁻¹ or more when the relationship between the shear stress (τ) and the shear rate (D) is considered to conform to the power law represented by the following formulas (Ia) and (Ib). Has a power exponent (n) of 0.6 or greater at speed (D):

τ = μ × D (Ia)

μ = η × D ^(n-1) (Ib)

(Wherein τ: shear stress; μ: viscosity; η: constant; D: shear rate; n: power exponent).

Preferably, the curable resin composition of this invention has a normal viscosity of 5 mPa * s or less at the shear rate (D) of 10 ³ s <^-1> or less. In addition, its surface tension is preferably at least 25 dyne / cm. Curable resin composition of this invention, Preferably it is used for application | coating of a die-coat system especially.

The color filter of this invention is manufactured using curable resin composition of this invention.

The liquid crystal display device of this invention arranges and manufactures the color filter of this invention.

Curable resin composition of this invention does not have the problem of the coating nonuniformity by the die-coat method, and is suitable for manufacture of a color filter by die-coat application, etc. The color filter using the said curable resin composition of this invention is a high quality color filter, and can provide the high quality liquid crystal display device mechanism by which an advanced pixel is formed by a uniform resist layer.

Brief description of the drawings

Fig. 1 (a) is a plan view of shims used in the color resist evaluation test, and Fig. 1 (b) is a perspective view of an application state using a slit die in which the shims are arranged.

In the figures, each 1 represents a shim; 2 represents a slit die; 3 represents a glass substrate; 4 represents a color resist; 5 represents non-uniform streaks.

Best Mode for Carrying Out the Invention

Embodiments for carrying out the invention are described in detail below.

(Curable Resin Composition of the Present Invention)

[1] rheological properties of the curable resin composition of the present invention

The curable resin composition of the present invention has a shear of 10 ³ s ⁻¹ or more when the relationship between the shear stress (τ) and the shear rate (D) is considered to conform to the power law represented by the following formulas (Ia) and (Ib). It has a power exponent (n) of 0.6 or greater in velocity:

τ = μ × D (Ia)

μ = η × D ^(n-1) (Ib)

(Wherein τ: shear stress; μ: viscosity; η: constant; D: shear rate; n: power exponent).

When the Newtonian fluid is in the shear flow state, the force (shear stress (τ)) and the velocity gradient of the shear fluid (shear velocity (D)) that induce a stress deformation of the fluid per unit area are expressed by equations (Ia) and (Ib). It is shown roughly by the relational expression which shows. When n = 1, the shear rate and shear stress are proportional, so the closer n is to 1, the better the flow profile is. Due to the poor distribution of the discharge flow rate due to the non-uniform slit by the die coat application method, each part has a different shear rate. However, if n is too small, the shear stress is not proportional to the magnitude of the shear rate, so that the shear stress is relatively smaller. Accordingly, non-uniformity in the coating layer occurs at portions having different shear rates, and non-uniformity of stripes occurs.

In the curable resin composition whose power index (n) is 0.6 or more at the shear rate (D) of 10 ³ s ^-1 or more, the shear rate and the shear stress are almost proportional. Therefore, the nonuniformity of the stripes due to the shear rate difference can be suppressed. On the basis of the above mentioned evidence, in addition, the power exponent (n) at a shear rate (D) of at least 10 ³ s ⁻¹ is preferably at least 0.8. In the present application, the upper limit of the power exponent (n) is 1.

[2] constant velocity, surface tension and vapor pressure of the curable resin composition of the present invention

In the curable resin composition of the present invention, the upper limit of the normal viscosity at a shear rate of 10 ³ s ⁻¹ or less is preferably 5 mPa · s or less, more preferably 4 mPa · s or less, particularly preferably 3.8 mPa * s or less, Specifically, it is 3.5 mPa * s or less.

The lower limit thereof is generally 1 mPa · s or more. In the manufacture of color filters of thin films (generally less than 1.5 μm; unless otherwise stated, said thickness is used herein as a definition of thin film), as a film thickness applied after drying (ie after the last step), the lower limit is Preferably it is 1.5 mPa * s or more, More preferably, it is 2 mPa * s or more, Especially preferably, it is 2.5 mPa * s or more. In the production of color filters for thick films (generally 1.5 μm or more; unless otherwise stated, the thickness is used herein as a definition of thick film), the lower limit as a film thickness after drying is preferably 3 mPa · s or more, more Preferably it is 3.2 mPa * s or more.

With a normal viscosity within this range, a color filter of thin film as film thickness after drying can be produced, without any coating streaks due to non-uniformity of the die lip tip by die coat application without liquid depletion even at higher application limit speeds. Can be. In the present application, the application limit rate means an upper application rate at which a uniform application can be performed without generating any striped film due to liquid depletion in a constant application portion. The application limit speed is generally 0.1 m / s, preferably 0.2 m / s, more preferably 0.3 m / s.

In manufacturing the color filter of the thick film as the applied film thickness after drying, maintaining a normal viscosity within the above range even when the thick film is applied using a die coat, while suppressing excessive flow during drying as well as non-uniform drying and hollow defects, The color filter can be made without any application streaks due to the nonuniformity of the die lip tip.

Liquid stability deteriorates if the normal viscosity is too low in the manufacture of any color filter of a thin film or a thick film.

Preferably, the curable resin composition of this invention has a surface tension of 25 dyne / cm or more, and therefore its leveling performance is excellent. The higher the surface tension, the more preferable. In general, however, the surface tension is 40 dyne / cm or less.

The curable resin composition with better leveling performance, through its leveling action, can make more uniform the striped nonuniformity due to die coat application, which is essentially weakened in accordance with the present invention, thereby eliminating nonuniformity.

When manufacturing a color filter of a thin film as a film thickness after drying, Preferably the surface tension (X) (dyne / cm) of the curable composition of this invention and the surface tension (Y) of the total solvent component contained in curable resin composition (dyne / between cm) is established by the following formula (II):

1 ≤ [(Y)-(X)] ≤ 3 (II)

Since the surfactant can appropriately reduce the surface tension gradient in the curable resin composition having the surface tension within the above range, the occurrence of coating streaks can be suppressed while leveling the nonuniformity, thereby solving the nonuniformity of the streaks.

[3] Structural Elements and Compositions of Curable Resin Compositions of the Present Invention

The curable resin composition of the present invention may be colored material [hereinafter abbreviated as component (a)], solvent component [hereinafter abbreviated as component (b)], binder resin [hereinafter abbreviated as component (c1)] and / or Monomers thereof [hereinafter abbreviated as component (c2)], and further including photopolymerization initiator [hereinafter abbreviated as component (d)] and additives other than components (a) to (d) [hereinafter, component (e Abbreviated), and the like.

Preferably, the curable resin composition according to the present invention is present at 2 to 50% by weight in the proportion (concentration) of the total solids used in the total curable resin composition. The proportion is more preferably 10 to 30% by weight, particularly preferably 15 to 25% by weight.

If the proportion of total solids is too large, undesirably, application streaks easily occur. If the proportion of total solids is too small, the viscosity is undesirably low, leading to the flow of the curable resin composition during drying, which undesirably leads to non-uniform drying and the occurrence of concave defects. As used herein, the term "total solids" includes all components except the solvent component [component (b)], namely components (a), (b), (c), (d) and (e) and the like.

In addition, when a color filter of a thin film as a film thickness applied after drying is produced, the ratio is generally 30% by weight or less, preferably 20% by weight or less, more preferably 18% by weight or less, particularly preferably 16 wt% or less. The proportion is generally at least 2% by weight, preferably at least 5% by weight, more preferably at least 10% by weight.

In addition, when a thin film color filter as a film thickness applied after drying is produced, the proportion is generally at least 10% by weight, preferably at least 16% by weight, more preferably at least 18% by weight, particularly preferably 18.5. By weight or more. The proportion is generally at most 50% by weight, preferably at most 30% by weight, more preferably at most 20% by weight.

Component (a) includes coloring the curable resin composition of the present invention. As the colorant, dyes and pigments can be used. In view of heat resistance and light resistance, pigments are preferred. As the pigment, various colored pigments such as blue pigments, green pigments, red pigments, yellow pigments, violet pigments, orange pigments, brown pigments and black pigments can be used. In view of its structure, organic pigments of azo series, phthalocyanine series, quinacridone series, benzimidazolone series, isoindolinone series, dioxazine series, indanthrene series and perylene series can be used. In addition, various inorganic pigments may be used. Specific examples of available pigments are shown below by pigment numbers. As used herein, the term "C.I." Means color index (C.I.).

In red pigment, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275 and 276. Among these, preferred red pigments include C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242 and 254. More preferred red pigments include C.I. Pigment red 177, 209, 224 and 225.

Blue pigments include C.I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, preferred blue pigments include C.I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4 and 15: 6. More preferred blue pigments include C.I. Pigment blue 15: 6.

Green pigments contain C.I. Pigment greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54 and 55. Among these, preferred green pigments include C.I. Pigment greens 7 and 36.

Yellow pigments contain C.I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207 and 208. Among these, preferred yellow pigments include C.I. Pigment yellows 83, 117, 129, 138, 139, 150, 154, 155, 180 and 185. More preferred yellow pigments include C.I. Pigment yellows 83, 138, 139, 150 and 180.

Orange pigments contain C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 and 79. Among these, preferred orange pigments include C.I. Pigment oranges 38 and 71.

Violet pigments contain C.I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49 and 50. Among these, preferred violet pigments include C.I. Pigment violets 19 and 23 are included. More preferred violet pigments include C.I. Pigment violet 23 is included.

In addition, when the color composition for color filters according to the present invention is a color composition for resin black matrices of a color filter, a black color material may be used as the color material. The black color material may be a single black color material or a mixture of red, green and blue and the like. In addition, the colorant may be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, the pigments are preferably dispersed to an average particle size of 1 μm or less, preferably 0.5 μm or less for use.

Colorants used in the mixture for the production of black colorants include Victoria Pure Blue (42595), Auramin O (41000), Catyl Brillant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safra OK 70: 100 (50240), eryoglausin (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Simeler Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Simeler Fast Red 4015 (12355), Lionol Red 7B4401 (15850 ), Fasten blue TGR-L (74160), Leonol blue SM (26150), Leonol blue ES (pigment blue 15: 6), Leonogen red GD (pigment red 168) and Leonol green 2YS (pigment green 36) ) [Values in each () indicate a color index (CI)].

Other pigments used in the mixture include, for example, C.I. Yellow pigments represented by numbers are included: 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154 and 166; Orange Pigment C.I. 36, 43, 51, 55, 59 and 61; Red Pigment C.I. 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 228 and 240; Violet Pigment C.I. 19, 23, 29, 30, 37, 40 and 50; Blue pigment C.I. 15, 15: 1, 15: 4, 22, 60 and 64; Green Pigment C.I. 7; And brown pigment C.I. 23, 25, and 26.

Additionally, the black colorants available alone include, for example, carbon black, acetylene black, lamp black, BON black, graphite, iron black, aniline black, cyanine black and titanium black.

Among these, carbon black and titanium black are preferable in view of light shielding ratio and image quality. Carbon blacks include, for example, the following carbon black types:

Mitsubishi Kagaku Co., Ltd. Carbon black produced by; MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B and OIL31;

Degussa Co., Ltd. Carbon black produced by;

Printex3, Printex30P, Printex30, Printex300P, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170;

Carbon black manufactured by Cabot International Capital Corporation;

Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R , REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN XC72R and FLFTEX-8; And

Colombian Carbon Co., Ltd. Carbon black produced by;

RAVEN 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22 RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890H, RAVEN 1000, RAVEN 1020, RAVEN 1040, RAVEN 1060U, RAVEN 1080U, RAVEN 1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN 2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 5250, RAVEN 5750 and RAVEN 7000.

In addition, those described below are listed as titanium black.

The method for producing titanium black includes, but is not limited to, a method of heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere for reduction (JP-A-49-5432), titanium tetrachloride at high temperature under a reducing atmosphere containing hydrogen. To reduce the ultrafine titanium dioxide obtained by hydrolysis (JP-A-57-205322), to reduce titanium dioxide or titanium hydroxide in the presence of ammonia (JP-A-60-65069 and JP-A-61-201610) and a method of attaching a vanadium compound on titanium dioxide or titanium hydroxide to reduce it in the presence of ammonia at high temperature (JP-A-61-201610).

Commercially available titanium black products include, for example, titanium black 10S, 12S, 13R, 13M and 13M-C manufactured by Mitsubishi Material Co., Ltd.

As another black pigment, for example, mixtures of black pigments such as aniline black and iron oxide series can be used as black pigments by mixing red, green and blue organic pigments with three organic colors.

In addition, barium sulfate, lead sulfate, titanium oxide, yellow, red oxide, and chromium oxide may be used as the pigment.

The various types of pigments described above can be used in combination of the various types thereof. For chromaticity adjustment, a green pigment and a yellow pigment may be used in combination as a pigment, or a blue pigment and a violet pigment may be used in combination.

Herein, the average particle size of the pigments is generally 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. Dyes available as colorants include, for example, azo-based dyes, anthraquinone-based dyes, phthalocyanine-based dyes, quinone imine-based dyes, quinoline-based dyes, nitro-based dyes, carbonyl-based dyes and methine-based dyes. Dyes are included.

Azo-based dyes include, for example, C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Mordant Red 7, C.I. Mordant Yellow 5 and C.I. Mordant Black 7 is included.

Anthraquinone-based dyes include, for example, C.I. Bat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56 and C.I. Disperse Blue 60 is included.

Additionally, phthalocyanine-based dyes include, for example, C.I. Pad Blue 5 is included; Quinone imine-based dyes include, for example, C.I. Basic Blue 3 and C.I. Basic Blue 9 is included; Quinoline-based dyes include, for example, C.I. Solvent Yellow 33, C.I. Acid Yellow 3 and C.I. Disperse Yellow 64 is included; Nitro-based dyes include, for example, C.I. Acid Yellow 1, C.I. Acid Orange 3 and C.I. Disperse Yellow 42 is included.

When the ratio of component (a) in curable resin composition of this invention is too big | large, the aggregated mass of component (a) will generate | occur | produce easily. If the ratio is too small, the applied film becomes essentially thick, which is undesirable in the composition of the applied film. Generally, the ratio of the component (a) employed in the total solids in the curable resin composition is suitably determined in the range of 5 to 80% by weight or more. Within this range, the ratio is preferably 10 to 70% by weight, more preferably 20 to 60% by weight.

Component (b) is a function of adjusting the viscosity of the curable resin composition of the present invention obtained by dissolving or dispersing the components (a) and (c) and, in some cases, the blended components (d) and (e) and the like. Do it.

Component (b) includes, for example, glycol ethers and / or alkoxy esters. Specific examples of glycol ethers include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-n-butyl ether , Ethylene glycol acetate, ethylene glycol diacetate, ethylene glycol diethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Ethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate and tripropylene glycol It includes ether.

Specific examples of alkoxy esters include methyl acetate, methyl isobutyrate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, butyl acetate, (n, sec, t-) butyl acetate, butyl stearate, ethyl propionate, ethyl benzoate, ethyl o-formate, Ethyl caprylate and propyl acetate.

Additionally, for example, diisopropyl ether, mineral spirits, n-pentane, amyl ether, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, n-octane, Valsol # 2, Apco # 18 solvent, di Isobutylene, amyl acetate, Apco thinner, butyl ether, diisobutyl ketone, methyl cyclohexane, methyl nonyl ketone, propyl ether, dodecane, Socal solvent Nos. 1 and 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, hexene, Shell TS28 solvent, butyl chloride, ethyl amyl ketone, amyl chloride, methoxymethyl pentanone, methyl butyl ketone, methyl hexyl ketone , Benzonitrile, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, amyl acetate, amyl formate, bicyclohexyl, dipentane, methoxymethyl pentanol, methyl amyl ketone, methyl isopropyl ketone, methyl ethyl Ketones, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl lactate, propylene glycol, 3-methoxypropionic acid, 3-ethoxypropionic acid, diglyme, ethylcarbitol, Mention may be made of butyl carbitol, 3-methyl-3-methoxybutanol and 3-methyl-3-methoxybutyl acetate. As component (b), one single said component may be used or two or more of said components may be used in combination.

Generally, the content of component (b) employed in the total curable resin composition of the present invention is suitably determined in the range of 50 to 95% by weight depending on the ratio (concentration) of the total solids. When the content of component (b) is too small, the viscosity of the curable resin composition is too large and the rheological properties (its power index) tend to be small, so that the resulting curable resin composition is not suitable for application. When the content of component (b) is too large, components (a) and (c) are contained too little, and the resulting curable resin composition is not suitable for coating film production. The content is preferably in the range of 70 to 90% by weight, particularly preferably 75 to 85% by weight.

In the case of color filter preparation of the thick film as the applied film thickness after drying, in addition, component (b) preferably contains a solvent (b1) having a vapor pressure of at least 3 Torr (400 Pa) at room temperature (23 ° C.) at a weight of 200 to solids. 50% by weight or more of the solvent (b2) containing 3% or more, or a vapor pressure of 3 Torr (400 Pa) to 6 Torr (800 Pa) at room temperature (23 ° C) at room temperature (23 ° C) and a vapor pressure at room temperature (23 ° C). A solvent (b3) of 6 Torr (800 Pa) or more should be included in an amount of 10 to 40% by weight or more based on solids, and a solvent (b4) having a vapor pressure of less than 3 Torr at room temperature in an amount of 10 to 40% by weight based on solids. Since the curable resin composition is never easily dried in a general atmosphere, the tip of the slit die lip is never dried. Since the curable resin composition is easily dried completely when the curable resin composition is dried under reduced pressure after application, defects due to non-uniform drying can be solved.

The solvent (b1), (b2) or (b3) having a vapor pressure of 3 Torr or more includes, for example, the glycol ether described above. In addition, solvents (b4) having a vapor pressure of less than 3 Torr include the alkoxy esters described above.

As (b1) or (b2), for example, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether acetate, ethylene glycol diacetate, diethylene glycol mono-n-butyl ether Acetate and cyclohexanone are preferred. Propylene glycol monomethyl ether acetate is particularly preferred.

As (b1) or (b3), for example, alkyl alcohol ethers such as propylene glycol monomethyl ether and propylene glycol mono-n-butyl ether are preferred, and propylene glycol monomethyl ether is particularly preferred. In addition to alkyl alcohol ethers, for example, butyl acetate, ethyl propionate and propyl acetate are listed.

As the alkoxy ester as (b4), in addition, ethyl 3-ethoxypropionate is particularly preferred. In addition to the alkoxy esters, for example, diethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether, diethylene glycol diethyl ether and diethylene glycol mono Ethyl ethers are listed.

Curable resin composition of this invention is preferably used as a coating solution in color filter manufacture by apply | coating a coating solution on a transparent substrate. The use of curable resin compositions for color filters is illustrated and described below. In the case of using component (c1) (binder resin) alone, a suitable type of component (c1) should be appropriately selected in consideration of the formation of the intended pixel image, its features and preferred manufacturing methods. Component (c2) (monomer) is used to modify the curable resin composition to a color filter, after curing (particularly after photocuring), its physical-chemical characteristics, such as compatibility with component (b), curable resin composition on a substrate It is used in combination with component (c1) for the purpose of improving film formation from, adhesion to the substrate, development of the resulting coating film, and the like.

Specific examples of component (c1) include single monomers such as (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamide, maleic acid, (meth) acrylonitrile, styrene, vinyl acetate, vinylidene chloride and maleimide Homopolymers of, or copolymers comprising said monomers; Polyethylene oxide, polyvinyl pyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetyl cellulose, novolac resin, resol resin, polyvinyl phenol and polyvinyl butyral; And JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP Known polymer compounds described in the publication of -A-2003-233179 and the like.

According to the invention, the term “(meth) acrylic acid” further means both acrylic acid and methacrylic acid; The same applies to the (meth) acrylate and (meth) acryloyl groups. The term "(co) polymer" means both homopolymers and copolymers. According to the invention, the term "acrylic resin" further means a (co) polymer comprising a copolymer and a (meth) acrylic acid comprising a (meth) acrylic acid ester with a carboxyl group.

Among those presented as component (c1), polymer compounds free of nitrogen atoms are preferred. 5 to 90 moles of acrylic resin containing monomers containing carboxyl or phenolic hydroxyl groups in the side or main chain thereof (hereinafter abbreviated as component (c11)) and / or (A) epoxy groups. %, And (B) 10 to 95 mol% of another radical-polymerizable compound copolymerizable with component (A), and (C) 10 to 100 mol% of unsaturated monovalent of the epoxy group contained in the obtained copolymerization product. Particular preference is given to resins obtained by adding basic acid and adding polybasic acid anhydride (hereinafter simply referred to as component (c12)) to 10 to 100 mol% of the hydroxyl groups produced during addition of component (C). Do. When the acrylic resin having the functional group is used as component (c12), the color filter obtained can be developed in an alkaline solution.

Acrylic resins having a carboxyl group which can be developed in a very alkaline solution, in an acrylic resin comprising a monomer having a carboxyl group or a phenolic hydroxyl group as the component (c11) in the side chain or main chain, for example acrylic acid (co) polymer, styrene Resin produced by modifying maleic anhydride resin and novolak epoxy acrylate with anhydrous acid is preferred. Among these, the (co) polymer containing (meth) acrylic acid or the (co) polymer containing the (meth) acrylic acid ester with a carboxyl group are especially preferable. The acrylic resins are excellent in development and transparency, and can be combined with various monomers to produce copolymers having different characteristics, and are excellent in terms of easily adjustable manufacturing methods.

Acrylic resin is a (co) polymer containing the following monomer as a main component. To the monomer, for example, (meth) acrylic acid and acids (anhydrous) such as succinic acid (succinic anhydride), phthalic acid (phthalic anhydride) and maleic acid (maleic anhydride) are added to hydroxyalkyl (meth) acrylates. It includes a compound prepared by. The said compound is succinic acid [2- (meth) acryloyloxyethyl] ester, adipic acid (2-acryloyloxyethyl) ester, and phthalic acid [2- (meth) acryloyloxyethyl] ester, for example. Hexahydrophthalic acid [2- (meth) acryloyloxyethyl] ester, maleic acid [2- (meth) acryloyloxyethyl] ester, succinic acid [2- (meth) acryloyloxypropyl] ester, Dipic acid (2- (meth) acryloyloxypropyl) ester, hexahydrophthalic acid [2- (meth) acryloyloxypropyl] ester, phthalic acid [2- (meth) acryloyloxypropyl] ester, maleic acid [2- (meth) acryloyloxypropyl] ester, succinic acid [2- (meth) acryloyloxybutyl] ester, adipic acid [2- (meth) acryloyloxybutyl] ester, hexahydrophthalic acid [ 2- (meth) acryloyloxybutyl] ester, phthalic acid [2- (meth) acryloyloxybutyl] ester and maleic acid [2- (meth) acrylo Oxybutylene] it includes ester.

Monomers polymerizable with the monomers described above include, for example, styrene-based monomers such as styrene, α-methylstyrene and vinyltoluene; Carboxylic acids containing unsaturated groups such as cinnamic acid, maleic acid, fumaric acid, maleic anhydride and itaconic acid; Esters of (meth) acrylic acid, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate and methoxyphenyl (meth) acrylate; Compounds prepared by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone to (meth) acrylic acid; Acrylonitrile such as acrylonitrile, and methacrylonitrile; Acrylamides such as (meth) acrylamide, N-methylol acrylamide, N, N-dimethylacrylamide, N-methacryloyl morpholine, N, N-dimethylaminoethyl (meth) acrylate and N, N Dimethylaminoethyl acrylamide; Vinylic acids such as vinyl acetate, vinyl versatate, vinyl propionate, vinyl cinnamate and vinyl pivalate.

As the preferred component (c11) for improving the strength of the film applied on the substrate, acrylic resins prepared by copolymerizing one or more of the following groups of the monomer (c111) and one or more of the following groups of the monomer (c112) are listed. Groups of the monomer (c111) include, for example, styrene, α-methylstyrene, benzyl (meth) acrylate, and monomers having a phenyl group such as hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, Hydroxyphenyl (meth) acrylamide, and hydroxyphenyl (meth) acrylsulfonamide. Groups of the monomer (c112) include, for example, (meth) acrylic acid esters having (meth) acrylic acid or carboxyl groups, such as succinic acid [2- (meth) acryloyloxyethyl] ester, adipic acid (2-acrylo) Yloxyethyl) ester, phthalic acid [2- (meth) acryloyloxyethyl] ester, hexahydrophthalic acid [2- (meth) acryloyloxyethyl] ester and maleic acid [2- (meth) acryloyloxy Ethyl] esters. The copolymerization ratio of the copolymers is preferably 10 to 98 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and (c112) monomer groups of (c112) monomer groups. 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%.

The acrylic resin as component (c11) preferably has an ethylenic double bond in the side chain. When acrylic resin having an ethylenic double bond in the side chain is used as component (c11), the photocuring ability of the curable resin composition for color filters according to the present invention can be improved, so that the dividing power and substrate adhesion of the color filter obtained This can be further improved.

As a method of introducing an ethylenic double bond into the side chain of the component (c11), for example, the method described in JP-B-50-34443 and JP-B-50-34444, that is, (1) the carboxyl group and the glyc of acrylic resin And a method including reacting a compound having both a cydyl group or an epoxycyclohexyl group and a (meth) acryloyl group, and (2) a reaction of a hydroxyl group and an acrylic chloride of the acrylic resin.

More specifically, the acrylic resin having an ethylenic double bond group in the side chain may be selected from the group consisting of glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, By reaction with compounds such as tonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) acrylic chloride and (meth) allyl chloride Can be obtained. Particularly preferred among these are products produced by reacting an acrylic resin having a carboxyl group or a hydroxyl group with an alicyclic epoxy compound such as (3,4-epoxycyclohexyl) methyl (meth) acrylate.

In order to introduce the ethylenic double bond into the acrylic resin having a carboxyl group or hydroxyl group in advance as described above, the compound having an ethylenic double bond is added to 2 to 50 mol% of the carboxyl group or the hydroxyl group of the acrylic resin, preferably Preference is given to a method comprising combining with 5 to 40 mole%. In addition, the content of the carboxyl group is preferably in the range of 5 to 200 as the acid value. When the acid value is less than 5, the obtained acrylic resin is not preferable because it is insoluble in the alkaline developing solution. If the acid value exceeds 200, the development sensitivity is sometimes reduced, which is undesirable.

The acrylic resin has a weight average molecular weight (Mw) measured by GPC in the range of 1,000 to 100,000. When the weight average molecular weight is less than 1,000, it is very difficult to obtain a uniform coating film, which is not preferable. If the weight average molecular weight exceeds 100,000, the development characteristics become poor, and the rheological properties (square power index) decrease, which is undesirable.

(A) 5 to 90 mol% of (meth) acrylate having an epoxy group and 10 to 95 mol% of another radical-polymerizable compound copolymerizable with component (A), and (C) the copolymerization product obtained Obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of the epoxy groups in the (D), and adding anhydrous polybasic acid as the component (c12) to 10 to 100 mol% of the hydroxyl groups generated during addition of the component (C). Resins are described below.

Examples of the epoxy group-containing (meth) acrylate as the component (A) include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and (3,4-epoxycyclohexyl) methyl (meth ) Acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether. Specifically, glycidyl (meth) acrylate is preferred. As (A), the said component can be used individually or in combination of 2 or more of the above.

Copolymerization ratio of epoxy group-containing (meth) acrylate as (A) [Copolymerization ratio in copolymerization production by copolymerization of components (A) and (B); Simply referred to as "copolymerization ratio" is 5 to 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, as described above. If the ratio is too large, the component (B) is less, so that heat resistance and strength may sometimes deteriorate. If the ratio is too small, the added copolymerizable component and the alkali soluble component are insufficient, which is undesirable.

On the other hand, the copolymerization ratio of another radical-polymerizable compound as component (B) copolymerizable with component (A) is 10 to 95 mol%, preferably 20 to 80 mol%, more preferably 30 to 30 as described above. 70 mol%. If the ratio is too large, component (A) is less, so that the added copolymerizable component and the alkali soluble component are insufficient. If the ratio is too small, heat resistance and strength deteriorate, which is not preferable.

As another radical-polymerizable compound as component (B) copolymerizable with component (A), one or two or more types of mono (meth) acrylates, preferably represented by the following general formula (1), are used.

(In formula (1), R ⁴ to R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl; R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or 1 carbon atom. An alkyl group such as a methyl group, an ethyl group or a propyl group, or R ¹⁰ and R ¹¹ may be bonded together to form a ring; the ring formed by the bonding of R ¹⁰ and R ¹¹ is preferably an aliphatic ring. , Saturated or unsaturated, preferably 5 or 6 carbon atoms).

In the formula (1), a mono (meth) acrylate having a structure represented by the following formula (2), (3) or (4) is preferable. By introducing the structure into the binder resin, heat resistance and strength can preferably be increased. Needless to say, the mono (meth) acrylates may be used alone or in combination of two or more types thereof.

As the mono (meth) acrylate having the structure represented by the formula (1), various known compounds can be used. In particular, mono (meth) acrylate represented by following General formula (5) is preferable.

(In formula (5), R <^12> represents a hydrogen atom or a methyl group; R <^13> represents general formula (1).).

The content of the mono (meth) acrylate having the structure of formula (1) in the copolymerizable monomer is generally 5 to 90 mol%, preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

Specific examples of radically polymerizable compounds other than those described above include, but are not limited to, styrene and ester derivatives of α-, o-, m- and p-alkyl, nitro, cyano, amide, styrene;

Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene;

(Meth) acrylate esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec- Butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dish Clohexyl (meth) acrylate, isoboroyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, Naphthyl (meth) ah Relate, anthracenyl (meth) acrylate, anthraniloyl (meth) acrylate, piperonyl (meth) acrylate, salicylic (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) Acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, (meth) acrylic acid-1, 1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, triphenylmethyl (meth) Acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, (meth) acrylic acid-2-hydroxyethyl and (meth) acrylic acid-2-hydroxypropyl;

(Meth) acrylate amides such as (meth) acrylate amide, (meth) acrylate N, N-dimethylamide, (meth) acrylate N, N-diethylamide, (meth) acrylate N, N-di Propylamide, (meth) acrylate N, N-di-iso-propylamide and (meth) acrylate anthracenylamide;

Vinyl compounds such as (meth) acrylate anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinyl pyridine and vinyl acetate ;

Unsaturated dicarboxylate diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate and diethyl itaconate;

Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide;

And N- (meth) acryloylphthalimide.

In order to provide better heat resistance and higher rigidity, at least one selected from styrene, benzyl (meth) acrylate and monomaleimide is effectively used as component (B).

In this case, the at least one copolymerization ratio selected from styrene, benzyl (meth) acrylate and monomaleimide is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.

Known solution polymerization methods are applicable to the copolymerization reaction of the components (A) and (B). Any solvent that is inert to radical polymerization can be used without limitation. General organic solvents can be used.

Specific examples thereof include ethyl acetate, isopropyl acetate, cellosolve acetate and ethylene glycol monoalkyl ether acetates such as ethylene glycol cellosolve acetate;

Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate;

Propylene glycol monoalkyl ether acetates;

Acetate esters such as dipropylene glycol monoalkyl ether acetates;

Ethylene glycol dialkyl ethers;

Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol and butyl carbitol;

Triethylene glycol dialkyl ether;

Propylene glycol dialkyl ethers;

Dipropylene glycol dialkyl ethers;

Ethers such as 1,4-dioxane and tetrahydrofuran;

Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone;

Hydrocarbons such as benzene, toluene, xylene, octane and decane; Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; Lactate esters such as methyl lactate, ethyl lactate and butyl lactate;

And dimethylformamide and N-methylpyrrolidone.

The solvents may be used alone or in combination of two or more thereof. The solvent is used in an amount of 30 to 1,000 parts by weight, preferably 50 to 800 parts by weight, per 100 parts by weight of the copolymer obtained. If the amount of solvent used is outside the above range, control of the molecular weight of the copolymer can be very difficult.

As the radical polymerization initiator for use in the copolymerization reaction, any radical polymerization initiator capable of initiating radical polymerization can be used without any limitation. Common organic peroxide catalysts and azo compounds can be used as the radical polymerization initiator.

Organic peroxide catalysts include, for example, known catalysts classified as known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxy esters and peroxy dicarbonates.

Specific examples of the radical polymerization initiator include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butyl peroxy-2 Ethyl hexanoate, t-hexyl peroxy-2-ethyl hexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2, 5-bis (t-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butylhydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) Peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3, 5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, azobisisobutyronitrile and azobiscar Bonamides are included. Depending on the polymerization temperature, one or two or more radical polymerization initiators with suitable half-lives can be selected and used.

The radical polymerization initiator is used in an amount of 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the monomer for copolymerization reaction, i.e., components (A) and (B).

The copolymerization reaction involves dissolving the monomer and radical polymerization initiator for use in the copolymerization reaction in a solvent, raising the temperature under stirring or adding a radical polymerization initiator to the monomer, raising the temperature of the obtained mixture and stirring the mixture under stirring. It can be carried out by dropwise addition to the solvent. In addition, the copolymerization reaction may be performed by adding a radical polymerization initiator to the solvent, raising the temperature of the obtained mixture, and then dropwise adding the monomer to the mixture. The reaction conditions can be freely modified depending on the intended molecular weight.

The component (C) added to the epoxy group contained in the copolymer of component (A) and (B) is unsaturated monovalent basic acid. As component (C), known ones can be used. For example, unsaturated carboxylic acids with ethylenically unsaturated double bonds can be enumerated, specifically monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p- Vinyl benzoic acid, (meth) acrylic acid substituted at the α position with haloalkyl, alkoxyl, halogen, nitro and cyano. Specifically, acrylic acid and / or methacrylic acid are preferable. The component (C) may be used alone or in combination of two or more of these types in a mixture.

Component (C) is 10 to 100 mol%, preferably 30 to 100 mol%, more preferably 50 to 100 mol of the epoxy groups contained in the copolymer obtained through the copolymerization reaction of the components (A) and (B). Is added in%. If the proportion of component (C) to be added is too small, for example, side effects of residual epoxy groups on stability over time may be a concern.

As the addition method of component (C) to the copolymer of component (A) and (C), a well-known method can be used.

As the polybasic acid anhydride (D) to be added to the hydroxyl group produced through the addition of component (C) to the copolymer of components (A) and (B), known ones can be used, for example bibasic free Hydroxyl acids such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and chloric anhydride; And polybasic anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride and biphenyltetracarboxylic anhydride. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferred.

Component (D) can be used alone or in combination of two or more of these types in a mixture. By adding the above components, the binder resin used according to the present invention can be made soluble in alkali.

Component (D) can be added to 10 to 100 mol%, preferably 20 to 90 mol%, more preferably 30 to 80 mol% of the hydroxyl groups produced through the addition of component (C). If the ratio is too large, the residual film ratio during development may sometimes be reduced. If the ratio is too small, the solubility is insufficient.

As a method of adding component (D) to the hydroxyl group produced through the addition of component (C) to the copolymer of components (A) and (B), known methods can be used.

In order to further improve the photosensitivity according to the invention, in addition, a glycidyl (meth) acrylate or glycidyl ether compound having a polymerizable unsaturated group may be added to a part of the carboxyl group formed after the addition of the polybasic anhydride (D). Can be. In order to improve the developing characteristics, a glycidyl ether compound without a polymerizable unsaturated group can be added to a part of the carboxyl group formed after addition of the polybasic acid anhydride (D). Otherwise both of these may be added. Specific examples of glycidyl ether compounds without a polymerizable unsaturated group include glycidyl ether compounds having a phenyl group and an alkyl group (manufactured by Nagase Chemtex Co., Ltd .; trade names Denacol EX-111, Denacol EX-121, Denacol EX-141 , Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192).

The structure of such resins is described, for example, in the publications of JP-A-8-297366 and JP-A-2001-89533 and are known.

The weight average molecular weight (Mw) measured by GPC of the said resin with component (c12) in a polystyrene base material becomes like this. Preferably it is 3,000-100,000, Especially preferably, it is 5,000-50,000. If the molecular weight is less than 3,000, heat resistance and film strength are poor. When the molecular weight exceeds 100,000, the solubility in the developing solution is not satisfactory, which is not preferable. In addition, the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 2.0 to 5.0.

Component (c1) may be used alone or in combination of two or more of these types.

The proportion of component (c1) in the total solids in the curable resin composition of the present invention is preferably selected in the range of 10 to 80% by weight, in particular 20 to 70% by weight.

For the purpose of improving the affinity between components (a) and (c1) at their surfaces, silane coupling agents can be blended. The proportion of the silane coupling agent is preferably selected in the range of 1 to 10% by weight of the total solids.

Component (c2) can be any of the above components, including low molecular weight compounds, which are polymerizable without any limitation. Likewise, polyfunctional monomers with functional groups are preferred. More preferred are compounds having at least one ethylenic double bond and addition polymerizable (hereinafter referred to as "ethylene-based compound"). In addition, the monomer may have an acid group.

The term ethylene-based compound is a compound having an ethylenic double bond which is further polymerized and cured by the action of the following component (d) (photopolymerization initiator series) under active light irradiation of the coloring composition for color filters according to the present invention. As used herein, the term "monomer" according to the present invention means a concept contrary to the so-called polymeric material, and conceptually includes "dimer", "trimer" and "oligomer" in addition to the "monomer" in consultation.

Examples of the ethylenic compound as the component (c2) include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, aromatic polyhydroxy compounds and unsaturated carboxylic acids. Esters of acids, unsaturated carboxylic acids and polyhydric carboxylic acids such as esters produced by esterification of aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and polyisocyanate compounds with (meth) acryloyl-containing Ethylene-based compounds having a urethane skeleton, which are prepared by the reaction of hydroxy compounds, are included.

Unsaturated carboxylic acids include, for example, (meth) acrylic acid, itaconic acid, crotonic acid and maleic acid.

Examples of esters of alicyclic polyhydroxy compounds and unsaturated carboxylic acids include, for example, acrylate esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane triacrylate, Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and glycerol acrylate do. In addition, these esters include, for example, methacrylate esters prepared by modification of the acrylate portion of the acrylate portion to the methacrylate portion, the acrylate portion of the acrylate being prepared by modifying the acrylate portion with the itaconate portion. Itaconate ester, crotonate ester prepared by modification of the acrylate portion of the acrylate to the crotonate portion, or maleate ester prepared by modification of the acrylate portion of the acrylate portion to the maleate portion Included.

Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include, for example, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate and pyrogallol triacrylate. do.

The esters produced by esterification of unsaturated carboxylic acids with polyhydric carboxylic acids and polyhydric hydroxy compounds are not essentially homogeneous, but may be mixtures. Typical examples thereof include, for example, condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol and acrylic acid, adipic acid, butanediol And condensates of glycerin.

Ethylene-based compounds having a urethane skeleton, prepared by the reaction of a polyisocyanate compound with a (meth) acryloyl-containing hydroxy compound, include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; Alicyclic diisocyanates such as cyclohexane diisocyanate, and isophorone diisocyanate; And aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate and (meth) acryloyl group-containing hydroxy compounds such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydrate Reaction products of hydroxy (1,1,1-triacryloyloxymethyl) propane and 3-hydroxy (1,1,1-trimethacryloyloxymethyl) propane.

In addition, ethylene-based compounds for use according to the invention include, for example, acrylamides such as ethylene bisacrylamide; Allyl esters such as diallyl phthalate; And vinyl group-containing compounds such as divinyl phthalate.

According to the invention, the monomer may be a polyfunctional monomer with acid groups such as carboxyl groups, sulfonate groups and phosphate groups. Accordingly, as described above, an ethylene compound having a non-reactive carboxyl group can be used as it is as a mixture. If desired, acid groups can be introduced there by reaction of the hydroxyl groups of the ethylene-based compounds with non-aromatic carboxylic anhydrides. In this case, specific examples of the non-aromatic carboxylic anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride and maleic anhydride.

According to the present invention, the monomer having an acid value is preferably an ester of an alicyclic polyhydroxy compound having an unsaturated carboxylic acid, which reacts to the reaction of non-reactive hydroxyl groups and non-aromatic carboxylic anhydrides in the aliphatic polyhydroxy compound. It is a polyfunctional monomer having an acid group introduced by. Especially preferably, the cycloaliphatic polyhydroxy compound in the ester is pentaerythritol and / or dipentaerythritol.

The monomers may be used alone or in combination of two or more of these types, since it is very difficult to use a compound alone in terms of preparation. If desired, in addition, a polyfunctional monomer without any acid group can be used simultaneously with the polyfunctional monomer with an acid group.

The acid value of the polyfunctional monomer with acid group is preferably 0.1 to 40 mg-KOH / g, particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too small, development and dissolution characteristics deteriorate. If the acid value thereof is too large, the multifunctional monomer causes very troublesome production and handling, leading to deterioration of the photopolymerization property, and deterioration of the curing ability such as surface smoothness of the pixel. When using two or more types of multifunctional monomers having different acid groups, or when using a multifunctional monomer without an acid group, the acid groups as the overall multifunctional monomer should be adjusted essentially within the ranges described above.

According to the invention, more preferred polyfunctional monomers having acid groups are Toa Gosei Co., Ltd. A mixture commercially available as TO 1382 produced by the company, namely, a mixture containing succinate ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate as main components. Multifunctional monomers can be used in combination with other multifunctional monomers.

The proportion of component (c2) is preferably selected in the range of 10 to 80% by weight of the total solids in the curable resin composition of the present invention. Specifically, the ratio is particularly preferably selected in the range of 20 to 70% by weight.

When the curable resin composition of the present invention comprises an ethylene-based compound as component (c2), component (d) having a function of causing decomposition or dehydrogenation reaction to provide polymerization-active radicals by direct light absorption or optical strengthening (d) ( Photoinitiator series) must be mix | blended with curable resin composition. According to the invention, additionally, the term “component (d): photopolymerization initiator series” refers to additives of photopolymerization initiators (abbreviated below as component (d1)), such as accelerators (abbreviated below as component (d2)) and By admixture with an enhancing dye (abbreviated below as component (d3)).

Component (d) means a compound having a sensitivity to ultraviolet to visible light since the image is exposed to light through a pattern mask throughout the black photopolymerizable layer in the production of the black photopolymerizable layer from the curable resin composition. For image exposure, an exposure light source, preferably corresponding to the compound, is used. The red, green, and blue pixel image patterns are formed between black matrix patterns on the red, green, and blue individual photopolymerizable layers by exposure through separate pattern masks or other methods, thereby providing sensitivity to ultraviolet to visible light. The compound should be used as component (d) as in the black matrix pattern. Specifically, compounds having spectrometer sensitivity to wavelengths of 450 nm or less, in particular 400 nm or less, are used.

As component (d1) which comprises component (d), For example, Metallocene compound containing the titanocene compound as described in the publication of JP-A-59-152396 and JP-A-61-151197; Hexaarylbiimidazole derivatives as described in JP-A-10-39503; Radical activators such as N-aryl-α-amino acids such as halomethyl-s-triazine derivatives and N-phenylglycine, N-aryl-α-amino acids and N-aryl-α-amino acid esters; α-aminoalkyl phenone-based compounds; And oxime ester-based initiators as described in the publication of JP-A-2000-80068.

Specific examples of component (d1) applicable in accordance with the invention are listed below:

Halomethylated triazine derivatives such as

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine,

2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine,

2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, and

2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine,

Halomethylated oxadiazole derivatives such as

2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole,

2-trichloromethyl-5- [β- (2'-benzofuryl) vinyl] -1,3,4-oxadiazole,

2-trichloromethyl-5- [β- (2 '-(6 "-benzofuryl) vinyl) -1,3,4-oxadiazole, and

2-trichloromethyl-5-furyl-1,3,4-oxadiazole;

Imidazole derivatives, such as

2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer,

2- (2'-chlorophenyl) -4,5-bis (3'-methoxydiphenyl) imidazole dimer,

2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer,

2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, and

(4'-methoxyphenyl) -4,5-diphenylimidazole dimer;

Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether;

Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone;

Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxybenzophenone;

Acetophenone derivatives such as

2,2-dimethoxy-2-phenylacetophenone,

2,2-diethoxy-2-phenylacetophenone,

1-hydroxycyclohexylphenyl ketone,

α-hydroxy-2-methylphenyl propanone,

1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone,

1-hydroxy-1- (p-dodecylphenyl) ketone,

2-methyl- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone, and

1,1,1-trichloromethyl- (p-butylphenyl) ketone;

Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diiso Propyl thioxanthone;

Benzoate ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and p- (p-methoxyphenyl) acridine; And phenazine derivatives such as 9,10-dimethylbenzphenazine; Antron derivatives such as benzanthrone;

Titanocene derivatives, such as

Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-di-phenyl,

Di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl,

Di-cyclopentadienyl-Ti-bis-2,3,4,5,6-tetrafluorophenyl-1-yl,

Di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl,

Di-cyclopentadienyl-Ti-bis-2,6-di-fluorophen-1-yl,

Di-cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl,

Di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl,

Di-methylcyclopentadienyl-Ti-bis-2,6-di-fluorophen-1-yl, and

Di-cyclopentadienyl-Ti-bis-2,6-di-fluoro-3- (phyl-1-yl) -phen-1-yl;

α-aminoalkylphenone-based compounds such as

2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one,

2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,

2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one,

4-dimethylaminoethylbenzoate,

4-dimethylaminoisoamylbenzoate,

4-diethylaminoacetophenone,

4-dimethylaminopropiophenone,

2-ethylhexyl-1,4-dimethylaminobenzoate,

2,5-bis (4-dimethylaminobenzyl) cyclohexanone,

7-diethylamino-3- (4-diethylaminobenzoyl) coumarin,

And 4- (diethylamino) chalcone; And

Oxime ester-based compounds such as 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl- and 1- (o-acetyloxime).

Component (d2) (accelerator) constituting component (d) is, for example, an N, N-dialkyl aminobenzoate alkyl ester such as ethyl N, N-dimethylaminobenzoate, a mercapto with a heterocyclic ring Compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzoimidazole and aliphatic multifunctional mercapto compounds. Compounds (d1) and (d2) can be used individually or in combination of two or more types thereof.

Specific photopolymerization initiator-based compounds include, for example, dialkyl acetophenone series described in "Fine Chemical" (1991, published March 1, Vol. 20, No. 4), pages 16 to 26. , Benzoin and thioxanthone derivatives; Hexaarylbiimidazole series and S-trihalomethyltriazine series described in, for example, the publications of JP-A-58-403023 and JP-B-45-37377; Compounded series of ethylenically saturated double bond-comprising compounds with amino or urethane groups, polymerized by addition method with titanocene and xanthene dyes as described in the publications of JP-A-4-221958 and JP-A-4-219756 Possible ones are included.

If the ratio of component (d) is too small, the sensitivity to exposure can sometimes be reduced. In contrast, if the ratio is too large, the solubility of the unexposed portions of the developing solution may be reduced to provide poor development. Accordingly, the proportion of component (d) is preferably selected in the range of 0.1 to 30% by weight of the total solids in the curable resin composition of the present invention. Specifically, the ratio is preferably in the range of 0.5 to 20% by weight, more preferably in the range of 0.7 to 10% by weight.

If necessary, component (d3) (sensitizing dye) corresponding to the wavelength of the image exposure can be blended into component (d) for the purpose of improving sensitivity. As said component (d3), Xanthene dye as described in the publication of JP-A-4-221958 and JP-A-4-219756; Coumarin dyes with heterocyclic rings described in the publications of JP-A-3-239703 and JP-A-5-289335; 3-ketocoumarin compounds described in the publications of JP-A-3-239703 and JP-A-5-289335; Mention may be made of the pyrromethene dyes described in the publication of JP-A-6-19240; Additionally JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP -A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240 and JP-A Dyes having the dialkylamino benzene backbone described in the publication of -4-288818 are included.

Among the above components (d3), an amino group-containing sensitizing dye is preferable, and a compound having both an amino group and a phenyl group in one molecule is more preferable. Particularly preferred are, for example, benzophenone-based compounds such as 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-amino Benzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone and 3,4-diaminobenzophenone; And p-dialkylaminophenyl group-containing compounds such as 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethyl Aminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2, 5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, ( p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine and (diethylaminophenyl) pyrimidine. Of these, 4,4'-dialkylaminobenzophenone is most preferred.

The proportion of component (d3) is preferably selected in the range of 0 to 20% by weight of the total solids of the curable resin composition of the present invention. The ratio is more preferably 0.2 to 15% by weight, even more preferably 0.5 to 10% by weight.

As described above, if necessary, components (e) and the like [components except components (a) to (d)] can be blended into the curable resin composition of the present invention. As component (e) and the like, for example, the following agents may be added: thermal polymerization inhibitor [hereinafter abbreviated as component (e1)], plasticizer [hereinafter abbreviated as component (e2)], dispersant [ Then abbreviated as component (e3)], dispersing aid [hereinafter abbreviated as component (e4)], surfactant [hereinafter abbreviated as component (e5)], storage stabilizer, surface protectant, leveling agent, coating aid , Adhesion improving agent, coating improver, developing agent and silane coupling agent.

Component (e1) includes, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol and β-naphthol. The compounding quantity of the said component (e1), Preferably it is selected in the range of 0 to 3 weight% of the total solid of curable resin composition.

Component (e2) includes, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate and triacetyl glycerine. The compounding quantity of the said component (e2), Preferably it is selected in the range of 0 to 10 weight% of the total solid of curable resin composition.

As component (e3), for example, acrylic acid and styrene, acrylic ester and methacrylic acid, acrylic acid and methacrylate ester, and copolymers of styrene and maleic acid, amide based compounds, urethane based compounds, lactam based compounds and vars Barbitulic acid family compounds can be used as the polymer dispersant; Resin type dispersants such as polyamide based compounds and polyurethane based compounds (Disper Big 130, Disper Big 161, Disper Big 182 and Disper Big 170 (manufactured by Big Chemie), and EFKA 46 and EFKA 47 (manufactured by EFKA)) are commercially available. Available) can be used. Specifically, a dispersant having a nitrogen-containing functional group is preferable. Acrylic dispersants, urethane-based dispersants and graft copolymer dispersants are more preferred.

As the acrylic dispersant, A-B block copolymers and / or B-A-B block copolymers are preferred, wherein block A has a quaternary ammonium base in the side chain and block B does not have such quaternary ammonium base.

A block forming the block copolymer of an acrylic dispersing agent is a quaternary ammonium base, preferably -N ⁺ R _1a R _2a R _3a and Y ^- (wherein, R _1a, R _2a and R _3a is independently hydrogen or a substituted or Cyclic or linear hydrocarbon groups which may not be substituted; otherwise, at least two of R _1a , R _2a and R _3a combine with each other to form a cyclic structure; Y ⁻ represents a counterion. The quaternary ammonium base may bind directly to the main chain, but may bind to the main chain via a divalent linking group.

-N ⁺ R _1a R _2a R _3a and Y ^- is at R _1a, R _2a, and an annular structure which is of two or more of R _3a are bonded to each other to form, for example, 5- to 7-membered nitrogen recalled including red single suit. Condensed rings prepared by condensing a ring or two or more such rings with one another. The nitrogen-containing heterocyclic ring may preferably be non-aromatic, more preferably saturated ring. Specifically, the cyclic structure includes, for example, the following structure:

( _Wherein R represents any group of R _1a , R _2a and R _3a ).

The cyclic structure may additionally include a substituent.

-N ⁺ R _1a R _2a R _3a and Y ^- in R _1a, R _2a and R _3a is more preferably an alkyl group having 1-3 carbon atoms that may have a substituent or no, you may have a substituent or may have no Phenyl group, or benzyl group, which may or may not have a substituent.

As the A block, a compound having a partial structure represented by the following formula (6) is preferable.

(In formula (6), R _1a , R _2a and R _3a each independently represent a hydrogen atom or a cyclic or linear hydrocarbon group which may or may not be substituted; otherwise, 2 of R _1a , R _2a and R _3a Two or more combine with each other to form a cyclic structure; R _4a represents a hydrogen atom or a methyl group; X represents a divalent bond group and Y ⁻ represents a pair ion.

In the formula (6), in the X as a divalent coupler, for example, an aryl group, a -CONH-R _5a alkylene group, a C 1 -C _{10 -, -COO-R 6a -} ( wherein, R _5a and R _6a are directly A bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (-R _7a -OR _8a- : R _7a and R _8a each independently represent an alkylene group). Preferably, X is -COO-R _6a - represents a.

Paired anion Y ^- include, for example, Cl ^- include ^{-, Br -, I -,} ClO 4 -, BF 4 -, CH 3 COO - , and PF _6.

Two or more types of partial structures comprising the quaternary ammonium bases described above may be included in one A block. In such cases, partial structures comprising two or more types of quaternary ammonium bases may be included in the A block in any manner of random copolymerization or block copolymerization. In addition, partial structures containing no quaternary ammonium base at all may be included in the A block. Examples of such partial structures include partial structures derived from the (meth) acrylate ester series monomers described below.

The content of the partial structure containing no quaternary ammonium base in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, the partial structure containing no quaternary ammonium base at all is never included in the A block.

On the other hand, B blocks constituting the block copolymer of the dispersant include, for example, styrene-based monomers such as styrene and α-methylstyrene; (Meth) acrylate ester-based monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth ) Acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, and N, N Dimethylaminoethyl (meth) acrylate; (Meth) acrylate salt-based monomers such as (meth) acrylic chloride; (Meth) acrylamide-based monomers such as (meth) acrylamide, N-methylol acrylamide, N, N-dimethylacrylamide, and N, N-dimethylaminoethyl acrylamide; Vinyl acetate; Acrylonitrile; Allylglycidyl ether, crotonate glycidyl ether; And polymer backbones prepared by copolymerization of a copolymer comprising N-methacryloyl morpholine.

The B block is particularly preferably a partial structure derived from a (meth) acrylate ester-based monomer as represented by the following general formula (7):

In formula (7), R ^9a represents a hydrogen atom or a methyl group; R ^10a has a cyclic or linear alkyl group which may or may not have a substituent, an aryl group or a substituent which may or may not have a substituent, or Or an aralkyl group which may not have).

Two or more types of partial structures derived from (meth) acrylate ester-based monomers may be included in one B block. Needless to say, the B block may include substructures other than the substructures described above. When two or more types of partial structures derived from said monomers are present in a B block that does not contain any quaternary ammonium base at all, each partial structure may be included in the B block in any manner of random copolymerization or block copolymerization. Can be. If a partial structure other than the partial structure derived from the (meth) acrylate ester-based monomer is present in the B block, the content of the partial structure except for the partial structure derived from the (meth) acrylate ester-based monomer in the B block is It is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, no such substructures other than those derived from (meth) acrylate ester-based monomers are included in the B block at all.

Acrylic dispersants used according to the invention are of the A-B block or B-A-B block copolymer type, which are polymer compounds comprising the A blocks and the B blocks. The block copolymer can be prepared, for example, by a living polymerization method described below.

The living polymerization method includes an anion living polymerization method, a cation living polymerization method and a radical living polymerization method. Anion living polymerization proceeds, for example by the following reaction formula, and a polymerization active species is an anion.

The radical living polymerization method is shown, for example in the following formula, and the polymerization active species is a radical.

For the synthetic preparation of the acrylic dispersant, JP-A-9-62002; P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984); B. C. Anderson, G. D. Andrews et al., Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, et al., Polym. J. 17, 977 (1985), 18, 1037 (1986); Koichi Migite, Kouichi Hatada, Polymer Processing (Kobunshi Kako), 36, 366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Articles (Kobunshi ronbun-shu), 46, 189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Sci., 109 m, 4737 (1987); Takuzo Aita, Shouhei Inoue, Organic Synthetic Chemistry (Yuki Gosei Kagaku), 43, 300 (1985); D. Y. Sogoh, W. R. Hertler et al., Macromolecules, 20, 1473 (1987); The known method described in the above can be used.

Even if the dispersant for use in the present invention is an AB block copolymer or a BAB block copolymer, preferably, the ratio (weight ratio) of the A block and the B block constituting the copolymer is generally 1/99 or more, specifically 5/95 or more to generally 80/20 or less, specifically 60/40 or less. Outside of this range, good heat resistance and dispersibility may sometimes not be provided.

In general, the amount of quaternary ammonium base in 1 g of A-B block copolymer or B-A-B block copolymer according to the invention is preferably from 0.1 to 10 mmol. Outside of this range, good heat resistance and dispersibility may sometimes not be provided.

In general, the block copolymer may include amino groups produced during the preparation process. The amine number is about 1 to 100 mg / KOH / g. Herein, the amine number is a value obtained by titrating a basic amino group with an acid to neutral, and represents an acid value provided in mg in KOH.

In addition, the acid value of the block copolymer generally depends on the presence or absence of an acid group as the origin of the acid value, but is preferably low. Generally, the acid value is 100 mg-KOH / g or less. The molecular weight in the weight average molecular weight (Mw) is generally at least 1,000 and no more than 100,000 on polystyrene as measured by GPC. If the molecular weight of the block copolymer is too small, the stability of the dispersion decreases. If its molecular weight is too large, the partitioning power tends to decrease.

According to the present invention, urethane series- and / or acrylic dispersants having the same structure as described above that are commercially available and may be applicable as dispersants.

As a urethane-based dispersant, for example, (1) a polyisocyanate compound, (2) a compound having one or two or more hydroxyl groups in one molecule, and (3) one molecule having an active hydrogen and a tertiary amino group Particular preference is given to dispersion resins obtained by reacting the compounds together.

(1) polyisocyanate compound

Examples of the polyisocyanate compound include aromatic diisocyanates such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene- 1,5-diisocyanate, and tolidine diisocyanate; Aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate; Alicyclic diisocyanates such as isophorone diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), and ω, ω'-diisocyanate dimethylcyclohexane; Aliphatic diisocyanates with aromatic rings such as xylylene diisocyanate, and α, α, α ', α'-tetramethylxylylene diisocyanate; Triisocyanates such as lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocy Anate, tris (isocyanate phenyl methane), and tris (isocyanate phenyl) thiophosphate; And trimers thereof, H ₂ O adducts thereof and polyol adducts thereof. As polyisocyanate, trimers of organic diisocyanate are preferable. Most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate. These may be used alone or in combination of two or more types thereof in a mixture.

In the process for the preparation of trimers of isocyanates, isocyanate groups in polyisocyanates are partially prepared as trimers, using catalysts suitable for trimerization, for example tertiary amines, phosphines, alkoxides, metal oxides and carboxylate salts, Addition of an inhibitor of the catalyst terminates the trimerization and solvent extraction or thin film evaporation removes the unreacted polyisocyanate groups to obtain the intended isocyanate group-containing polyisocyanate.

(2) compounds having one or more hydroxyl groups in one molecule

Compounds having one or two or more hydroxyl groups in one molecule include, for example, polyether glycols, polyester glycols, polycarbonate glycols and polyolefin glycols, compounds having alkoxyl groups having 1 to 25 carbon atoms. Compounds prepared by alkoxylation of hydroxyl groups at one single terminus, and mixtures of two or more types thereof.

Polyether glycols include polyether diols, polyether ester diols and mixtures of two or more types thereof. Polyether diols include alkylene oxides such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and two of these Mixtures of the above types are included. The polyether ester diols can be reacted with, for example, ether group-containing diols or mixtures thereof with another glycol or anhydride thereof with dicarboxylic acids or with polyester glycols and alkylene oxides such as poly ( Included are those obtained by reacting polyoxytetramethylene) adipate. Polyether glycols are most preferred as polyethylene ethers, polypropylene glycols, polyoxytetramethylene glycols or compounds prepared by alkoxylating hydroxyl groups at one single end of a compound having an alkoxyl group having 1 to 25 carbon atoms.

Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycols (aliphatic glycols such as ethylene glycol, diethylene diglycol, tri Ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butane diol, 1,3-butane diol, 1,4-butane diol, 2,3-butane diol, 3-methyl-1,5- Pentane diol, neotyl glycol, 2-methyl-1,3-propane diol, 2-methyl-2-propyl-1,3-propane diol, 2-butyl-2-ethyl-1,3-propane diol, 1, 5-pentane diol, 1,6-hexane diol, 2-methyl-2,4-pentane diol, 2,2,4-trimethyl-1,3-pentane diol, 2-ethyl-1,3-hexane diol, 2 , 5-dimethyl-2,5-hexane diol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol and 1,9-nonan diol; alicyclic glycols such as bis hydroxymethylcyclohexane Aromatic glycols such as xylylene glycol And bishydroxyethoxybenzenes; and those obtained by condensation of N-alkyldialkanol amines such as N-methyl diethanol, for example polyethylene adipate, polybutylene adipate, polyhexamethylene adipate and polyethylene Propylene adipate; Or polyacetone diols or polyacetone mono-ols obtained using diols or monohydric alcohols having 1 to 25 carbon atoms as initiators, for example polycaprolactone glycol, polymethylvalerolactone and mixtures of two or more types thereof This includes. As polyester glycol, polycaprolactone glycol or polycaprolactone prepared using an alcohol having 1 to 25 carbon atoms as an initiator is most preferred. More specifically, the compound obtained by ring-opening (epsilon) -caprolactone and then superposing | polymerizing the obtained ring-opened caprolactone and mono-ol together by addition polymerization system is preferable.

Polycarbonate glycols include, for example, poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate; Polyolefin glycols include, for example, polybutadiene glycol, hydrogenated polybutadiene glycol and hydrogenated polyisoprene glycol.

Among the compounds having one or two hydroxyl groups in one molecule, polyether glycols and polyester glycols are particularly preferred.

The number average molecular weight of the compound having one or two hydroxyl groups in one molecule is 300 to 10,000, preferably 500 to 6,000, more preferably 1,000 to 4,000.

(3) compounds having active hydrogen and tertiary amino groups in one molecule

Compounds having active hydrogens and tertiary amino groups in one molecule for use according to the invention are described below. Active hydrogen, ie, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, includes, for example, a hydrogen atom in a functional group including a hydroxyl group, an amino group and a thiol group. Among these, the hydrogen atom in an amino group, especially a primary amino group is preferable. The tertiary amino group is not particularly limited. Additionally, tertiary amino groups include, for example, alkyl groups having 1 to 4 carbon atoms or amino groups having a heterocyclic structure, specifically an imidazole ring or a triazole ring.

Compounds having active hydrogen and tertiary amino groups in one molecule as described above include, for example, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylene Diamine, N, N-dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butane Diamine and N, N-dibutyl-1,4-butanediamine.

Additionally, nitrogen-containing hetero-rings as tertiary amino groups include, for example, nitrogen (N) -containing hetero, 5-membered rings such as pyrazole rings, imidazole rings, triazole rings, tetrazole rings, indole rings, carbs Bazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring and benzothiadiazole ring; And N-comprising hetero, six-membered rings such as pyridine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, acridine rings and isoquinoline rings. Imidazole rings or triazole rings are preferred as nitrogen-containing hetero rings.

Compounds having such imidazole rings and primary amino groups specifically include, for example, 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole and 1- (2-aminoethyl) imidazole. . Examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1,2,4 -Triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1, 4-diphenyl-1,2,3-triazole and 3-amino-1-benzyl-1H-2,4-triazole. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole and 3-amino-1,2,4 -Triazole is preferred.

The compounding ratio of the raw material to the urethane-based dispersant is preferably a compound having a number average molecular weight of 300 to 10,000 with one or two hydroxyl groups in one molecule per 100 parts by weight of the polyisocyanate compound, preferably 10 to 200 parts by weight. , Preferably 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, and a compound having active hydrogen and tertiary amino groups in one molecule is 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight.

The weight average molecular weight (Mw) of the urethane-based dispersant measured by GPC on a polystyrene basis is generally in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. When the molecular weight is less than 1,000, the dispersibility and stability of the dispersion are poor. When the molecular weight exceeds 200,000, the solubility decreases, resulting in deterioration of dispersibility and difficulty in controlling the reaction.

The urethane-based dispersant is prepared by a known method for producing a polyurethane resin. As solvents in the preparation, generally the following compounds are used: one or two or more ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone; Esters such as ethyl acetate, butyl acetate and cellosolve acetate; Hydrocarbons such as benzene, toluene, xylene and hexane; Certain alcohols such as diacetone alcohol, isopropanol, secondary butanol and tertiary butanol; Chlorides such as methylene chloride and chloroform; Ethers such as tetrahydrofuran and diethyl ether; And aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.

For the preparation, general reaction catalysts for the production of urethanes are used. The catalysts include, for example, tin series, such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and azutin octoate; Iron series such as iron acetylacetonate and iron chloride; And tertiary amines such as triethylamine and triethylenediamine.

The amount of the compound having active hydrogen and tertiary amino groups in one molecule to be introduced is preferably in the range of 1 to 100 mg-KOH / g as amine value after the reaction. More preferred is the range from 5 to 95 mg-KOH / g. The amine number is a value obtained by titrating a basic amino group to neutral using an acid, and represents the acid value in KOH in mg. When the amine number is smaller than the above-described range, the dispersion strength tends to decrease, and when the amine value exceeds the above range, the developing characteristics deteriorate easily.

If isocyanate groups still remain in the dispersion resin obtained through the reaction, the isocyanate groups are further decomposed into alcohols and amino compounds, preferably to increase the stability of the product obtained over time.

As the dispersant of the graft copolymer, a compound having a repeating unit containing a nitrogen atom in the main chain is preferable. Specifically, the compound has a repeating unit represented by the general formula (I) and / or a repeating unit represented by the general formula (II).

(Wherein R ₁ represents an alkylene group having 1 to 5 carbon atoms; A represents a hydrogen atom or any of the following formulas (III) to (V)):

In formula (I), R ₁ represents a linear or branched alkylene group having 1 to 5 carbon atoms, preferably 2 or 3 carbon atoms such as methylene, ethylene and propylene; R ₁ is preferably an ethylene group. A represents a hydrogen atom or any of the following general formulas (III) to (V). Preferably, A represents formula (III).

In formula (II), R ₁ and A have the same meaning as R _1, and A each has the same meaning as in formula (I).

In the formula (III), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, preferably an alkylene group having 4 to 7 carbon atoms, such as butylene, pentylene and hexylene. P represents an integer of 1 to 20, preferably an integer of 5 to 10.

In formula (IV), Y ₁ represents a divalent bonding group, and specifically, preferably an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy Includes; W ₂ represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene and butylene, and specifically includes alkylene groups having 2 to 3 carbon atoms such as ethylene and propylene; Y ₂ represents a hydrogen atom or —CO—R ₂ (R ₂ represents an alkyl group having 1 to 10 carbon atoms such as propyl, butyl, pentyl and hexyl, and specifically preferably an alkyl group having 2 to 5 carbon atoms such as ethyl, propyl , Butyl and pentyl are included); q represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the formula (V), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 50 carbon atoms and a hydroxyl group, and particularly preferably an alkyl group having 10 to 20 carbon atoms, such as a stearyl group And hydroxyalkyl groups having 10 to 20 carbon atoms and 1 to 2 hydroxyl groups such as monohydroxy-cis-stearyl.

The content of the repeating units represented by the formula (I) or (II) in the graft copolymer of the present invention is preferably higher, generally at least 50 mol%, preferably at least 70 mol%. The graft copolymer may include both the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) without any limitation in any content ratio. Preferably, the graft copolymer may preferably contain repeating units represented by the chemical formula (I). The total number of repeating units represented by the formula (I) or (II) is generally 1 to 100, preferably 10 to 70, more preferably 20 to 50. Additionally, the graft copolymers of the present invention may satisfactorily include repeat units other than those of formulas (I) and (II). The repeating unit includes, for example, an alkylene group and an alkyleneoxy group. The graft copolymers of the present invention include -NH ₂ and -R ₁ -NH ₂ (R ₁ has the same meaning as R ₁ described above) at its ends.

The backbone of the graft copolymers of the invention can be linear or branched.

The amine number of the graft copolymer of the present invention is generally 5 to 100 mg KOH / g, preferably 10 to 70 mg KOH / g, more preferably 15 or 40 mg KOH / g or less. If the amine number is too small, the stability of the dispersion is sensitive and the viscosity can sometimes be unstable. Conversely, if the amine number is too large, the residue may increase, and the electrical properties may sometimes deteriorate after the liquid crystal panel formation.

The weight average molecular weight of the dispersion assayed by GPC is preferably 3,000 to 100,000, particularly preferably 5,000 to 50,000. If the weight average molecular weight is less than 3,000, aggregation of the colorant cannot be prevented, leading to higher viscosity or gelation. When the weight average molecular weight exceeds 100,000, its dispersant is not preferable because it obtains a larger viscosity and lacks its solubility in an organic solvent.

As a method for the synthesis of the dispersant, a known method can be used. For example, the method described in JP-B-63-30057 can be used.

Dispersants may be used alone or in combination of two or more of the above types in a mixture. The amount of component (e3) to be blended is preferably selected in the range of 0 to 30% by weight of the total solids of the curable resin composition. The content of component (e3) in the coloring composition for color filters according to the present invention is generally 10 to 300% by weight, preferably 20 to 100% by weight of the colorant, particularly preferably 30 to 80% by weight. If the content of the dispersant is too small, its adsorption to the colorant is too low to prevent aggregation, leading to higher viscosity or gelation. On the contrary, when the content is too large, the film thickness becomes too large, which results in poor cell gap control in the liquid crystal cell manufacturing step when the dispersant is used in the color filter. All these cases are undesirable.

Component (e4) includes, for example, pigment derivatives. Examples of the pigment derivative include azo series, phthalocyanine series, quinacridone series, benzimidazolone series, quinophthalone series, isoindolinone series, dioxazine series, anthraquinone series, indanthrene series, and perylene series. , Perinone series, diketopyrrolopyrrole derivatives are included, dioxazine series pigments may be used. Substituents for the pigment derivatives include, for example, sulfonate groups, sulfonamide groups and quaternary salts thereof, phthalimidemethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups and amide groups, which are incorporated directly into the pigment skeleton. Or an alkyl group, an aryl group, or a heterocyclic group. Preferably, the substituent is a sulfonamide group and its quaternary salts, sulfonate groups and the like. More preferably, the substituent is a sulfonate group. In addition, several of these substituents may be substituted in one pigment backbone, or the derivatives may be mixtures of compounds with different numbers of substitutions. Specific examples of the pigment derivatives include, for example, sulfonate derivatives of azo pigments, sulfonate derivatives of phthalocyanine pigments, sulfonate derivatives of quinophthalone pigments, sulfonate derivatives of anthraquinone pigments, sulfonate derivatives of quinacridone pigments, Sulfonate derivatives of diketopyrrolopyrrole pigments and sulfonate derivatives of dioxazine pigments.

Commercially available pigment derivatives include Azo Solsperse 22000 from Avecia, Phthalocyanine Solsperse 5000 from Avecia, EFKA 475 from EFKA, and the like. The pigment derivatives may be used alone or in combination of two or more types thereof in a mixture. Its compounding quantity is preferably in the range of 0 to 20% by weight of the total solids in the curable resin composition.

As component (e5), various surfactants can be used, such as anionic-based, cation-based, nonionic-based and zwitterionic surfactants. In view of the low likelihood of adverse effects on the various features, preferably nonionic-based surfactants can be used.

Anionic-based surfactants include, for example, alkyl sulfate ester salt-based surfactants such as Emal 10 manufactured by Kao, alkylnaphthalene sulfonate salt-based surfactants such as Pelex NB-L manufactured by Kao and specific polymers. Surfactants such as Homogenol L-18, L-100 manufactured by Kao. Of these, specific polymer surfactants are preferred. Specific polycarboxylate type polymer surfactants are more preferred.

Cationic-based surfactants include, for example, alkylamine salt-based surfactants such as Acetamine 24 from Kao, and quaternary ammonium salt-based surfactants such as QUARTAMINE 24P and 86W from Kao. Of these, quaternary ammonium salt-based surfactants are preferred. Stearyltrimethylammonium salt-based surfactants are more preferred.

Nonionic-based surfactants include, for example, silicone-based surfactants such as Toray Silicone Co., Ltd. SH8400, and Silicone Co., Ltd. KP341, produced by Sumitomo 3M, such as fluorine-based surfactants such as FC430, Dainippon Ink and Chemicals, F470 and R-08, manufactured by Incorporated, fluorine-based surfactants, such as DFX-18, and poly, manufactured by Neos Oxyethylene-based surfactants such as Emalgen 104P, A60 manufactured by Kao. Of these, silicone-based surfactants are preferred. More preferred are polyether-modified silicone-based surfactants.

Two or more types of surfactants may be used in combination. In the above combinations, for example, combinations of silicone-based surfactants / fluorine-based surfactants, silicone-based surfactants / specific polymer-based surfactants, and fluorine-based surfactants / specific polymer surfactants are listed. do. Specifically, combinations of silicone-based surfactants / fluorine-based surfactants are preferred.

Combinations of silicone-based surfactants / fluorine-based surfactants may additionally include, for example, DFX-18, manufactured by TSF4460 / Neos, manufactured by GE Toshiba Silicone, and S-, manufactured by BYK-300 / Seimi Chemical, manufactured by Big Chemie. 393, KP340 / Dainippon Ink and Chemicals manufactured by Shin-etsu Silicone, F-478 manufactured by Incorporated, DS-401 manufactured by SH7PA / Daikin manufactured by Toray Silicone, and Nippon Unitika, Ltd. FC4430 manufactured by L-77 / Sumitomo 3M manufactured by the company is included.

The compounding quantity of component (e5) is generally 0.01 weight% or more and 1 weight% or less of the total solid of curable resin composition. If the blending amount of (e5) is too small, undesirably, its effect on the improvement of the wettability is hardly revealed. If the amount is too large, the decrease in surface tension becomes excessive, and the smoothing characteristic is deteriorated, which is not preferable.

[4] Method for producing curable resin composition of the present invention

The manufacturing method of curable resin composition for color filters which concerns on this invention is demonstrated below.

First, ingredients (a) and (b) are weighed in the amounts shown; Component (a) is dispersed in component (b) in the dispersing step of preparing the curable resin composition (ink-like material) in the liquid. In the dispersing step, paint conditioners, sand grinders, ball mills, roll mills, stone mills, jet mills and homogenizers and the like can be used. By the dispersion method, component (a) is prepared as microparticles. Thus, the resulting curable resin composition can obtain improved coating properties, thereby providing a color filter having improved transmittance of transmitted light.

In order to disperse component (a) in component (b), component (c1) and / or component (c2), component (e3), component (e4) and the like can be used in combination as appropriate. In particular, when a polymer dispersant (e3) is used, dispersion stability with time is large. When the dispersion method is carried out, preferably sand grinders, glass beads or zirconia beads with a diameter of 0.1 μm to several millimeters, for example, are used. During the dispersion method, the temperature is generally in the range of 0 ° C to 100 ° C, preferably room temperature to 80 ° C. The suitable time required for the dispersion method varies depending on the composition of the ink-like materials [components (a), (b), (e3), (e4)) and the dimensions of the sand grinder's mechanism, so the time should be adjusted accordingly. . If the time is too short, component (a) cannot be produced sufficiently with micro particles. This deteriorates the optical properties, which is undesirable. If this time is too long, component (a) is made excessively with microparticles, leading to an increase in viscosity and structural viscosity. Therefore, the rheological properties (square power index) tend to decrease, which is not preferable.

A pattern with large rheological properties (square power) with a power exponent (n) of 0.6 or greater at shear rates (D) of 10 ³ s ^-1 or higher, in accordance with the power law represented by formulas (Ia) and (Ib) In order to prepare the curable resin composition of the invention, an important dispersion state must be achieved in the dispersing step. Depending on the decomposition conditions including the concentration of the total solids, the amount and type of component (a), the amount of component (c), the quantitative ratio of components (c1) and (c2), the type of component (e3), and the component ( The type of e4), the dispersion time, the amount of component (e3) and the amount of component (e4) must be properly adjusted to achieve a suitable dispersion state without excessive dispersion.

Component (c1) and / or component (c2), a given amount of component (d) and other components such as component (e) are mixed with the ink-like material obtained in the dispersing step to produce a homogeneous dispersion. In separate stages of dispersion and mixing, very fine dust can sometimes be contaminated. Therefore, it is preferable to filter the obtained ink-like material through a filter or the like.

[Color filter of the present invention]

Next, the color filter in the second aspect of the present invention is described below.

The color filter of this invention has a pixel or black matrix formed from the curable resin composition of this invention on a board | substrate.

As long as any material is transparent and has a suitable strength, it can be used for the transparent substrate of the color filter. Such materials include, for example, polyester based resins such as polyethylene terephthalate, polyolefin based resins such as polypropylene and polyethylene, thermoplastic resins such as polycarbonate, polymethyl methacrylate and polysulfone, epoxy Curable resin sheets derived from resins, unsaturated polyester resins, and poly (meth) acrylic resins or of various glass types. Among these, glass and heat resistant resin are preferable at the point of heat resistance.

In order to improve the surface properties such as adhesion, if necessary, the transparent substrate and the black matrix substrate can be processed for corona discharge treatment, ozone treatment and thin film production using various resins such as silane coupling agent and urethane-based resin. The thickness of the transparent substrate is generally in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When thin film production using various resins is carried out, the film thickness is generally in the range of 0.01 to 10 mu m, preferably 0.05 to 5 mu m.

By aligning the black matrix on the transparent substrate and forming pixel images of red, green and blue in general, the color filter of the present invention can be produced. The curable resin composition is used as a coating solution for producing one or more resists of black, red, green and blue. Individual processes of application, heating and drying, image exposure, development, and thermosetting are transparent substrates of simple glass for black resists, resin black matrix-forming surfaces formed on transparent substrates, or metal black matrix-forming surfaces prepared using chromium compounds. And other shading metal materials for red, green, and blue to form pixel images of individual colors.

Black matrices are prepared on transparent substrates using light-shielding metal thin films or pigment dispersions for black matrices. As the light shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, and nickel and tungsten alloys can be used. Metallic materials may be a stack of the above layers of the compound.

The light shielding metal film is generally manufactured by sputtering. After forming a desired pattern on the film with a positive photoresist, etching is performed using an etching solution prepared by mixing together perchloric acid for cerium (IV) nitrate ammonium and chromium and another material, Finally, the positive photoresist was peeled off using a dedicated release agent to prepare a black matrix.

In this case, first, a thin film of metal, metal or metal oxide is produced on the transparent substrate by vapor deposition or sputtering. After the coating film of the curable resin composition was prepared on the thin film, the coated film was exposed and developed using a photomask having a repeating pattern such as stripes, mosaics, or triangles to prepare a resist image. Subsequently, the applied film was subjected to etching to provide a black matrix.

When using the curable resin composition containing the pigment dispersion with respect to a black matrix, and also a black color material, a black matrix is formed. Curable resin compositions comprising alone or several of black colorants such as carbon black, graphite, iron black, aniline black, cyanine black and titanium black, suitably selected from inorganic or organic pigments or dyes, or inorganic or organic Using the curable resin composition comprising a black colorant in a mixture of red, green, blue, and the like suitably selected from pigments or dyes, the black matrix is prepared in the same manner as the following method of providing red, green, and blue pixel images. Can be prepared.

A curable resin composition for color filters comprising a colorant of one of red, green and blue colors is applied onto a transparent substrate aligned with a black matrix, the curable resin composition is dried, and a photomask on a subsequently applied film. Are superimposed, a pixel image is formed through image exposure, development and thermosetting, and if necessary, thermosetting through a photomask to produce a colored layer. The process is performed on individual curable resin compositions for color filters of three colors, red, green and blue, to provide a color filter image.

Curable resin composition for color filters can be apply | coated by the spinner method, the wire bar method, the flow coat method, the die coat method, the roll coat method, and the spray coat method, for example. Specifically, the die coating method is generally preferred in that the amount of coating solution used is clearly reduced, there is absolutely no influence of mist deposited during the spin coating method, etc., and generation of foreign substances is suppressed.

Application conditions by the diecoat method may be appropriately selected depending on the composition of the curable resin composition of the color filter, the type of color filter to be produced, and the like. For example, preferably, the lip width of the nozzle tip is 50 to 500 μm and the distance between the nozzle tip and the substrate surface is 30 to 300 μm. In order to adjust the thickness of the applied film, the advancing speed of the lip and the filling speed of the curable resin composition which is liquid from the lip can be satisfactorily adjusted.

The applied film after applying the curable resin composition on the substrate is preferably dried by a drying method using a hot plate, an IR oven and a convection oven. Generally, the applied film is dried in advance and then dried under reheating. The conditions of predrying are appropriately selected depending on the type of component (b), the characteristics of the dryer to be used, and the like. Depending on the type of component (b), the performance of the dryer used, and the like, the drying time generally ranges from 15 seconds to 56 minutes at a temperature of 40 to 80 ° C., preferably from 30 seconds to 3 minutes at a temperature of 50 to 70 ° C. Is selected.

The temperature conditions for drying under reheating are preferably 50 to 200 ° C., specifically 70 to 160 ° C., in particular 70 to 130 ° C. higher than the predrying temperature. In addition, the drying temperature depends on the heating temperature, preferably 10 seconds to 10 minutes, specifically 15 seconds to 5 minutes. Higher drying temperatures improve adhesion to the transparent substrate. However, too high a temperature decomposes component (d) to induce thermal polymerization, which sometimes leads to poor phenomena. The thickness of the applied film of the curable resin composition to the color filter after drying is generally at least 0.4 μm, preferably at least 0.6 μm and generally at most 1.5 μm, preferably at most 1.0 μm when the color filter is produced as a thin film. . In the case of the production of color filters of thin films, the thickness of the applied film is generally at least 0.4 m, preferably at least 0.6 m and generally at most 1.5 m, preferably at most 1.0 m. In the case of the production of color filters for thick films, the thickness of the applied film is generally 1.5 µm or more, preferably 3 µm or more and generally 10 µm or less, preferably 5 µm or less. In the drying step of the applied film, the drying process under reduced process including drying in the chamber under reduced pressure can be satisfactory without temperature rise.

Image exposure is carried out by superimposition of the negative matrix pattern on the coated film of the curable resin composition and ultraviolet or visible light irradiation from the light source through the mask pattern. If necessary, an oxygen barrier layer, such as a polyvinyl alcohol layer, is then satisfactorily formed on the photopolymerizable layer to block the reduction of the photopolymerizable layer due to oxygen. Subsequently, exposure is performed. Light sources for use in imaging exposures include, for example, but are not limited to lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps. , Carbon arc and fluorine lamps; And laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers and semiconductor lasers. In the case of using light of a specific wavelength for irradiation, an optical filter may be used.

The color filter of the present invention exposes the image to a light source as described above on the coated film of the curable resin composition of the present invention, and develops the image using an organic solvent or an aqueous solution containing a surfactant and an alkali compound to form a substrate on the substrate. It can be made by forming an image. The aqueous solution may additionally include organic solvents, buffers, complexing agents, dyes or pigments.

Examples of the alkaline compound include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, Sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; And organic alkaline compounds such as mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, etirenimine , Ethylenediimine, tetramethylammonium hydroxide (TMAH) and choline. These alkaline compounds may be used alone or in combination of two or more types thereof.

Surfactants include, for example, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters; Anionic surfactants such as alkylbenzene sulfonate salts, alkylnaphthalene sulfonate salts, alkylsulfate salts, alkylsulfonate salts and sulfosuccinate esters; And zwitterionic surfactants such as alkylbetaines and amino acids.

Organic solvents include, for example, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol and diacetone alcohol. The organic solvents may be used alone or in combination of two or more types thereof.

The developing conditions include, but are not limited to, for example, generally 10 to 50 ° C, preferably 15 to 45 ° C, particularly preferably 20 to 40 ° C as the developing temperature. The developing method includes, for example, any of a submerged developing method, a spray developing method, a brush developing method, and an ultrasonic developing method.

The color filter of this invention also apply | coats curable resin composition containing (1) component (b), the phthalocyanine pigment as component (a), and the polyimide-type resin as component (c) on a board | substrate, and pixel by an etching method It can be produced by a method for forming an image. In addition, the color filter of the present invention comprises (2) a method of forming a pixel image directly on a transparent substrate with a printing machine, using a curable resin composition containing a phthalocyanine pigment as a coloring ink; And (3) a substrate is immersed in the curable resin composition containing a phthalocyanine pigment as an electrodeposition liquid, and a colored film is deposited on an ITO electrode in a given pattern. In addition, the color filter of the present invention also adheres a film coated with a curable resin composition comprising, for example, (4) a phthalocyanine pigment to a transparent substrate, and then peels off the film, and the film is exposed and developed to obtain a pixel image. How to; And (5) a curable resin composition containing a phthalocyanine pigment as a coloring ink, and may also be produced by a method of forming a pixel image with an inkjet printer. The method suitable for the composition of curable resin composition for color filters is used as a manufacturing method of a color filter.

As described above, the curable resin composition of the present invention has excellent rheological properties (square power index) and excellent applicability using a die coat method. Therefore, the color filter of this invention manufactured at the application | coating step by the die-coat method using curable resin composition of this invention is preferable at the point of yield and quality.

After development, the color filter is treated with thermosetting. The conditions for the thermosetting process are selected from a temperature range of 100 to 280 ° C., preferably 150 to 250 ° C. and a time range of 5 to 60 minutes. Through this series of steps, a single colored pattern image can be formed completely. By repeating the above steps sequentially, black, red, green and blue are patterned to form a color filter. In this application, the order of the four colored patterns is not limited to the order described above.

In this state, the color filter of the present invention can be used as an accessory of a member of a color display device and a liquid crystal display device by forming a transparent electrode such as ITO on an image. In order to enhance surface smoothness and durability, top coat layers of polyamide and polyimide may be aligned on the image, if necessary. In addition, some color filters do not place the transparent electrode for use in an "in plain switching" scheme.

Example

The invention is described in more detail in the following examples and comparative examples. However, the present invention is not limited by the following examples without departing from the scope of the present invention.

Example 1

Pigment dispersions were prepared by mixing the following components together in the following proportions.

(Composition of Pigment Dispersion)

Pigment: Pigment Red 177: 10 g

Dispersant: byk-161 manufactured by Big Chemie (30% by weight of active ingredient): 13.3 g

menstruum:

Propylene glycol monomethyl ether acetate (surface tension is 27.3 dyne / cm; vapor pressure is 3.7 Torr): 32.7 g

Alternatively, transparent resists were prepared by mixing the following components together in the following proportions.

Transparent resist composition

bookbinder:

Acrylic resin with a repeating unit represented by following General formula (6): 4.0 g

Ethylene Compounds:

Dipentaerythritol hexaacrylate: 4.0 g

Photopolymerization Initiator:

2- (2-chlorophenyl) -4,5-diphenylimidazole dimer: 0.4 g

4,4'-bis (diethylamino) benzophenone: 0.2 g

2-methylbenzothiazole: 0.4 g

Surfactants:

FC430 from Sumitomo 3M: 0.023 g

menstruum:

Propylene glycol monomethyl ether acetate: 50.0 g

The pigment dispersion was mixed with the transparent resist for homogenization under stirring and 300 g of zirconia beads with a particle size of 0.5 mm were added. For dispersion, the obtained mixture was shaken with a paint conditioner for 5 hours and then filtered to obtain a uniform color resist. The rheological properties of the color resists were measured by rheometers manufactured by Rheometrix. The normal viscosity at shear rate up to 10 ³ s ⁻¹ was 4.1 mPa · s; The power exponent at shear rate 10 ³ s ⁻¹ or more was 0.8. In addition, surface tension was measured with a surface tension meter manufactured by Kyowa Surface Tension Science. The surface tension was a value of 26.0 dyne / cm.

Example 2

A color resist was prepared in the same procedure as for the color resist in Example 1, except that the shaking time with the paint conditioner was 8 hours. The rheological properties of the color resists were measured by rheometers manufactured by Rheometrix. The normal viscosity at shear rate below 10 ³ s ⁻¹ was 4.6 mPa · s; The power exponent at shear rate 10 ³ s ⁻¹ or more was 0.6. In addition, surface tension was measured with a surface tension meter manufactured by Kyowa Surface Tension Science. The surface tension was a value of 26.0 dyne / cm.

Comparative Example 1

A color resist was prepared in the same procedure as for the color resist preparation in Example 1, except that the shaking time with the paint conditioner was 10 hours. The rheological properties of the color resists were measured by rheometers manufactured by Rheometrix. The normal viscosity at shear rate below 10 ³ s ⁻¹ was 5.4 mPa · s; The power exponent above the shear rate 10 ³ s ⁻¹ was 0.4. In addition, surface tension was measured with a surface tension meter manufactured by Kyowa Surface Tension Science. The surface tension was a value of 26.0 dyne / cm.

Comparative Example 2

Color resist was prepared in the same procedure as for the color resist preparation in Example 1, except that the amount of propylene glycol monomethyl ether acetate added was 27 g. The rheological properties of the color resists were measured by rheometers manufactured by Rheometrix. The normal viscosity at shear rate below 10 ³ s ⁻¹ was 5.8 mPa · s; The power exponent at shear rate 10 ³ s ⁻¹ or more was 0.5. In addition, surface tension was measured with a surface tension meter manufactured by Kyowa Surface Tension Science. The surface tension was a value of 26.0 dyne / cm.

Comparative Example 3

A color resist was prepared in the same procedure as that for the color resist preparation in Comparative Example 1, except that the amount of the surfactant FC430 added was 0.07 g. The rheological properties of the color resists were measured by rheometers manufactured by Rheometrix. The normal viscosity at shear rate below 10 ³ s ⁻¹ was 5.4 mPa · s; The power exponent above the shear rate 10 ³ s ⁻¹ was 0.4. In addition, surface tension was measured with a surface tension meter manufactured by Kyowa Surface Tension Science. Surface tension was a value of 24.2 dyne / cm.

(Evaluation test)

Using the color resists prepared in Examples 1 and 2 and Comparative Examples 1 to 3, the following evaluation test for die coat coatability was performed. The results are shown in Table 1.

By discharging the color resist discharged from the discharge port 2a of the 500 mm wide slit die 2 with the shim 1 having a protrusion integrated therein in the manner as shown in Fig. 1 (b), in the manner of Fig. 1A, The color resist 4 was produced several times on the glass substrate 3 on the conditions of the application | coating speed | rate 100 mm / s, the coating gap 100 micrometers, and the wet coating thickness 15 micrometers.

Next, the variation of the film thickness of the stripe 5 due to the protrusion 1a of the shim 1 was investigated. In addition, the generation of very fine nonuniformity of streaks at the starting point of application of the applied substrates was evaluated by magnification using a Na lamp.

The applied film was treated with a drying apparatus for 60 seconds under a reduced pressure of 0.5 Torr and prebaked at 90 ° C. for 1 minute on a hot plate. Subsequently, the applied film was optically cured under 100 mg / cm ² irradiation using a UV exposure apparatus and treated at 230 ° C. for 1 hour in a convection oven. The dried film thickness of the coated film produced by this method is shown in Table 1.

The results in Table 1 indicate that the curable resin composition of the present invention never causes a problem of streaked nonuniform defects due to nonuniform discharge in the slit nozzle width direction by the die coat, and thus the curable resin composition is very It has a large die coat applicability.

The invention has been described in detail in specific embodiments. However, various modifications and variations are possible without departing from the spirit and scope of the invention and are apparent to those skilled in the art.

In addition, this application is a Japanese patent application (Japanese Patent Application 2004-38554) filed February 16, 2004, a Japanese patent application (Japanese Patent Application 2004-66758) filed March 10, 2004, 2004 It is based on the Japanese patent application (Japanese Patent Application 2004-66759) filed on March 10. All of these are incorporated by reference.

The curable resin composition of the present invention never provides nonuniformity in the die coat process. Therefore, curable resin composition of this invention is suitable for color filter manufacture etc. by die-coat application. The color filter using the curable resin composition of the present invention can provide a liquid crystal display device as well as a high quality color filter having good pixels manufactured through a uniform resist layer.

Claims (6)

When the relationship between the shear stress (τ) and the shear rate (D) satisfies the power law represented by the following formulas (Ia) and (Ib), the power exponent (n) at the shear rate (D) 10 ³ s ^-1 or more (n) Curable resin composition used for the application | coating of a die-coat system whose () is 0.6 or more: τ = μ × D (Ia) μ = η × D ^(n-1) (Ib) Where τ: shear stress; μ: viscosity; η: constant; D: shear rate; n: power exponent. Curable resin composition of Claim 1 whose normal viscosity in shear rate (D) 10 ³ s <^-1> or less is 5 mPa * s or less. The curable resin composition of Claim 1 or 2 whose surface tension is 25 dyne / cm or more. delete The color filter formed using the curable resin composition of Claim 1 or 2. A liquid crystal display device in which the color filters according to claim 5 are arranged.

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