KR20110123668A

KR20110123668A - Colored photosensitive composition, method of producing color filter, color filter and liquid crystal display device

Info

Publication number: KR20110123668A
Application number: KR1020110041392A
Authority: KR
Inventors: 료 사타케; 코우타로 오카베
Original assignee: 후지필름 가부시키가이샤
Priority date: 2010-05-07
Filing date: 2011-05-02
Publication date: 2011-11-15
Also published as: CN102236257A

Abstract

Colored photosensitive composition containing the coloring material which has (A) phthalocyanine frame | skeleton, (B) solvent, (C) polymerizable monomer, (D) binder resin, (E) photoinitiator, and (F) polymeric compound which has a radical trapping ability. And a color filter using the colored photosensitive composition and the color filter.

Description

Colored photosensitive composition, the manufacturing method of a color filter, a color filter, and a liquid crystal display device {COLORED PHOTOSENSITIVE COMPOSITION, METHOD OF PRODUCING COLOR FILTER, COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention provides a coloring photosensitive composition having both excellent light resistance, developability and solvent resistance while maintaining high transparency of a color material and high color purity, a color filter containing the same in a coloring pattern, a method for producing a color filter, and a liquid crystal display. Relates to a device.

Conventionally, small liquid crystal display devices such as mobile phones, mobile game consoles, PDAs, and the like have required the use of backlight light sources with limited capacities, such as secondary batteries or batteries, so that the color material of the color filters used in these display devices is highly transparent. A colorant which can transmit the bright lines of the backlight well and display the color has been advantageously used.

In recent years, the enlargement of the liquid crystal display device has progressed to the use of a liquid crystal display monitor, a liquid crystal television, etc. of a PC, and these liquid crystal display devices have no power supply limitation of a backlight, and RGB color reproduction of the display device is emphasized. Therefore, in addition to the conventional transparency, the color material of the color filter is required to have a higher level of image quality, i.e., contrast and color purity.

In response to the above-mentioned demands, alkali-soluble resins, photopolymerizable compounds, photopolymerization initiators and other components are further referred to as pigment compositions in which the particle diameter of the pigment is further refined. Color filters in which three color patterns of red, green, and blue are formed on a substrate have been developed and put into practical use.

Among them, green pigments such as chlorinated copper phthalocyanine pigments (C. I. PIGMENT Green 7) and chlorinated brominated phthalocyanine pigments (C. I. PIGMENT Green 36) are generally used for the green coloring pattern. Recently, polyhalogenated metal phthalocyanine pigments, such as aluminum, titanium, cobalt, nickel, zinc, tin, and lead, whose core metals are not copper, have been studied for the purpose of increasing the saturation (color purity and color density) of the pigment, and in particular, the saturation Various pigments are proposed regarding the high polyhalogenated zinc phthalocyanine pigment (CI PIGMENT Green 58). For example, detailed studies such as substitution degree of Br and Cl (for example, refer to Patent Document 1 or Patent Document 2), pigment treatment method using betaine-type surfactant, various crystal forms, etc. are carried out. The polyhalogenated copper phthalocyanine having a maximum diffraction peak at 26.4 ° or 25.5 ° for the Bragg angle (2θ ± 0.2 °) with respect to the Cu-Kα ray is high in saturation (color purity and color density) and also has excellent stability over time. Is reported (for example, refer patent document 3). It is also proposed that color filters having high transparency and high color purity are obtained using these pigments.

On the other hand, the color filter needs light resistance in order not to fade or discolor to light from the backlight. In order to improve light resistance, the coloring photosensitive composition which improved the coloring material itself (for example, refer patent document 4-patent document 6), and the coloring photosensitive composition which added the compound, such as a quencher and an optical stabilizer, are reported (for example, , Patent Document 7 and Patent Document 8.). Moreover, although the polymerizable monomer which can improve light resistance is also reported (for example, refer patent document 9), the example which used the polymerizable monomer for a color filter and coloring photosensitive composition is not reported.

In general, dyes are poor in light resistance compared to pigments, and thus, dyes are particularly actively improved in light resistance. However, also in pigments, it is known that the light resistance deteriorates when it is made finer for improving the brightness, and it is necessary to improve the light resistance while maintaining the characteristics of high transparency and high color purity with respect to the pigment as described above.

Japanese Patent Publication No. 2003-161823 Japanese Patent Publication No. 2007-284592 Japanese Patent Publication No. 2008-24743 Japanese Patent Publication No. 2008-138037 Japanese Patent Publication No. 2009-149779 Japanese Patent Publication No. 2009-215380 Japanese Patent Laid-Open No. 2000-214580 Japanese Patent Publication No. 2004-139050 Japanese Patent Publication No. 2004-155812

This invention is made | formed in view of the above-mentioned problem, The objective is to provide the coloring photosensitive composition for color filters which can form the coloring pattern excellent in light resistance. Moreover, using the coloring photosensitive composition mentioned above, it is providing the color filter which is excellent in light resistance, and has favorable color characteristic, and also provides the manufacturing method and liquid crystal display device of this color filter.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the said problem was markedly improved by adding the polymeric compound which has a radical trapping ability to the coloring photosensitive composition using the coloring material which has a phthalocyanine skeleton, and reached this invention. did.

That is, this invention is as follows.

<1> A colorant having a (A) phthalocyanine skeleton, (B) a solvent, (C) a polymerizable monomer, (D) a binder resin, (E) a photopolymerization initiator, and (F) a polymerizable compound having a radical trapping ability The coloring photosensitive composition characterized by the above-mentioned.

<2> As described in <1>,

Content of the polymeric compound which has the said (F) radical trapping ability is 0.1 mass% or more and 5.0 mass% or less with respect to a total solid, The coloring photosensitive composition characterized by the above-mentioned.

<3> The above-mentioned <1> or <2>,

The polymeric compound which has said (F) radical trapping ability has an amine structure or a phenol structure, The coloring photosensitive composition characterized by the above-mentioned.

<4> In any one of <1>-<3>,

The polymeric compound which has the said (F) radical trapping ability has at least 1 chosen from acryloyl group and methacryloyl group as a polymeric group, The coloring photosensitive composition characterized by the above-mentioned.

<5> In any one of said <1>-<4>,

The polymeric compound which has said (F) radical trapping ability is at least 1 chosen from following General formula (1), (5), and (6), The coloring photosensitive composition characterized by the above-mentioned.

[In the formulas (1), (5) and (6), each of R ¹ , R ^2, and R ³ independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a cyano group, a hydroxyl group, and 10 or less carbon atoms. Alkyl group, alkoxycarbonyl group of 10 or less carbon atoms, alkylsulfonylaminocarbonyl group of 10 or less carbon atoms, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, acylaminosulfonyl group of 10 or less carbon atoms, 10 or less carbon atoms An alkoxy group, an alkylthio group having 10 or less carbon atoms, an aryloxy group having 10 or less carbon atoms, a nitro group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an acyloxy group having 10 or less carbon atoms, or 10 carbon atoms The following acyl group, carbamoyl group, sulfamoyl group, a C10 or less aryl group, substituted amino group, substituted ureido group, substituted phosphono group, or heterocyclic group are shown. R ⁴ represents a hydrogen atom or an alkyl group having 30 or less carbon atoms. R ⁵ and R ⁶ each independently represent a branched alkyl group having 30 or less carbon atoms. X represents a single bond, an ester group, an aliphatic alkyl chain having 30 or less carbon atoms, an aromatic chain, a polyethylene glycol chain, or a (m + n) valent linking group formed by combining them. m and n each independently represent an integer of 1 or more and 3 or less.]

<6> In any one of <1>-<5>,

At least 1 sort (s) of the said (A) coloring material contains a metal in a chemical structure, The coloring photosensitive composition characterized by the above-mentioned.

<7> In any one of <1>-<6>,

At least 1 sort (s) of the said (A) color material is a coloring pigment, The coloring photosensitive composition characterized by the above-mentioned.

<8> In any one of <1>-<7>,

Coloring photosensitive composition comprising (A) at least one selected from the group of C. I. PIGMENT Green 7, C. I. PIGMENT Green 36 and C. I. PIGMENT Green 58 as the colorant.

<9> The process of forming the colored layer by providing the colored photosensitive composition in any one of said <1>-<8> on a board | substrate, and exposing the said colored layer in pattern shape, and developing and removing an uncured part with a developing solution, The manufacturing method of the color filter characterized by including the process of forming a coloring pattern.

<10> The color filter manufactured by the manufacturing method of the color filter as described in said <9>.

<11> The liquid crystal display device which comprises the color filter as described in said <10>.

Effect of the Invention

By using the coloring photosensitive composition of this invention, the coloring pattern excellent in light resistance is obtained. Moreover, the color filter and liquid crystal display device which are excellent in light resistance and are excellent in color characteristics are obtained.

Hereinafter, the colored photosensitive composition of this invention, the color filter using the said colored photosensitive composition, and the liquid crystal display device using the said color filter are demonstrated in detail.

The coloring photosensitive composition of this invention is the coloring material which has at least (A) phthalocyanine frame | skeleton, (B) solvent, (C) polymerizable monomer, (D) binder resin, (E) photoinitiator, (F) polymerization with radical trapping ability It is a coloring photosensitive composition containing a sexual compound.

Hereinafter, the component which comprises the coloring photosensitive composition of this invention is described.

<(A) Color material having a phthalocyanine skeleton>

Since the coloring material which has a phthalocyanine frame | skeleton is used for the coloring photosensitive composition of this invention, a color filter with high color purity and contrast is obtained.

Since the color material having a phthalocyanine skeleton has 16 hydrogen atoms in the phthalocyanine ring, these hydrogen atoms can be replaced with up to 16 bromine atoms and / or chlorine atoms. All of these halogen atoms may be the same or different.

As substitution number of a halogen atom, it is preferable that they are 8 or more and 16 or less, More preferably, it is the range of 10 or more and 16 or less.

It is preferable that at least 1 type of said (A) color material is a green pigment, and a phthalocyanine type green pigment shows the greenish yellowish brightness by substitution with 8 or more bromine atoms, and uses it for the green pixel part pattern of a color filter. It is suitable for. In particular, the bromine atom having 10 to 16 substituents is preferably used in the present invention because of its higher brightness.

In the present invention, at least one of the above-mentioned (A) color materials preferably contains a metal in the chemical structure from the viewpoint of obtaining a color having high luminance, and it is preferable to use a phthalocyanine pigment containing a metal in the center portion.

The central metal is not particularly limited as long as it can maintain the stability of the colorant, but copper, aluminum, titanium, cobalt, nickel, zinc, tin, lead, and the like are preferable, and zinc is preferably contained from the viewpoint of saturation.

A phthalocyanine pigment can be manufactured by well-known manufacturing methods, such as the chlorosulfonic acid method, the halogenated phthalonitrile method, the melting method, etc., for example. More specific manufacturing methods are described in detail in Japanese Patent Laid-Open No. 2008-19383, Japanese Patent Laid-Open No. 2007-320986, Japanese Patent Laid-Open No. 2004-70342, and the like.

Of these, zinc halide phthalocyanine pigments disclosed in Japanese Patent Laid-Open No. 2004-70342, which have a simple manufacturing process, are preferable in terms of cost. In addition, in terms of stability, the crystal-converted zinc halide phthalocyanine pigment disclosed in Japanese Patent Laid-Open No. 2008-19383 is preferred, although it is also based on other additives or a combination method of subsequent steps. Moreover, especially for the improvement of dispersibility, the resin-coated zinc halide phthalocyanine pigment disclosed by Unexamined-Japanese-Patent No. 2007-320986 is a preferable form.

As a specific example of said (A) color material, C. I. PIGMENT Green 7, C. I. PIGMENT Green 36, C. I. PIGMENT Green 58, etc. are mentioned.

The range of 10 nm-100 nm is preferable, and, as for the average primary particle diameter of the phthalocyanine pigment of this invention, the range of 10 nm-70 nm is more preferable. By using the phthalocyanine type pigment of the average primary particle diameter of this range, the coloring photosensitive composition for color filters which is excellent in dispersibility stability and coloring power, and has high brightness and high contrast can be obtained.

In addition, the average primary particle diameter in this invention is a long diameter (long diameter) with respect to 100 primary particles of the phthalocyanine pigment which image | photographs the particle | grains in a visual field with a transmission electron microscope, and comprises the aggregate on a two-dimensional image. The average value of the diameter and the shorter diameter is obtained, and the average value is obtained.

As for the primary particle of the phthalocyanine pigment of this invention, if the aspect-ratio aspect ratio is 1-3, the viscosity characteristic will improve in each application field, and fluidity will become higher. In order to determine the aspect ratio, the particles in the field of view are taken by a transmission electron microscope or a scanning electron microscope in the same manner as when the average particle diameter of the primary particles as described above is obtained. And the average value of the long side diameter (long diameter) and the short side diameter (short diameter) is calculated | required about 100 of the primary particles which comprise the aggregate on a two-dimensional image, and it calculates using these values.

For obtaining a phthalocyanine pigment having an average primary particle diameter in the range of 10 nm to 100 nm, it may be finely granulated by any method, but pigment particles that can easily suppress crystal growth and have relatively small average primary particle diameters It is preferable to employ | adopt the solvent salt milling process from the point which can be obtained.

This solvent salt milling means kneading and grinding a phthalocyanine pigment, an inorganic salt, and an organic solvent. The phthalocyanine pigment having a large particle diameter may be subjected to solvent salt milling after dry grinding. Specifically, a phthalocyanine-based pigment, an inorganic salt, and an organic solvent which does not dissolve it are added to the kneader, and kneading and grinding is performed therein. As the kneader at this time, kneader, mix mara, etc. can be used, for example.

As the inorganic salt, a water-soluble inorganic salt can be preferably used, and for example, inorganic salts such as sodium chloride, potassium chloride and sodium sulfate are preferably used. Moreover, it is more preferable to use the inorganic salt of average particle diameters 0.5-50 micrometers. Such an inorganic salt is easily obtained by pulverizing a normal inorganic salt.

About obtaining the phthalocyanine pigment of the range whose average primary particle diameter is 10 nm-100 nm, it is preferable to make ratio of the usage-amount of the inorganic salt with respect to the usage-amount of the phthalocyanine pigment in solvent salt milling high. That is, it is preferable to set it as 5-20 parts with respect to 1 part of phthalocyanine pigments, and, as for the usage-amount of the said inorganic salt, it is more preferable to set it as 7-15 parts.

As the organic solvent, it is preferable to use an organic solvent capable of suppressing crystal growth, and as such an organic solvent, a water-soluble organic solvent can be preferably used. For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid Polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, di Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol mono Methyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, etc. can be used.

Although the usage-amount of the water-soluble organic solvent at this time is not specifically limited, 0.01-5 parts and 0.8-2 parts are preferable with respect to 1 part of phthalocyanine pigments by mass conversion.

30-150 degreeC is preferable and, as for the temperature at the time of solvent salt milling, 80-100 degreeC is more preferable. 5-20 hours are preferable and, as for the time of solvent salt milling, 8-18 hours are more preferable.

In this way, a mixture containing a phthalocyanine pigment, an inorganic salt and an organic solvent as a main component is obtained, but the organic solvent and the inorganic salt are removed from the mixture, and, if necessary, the solids mainly composed of the phthalocyanine pigment are washed, filtered, dried, The fine powder of phthalocyanine pigment can be obtained by pulverizing or the like.

As washing | cleaning, any of water washing and hot water can be employ | adopted. The number of washings may be repeated in a range of 1 to 5 times. In the case of the mixture using a water-soluble inorganic salt and a water-soluble organic solvent, the organic solvent and the inorganic salt can be easily removed by washing with water.

As said filtration fractionation and the drying after washing | cleaning, the batch-type or continuous drying etc. which perform dehydration of a pigment and / or a solvent by heating at 80-120 degreeC by the heating source installed in the dryer, etc. are mentioned, for example, Generally, box type dryer, band dryer, spray dryer, etc. are mentioned. In addition, the grinding | pulverization after drying is not an operation for increasing a specific surface area or making the average particle diameter of a primary particle small, For example, like a case of drying using a box type drier or a band drier, a pigment may become a lamp shape. It is performed in order to loosen and powder a pigment at the time, for example, grinding | pulverization with a mortar, a hammer mill, a disk mill, a pin mill, a jet mill, etc. are mentioned.

Although the coloring agent which has the (A) phthalocyanine frame | skeleton of this invention can be obtained, for example by the method mentioned above, it is also possible to use the product of the pigment or pigment dispersion which are generally circulated.

Thus, the coloring agent which has the (A) phthalocyanine frame | skeleton obtained is weak in cohesion force of a primary particle, and has a property which is easy to unwind, so covering power becomes large and manufacture of a high contrast coloring film becomes easy.

In this invention, these phthalocyanine pigments may be used independently, but may use multiple types together. In addition, when used together, it can be used in mixture with other brominated phthalocyanine pigments with a different bromination rate or chlorination rate, or a brominated phthalocyanine with different center metals. By changing the bromination rate and the chlorination rate or by changing the center metal, the color tone as the pigment is changed, and variation in reproducible color is expected to increase.

In the coloring photosensitive composition of this invention, the color of a coloring photosensitive composition can be adjusted and a transmittance can be enlarged by combining another color material with the color material which has (A) phthalocyanine frame | skeleton.

For example, you may use together a yellow pigment and an orange pigment with respect to a phthalocyanine green pigment for green pixel formation. Examples of yellow pigments include diketopyrrolopyrrole orange pigments, in addition to yellow pigments such as disazo yellow pigments, isoindolin yellow pigments, quinophthalone yellow pigments, benzimidazolone yellow pigments and nickel azo yellow pigments; Orange pigments, such as a perinone orange pigment, can also be used as needed.

Specific examples include CI Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32 , 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83 , 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127 , 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173 , 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 and CI Pigment Oragne 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 and the like.

Among them, CI Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, and the like, more preferably CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Yellow 138, CI Pigment Yellow 139.

In particular, the use of C. I. Pigment Yellow 150, C. I. Pigment Yellow 138, and C. I. Pigment Yellow 139 is preferable because of high transmittance and high contrast.

In addition, in order to form a blue pixel, you may use together a purple pigment with respect to a phthalocyanine blue pigment. Examples of the purple pigment include a quinacridone purple pigment, an oxazine purple pigment, an anthraquinone purple pigment, an indigoide purple pigment, and a xanthene purple pigment.

Specific examples include C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, and C. I. Pigment Violet 23 is particularly preferred because of its high transmittance and high contrast.

The average primary particle diameter of these pigments is preferably in the range of 10 nm to 40 nm, because the transmittance is high and the contrast is high. More preferably, it is the range of 10 nm-30 nm. In order to make an average primary particle diameter small and fine, the salt milling method is effective similarly to phthalocyanine, may be salt-milled with a phthalocyanine pigment, and may be salt milled separately.

The average primary particle diameter is observed by SEM or TEM, and is calculated | required by measuring 100 particle sizes in the part which particle | grains do not aggregate, and calculating an average value.

In the coloring photosensitive composition of this invention, the total amount of the pigment containing a phthalocyanine pigment removes the total amount except the (B) solvent in the coloring photosensitive composition of this invention (Hereinafter, this "total amount except the (B) solvent in a coloring photosensitive composition"). It is preferable that it is 5 to 60% in mass conversion with respect to "total solid content". It is more preferable that it is 10 to 50%, and it is 15 to 45% optimally. By using the addition amount in this range, the color filter excellent in color characteristics, high contrast, and high brightness can be obtained.

Pigment Dispersion Composition

About adjustment of the coloring photosensitive composition of this invention, it is a preferable aspect to previously disperse | distribute the pigment which has a (A) phthalocyanine frame | skeleton, and another color material together or separately, and to make it as a pigment dispersion composition.

Although the pigment dispersion composition disperse | distributed the said pigment and solvent, it adds and uses a dispersing agent, resin, etc. as needed. Moreover, it can be comprised using another component as needed, such as a pigment derivative.

-Preparation of Pigment Dispersion Composition-

Although the preparation form of the pigment dispersion composition of this invention is not specifically limited, For example, a pigment and a pigment dispersant and a solvent are made into a 0.01-1 mm particle diameter using a longitudinal or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, etc. It can obtain by performing a microdispersion process with the beads which consist of glass, a zirconia, etc.

Before dispersing the beads, kneading and dispersing treatment is performed using two rolls, three rolls, a ball mill, a trom mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single screw, or a twin screw extruder. It is also possible to do this.

Further details on kneading and dispersion are described in T. C. Patton, "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, Inc., 1964).

Pigment Concentration

As content in the pigment dispersion composition of a pigment, 10-60 mass% is preferable with respect to the total solid (mass) of the said composition, and 15-50 mass% is more preferable. If content of a pigment is in the said range, it is effective also in ensuring the color characteristic excellent in color density.

-Dispersants-

It is preferable that a pigment dispersion composition contains at least 1 sort (s) of a dispersing agent. By containing this dispersing agent, the dispersibility of a pigment can be improved.

As a dispersant, a well-known pigment dispersant and surfactant can be selected suitably, for example.

Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP 341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 90, no. Cationic surfactants such as 95 (manufactured by KYOEISHA CHEMICAL Co., LTD.) And W001 (manufactured by YUSHO Co., Ltd.); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005, and W017 (manufactured by YUSHO Co., Ltd.); Amphoteric surfactants having a carboxybetaine structure, an amidebetaine structure, a sulfobetaine structure, a hydroxybetaine structure, and the like; Fluorine-based surfactants such as Megafac F171, F172, and F173 (manufactured by DIC Corporation); EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (all from BASF Japan Ltd. (formerly Chiba Specialty Chemicals, Inc.)), Disperse aid 6, Disperse polymeric dispersants such as aid 8, Disperse aid 15, Disperse aid 9100 (all manufactured by SAN NOPCO LIMITED); Various Solsperse dispersants (manufactured by The Lubrizol Corporation) such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (product of ADEKA CORPORATION) and IONET S-20 ( Sanyo Chemical Industries, Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by BYK Japan KK) are listed. In addition, an acrylic copolymer, an oligomer or polymer having a N, N-disubstituted amino group or an acidic group polar group at the terminal or side chain thereof, a polyurethane resin modified with a tertiary amine, AB described in JP2009-52010A Type, ABA type block copolymer, etc. are mentioned.

As content in the pigment dispersion composition of a dispersing agent, 1-100 mass% is preferable with respect to the total mass of a pigment, and 3-70 mass% is more preferable.

-Pigment derivatives-

Pigment derivative is added to a pigment dispersion composition as needed. By adsorbing a pigment derivative having affinity with a dispersant or a polar group introduced thereon onto the surface of the pigment, and using it as the adsorption point of the dispersant, the pigment can be dispersed as fine particles in the colored photosensitive composition to prevent re-agglomeration. Is high and is effective for constructing a color filter excellent in transparency.

A pigment derivative is the compound which introduce | transduced an acidic group, a basic group, and an aromatic group into a side chain specifically, using an organic pigment as a mother skeleton. Specific examples of the organic pigment include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindolin pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments and benzimidazolones. Pigments and the like. Generally, pale yellow aromatic polycyclic compounds, such as naphthalene series, anthraquinone series, triazine series, and quinoline series, which are not called dyes, are also included. As a pigment derivative, Unexamined-Japanese-Patent No. 11-49974, Unexamined-Japanese-Patent No. 11-189732, Unexamined-Japanese-Patent No. 10-245501, Unexamined-Japanese-Patent No. 2006-265528, Unexamined-Japanese-Patent No. 8-295810 What is described in Unexamined-Japanese-Patent No. 11-199796, Unexamined-Japanese-Patent No. 2005-234478, Unexamined-Japanese-Patent No. 2003-240938, Unexamined-Japanese-Patent No. 2001-356210, etc. can be used.

As content in the pigment dispersion composition of a pigment derivative, 1-30 mass% is preferable with respect to the mass of a pigment, and 3-20 mass% is more preferable. When content of a pigment derivative is in this range, dispersion can be performed favorably, suppressing the viscosity of a pigment dispersion composition low, and the dispersion stability after dispersion can be improved.

Thereby, the coloring photosensitive composition which has a high transmittance | permeability and obtains the outstanding color characteristic is obtained, and when the said coloring photosensitive composition is applied to the manufacturing use of a color filter, for example, it has a favorable color characteristic and obtains a high contrast color filter. Can be.

Moreover, it is also possible to further add high molecular compounds, such as alkali-soluble resin mentioned later, to a pigment dispersion composition. It is considered that polar groups, such as acidic radicals contained in alkali-soluble resin, are effective also for dispersion of a pigment, and are effective for dispersion stability of a pigment dispersion liquid in many cases.

Solvent

It will not specifically limit, if it is an organic solvent used for a general pigment dispersible composition as a solvent in a pigment dispersion composition. For example, 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, acetone, methyl ethyl ketone And solvents such as methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene, melting point and viscosity, pigment In order to adjust the dispersibility of these, it is also possible to use multiple together.

Content of the solvent in a pigment dispersion composition is suitably selected according to the use of a pigment dispersion composition, etc. When a pigment dispersion composition is used for preparation of the coloring photosensitive composition mentioned later, 5-50 mass% of solid content concentration (total amount except a solvent in a pigment dispersion composition) containing a pigment and a pigment dispersant from a viewpoint of handleability is It may contain as much as possible.

As content of the pigment dispersion composition in the coloring photosensitive composition of this invention, content in which the content of a pigment becomes the range of 5-70 mass% with respect to the total solid (mass) of a coloring photosensitive composition is preferable, and it is 15-60 mass% The amount which becomes a range is more preferable. When content of a pigment dispersion composition exists in the said range, it is effective in ensuring the color characteristic excellent in color density.

<(B) solvent>

The coloring photosensitive composition of this invention can be preferably prepared using a solvent generally with the said component.

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoam acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate and 3-oxypropionate and 3 3-oxypropionate alkyl esters such as ethyl oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate) and 2-oxy 2-oxypropionate alkyl esters such as methyl propionate, ethyl 2-oxypropionate and propyl 2-oxypropionate (for example, 2- Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2-methylpropionic acid Ethyl, 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate) and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2 Ethyl oxobutyrate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate and the like;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like;

Aromatic hydrocarbons such as toluene, xylene and the like.

Among these, 3-ethoxy propionate, ethyl 3-ethoxy propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, Ethyl calbitol acetate, butyl calbitol acetate, propylene glycol monomethyl ether acetate, and the like are preferable.

A solvent may be used independently and may be used in combination of 2 or more type.

<(C) Polymerizable Monomer>

In this invention, a polymeric monomer is used as a hardening component of a coloring photosensitive composition.

The polymerizable monomer of the present invention is not particularly limited as long as the polymerizable monomer can be polymerized. Compounds capable of addition polymerization such as low molecular compounds, dimers, trimers, and oligomers having at least one ethylenic double bond can be preferably used.

Examples of the ethylenic compound include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, and unsaturated Ester obtained by esterification reaction of carboxylic acid, polyhydric carboxylic acid, and polyhydric hydroxy compounds, such as fatty acid polyhydroxy compound and aromatic polyhydroxy compound, polyisocyanate compound, and (meth) acryloyl containing hydroxy compound The ethylenic compound etc. which have a urethane skeleton which reacted are mentioned.

Although a specific polymeric compound can be classified into the number of polymeric groups in 1 molecule as shown below, it is not limited to this.

[Compound having one polymerizable group in one molecule]

Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth ) Acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate , Cyanoethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth ) Acrylate, 1H, 1H, 2H, 2H perfluorodecyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylic Latex, phenoxymethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate , Glycidyloxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) ) Acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified Cresol (meth) acrylate, EO modified nonylphenol (meth) acrylate, PO modified nonylphenol (meth) acrylate, EO modified 2-ethylhexyl (meth) acrylate, etc. are mentioned.

[Compound having two polymerizable groups in one molecule]

Examples of the compound having two (meth) acryloyl groups in the same molecule as the polymerizable group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene glycol di (Meth) acrylate, 1, 3- butylene glycol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, neopentyl glycol di ( Meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-hydroxy-1 , 3-diacryloxypropane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, bis (acryl) of bisphenol A Loyloxyethyl) ether, bisphenol A epoxy resin (Meth) acrylic acid modified compound, 3-methylpentanediol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dimethylol-tricyclodecanedi (meth) acrylate, and the like Dimethylol-tricyclodecanedi (meth) acrylate, neopentylglycoldi (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, and (meth) acrylic acid of bisphenol A epoxy resin Modified substances;

[Compound having three polymerizable groups in one molecule]

For example, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, alkylene oxide modified tri (meth) acrylate of trimethylolpropane, pentaerythritol tri (meth) acrylate, dipenta Erythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanurate alkylene oxide modified tri (meth) acrylate, propionate dipentaerythritol tri (meth) acrylate, Tri ((meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde modified dimethylol propane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylic Elate, ethoxylated glycerine triacrylate, etc. can be mentioned.

[Compound having 4 or more polymerizable groups in 1 molecule]

As a compound which has four or more polymerizable groups in 1 molecule, for example, pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, and propionate dipentaerythritol tetra (meth) ) Acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate , Alkylene oxide modified hexa (meth) acrylate of phosphazene, captolactone modified dipentaerythritol hexa (meth) acrylate, KYOEISHA CHEMICAL Co., LTD. The urethane acrylates, such as the product UA-306H, UA-306T, UA-306I, are mentioned.

A preferable compounding quantity of a polymerizable monomer is 5-80 mass%, Preferably it is 10-60 mass%, More preferably, it is the range of 15-50 mass% when the total solid of the coloring photosensitive composition of this invention is 100 mass%. .

Among these, from the viewpoint of maintaining solvent resistance and ITO sputter aptitude preferably in a later step, a (meth) acrylate monomer having two or more (meth) acryloyl groups in the same molecule is preferable, and three or more polymerizable groups It is more preferable to have. In particular, it is advantageous to have four or more polymerizable groups, for example, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate or mixtures thereof (mixing ratio in terms of mass is dipentaerythritol pentaacrylate: dipentaerythritol hexa). Acrylate = 2-4: 8-6) is used preferably from a solvent tolerance or an ITO sputtering aptitude.

From the viewpoint of developing latitude, it is advantageous to have one to three hydrophilic groups in the same molecule, and in particular, a compound having a hydroxyl group or a carboxyl group in the molecule contributes to improvement of developability. From this viewpoint, the compound which has acidic groups, such as a carboxyl group, in the terminal of an acrylate monomer is preferable. Specifically, an acid-modified compound in which an acid group such as a carboxyl group is introduced into an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or maleic acid, or a polyfunctional acrylate compound (for example, ARONIX manufactured by TOAGOSEI CO., LTD.) M-510, ARONIX M-520, ARONIX TO-2349, etc.) are mentioned, Especially ARONIX M-520 and ARONIX TO-2349 are used preferably.

In order to make solvent resistance, ITO sputter aptitude and development latitude compatible, in addition to using a compound containing three or more polymerizable groups and an acid group in the same molecule, a compound having an acid group and a compound having three or more polymerizable groups in one molecule It can also be used in combination. When used in combination, when the polymerizable compound is 100 parts by mass, the compound containing an acid group is used in the range of 1 to 50% by mass, preferably in the range of 1 to 40% by mass, and in the range of 5 to 20% by mass. More preferred.

<(D) Binder Resin>

As the (D) binder resin of the present invention, any of the polymer compounds soluble in the solvent can be used, but as the preferred binder resin, alkali-soluble resins are preferable in view of alkali developability by the photolithography method.

Alkali-soluble resin can also be contained in the step of adjustment of a pigment dispersion composition, and it can also divide and add in both steps of adjustment of a pigment dispersion composition and adjustment of a coloring photosensitive composition.

As alkali-soluble resin, it is a linear organic polymer polymer which is an alkali-soluble polymer which has at least 1 alkali-soluble group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.) in it, More preferably, it is soluble in an organic solvent, It is preferable that it can develop.

For the production of alkali-soluble resin, for example, a method by a known radical polymerization method can be applied. The polymerization conditions such as the temperature, pressure, the kind and amount of the radical initiator, the kind of the solvent, and the like when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and the conditions can be determined experimentally. .

As said linear organic high polymer, the polymer which has a carboxylic acid in a side chain is preferable. For example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication 54-34327, Japanese Patent Publication 58-12577, Japanese Patent Publication 54-25957, Japanese Patent Publication 59-53836, Japan Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like, as described in the respective publications of Patent Publication No. 59-71048 The acid cellulose derivative which has a carboxylic acid, the thing which added an acid anhydride to the polymer which has a hydroxyl group, etc. are mentioned, The high molecular polymer which has a (meth) acryloyl group in a side chain is also mentioned as a preferable thing.

Among these, in particular, a multicomponent copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid copolymer or benzyl (meth) acrylate / (meth) acrylic acid / other monomer is preferable. In addition, copolymers of methacrylic acid 2-hydroxyethyl and the like are also listed as useful. The said polymer can be mixed and used in arbitrary quantity.

In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and 2-hydroxy-3-phenoxypropyl described in JP-A-7-140654 Acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macro monomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxy Ethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like.

As other alkali-soluble binder resin, Unexamined-Japanese-Patent No. 7-207211, Unexamined-Japanese-Patent No. 8-259876, Unexamined-Japanese-Patent No. 10-300922, Unexamined-Japanese-Patent No. 11-140144, Japan The well-known high molecular compound of Unexamined-Japanese-Patent No. 11-174224, Unexamined-Japanese-Patent No. 2000-56118, Unexamined-Japanese-Patent No. 2003-233179, Unexamined-Japanese-Patent No. 2009-52020, etc. can be used.

About the specific structural unit of alkali-soluble resin, especially the copolymer of (meth) acrylic acid and the other monomer copolymerizable with this can be easily obtained, and it is used preferably from the point which is easy to adjust alkali solubility.

As another monomer copolymerizable with the said (meth) acrylic acid, an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned. Here, the hydrogen atom of an alkyl group and an aryl group may be substituted by the substituent.

Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth). Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate Can be enumerated.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl (meth) acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl (meth) acrylate, Polystyrene macromonomer, polymethylmethacrylate macromonomer, CH ₂ = CR ³¹ R ³² [wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms ], CH ₂ = C (R ³¹ ) (COOR ³³ ) [wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³³ represents an alkyl group having 1 to 8 carbon atoms or 6 to 12 carbon atoms An aralkyl group.] May be enumerated.

These copolymerizable other monomers can be used individually by 1 type or in combination of 2 or more types. Preferred copolymerizable other monomers are at least one selected from CH ₂ = CR ³¹ R ³² , CH ₂ = C (R ³¹ ) (COOR ³³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene, Especially preferred are CH ₂ = CR ³¹ R ³² and / or CH ₂ = C (R ³¹ ) (COOR ³³ ). R ³¹ , R ^32, and R ³³ are synonymous with those described above, respectively.

In the present invention, the binder resin (D) may be used as a single compound or a plurality of compounds may be used in combination. As content of binder resin, such as alkali-soluble resin in a coloring photosensitive composition, 1-20 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 2-15 mass%, Especially preferably, it is 3-12 Mass%.

Moreover, the range of 0.1-10 is preferable at mass ratio, as for the mix | blending of (C) polymeric monomer / (D) binder resin, the range of 0.4-8 is more preferable, The range of 0.5-5 is still more preferable.

<(E) Photoinitiator>

The (E) photoinitiator in this invention can be used widely without limitation as long as it is a well-known compound which has the ability to start superposition | polymerization by light irradiation.

Known photopolymerization initiators generally used are, for example, camphor quinone, benzophenone, benzophenone derivatives, acylphosphine, acylphosphine derivatives, acetophenone, acetophenone derivatives, for example α-hydroxycycloalkylphenylketones or 2-hydroxy-2-methyl-1-phenyl-propane, dialkoxyacetophenones, α-hydroxy- or 4-aloyl-1,3-dioxolanes, benzoin alkyl ethers and benzyl ketals Benzyldimethyl ketal, phenyl glyoxalate and its derivatives, dimeric glyoxalate, peresters, for example benzophenonetetracarboxylic acid peresters (for example those described in EP 1126,541). ), Halomethyltriazines, for example 2- [2- (4-methoxy-phenyl) -vinyl] -4,6-bis-trichloromethyl [1,3,5] triazine, 2- (4 -Methoxy-phenyl) -4,6-bis-trichloromethyl [1,3,5] triazine, 2- (3,4-dimethoxy-phenyl) -4,6-bis-trichloromethyl [1 , 3, 5] triazine, 2-methyl-4,6-bis-trichloromethyl [1,3,5] triazine, hexaarylbisimidazole / co-initiator system, for example in combination with 2-mercaptobenzothiazole Ortho-chlorohexaphenyl-bisimidazole; Ferrocenium compounds or titanocenes such as dicyclopentadienyl-bis (2,6-difluoro-3-pyrrolo-phenyl) titanium; For example, a mixture with an O-acyl oxime ester compound as described in GB 2,339,571 may be used. Boric acid compounds can also be used as co-initiators.

As for content of the photoinitiator in the composition of this invention, about 0.05-30 mass% of a total solid is preferable, It is more preferable that it is 0.1-20 mass%, It is more preferable that it is 0.2-10 mass%.

It is also preferable that the coloring photosensitive composition of this invention contains a co-sensitizer. In the present invention, the sensitizer has an effect of further improving the sensitivity of the sensitizing dye and the initiator to the actinic radiation, or inhibiting the polymerization inhibition of the photopolymerizable compound by oxygen.

Examples of such a desensitizer include, for example, MR Sander et al., Journal of Polymer Society, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Japanese Patent Application Laid-Open No. 52-134692, Japanese Patent Publication No. 59-138205, Japanese Patent Publication No. 60-84305, Japanese Patent Publication No. 62-18537, Japanese Patent Publication No. 64-33104, Research Disclosure The compound of 33-33 etc. are mentioned, Specifically, a triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthio dimethylaniline, etc. are mentioned.

As another example of a sensitizer, thiols and sulfides such as thiol compounds described in Japanese Patent Application Laid-Open No. 53-702, Japanese Patent Application Laid-Open No. 55-500806, Japanese Patent Application Laid-Open No. 5-142772, and Japanese Patent The disulfide compound of Unexamined-Japanese-Patent No. 56-75643, etc. are mentioned, Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 ( 3H) -quinazolin, β-mercaptonaphthalene, and the like.

As another example, an amino acid compound (e.g., N-phenylglycine), an organometallic compound described in Japanese Patent Publication No. 48-42965 (e.g., tributyltin acetate, etc.), Japanese Patent Publication No. 55-34414 The hydrogen donor of description, the sulfur compound of Unexamined-Japanese-Patent No. 6-308727 (for example, trithiane etc.), etc. are mentioned.

As for content of a sensitizer, the range of 0.1-30 mass% is preferable with respect to the mass of the total solid of a photosensitive composition from a viewpoint of the hardening speed improvement by the balance of a polymerization growth rate and a chain transfer, and the range of 1-25 mass% is more Preferably, the range of 0.5-20 mass% is more preferable.

<(F) Polymerizable Compound Having Radical Capture Capability>

The coloring photosensitive composition of this invention contains the polymeric compound (Hereinafter, it may be called an "additive.") Which has (F) radical trapping ability.

The coloring photosensitive composition of this invention is heat-processed (postbaking) at the temperature of 100-250 degreeC in the formation process of the coloring pattern for color filters as mentioned later. Generally, many compounds have been reported as additives having a radical trapping ability, but it is required that the radical trapping ability is not deactivated after the heat treatment. Since a polymeric compound is especially hard to volatilize or decompose | disassemble by heat, since it is excellent in heat resistance, it exhibits a remarkable effect in the aspect of this invention.

The characteristic of the coloring photosensitive composition of this invention is the point which used the polymeric compound which has (F) radical trapping ability, and by this point, the light resistance after ITO sputter | spatter, and also developability, without impairing the intrinsic transparency and color purity of a colorant. It becomes possible to cope with solvent resistance.

Although the effect of improving light resistance by the polymerizable compound having radical trapping ability is not clearly understood, discoloration at the time of light resistance test is suppressed by trapping colored radicals generated when the phthalocyanine-based color material is excited by light irradiation at the present time. It is estimated to be. In particular, the polymerizable compound having a radical trapping ability is less volatile and decomposed by heating as compared with other nonpolymerizable radical trapping agents, and it is estimated that the polymer compound captures radicals most effectively in light irradiation after postbaking.

The additive of the present invention is composed of a polymerizable moiety and a radical trapping moiety. The polymerizable moiety and the radical trapping moiety may be directly bonded, or a linking moiety for binding both may be introduced. You may use together 2 or more types of additives. Hereinafter, each part is demonstrated.

The radical capture site exhibits the effect of suppressing deterioration due to radical generation by light irradiation. It is preferable that the polymeric compound which has the said (F) radical trapping ability is a compound which has an amine structure or a phenol structure, and the structure of a hindered amine type, a hindered phenol type, a sulfur type, and a phosphorus type is mentioned as what is generally known. . Among them, a hindered amine structure or a hindered phenol structure is preferable in view of radical trapping ability. Specifically, as a hindered amine type, a (1,2,2,6,6-pentamethyl-4-piperidinyl) group, a (2,2,6,6-tetramethyl-4-piperidinyl) group, As a hindered phenol type, it is a 3, 5- t- butyl- 4-hydroxyphenyl group.

Here, the hindered means a three-dimensional obstacle. Due to steric hindrance, the reaction rate of the radical trapping site is lowered, and thus it is preferably used as a radical trapping agent in that it is possible to efficiently trap only highly active radicals.

The polymerizable moiety has an effect of preventing volatilization and decomposition of the radical trapping moiety. As a polymerizable site | part of the additive of this invention, as long as it is a structure in which a polymerization reaction advances by heat or light irradiation, generally well-known polymeric group can be used without a restriction | limiting. As a specific polymerization group, a (meth) acryloyl group, a (meth) acryloyloxy group, a (meth) acrylamide group, a vinyl group, a vinyloxy group, a maleimide group, an epoxy group, glycidyl group, etc. are mentioned. In addition, some of these polymerizable groups may be substituted. It is preferable to have at least 1 chosen from an acryloyl group and a methacryloyl group as a polymeric group among these, and specifically, as a polymeric site | part, a (meth) acryloyl group and a (meth) acryloyloxy group are the simplicity of a synthesis | combination. It is preferable at the point of.

If the linking site is a general organic group, it can be widely used without particular limitation such as a cyclic aliphatic group, a chain aliphatic group, an aromatic group, but an alkyl group or a polyethylene glycol chain is particularly preferable. The said organic group may have a branch, and, when it has a branch, may have several polymeric site | part or radical capture site | part in each terminal. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, cyclohexyl, cyclopentyl, neopentyl, isopropyl and isobutyl. And the like. As number of carbon atoms of the said alkyl group, 1-30 are preferable and 1-10 are more preferable. Regarding the polyethylene glycol chain, the preferred range of carbon atoms is the same as in the case of an alkyl group.

As for content of the polymeric compound which has the (F) radical trapping ability in this invention, about 0.1-5.0 mass% is preferable with respect to the total solid of a coloring photosensitive composition, It is more preferable that it is 0.2-4.0 mass%, 0.5- It is more preferable that it is 2.0 mass%.

When the addition amount is less than 0.1%, the radical trapping effect may not be sufficiently exhibited. When it exceeds 5.0%, the sensitivity to exposure decreases, and when used as a color filter, a desired pattern cannot be formed, or surface roughness or dropping out occurs. It may occur.

Hereinafter, a hindered amine type polymeric compound and a hindered phenol type polymeric compound are demonstrated concretely.

As a radical trapping site in the hindered amine type polymerizable compound, piperidine, pyridine, pyrazine, triazine, pyrimidine, pyrrole, pyrrolidone, pyrrolidine, indole, imidazole and tria from the viewpoint of radical trapping ability It is preferably a sol, purine, putrin or pyrazole, more preferably piperidine, pyrrole or pyrrolidine, still more preferably piperidine.

As the hindered piperidine, the carbon atoms (2-position and 6-position) adjacent to the nitrogen atom of piperidine preferably do not have a hydrogen atom, and the hydrogen atom is preferably substituted with an alkyl group. The nitrogen atom of piperidine preferably has a hydrogen atom or is substituted with an alkyl group.

It is preferable that it is 3-position or 4-position, and, as for the substitution position of a polymeric site in piperidine, it is more preferable that it is 4-position.

As a polymeric site | part in a hindered amine type polymeric compound, a (meth) acryloyl group or a (meth) acryloyloxy group is preferable and a (meth) acryloyloxy group is more preferable.

In the hindered amine polymerizable compound, the radical trapping site and the polymerizable site may be directly bonded or may be bonded to the linking site.

The compound which has a structure of following General formula (1) from a viewpoint of the stability and the ease of handling of a compound among a hindered amine type polymeric compound is preferable.

In the general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a cyano group, a hydroxy group, an alkyl group of 10 or less carbon atoms, or an alkoxy of 10 or less carbon atoms. Carbonyl group, C10 or less alkylsulfonylaminocarbonyl group, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, C10 or less acylaminosulfonyl group, C10 or less alkoxy group, C10 or less Alkylthio group, C10 or less aryloxy group, nitro group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, C10 or less acyl group, C10 or less acyloxy group, carbamoyl group, A sulfamoyl group, a C10 or less aryl group, a substituted amino group, a substituted ureido group, a substituted phosphono group or a heterocyclic group. R ⁴ represents a hydrogen atom or an alkyl group having 30 or less carbon atoms. X represents a single bond, an ester group, an aliphatic alkyl chain having 30 or less carbon atoms, an aromatic chain, a polyethylene glycol chain, or a (m + n) valent linking group formed by combining them. m and n respectively independently represent the integer of 1 or more and 3 or less.

R ¹ , R ² and R ³ in General Formula (1) each independently represent a hydrogen atom, a halogen atom, an alkyl group of 10 or less carbon atoms, an alkoxy group of 10 or less carbon atoms, an alkoxycarbonyl group of 10 or less carbon atoms, or carbon atoms. 10 or less aryloxy groups, an acyl group of 10 or less carbon atoms, an acyloxy group of 10 or less carbon atoms, more preferably a hydrogen atom or an alkyl group of 10 or less carbon atoms, a hydrogen atom or an alkyl group of 5 or less carbon atoms Is more preferable, and a hydrogen atom or a methyl group is more preferable. In particular, R ¹ and R ² are preferably hydrogen atoms.

R ⁴ in General Formula (1) is preferably a hydrogen atom or an alkyl group having 30 or less carbon atoms, more preferably a hydrogen atom or an alkyl group having 10 or less carbon atoms, still more preferably a hydrogen atom or a methyl group.

In General Formula (1), X is preferably a single bond or a linking group represented below. In the following linking group, * represents the position of connection with a radical capture site or a polymerizable site. n respectively independently represents the integer of 30 or less, It is preferable that it is an integer of 3 or more and 15 or less, It is more preferable that it is an integer of 3 or more and 10 or less.

It is preferable that m and n in General formula (1) are 1 or 2 each independently.

Although the specific example of a compound represented by General formula (1) is shown below, it is not limited to these compounds.

Among the compounds represented by the general formula (1), in particular, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate (formula (3) below), 2,2,6,6-tetra Methyl-4-piperidinyl methacrylate (formula (4)) etc. are used preferably.

(Equation (3))

(Equation (4))

The radical trapping site in the hindered phenolic polymerizable compound is a phenolic hydroxyl group, and the carbon atoms (2-position and 6-position) adjacent to the hydroxyl group of the phenol preferably do not have a hydrogen atom. It is preferable that the atom is substituted by the alkyl group, It is more preferable that the said alkyl group is a branched alkyl group, It is still more preferable that it is a branched alkyl group of 30 or less carbon atoms.

The substitution position of the polymerizable moiety in the phenol is preferably 2 or 4 positions.

As a polymeric site | part in a hindered phenol type polymeric compound, a (meth) acryloyl group or a (meth) acryloyloxy group is preferable, and a (meth) acryloyloxy group is more preferable.

In the hindered phenol type polymerizable compound, the radical trapping site and the polymerizable site may be directly bonded or may be bonded to the linking site.

The compound which has a structure of following General formula (5) or (6) from a viewpoint of the stability and the ease of handling of a compound among a hindered phenol type polymeric compound is preferable.

In the general formulas (5) and (6), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a cyano group, a hydroxy group, an alkyl group having 10 or less carbon atoms, C10 or less alkoxycarbonyl group, C10 or less alkylsulfonylaminocarbonyl group, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, C10 or less acylaminosulfonyl group, C10 or less alkoxy group , C10 or less alkylthio group, C10 or less aryloxy group, nitro group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, C10 or less acyloxy group, C10 or less acyl A real group, a carbamoyl group, a sulfamoyl group, a C10 or less aryl group, a substituted amino group, a substituted ureido group, a substituted phosphono group, or a heterocyclic group is shown. R ⁵ and R ⁶ each independently represent a branched alkyl group having 30 or less carbon atoms. X represents a single bond, an ester group, an aliphatic alkyl chain having 30 or less carbon atoms, an aromatic chain, a polyethylene glycol chain, or a (m + n) valent linking group formed by combining them. m and n respectively independently represent the integer of 1 or more and 3 or less.

R <^1> , R <^2> and R <^3> in General formula (5) and (6) are respectively independently a hydrogen atom, a halogen atom, a C10 or less alkyl group, a C10 or less alkoxy group, or a C10 or less Alkoxycarbonyl group, C10 or less aryloxy group, C10 or less acyl group, C10 or less acyloxy group are preferable, A hydrogen atom or a C10 or less alkyl group is more preferable, A hydrogen atom or C5 More preferably, no more than two alkyl groups are more preferable, and a hydrogen atom or a methyl group is more preferable. In particular, R ¹ and R ² are preferably hydrogen atoms.

R <^5> and R <^6> in General formula (5) and (6) respectively independently have a C15 or less branched alkyl group, More preferably, a C10 or less branched alkyl group is more preferable, t-butyl group, 2 More preferably, they are a dimethylpropyl group, 2-dimethylbutyl group, 2,3-dimethylbutyl group, a phenyl group (which may be substituted), or a benzyl group (which may be substituted), and t-butyl group or 2-dimethylpropyl group. More preferred.

It is preferable that X in General formula (5) and (6) is a coupling group shown below. In the following linking group, * indicates a linking position with a radical trapping site or a polymerizable site. n respectively independently represents the integer of 30 or less, It is preferable that it is an integer of 3 or more and 15 or less, It is more preferable that it is an integer of 3 or more and 10 or less. In the following linking group, R represents a hydrogen atom or an alkyl group having 10 or less carbon atoms.

It is preferable that m and n in General formula (5) and (6) are 1 or 2 each independently.

Although the specific example of a compound represented by General formula (5) and (6) is shown below, it is not limited to these compounds.

Among the compounds represented by the general formulas (5) and (6), the compound represented by the following general formula (7) is preferable.

In General formula (7), R <^7> represents a hydrogen atom or a C5 or less alkyl group, R <^8> represents a C15 or less branched alkyl group or an aryl group, and R <^9> represents a C15 or less alkyl group.

R <^8> in General formula (7) has a C10 or less branched alkyl group or an aryl group, A t-butyl group, a 2, 2- dimethyl propyl group, a 2, 2- dimethyl butyl group, 2, 3- dimethyl group It is more preferable that it is a butyl group, a phenyl group (which may be substituted), or a benzyl group (which may be substituted), and it is still more preferable that it is a t-butyl group or a 2, 2- dimethylpropyl group.

R ⁹ in General Formula (7) is preferably an alkyl group having 10 or less carbon atoms, and more preferably an alkyl group having 5 or less carbon atoms.

Among the compounds represented by the general formula (7), the following compound I (Sumitomo Chemical Co., Ltd. Sumilizer GM), the following compound II (Sumitomo Chemical Co., Ltd. Sumilizer GS) and the like are preferably used.

(Compound I)

(Compound II)

The coloring photosensitive composition of this invention can contain various additives, such as a ultraviolet absorber, a thermal-polymerization initiator, surfactant, a development accelerator, a thermal polymerization inhibitor, a filler, a dispersing agent, and an aggregation inhibitor, as needed.

You may add the normal ultraviolet absorber which does not contain a polymeric group in the range which does not harm with respect to the polymeric compound which has the said (F) radical trapping ability. In this case, it is preferable to use an organic ultraviolet absorbent having good compatibility with the polymerizable compound having (F) radical trapping ability, and thus a synergistic effect can be expected. In particular, the compound derivative whose main skeleton is a hydroxy benzophenone type, a benzotriazole type, a cyanoacrylate type, and a triazine type is preferable. Moreover, polymers, such as a vinyl polymer, containing these ultraviolet absorbers in a side chain may be sufficient.

Specifically 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy Benzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-benzyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-diethoxybenzophenone, 2,2'-dihydroxy-4,4 '-Dipropoxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-propoxybenzophenone, 2 , 2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2- (2-hydroxy-5-t-methylphenyl) benzotriazole , 2- (2-hydroxy-5-t-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, ethyl-2-cyano- 3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2- (2-hydroxy-4-hex (Co) polymer of siloxyphenyl) -4,6-diphenyltriazine, 2-hydroxy-4- (2-acryloxyethoxy) benzophenone, 2- (2'-hydroxy-5'-meta And (co) polymers of krilloxyethylphenyl) -2H-benzotriazole and the like. You may use together 2 or more types of these organic type ultraviolet absorbers.

It is also effective to contain a thermal polymerization initiator in the colored photosensitive composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds, and examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketone peroxide, peroxy ketal, and hydroperoxide. , Dialkyl peroxide, diacyl peroxide, peroxy ester, peroxydicarbonate, and the like.

It is preferable to comprise in the coloring photosensitive composition of this invention using various surfactant from a viewpoint of improving applicability | paintability. The liquid characteristics (particularly fluidity) at the time of using a surfactant as a coating liquid can be improved, and the uniformity of coating thickness and liquid saving property can be improved. That is, since the interfacial tension between the substrate and the coating liquid is decreased, the wettability to the substrate is improved, and the coating property to the substrate is improved, so that even when a thin film having a thickness of several micrometers is formed with a small amount of liquid, a uniform thickness with a small thickness unevenness is obtained. It is effective in that film formation is possible. Moreover, it is effective also in slit application | coating which is easy to produce liquid fall.

As surfactant, various surfactant of nonionic, cationic, and anionic type can be used. Especially, the fluorine-type surfactant which has a perfluoroalkyl group as a nonionic surfactant is preferable.

3-40 mass% is preferable, as for the fluorine content rate of a fluorine-type surfactant, More preferably, it is 5-30 mass%, Especially preferably, it is 7-25 mass%. If the fluorine content is in the above range, it is effective in terms of coating thickness uniformity and liquid saving property, and the solubility in the composition is also good.

As the fluorine-based surfactant, for example, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437 (above, manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, Sumitomo 3M), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, ASAHI GLASS CO., LTD.), Etc. are mentioned.

Examples of surfactants other than fluorine-based include phthalocyanine derivatives (commercially available EFKA-745 (manufactured by MORISHITA SANGYO CORPORATION), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer polymer No) 75, No. 90, No. 95 (produced by KYOEISHA CHEMICAL Co., LTD.), W001 (produced by YUSHO Co., Ltd.) and other cationic surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl Ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (BASF Pluronic L10, L31, L61, L62 And nonionic surfactants such as 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, and anionic surfactants such as W004, W005, and W017 (manufactured by YUSHO Co., Ltd.). .

As for the addition amount of surfactant, 0.001-2.0 mass% is preferable with respect to the total mass of a pigment dispersion composition or a coloring photosensitive composition, More preferably, it is 0.005-1.0 mass%.

In addition, when promoting alkali solubility of an uncured part and aiming at further improving developability of a coloring photosensitive composition, addition of organic carboxylic acid, preferably low molecular weight organic carboxylic acid of molecular weight 1000 or less to a coloring photosensitive composition. Can be done. Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sublinic acid, azelaic acid, sebacic acid, brazilian, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; Other carboxyl such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildeacetic acid, coumalic acid, umbelic acid Acids are listed.

It is preferable to further add a thermal polymerization inhibitor to the colored photosensitive composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzo Quinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzoimidazole, etc. This is useful.

<Dispersants, Fillers, Agglomeration Agents>

In addition to the above, specific examples of the additive in the colored photosensitive composition include EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (above, MORISHITA SANGYO CORPORATION), and Disperse aid. 6, Disperse aid 8, Disperse aid 15, Disperse aid 9100 (manufactured by SAN NOPCO LIMITED);

Various Solsperse dispersants (manufactured by AstraZeneca) such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000;

Fillers such as glass and alumina; And

Agglomeration inhibitors, such as sodium polyacrylate, can be mentioned.

The coloring photosensitive composition of this invention is a (C) polymerizable monomer, (D) binder resin, (E) photoinitiator, (F) in the solution or dispersion of the (A) color material containing the (B) solvent of this invention mentioned above. A polymerizable compound (preferably with (B) solvent) which has a radical trapping ability is contained, and it can prepare by mixing other additives, such as surfactant, as needed.

The color filter of this invention is produced by forming the colored film (coloring pattern) on the board | substrate, such as glass, using the coloring photosensitive composition of this invention mentioned above, For example, the coloring photosensitive composition of this invention directly to a board | substrate. Or through another layer (preferably applied by a coating method such as rotation coating, slit coating, flexible coating, roll coating, etc.) to form a photosensitive film, and exposure to the formed photosensitive film (coloring layer) through a predetermined mask pattern. After the exposure, the uncured portion is developed and removed by the developer to form a color filter (e.g., a colored pixel) of each color (e.g., three or four colors) most preferably to produce a color filter. .

Thereby, the color filter used for a liquid crystal display device or a solid-state image sensor has little difficulty in a process, and can manufacture high quality and low cost.

At this time, as radiation used for exposure, especially ultraviolet rays, such as g line | wire, h line | wire, i line | wire, j line | wire, are preferable.

In addition to the general proximity exposure method, an exposure method using a laser light source can also be preferably used. In the laser exposure method, an ultraviolet light laser is used as the light source. Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Oscillators and amplifiers that produce monochromatic light with high coherence and directivity by amplifying and oscillating light waves by using the phenomenon of induced emission among materials with inversion distribution, and crystals, glass, liquids, pigments, and gases as excitation media. From these media, lasers having an oscillation wavelength can be used for known ultraviolet light such as solid lasers, liquid lasers, gas lasers and semiconductor lasers. Especially, a solid state laser and a gas laser are preferable from a viewpoint of a laser output and an oscillation wavelength.

As a wavelength which can be used for this invention, the ultraviolet light laser of the wavelength range of 300 nm-380 nm is preferable, More preferably, the ultraviolet light laser of the wavelength of 300 nm-360 nm is matched with the photosensitive wavelength of a resist. Preferred at

Specifically, the third harmonic (355 nm) of the Nd: YAG laser of a solid laser having a large output and relatively low cost, and the XeCl (308 nm) and XeF (353 nm) of the excimer laser can be preferably used.

As exposure amount of a to-be-exposed object (pattern), it is the range of 1mJ / cm <2> -100mJ / cm <2>, and the range of 1mJ / cm <2> -50mJ / cm <2> is more preferable. It is preferable at the point of the productivity of pattern formation that an exposure amount is the range.

Although there is no restriction | limiting in particular as an exposure apparatus which can be used for this invention, As what is marketed, Callisto (made by V Technology Co., Ltd.), EGIS (made by V Technology Co., Ltd.), and DF2200G (DAINIPPON SCREEN MGF.CO. , LTD. Products). Moreover, the apparatus of that excepting the above is also used preferably.

It is also possible to use light emitting diodes (LED) and laser diodes (LD) as active radiation sources. In particular, when an ultraviolet source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia CORPORATION markets purple LEDs with a extraction spectrum of wavelengths between 365 nm and 420 nm. In addition, US Patent No. 6,084,250 discloses LEDs capable of emitting active radiation centered between 300 nm and 370 nm when a shorter wavelength is required. In addition, other ultraviolet LEDs are also available and can irradiate radiation in other ultraviolet bands. Particularly preferred active radiation sources in the present invention are UV-LEDs, particularly preferably UV-LEDs having a peak wavelength at 340-370 m.

Since the ultraviolet light laser has good parallelism, the pattern exposure can be performed without using a mask at the time of exposure. However, when pattern exposure is performed using a mask, the linearity of the pattern is further increased, which is more preferable.

Drying (prebaking) of the film by the colored photosensitive composition of the present invention imparted (preferably applied) on a substrate can be performed under a condition of 10 to 300 seconds in a temperature range of 50 to 140 ° C. using a hot plate or an oven. have.

In image development, the uncured part after exposure is eluted to a developing solution, and only a hardened part remains. As image development temperature, it is 20-30 degreeC normally, and as image development time, it is 20 to 90 second.

As a developing solution, as long as it melt | dissolves the film | membrane of the coloring photosensitive composition in an uncured part, as long as it does not melt a hardened part, any can be used. Specifically, a combination of various organic solvents and an alkaline aqueous solution can be used.

As said organic solvent, what was listed as the above-mentioned solvent which can be used when preparing the pigment dispersion composition or colored photosensitive composition of this invention is mentioned.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and tetraethylammonium. The concentration of the alkaline compounds such as hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001-10% by mass, preferably 0.01- The alkaline aqueous solution dissolved so that it may become 1 mass% is mentioned.

In addition, when alkaline aqueous solution is used as a developing solution, washing | cleaning (rinse) with water is generally performed after image development.

After image development, excess developer is wash | cleaned and removed, and after drying, heat processing (post-baking) is generally performed at the temperature of 100-250 degreeC.

Post-baking is the heating after image development to make hardening perfect, and heat (hard baking) of about 200 degreeC-250 degreeC is normally performed. This post-baking process can be performed continuously or batchwise using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater, so that the coating film after image development may be in said condition.

By repeating the above operation sequentially for each color in accordance with the desired number of colors, it is possible to produce a color filter in which a cured film in which a plurality of colors are colored is formed.

When providing the coloring photosensitive composition of this invention on a board | substrate and forming a film, as a dry thickness of a film, it is generally 0.3 micrometer-5.0 micrometers, Preferably it is 0.5 micrometer-3.5 micrometers, Most preferably, it is 1.0 micrometer-2.5 micrometers. .

Examples of the substrate include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used in liquid crystal displays, and the like, and a photoconductive device substrate used for attaching a transparent conductive film thereto or a solid-state image sensor, for example. Silicon substrates and the like and plastic substrates. On these board | substrates, the black stripe which isolate | separates each pixel normally is formed.

It is preferable that the plastic substrate has a gas barrier layer and / or a solvent-resistant layer on its surface.

As another layer in the case of providing a coloring photosensitive composition through another layer on a board | substrate, a gas barrier layer, a solvent-resistant layer, etc. are mentioned.

[Liquid crystal display device]

The color filter of this invention is especially preferable as a color filter for liquid crystal display devices. The liquid crystal display device provided with such a color filter can display a high quality image.

For the definition of the display device and the description of each display device, for example, "Electronic display device" by Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd. 1990), "Display device (by Ibuki Sumiaki, Sangyo Tosho Publishing Co) ., Ltd., issued in 1989). In addition, about a liquid crystal display device, it describes in the "next-generation liquid crystal display technology (Tatsuo Uchida editing, Kogyo Chosakai Publishing Co., Ltd. 1994 issuance)." There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in said "next-generation liquid crystal display technology."

The color filter of this invention is especially effective especially with respect to the liquid crystal display device of a color TFT system. About the liquid crystal display device of a color TFT system, it describes in a "color TFT liquid crystal display (KYORITSU SHUPPAN CO., LTD. 1996 issuance)", for example. In addition, the present invention can also be applied to a liquid crystal display device having an enlarged viewing angle such as a transverse electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB.

In addition, the color filter of the present invention can be provided in a bright and high-definition color-filter on array (COA) method. In the COA type liquid crystal display device, the required characteristics for the color filter layer need to be required for the interlayer insulating film, that is, low dielectric constant and peeling liquid resistance in addition to the usual required characteristics as described above. The color filter of this invention is considered to improve the transmittance | permeability of the ultraviolet light laser which is exposure light by selecting the color and film thickness of the pixel prescribed | regulated by this invention in addition to the exposure method by an ultraviolet light laser. As a result, the curability of the colored pixel can be improved, and since a pixel without missing, peeling or wrinkles can be formed, especially the peeling liquid resistance of the colored layer provided directly or indirectly on the TFT substrate is improved, and the liquid crystal of the COA system is improved. It is useful for display devices. In order to satisfy the required characteristic of low dielectric constant, you may form a resin film on a color filter layer.

Further, in the colored layer formed by the COA method, a rectangular through hole or a U-shape having a length of about 1 to 15 µm on one side in order to conduct the terminal of the ITO electrode disposed on the colored layer and the terminal for driving the substrate below the colored layer. It is necessary to form a conductive path such as a pit, and the dimension (that is, the length of one side) of the conductive path is preferably set to 5 µm or less in particular, but it is also possible to form a conductive path of 5 µm or less by using the present invention. It is possible.

These image notation methods are described, for example, in page 43 of "EL, PDP, LCD display technology and the latest trends in the market (issued in 2001 by TORAY RESEARCH CENTER research).

The liquid crystal display device of this invention is comprised from various members, such as an electrode substrate, a polarizing film, retardation film, a backlight, a spacer, a viewing angle guarantee film, in addition to the color filter of this invention. The color filter of this invention can be applied to the liquid crystal display device comprised from these well-known members.

For these members, for example, the '94 market for liquid crystal display peripheral materials and chemicals (Kenma Kentarou CMC Publishing CO., LTD. 1994 issuance), '' the current status and future prospects of the 2003 liquid crystal market (the lower volume) (Omote Ryokichi Fuji Chimera Research Institute, Inc., 2003).

Backlights are described in SID meeting Digest 1380 (2005) (A. Konno et al.) Or pages 18-24 (Shima Yasuhiro, pages 25-30 (Yagi Takaaki)) of the December 2005 issue of Monthly Display.

When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a three-wavelength tube of a conventionally known cold cathode tube, but luminance is achieved by using red, green, and blue LED light sources (RGB-LEDs) as backlights. It is possible to provide a liquid crystal display device having a high, high color purity and good color reproducibility.

Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. In addition, "%" and "part" are mass references | standards unless there is particular notice.

Synthesis of Phthalocyanine Pigment

Zinc phthalocyanine was manufactured using phthalodinitrile and zinc chloride as a raw material.

Halogenation was performed by mixing 3.1 parts of sulfuryl chloride, 3.7 parts of anhydrous aluminum chloride, 0.46 parts of sodium chloride, and 1 part of zinc phthalocyanine at 40 ° C, and dropping 2.2 parts of bromine. The mixture was reacted at 80 ° C for 15 hours, after which the reaction mixture was poured into water to precipitate a partially zinc bromide phthalocyanine crude pigment. This aqueous slurry was filtered, washed with warm water at 80 ° C, and dried at 90 ° C to obtain 2.6 parts of purified partially zinc bromide phthalocyanine pigment.

1 part of this partial zinc bromide phthalocyanine pigment, 7 parts of crushed sodium chloride, 1.6 parts of diethylene glycol, and 0.09 parts of xylene were added to a twin kneader, and kneaded at 100 ° C for 6 hours. After kneading, the mixture was taken out with 100 parts of 80 ° C water, and after stirring for 1 hour, a partially filtered zinc bromide phthalocyanine pigment was obtained by filtration, hot water, drying and pulverization.

The obtained partially zinc bromide phthalocyanine pigment contained ZnPcBr ₁₀ Cl ₄ H ₂ (Pc; phthalocyanine) as an average composition from halogen content analysis by mass spectrometry containing an average of 10 bromine and 4 chlorine in one molecule.

In addition, the average value of the primary particle diameter measured by the transmission electron microscope (JEM-2010 by JEOL Ltd.) was 0.065 micrometer.

-Synthesis of Quinophthalone Compound-

Quinophthalone pigment (4,5,6,7-tetrachloro-2- [2- (4,5,6,7-tetrachloro-2,3-dihydro-1,3-dioxo-1H-indene 2-yl) -8-quinolinyl] -1H-isoindole-1,3 (2H) -dione ("Paliotol" Yellow K0961HD from BASF) fuming sulfuric acid (25% SO ₃ ) at 15 ° C. with stirring ) Was put in 130g. After stirring for 3 hours, it was added to 250 g of ice. After leaving for 30 minutes, the resulting suspension was filtered, and the obtained product was washed with 50 ml of water.

The product was added to 330 ml of water, and neutralized with an aqueous ammonia solution (added with an aqueous ammonia solution until pH reached 7). 75 g of ammonium chloride was added, and the mixture was stirred at 80 ° C for 30 minutes, and the precipitated precipitate was filtered at 60 ° C. The obtained wet crystal was washed with water, dried at 80 ° C., and an ammonium salt (3) of 17 g of quinophthalone derivative sulfonate was obtained.

Ammonium salt (3) of this quinophthalone derivative sulfonate was heat-treated at 180 ° C. for 3 hours to obtain 16 g (yield 94%) of quinophthalone derivative sulfonate (4) from which the ammonium salt was removed.

To 10 g of sulfonate (4) was added 2.2 g of oxalyl chloride (from Wako Pure Chemical Industries, Ltd.) under ice cooling in chloroform, 1 mL of N, N-dimethylformamide (from Wako Pure Chemical Industries, Ltd.), and 50 It stirred at 2 degreeC. The reaction mixture was added to 150 mL of water in an ice bath, and the precipitated crystals were filtered to obtain 7.4 g of sulfonic acid chloride compound (5). (72% yield)

To 5.0 g of compound (5), 0.9 g of 6-chloro-1-hexylamine (manufactured by Rare Chemicals) was added under ice cooling in chloroform, followed by stirring at room temperature for 2 hours. The reaction mixture was added to 150 mL of water, and the precipitated crystals were filtered, washed with water and dried under reduced pressure to obtain 4.3 g of a sulfoamide alkyl chloride compound (6). (Yield 76%)

An excess amount of water and anhydrous sodium sulfite (manufactured by KANTO CHEMICAL CO., INC.) Was added to 4.3 g of the compound (6), and the mixture was heated at 180 ° C in an autoclave for 12 hours. After allowing to cool, the crystals were filtered to obtain 3.7 g of a sulfoamide alkylsulfonic acid compound (7). (Yield 82%)

Synthesis of Resin (J-1)

(1) Synthesis of Resin (i-1)

6.4 g of n-octanoic acid, 200 g of epsilon -caprolactone, and 5 g of titanium (IV) tetrabutoxide were mixed, heated at 160 ° C for 8 hours, and then cooled to room temperature to obtain a polyester resin (i-1).

The synthetic scheme is shown below.

(2) Synthesis of Resin (J-1)

10 g of polyethyleneimine (SP-108, number average molecular weight 1800, product of NIPPON SHOKUBAI CO., LTD.) And 100 g of polyester resin (i-1) were mixed and heated at 120 ° C. for 3 hours to obtain an intermediate (J-1B). Got it. Then, it cooled to 65 degreeC, 200g of propylene glycol 1-monomethyl ether 2-acetate (henceforth PGMEA) containing 3.8g of succinic anhydride was added gradually, and it stirred for 2 hours. Then, PGMEA was added and the 10 mass% solution of PGMEA of resin (J-1) was obtained. Resin (J-1) has a side chain derived from polyester resin (i-1), and a carboxyl group derived from succinic anhydride.

The synthetic scheme is shown below.

Preparation of Phthalocyanine Pigment Dispersion PG58

11.9 parts of said partially zinc bromide phthalocyanine pigment (referred to as PG58), 3.1 parts of compound (7) as a quinophthalone compound, 9.0 parts of Solsperse 24000GR (manufactured by The Lubrizol Corporation) as a dispersant, and propylene glycol monomethyl ether acetate as a solvent (PGMEA) ) 76 parts were mixed and dispersed in a sand grinder for 3 hours to obtain a phthalocyanine pigment dispersion PG58. When the viscosity of the obtained pigment dispersion composition PG58 was measured with the E-type viscosity meter, it was confirmed that it is very stable at 9.2 mPa * S and the favorable dispersion stability is obtained.

-Preparation of Pigment Dispersion PY150-Containing Yellow Pigment PY150

40 parts of CI PIGMENT YELLOW 150 (PY150) as a pigment (average particle diameter of 60 nm), and 223 parts of PGMEA 10 mass% solution of the said resin (J-1) (22.3 parts in terms of solid content) are mixed with a bead mill (zirconia beads 0.3mm) ) Was mixed and dispersed for 3 hours to prepare a pigment dispersion liquid PY150 containing a yellow pigment PY150.

-Preparation of Pigment Dispersion PY138-Containing Yellow Pigment PY 138

40 parts of CI PIGMENT YELLOW 138 (PY138) as a pigment (average particle diameter 60 nm), and 223 parts of PGMEA 10 mass% solution of the said resin (J-1) (22.3 parts in terms of solid content) are mixed with bead mill (zirconia beads 0.3mm) ) Was mixed and dispersed for 3 hours to prepare a pigment dispersion liquid PY138 containing a yellow pigment PY138.

Preparation of pigment dispersion PB15: 6 containing blue pigment PB15: 6-

40 parts of CI PIGMENT BLUE 15: 6 (PB15: 6) as a pigment (average particle diameter 60 nm), and 223 parts (22.3 parts of solid content conversion) solution of PGMEA of the said resin (J-1) were mixed with bead mill (zirconia) 0.3 mm of beads) was mixed and dispersed for 3 hours to prepare pigment dispersion PB15: 6 containing blue pigment PB15: 6.

-Preparation of Pigment Dispersion PG36-Containing Green Pigment PG36

As a pigment, the mixture liquid consisting of 40 parts of CI PIGMENT GREEN 36 (PG36) (average particle diameter 60 nm) and 200 parts of PGMEA 10 mass% solution (20 parts in terms of solid content) of resin (J-1) was bead mill (zirconia beads 0.3mm). ) Was mixed and dispersed for 3 hours to prepare pigment dispersion liquid PG36 containing green pigment PG36.

About the obtained dispersion liquid, the average primary particle diameter of the pigment was 25 nm when it measured using the dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (made by NIKKISO CO., LTD.)).

-Synthesis of Compound 1 as Photopolymerization Initiator-

(1) Synthesis of Compound A

First, compound A was synthesize | combined with the following scheme.

Ethylcarbazole (100.0 g, 0.512 mol) is dissolved in 260 ml of chlorobenzene, cooled to 0 ° C. and aluminum chloride (70.3 g, 0.527 mol) is added. Then, o-toluyl chloride (81.5g, 0.527mol) is dripped over 40 minutes, it warms up to room temperature and stirred for 3 hours. Then, after cooling to 0 ° C., aluminum chloride (75.1 g, 0.563 mol) is added. 4-chlorobutyryl chloride (79.4 g, 0.563 mol) is added dropwise over 40 minutes, the temperature is raised to room temperature and the mixture is stirred for 3 hours. The mixed solution of 156 ml of 35 mass% hydrochloric acid aqueous solution and 392 ml of distilled water is cooled to 0 degreeC, and the reaction solution is dripped. The precipitated solid was washed with distilled water and methanol after suction filtration and recrystallized with acetonitrile to obtain Compound A (amount 164.4 g, yield 77%) having the following structure.

(2) Synthesis of Compound B

Subsequently, compound B was synthesize | combined using the compound A by the following scheme.

Compound A (20.0 g, 47.9 mmol) is dissolved in 64 ml of THF, and 4-chlorobenzenethiol (7.27 g, 50.2 mmol) and sodium iodide (0.7 g, 4.79 mmol) are added. Subsequently, sodium hydroxide (2.0 g, 50.2 mmol) is added to the reaction solution, and the mixture is refluxed for 2 hours. Subsequently, after cooling to 0 degreeC, sodium methylate 28% methanol solution (NIPPON SHOKUBAI CO., LTD. Product: SM-28) (11.1 g, 57.4 mmol) was dripped over 20 minutes, it heated up to room temperature, and stirred for 2 hours. do. Subsequently, after cooling to 0 degreeC, nitrite nitrite (6.73g, 57.4mmol) is dripped over 20 minutes, it warms up to room temperature, and it stirred for 3 hours. The reaction solution was diluted with 120 ml of acetone and added dropwise to 0.1N aqueous hydrochloric acid solution cooled to 0 ° C. The precipitated solid was washed with distilled water after suction filtration. Subsequently, the compound B (amount 17.0 g, yield 64%) of the following structure was obtained by recrystallization with acetonitrile.

(3) Synthesis of Compound 1

Subsequently, initiator 1 was synthesize | combined using the compound B by the following scheme.

Compound B (18.0 g, 32.4 mmol) was dissolved in 90 ml of N-methylpyrrolidone and triethylamine (3.94 g, 38.9 mmol) was added. Subsequently, after cooling to 0 degreeC, acetyl chloride (3.05g, 38.9mmol) is dripped over 20 minutes, after that, it raises to room temperature and stirs for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0 ° C., and the precipitated solid was washed with 200 ml of isopropyl alcohol cooled to 0 ° C. after suction filtration, and dried to obtain compound 1 (amount 19.5 g, 99% yield) of the following structure. Got.

(Example 1)

The component shown in the following composition 1 was stirred and mixed, and the coloring photosensitive composition of Example 1 was prepared.

(Composition 1)

Pigment dispersion PG58: 36.6 parts of pigment dispersion comprising green pigment PG58

Pigment dispersion PY150: 12.6 parts of pigment dispersion containing yellow pigment PY150

ㆍ PGMEA Part 25.8

ㆍ Solvent (EEP) 16.7 parts

1.76 parts of binder resin (allyl methacrylate-methacrylic acid (= copolymerization molar ratio 8: 2) copolymer, weight average molecular weight 30000)

Polymerizable monomer: 3.77 parts of ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.)

Photopolymerization initiator 1: 0.71 parts of IRGACURE OXE01 (manufactured by BASF)

Photopolymerization initiator 2: 0.35 parts of 2-chlorophenyl-4,5-bisphenylimidazole dimer (manufactured by HODOGAYA CHEMICAL CO., LTD., B-CIM)

0.49 parts of the following Compound III

0.1-part of N-phenyl mercaptobenzimidazole

Additive: 0.10 part of (1,2,2,6,6-pentamethyl-4-piperidinyl) methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-711MM)

ㆍ 0.033 parts of surfactant (fluorine-based surfactant, DIC Corporation product, Megafac F781-F)

The solvent is the following abbreviation.

PGMEA = propylene glycol monomethyl ether acetate

EEP = 3-Ethoxyethyl Propionate

(Compound III)

The coloring pattern was formed on the glass substrate as follows using the coloring photosensitive composition obtained by the above.

Formation of colored photosensitive composition layer

The obtained coloring photosensitive composition was apply | coated to the glass substrate (Corning Millennium, 0.7 mm thickness). Specifically, the space | interval of a slit nozzle and a board | substrate, and discharge amount were adjusted and apply | coated at the application | coating speed 120mm / sec so that the film thickness of the coloring composition layer after postbaking might be about 2.4 micrometers.

-Prebaking Process-

Subsequently, the colored photosensitive composition layer was dried in a vacuum drying apparatus until the degree of vacuum reached 66 Pa, and then heated (prebaked treatment) at 90 ° C. for 120 seconds using a hot plate.

Exposure process (proxy exposure)

After prebaking process, it exposed at 40 mJ / cm <2> using the Proximity exposure machine (The Hitachi High-Technologies Corporation make, LE 5565A).

-Developing process, Baking (post-baking) process-

Subsequently, a 1.0% developer (1 part by mass of CDK-1 and 99 parts of pure water) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was developed using a developing apparatus (manufactured by Hitachi High-Technologies Corporation). 25 degreeC), the shower pressure was 0.2MPa, developed for 60 second, and it wash | cleaned with pure water.

After sufficient drying, it was postbaked for 40 minutes in an oven at 230 ° C.

(Example 2-Example 37, Comparative Example 1-Comparative Example 18)

In the composition 1 of Example 1, the kind of pigment dispersion liquid, the kind of photoinitiator 1, the kind of additive, and the addition amount are changed as shown in Table 1-Table 3, except the same as Example 1 except an Example. Each coloring photosensitive composition of 2- Example 37 and Comparative Examples 1- 18 was prepared. In addition, the coloring pattern was produced like Example 1 except having changed the exposure system in an exposure process using the obtained each colored photosensitive composition as shown in Tables 1-3.

The detail of the exposure system shown by the proxy in Tables 1-3 is the exposure system (proxy exposure) applied by the exposure process in Example 1. FIG. In addition, the detail of the exposure system represented by a laser in Tables 1-3 is as follows.

Exposure process (laser exposure)

After the prebaking treatment, pulse irradiation of about 1 mJ / cm 2 was applied to the surface of the photosensitive resin composition layer using EGIS (V Technology Co., Ltd., the third high-frequency wavelength of 355 nm, pulse width of 6 nsec) as the laser exposure apparatus. It was carried out through photomask once.

In the table,-is not added, G is green, and B is blue.

Compound I: Sumilizer GM from Sumitomo Chemical Co., Ltd.

Compound II: Sumilizer GS from Sumitomo Chemical Co., Ltd.

Compound 2: the following structure

Compound 3: the following structure

Compound 4: the following structure

Karenz MTBD-1: butanediol bis (3-mercaptobutyrate)

About each color pattern obtained, each item of linearity, a shape and a missing | missing, solvent resistance, and light resistance was evaluated. Evaluation methods and evaluation criteria are shown below.

1. Evaluation of coloring pattern linearity

Evaluation of the coloring pattern linearity observed the pixel edge part in the photograph of 5 cm x 5 cm, making the edge part of a coloring pattern into a photograph 200 times the reflection using an optical microscope, and evaluated by the reference | standard below.

- Evaluation standard -

(Circle): The edge part of a coloring pattern looks linear.

(Triangle | delta): A part of coloring pattern (1/4 or less of whole length) is serrated

X: The edge part of a coloring pattern is serrated more than 1/4 of the whole length

It is preferable that the edge part of a coloring pattern is linear.

In other words, when the edge portion of the colored pattern becomes serrated due to residual film, undercut, or the like, overlapping with the black matrix in the case of forming the colored pattern (pixel pattern) of the color filter by the colored photosensitive composition of the present invention It is necessary to make it large, and widens the width of a black matrix, and reduces an aperture ratio. In addition, in the case where the overlap with the black matrix is not large, there is a fear that a portion may fall out due to no coloring pattern near the edge of the black matrix. Moreover, when the edge part of a coloring pattern is serrated, a practical problem may arise, for example, the transparent electrode formed on it disconnected and a resistance value becomes high.

2. Evaluation of Shape, Luminance, and Dropout of Colored Pattern

The shape and the missing of the colored pattern were evaluated according to the following criteria for the respective color filters obtained as described above using the optical microscope as a photograph with the edge portion of the colored pattern as a photograph at 200 times reflection.

Here, about the fragment, the shape in which the edge part is missing on the half moon shape, (B) It is also seen if it is thinner and longer than (A), but the shape recognized as being discontinuously thinner and missing than the surroundings It was assumed that either one was observed. In this evaluation, it was said that a missing piece existed even if one fragment was seen.

If a deletion occurs, the part is white, and thus light is not preferable.

In addition, brightness was measured by OSP-SP100: OLYMPUS CORPORATION.

- Evaluation standard -

○: The shape of the colored pattern (2-1) is pure tapered or rectangular, without (2-2) debris, and (2-3) with high luminance.

X: At least 1 item among the items of said (2-1)-(2-3) does not correspond.

3. Evaluation of solvent resistance

The post-baking of the glass substrate in which the coloring pattern after completion | finish of image development process was formed was carried out by 230 degreeC x 30 minutes in the convection oven. The chromaticity of the obtained substrate after baking was measured by OSP-SP100: OLYMPUS CORPORATION, immersed in N-methyl-2-pyrrolidone (hereinafter abbreviated as "NMP") at 23 ° C for 30 minutes, and coloring before and after immersion. ΔE ^* ab was calculated from the chromaticity of the pattern. Chromaticity was measured by OSP-SP100: OLYMPUS CORPORATION.

When ΔE ^* ab is 3 or more, various solvent resistances used for the panel treatment are insufficient in the production of the liquid crystal display device, and the like, which is a problem in practical use.

In addition, the shape change with the coloring pattern before and after immersion in NMP was observed by optical microscope observation.

The obtained result was evaluated by the following evaluation criteria.

- Evaluation standard -

○: (3-1) ΔE ^* ab is 3.0 or less, and no change is observed in the shape of the (3-2) colored pattern.

X: At least 1 item among the items of said (3-1) and (3-2) does not correspond.

4. Evaluation of light resistance

ITO sputtering was performed on the glass substrate which has a coloring pattern after postbaking similarly to the said solvent resistance evaluation on the conditions shown in Table 4 below.

The substrate after ITO sputtering was put into Xenon Weather Meter `` SX-75 '': Suga Test Instruments, Co., Ltd., and 180W 120 hours at ITO side under the conditions of temperature 30 ° C, humidity 50%, and black panel temperature 63 ° C. I did an investigation.

Then, the chromaticity of the board | substrate was measured by OSP-SP100: OLYMPUS CORPORATION, and (DELTA) E ^* ab was calculated | required from the chromaticity of the coloring pattern before and behind irradiation.

In this evaluation, it was evaluated that (DELTA) E ^* ab was 3.0 or less as excellent in light resistance.

The above evaluation results are shown in Table 5 below.

As shown in Table 5, each colored pattern (colored film) obtained using the colored photosensitive composition of the Example was excellent in linearity, the shape was also good, there was no fallout, and the light resistance and solvent resistance were also favorable. On the other hand, in each coloring pattern obtained using the coloring photosensitive composition of Comparative Example 1- Comparative Example 18, (DELTA) E ^* ab in light before and behind was more than 3.0, and was poor in light resistance.

From Comparative Example 3, Comparative Example 4, Comparative Example 8, and Comparative Example 9, the nonpolymerizable radical scavenger has a slight light resistance improvement effect, but the polymerizable compound having (F) radical scavenging ability in the present invention is improved. It was found that the effect was more remarkable and long-term reliability could be realized.

In addition, according to the contrast between Example 2 and Example 1, the same good results are obtained in both of the examples, and this is also excellent effect of the present invention as in the case of applying the pattern exposure by the laser exposure machine as in the exposure by the high pressure mercury lamp. Was found to be obtained.

Claims

(A) A colorant having a phthalocyanine skeleton, (B) solvent, (C) polymerizable monomer, (D) binder resin, (E) photoinitiator, and (F) polymerizable compound having radical trapping ability Colored photosensitive composition to be used.

The method of claim 1,
Content of the polymeric compound which has the said (F) radical trapping ability is 0.1 mass% or more and 5.0 mass% or less with respect to a total solid, The coloring photosensitive composition characterized by the above-mentioned.

The method of claim 1,
The polymeric compound which has said (F) radical trapping ability has an amine structure or a phenol structure, The coloring photosensitive composition characterized by the above-mentioned.

The method of claim 1,
The polymeric compound which has said (F) radical trapping ability has one or more selected from acryloyl group and methacryloyl group as a polymeric group, The coloring photosensitive composition characterized by the above-mentioned.

The method of claim 1,
The polymeric compound which has the said (F) radical trapping ability is 1 or more selected from following General formula (1), (5), and (6), The coloring photosensitive composition characterized by the above-mentioned.

The method of claim 1,
At least 1 type of said (A) color material contains a metal in a chemical structure, The coloring photosensitive composition characterized by the above-mentioned.

The method of claim 1,
At least 1 type of said (A) color material is a coloring pigment, The coloring photosensitive composition characterized by the above-mentioned.

The method of claim 1,
Coloring photosensitive composition comprising (A) at least one selected from the group of CI PIGMENT Green 7, CI PIGMENT Green 36 and CI PIGMENT Green 58 as the colorant.

The process of providing the coloring photosensitive composition of any one of Claims 1-8 on a board | substrate, and forming a colored layer,
And exposing the colored layer in a pattern shape, and then developing and removing the uncured portion from the developer to form a colored pattern.

It is manufactured by the manufacturing method of the color filter of Claim 9. The color filter characterized by the above-mentioned.

It comprises the color filter of Claim 10, The liquid crystal display device characterized by the above-mentioned.