KR20120022668A - Colored photosensitive composition, method of producing color filter, color filter, and liquid crystal display - Google Patents

Abstract

PURPOSE: A colored photo-sensitive composition, a method for manufacturing a color filter, the color filter, and a liquid crystal display device are provided to improve the color purity and the contrast of the color filter and the solvent resistance characteristic of a colored cured film. CONSTITUTION: A colored photo-sensitive composition includes a zinc phthalocyanine halide pigment, acidic polymerizable monomers, binder resin, a photo-polymerization initiator, a chain transferring agent selected from secondary or tertiary aliphatic thiol compound, and a solvent. The secondary or tertiary aliphatic thiol compound is mono-functional or bi-functional aliphatic thiol compound. The photo-polymerization initiator is hexaarylbiimidazole compound. The binder resin is acidic resin. The colored photo-sensitive composition further includes a photo-sensitizer.

Description

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

The present invention relates to a colored photosensitive composition, a manufacturing method of a color filter using the colored photosensitive composition, a color filter, and a liquid crystal display device.

Conventionally, in small liquid crystal display devices such as mobile phones, mobile game machines, PDAs, and the like, the use of a backlight light source with limited capacitance such as a secondary battery or a battery is essential, so that the color material of the color filter used in these display devices is highly transparent. Color materials that can transmit the bright lines of the backlight well and display colors have 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 personal computer, and these liquid crystal display devices have no restrictions on the power supply of the backlight, and the display device RGB color reproducibility has been emphasized. Therefore, in addition to the conventional transparency, the color material of the color filter requires a higher level of image quality, namely, contrast and color purity.

Alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and other components are further made into the pigment | dye composition which refine | miniaturized the particle size of a pigment with respect to the said request | requirement, and it uses this on a transparent substrate, such as glass, by a photolithography method. The color filter in which the pattern of three colors of red, green, and blue was formed was developed and put into practical use.

Green pigments, such as a chlorinated copper phthalocyanine pigment (C. I. Pigment Green 7) and a chlorinated copper phthalocyanine pigment (C. I. Pigment Green 36), are generally used for the green coloring pattern from a viewpoint of color tone and color fastness.

As a green pigment, a halogen metal phthalocyanine pigment such as aluminum, titanium, cobalt, nickel, zinc, tin, and lead, instead of copper, is used for the purpose of increasing the saturation (color purity and color density) of the pigment in recent years. 1), and various pigments are proposed especially with respect to highly saturated zinc halide phthalocyanine pigment (CI Pigment Green 58) (for example, refer patent document 2-4). For example, detailed studies on the degree of substitution of Br and Cl, pigment treatment methods using betaine-type surfactants, various crystal forms, etc. have been conducted, and the Bragg angle (2θ ± 0.2 °) with respect to Cu-Kα rays in the X-ray diffraction spectrum is determined. It has been reported that copper halide phthalocyanine having a maximum diffraction peak at 26.4 ° or 25.5 ° is high in saturation (color purity and color concentration) and excellent in stability over time (see Patent Document 5, for example). In addition, it is suggested that color pigments having high transparency and high color purity are obtained using these pigments.

However, high brightness, high color, and high contrast metal halide phthalocyanine pigments have a smaller particle size, resulting in a narrower development latitude than in the prior art, and in some cases, deterioration in performance over time when stored as a colored photosensitive composition. In order to improve the stability over time, it is proposed to use a thiol compound having a branched structure (for example, refer to Patent Document 6), but it is required to improve the working environment due to higher stability over time and odor, and solvent resistance of the cured film. It is becoming.

Japanese Patent Publication No. 2003-161823 Japanese Patent Publication No. 2007-284592 Japanese Patent Publication No. 2004-70342 Japanese Patent Publication No. 2008-24743 Japanese Patent Publication No. 2009-223288 Japanese Patent Publication No. 2004-264435

This invention is made | formed in view of the above-mentioned problem, The subject of this invention is the coloring which is excellent in the stability with time in a liquid state, the development latitude is large, there is no problem of a bad smell, and can form the colored cured film with favorable solvent resistance. It is to provide a photosensitive composition. In addition, another object of the present invention is to provide a color filter having a high color purity and good contrast with a high color purity made using the colored photosensitive composition of the present invention, a manufacturing method of a color filter, and a liquid crystal display device including the color filter. To provide.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the subject of this invention was achieved by the following means, and reached this invention.

<1> A chain transfer agent selected from (A) zinc halide phthalocyanine pigment, (B) polymerizable monomer having an acid group, (C) binder resin, (D) photopolymerization initiator, (E) secondary or tertiary aliphatic thiol compound And (F) a coloring photosensitive composition containing a solvent.

<2> in <1>,

The secondary or tertiary aliphatic thiol compound is a monofunctional or bifunctional aliphatic thiol compound colored photosensitive composition.

<3> In <1> or <2>,

The colored photosensitive composition of the said (D) photoinitiator is a hexaarylbisimidazole compound.

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

The said (C) binder resin is colored photosensitive composition which is resin which has an acidic radical.

<5> In any one of <1>? <4>,

(G) The coloring photosensitive composition containing a photosensitizer further.

<6> Colored layer formation process which provides the coloring photosensitive composition in any one of <1>? <5> on a board | substrate, and forms a colored layer;

An exposure step of hardening an exposure area by performing exposure in a pattern form to the formed colored layer; And

The pattern formation method containing the image development process of developing and removing the unexposed part in the colored layer after the said exposure, and forming a pattern.

<7> A color filter manufactured by the pattern formation method as described in <6>.

<8> A liquid crystal display device comprising the color filter according to <7>.

ADVANTAGE OF THE INVENTION According to this invention, the coloring photosensitive composition which is excellent in the stability with time in a liquid state, the development latitude is large, there is no problem of a bad smell, and can be formed the colored cured film with favorable solvent resistance. Further, a color filter having a high color purity and a high contrast high color characteristic made using the colored photosensitive composition of the present invention, a manufacturing method of a color filter, and a liquid crystal display device having the color filter can be provided.

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

<Coloring Photosensitive Composition>

The colored photosensitive composition of the present invention is prepared from (A) zinc halide phthalocyanine pigment, (B) polymerizable monomer having an acid group, (C) binder resin, (D) photopolymerization initiator, (E) secondary or tertiary aliphatic thiol compound It is characterized by containing the selected chain transfer agent, and (F) solvent.

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

<(A) Zinc halide phthalocyanine pigment>

The pigment used in the colored photosensitive composition of the present invention is zinc halide phthalocyanine.

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

The halogen atoms to be substituted are each independently a hydrogen atom, a chlorine atom or a bromine atom, and at least one of them is preferably a chlorine atom or a bromine atom.

Zinc halide phthalocyanine pigments are substituted with eight or more bromine atoms, resulting in a high gloss-bright green color, which is suitable for use as a green pixel portion pattern of a color filter.

In particular, the bromine atom having 10 to 16 substitutions is more suitably used in the present invention because of its higher brightness.

The zinc halide phthalocyanine pigment used in the present invention can be produced by a known production method such as, for example, chlorosulfonic acid method, halogenated phthalonitrile method, melting method and the like.

For a more specific manufacturing method, a method for producing a zinc halide phthalocyanine pigment disclosed in Japanese Patent Laid-Open No. 2004-70342 is preferable in view 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 of subsequent steps.

In particular, a resin-coated zinc halide phthalocyanine pigment disclosed in Japanese Patent Laid-Open No. 2007-320986 is a preferred form for improving dispersibility.

The range of 10 nm-100 nm is preferable, and, as for the average primary particle diameter of the zinc halide phthalocyanine pigment of this invention, the range of 10 nm-40 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 dispersion 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. It is the value which calculated | required the average value of the shorter diameter (short diameter), respectively, and averaged it.

If the primary particle of the zinc halide phthalocyanine pigment of this invention is a range of aspect ratio 1-3, the viscosity characteristic will improve further and fluidity will become higher in each application field.

In order to determine the aspect ratio, the particles in the field of view are photographed using a transmission electron microscope or a scanning electron microscope as in the case of obtaining the average particle diameter of the primary particles as described above.

And the average value of the long side diameter (long diameter) and the short side diameter (short diameter) is calculated | required about 100 primary particles which comprise the aggregate on a two-dimensional image, and it calculates using these values.

In order to obtain a zinc halide 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 crystal growth can be easily suppressed and the average primary particle diameter is relatively small. It is preferable to employ the solvent salt milling process from the point that a pigment particle is obtained.

This solvent salt milling means kneading and grinding the halogenated zinc phthalocyanine pigment, the inorganic salt, and the organic solvent.

Zinc halide phthalocyanine pigments with a large particle diameter may be subjected to solvent salt milling after dry grinding.

Specifically, a zinc halide phthalocyanine pigment, an inorganic salt, and an organic solvent which does not dissolve it are added to a kneader, and kneading grinding is performed therein.

As a kneader at this time, kneader, a mix muller, etc. can be used, for example.

As said inorganic salt, a water-soluble inorganic salt can be used suitably, For example, it is preferable to use inorganic salts, such as sodium chloride, potassium chloride, sodium sulfate.

Moreover, it is more preferable to use the inorganic salt of average particle diameters 0.5-50 micrometers.

Such inorganic salts are easily obtained by pulverizing ordinary inorganic salts.

In obtaining a halogenated zinc phthalocyanine pigment with an average primary particle diameter of 10 nm-100 nm, it is preferable to make the ratio of the amount of inorganic salt usage with the usage-amount of the halogenated zinc phthalocyanine pigment in solvent salt milling high.

That is, the amount of the inorganic salt used is preferably 5 to 20 parts, more preferably 7 to 15 parts, based on 1 part of the zinc halide phthalocyanine pigment in terms of mass.

As the organic solvent, it is preferable to use an organic solvent capable of suppressing crystal growth. As such an organic solvent, a water-soluble organic solvent can be suitably 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, diethylene 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 monomethyl Ether, dipropylene glycol monomethyl ether, dipropylene glycol and the like can be used.

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

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 solvent salt milling time, 8-18 hours are more preferable.

In this way, a mixture containing a zinc halide 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 this mixture, and the solids mainly containing the halogenated zinc phthalocyanine pigment are washed as necessary. The fine powder of a zinc halide phthalocyanine pigment can be obtained by performing filtration, drying, and grinding.

As washing | cleaning, both water washing and hot water washing | cleaning 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 80-120 degreeC heating etc. by the heating source provided in the dryer, etc. are mentioned, for example, As a drier, there are generally a box drier, a band drier and a spray drier.

In addition, the grinding | pulverization after drying is not operation which makes a specific surface area large or the average particle diameter of primary particle | grains small, for example, like a case of drying using a box type drier and a band drier, a pigment turns into a lamp shape etc. It is performed in order to disintegrate and grind | pulverize a pigment, for example, and grind | pulverizes with a mortar, a hammer mill, a disk mill, a pin mill, a jet mill, etc., for example.

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

Since the (A) zinc halide phthalocyanine pigment obtained in this way has weak cohesion force of primary particle | grains, and has a property which is easy to disintegrate, covering power becomes large and preparation of a high contrast coloring film becomes easy.

In the present invention, these zinc halide phthalocyanine pigments may be used alone, but can be used in combination with other halogenated zinc phthalocyanine pigments having different bromination rates or chlorination rates, or brominated phthalocyanine substituted with a metal having a different central metal.

By changing the bromination rate and chlorination rate or by changing the center metal, it is expected that the color tone as the pigment changes to increase the variation of the color that can be reproduced.

In the coloring photosensitive composition of this invention, the transmittance | permeability can be enlarged by adjusting the color of a coloring photosensitive composition by combining another color material with (A) zinc halide phthalocyanine pigment.

For example, in order to form a green pixel, you may use together a yellow pigment and a orange pigment with respect to a zinc halide phthalocyanine pigment.

Examples of the yellow pigments include diketopyrrolopyrrole orange pigments, in addition to yellow pigments such as disazo yellow pigments, isoindolin yellow pigments, quinophthalone yellow pigments, benzimazolone yellow pigments and nickel azo yellow pigments; Tangerine pigments, such as a perinone series 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 Orange 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.

Particularly, 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 zinc halide phthalocyanine 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 of high transmittance and high contrast. 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 like a zinc halide phthalocyanine pigment, and it may be salt milled together with a zinc halide phthalocyanine pigment, and may be salt milled separately.

An 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 are not aggregated, and calculating an average value.

In the coloring photosensitive composition of this invention, it is preferable that the total amount of the pigment containing a halogenated zinc phthalocyanine pigment is 5 to 60% by mass conversion with respect to the total solid except the solvent in the coloring photosensitive composition of this invention, and is 10 to 50% It is more preferable that 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.

In addition, the "solid content" of the coloring photosensitive resin composition in this invention includes all the components of the coloring photosensitive composition except a solvent.

Pigment Dispersion Composition

When using several pigments together in the adjustment of the coloring photosensitive composition of this invention, it is a preferable aspect to disperse | distribute (A) zinc halide phthalocyanine pigment and another pigment together previously or separately, and to put as a pigment dispersion composition.

Although the pigment dispersion composition disperse | distributes the said pigment and a solvent, at this time, a dispersing agent, resin, etc. are added and used as needed.

Moreover, other components, such as a pigment derivative, can be further used as needed.

Preparation of Pigment Dispersion Composition

Although the preparation form of the pigment dispersion composition of this invention is not restrict | limited, For example, a pigment, a pigment dispersant, and a solvent of a particle size of 0.01-1 mm are used using a vertical or horizontal sand grinder mill, 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 dispersion treatment is performed while applying strong shearing force using 2 rolls, 3 rolls, ball mills, trom mills, dispersers, kneaders, kneaders, homogenizers, blenders, single screw or twin screw extruders. It is also possible.

In addition, the details of kneading | mixing and dispersion | distribution are detailed in T.C. Patton Flow and Pigment Dispersion (published by John Wiley and Sons, 1964).

Pigment concentration

As content in the pigment dispersion composition of a pigment, 10-60 mass% is preferable in mass conversion with respect to the total solid except the solvent of the said composition, and 15-50 mass% is more preferable.

When content of a pigment is in the said range, color concentration is enough and it is effective in ensuring the outstanding color characteristic.

Dispersant

The pigment dispersion composition contains at least one kind of dispersant.

By containing this dispersing agent, the dispersibility of a pigment can be improved.

As a dispersing agent, a well-known pigment dispersing agent 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 Industry Co., Ltd.), (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 90, no. Cationic surfactants such as 95 (above, Kyoeisha Chemical Industry Co., Ltd.) and W001 (Yusho Co., Ltd. product); 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 surfactant, such as W004, W005, W017 (above, Yusho Co., Ltd. product); Amphoteric surfactants having a carboxybetaine structure, an amidebetaine structure, a sulfobetaine structure, a hydroxybetaine structure, and the like; Fluorine-based surfactants such as MEGAFACE F171, F172, and F173 (above, manufactured by DIC Corporation); EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, EFKA POLYMER 450 (above, from Ciba Specialty chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid Polymeric dispersants such as 9100 (above, manufactured by SAN NOPCO LIMITED); Various SOLSPERSE dispersants such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 (above, The Lubrizol Corp.); ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (from ADEKA Corp.) and ISONET S -20 (manufactured by Sanyo Chemical Industries), 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 (above, BYK Japan KK) is mentioned.

In addition, an acrylic copolymer, an oligomer or polymer having a polar group such as N, N-disubstituted amino group or acidic group at the molecular terminal or side chain, a polyurethane resin modified with tertiary amine, described in Japanese Unexamined Patent Publication No. 2009-52010 AB 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 to the 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. It is effective in constructing a high and excellent color filter.

A pigment derivative is a compound which made an organic pigment a mother skeleton specifically, and introduce | transduced the acidic group, basic group, and aromatic group into the side chain as a substituent.

Specifically, the organic pigment serving as the parent skeleton is a quinacridone pigment, a phthalocyanine pigment, an azo pigment, a quinophthalone pigment, an isoindolin pigment, an isoindolinone pigment, a quinoline pigment, a diketopyrrolopyrrole pigment, And benzimidazolone pigments. Generally, pale yellow aromatic polycyclic compounds such as naphthalene, anthraquinone, triazine, and quinoline, 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 gross mass of a pigment, and 3-20 mass% is more preferable.

When content of a pigment derivative exists 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. As a result, a colored photosensitive composition having a high transmittance and excellent color characteristics is obtained. Therefore, when the colored photosensitive composition is applied to, for example, a color filter production application, a color filter having good color characteristics and high contrast can be obtained. You can get it.

Moreover, it is also possible to further add high molecular compounds, such as alkali-soluble resin mentioned later, to a pigment dispersion composition.

Polar groups such as acid groups contained in alkali-soluble resins are considered to be effective for dispersion of pigments, and are often effective for dispersion stability of pigment dispersions.

-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, and melting point and viscosity, In order to adjust dispersibility, it is also possible to use multiple together.

Moreover, the (F) solvent used for preparation of the coloring photosensitive composition mentioned later can also be used.

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, it can contain from a viewpoint of handleability so that the sum total of a pigment and a pigment dispersant may be 5-50 mass% with respect to the gross mass except the solvent of a pigment dispersion composition.

As content of the pigment dispersion composition in the coloring photosensitive composition of this invention, content with the pigment content in the range of 5-70 mass% with respect to the mass of the total solid except the solvent of a coloring photosensitive composition is preferable, and it is 15-60 mass The amount which becomes the range of% is more preferable.

When content of a pigment dispersion composition is in the said range, color concentration is enough and it is effective in ensuring the outstanding color characteristic.

As the (A) zinc halide halogenated phthalocyanine pigment of the colored photosensitive composition of the present invention, a dye may be used in addition to the above pigment. By using a dye together, the contrast of a color filter can be anticipated.

The dye used in the colored photosensitive composition of the present invention is not particularly limited as long as it is a dye soluble in an organic solvent, but may be classified into chemical structures such as azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, Nitro dyes, carbonyl dyes, methine dyes, and derivatives thereof.

As an azo dye, CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, etc. are mentioned.

Examples of the anthraquinone dyes include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, CI Disperse Blue 60, and the like. Can be mentioned.

Other phthalocyanine-based dyes such as CI Vat Blue 5 and the like, and quinoneimine dyes such as CI Basic Blue 3 and CI Basic Blue 9, and the quinoline dyes, for example, CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64 and the like include, for example, CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42 and the like.

<Polymerizable monomer having an acid group (B)>

In the coloring photosensitive composition of this invention, at least 1 type or more of the polymerizable monomer which has an acidic radical (B) is contained as a curable component.

By using a polymerizable monomer having an acid group in the structure, the development of the unexposed part is promoted, and the development latitude is greatly improved. Among them, polymerizable monomers having acid groups such as carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and phosphoric acid groups are particularly preferred because of their high alkali solubility and their contribution to improvement in development and residue suppression. In addition to the alkali solubility-providing effect of (C) binder resin mentioned later, since the brightness improves by the effect of using the polymerizable monomer which has an acidic radical, the developing latitude becomes wider and the stable color filter also in the coloring resin composition which increased the pigment concentration. Can be manufactured.

Examples of the polymerizable monomer containing a carboxyl group include polyfunctional acrylate compounds modified with a carboxyl group in addition to unsaturated fatty acids such as acrylic acid, methacrylic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, and cinnamic acid. As the carboxyl-modified polyfunctional acrylate compound, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified trimethylolpropane triacrylate, succinic acid-modified pentaerythritol tetraacrylate, succinic acid-modified dipentaerythritol pentaacrylate, succinic acid-modified dipentaerythritol hexaacrylic acid Adipic acid modified pentaerythritol triacrylate, adipic acid modified trimethylolpropane triacrylate, adipic acid modified pentaerythritol tetraacrylate, adipic acid modified dipentaerythritol pentaacrylate, adipic acid modified dipenta Erythritol tetraacrylate; commercially available compounds such as ARONIX M-510, ARONIX M-520, ARONIX TO-2349, ARONIX TO-2359 (above, manufactured by TOAGOSEI CHEMICAL INDUSTRY CO., LTD.) Can be used.

Examples of the polymerizable monomer containing a phenolic hydroxyl group include p-hydroxy styrene, 3,4-dihydroxy styrene, 3,5-dihydroxy styrene, 2,4,6-trihydroxy styrene, and (p-hydroxy ) Benzyl acrylate, salicylic acid modified pentaerythritol triacrylate, salicylic acid modified trimethylolpropane triacrylate, salicylic acid modified pentaerythritol tetraacrylate, salicylic acid modified dipentaerythritol pentaacrylate, salicylic acid modified dipentaerythritol hexaacrylate, etc. Preferably, salicylic acid modified dipentaerythritol hexaacrylate and salicylic acid modified dipentaerythritol pentaacrylate are preferable.

Examples of the polymerizable monomer containing a sulfonic acid group include vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, and butyl sulfonic acid modified acrylamide. Examples of the polymerizable monomer containing a phosphoric acid group include vinyl phosphoric acid, styrene phosphoric acid, and butyl phosphoric acid modified acrylamide. Preferred among these is butyl sulfonic acid-modified acrylamide, and commercially available compounds include ATBS (manufactured by TOAGOSEI CHEMICAL INDUSTRY CO., LTD.).

Among the polymerizable monomers having these acid groups, polymerizable monomers having a carboxyl group and polymerizable monomers having a phenolic hydroxyl group are preferable, and polymerizable monomers having a carboxyl group are more preferable from the viewpoint of production suitability and cost.

In the coloring photosensitive composition of this invention, the polymeric monomer which has an acidic radical may be used individually as a polymeric monomer, and the polymeric monomer which has several acidic groups may be used together. Moreover, you may use together 1 or more types of the polymerizable monomer containing an acidic radical, and the polymerizable monomer which does not have an acidic radical, respectively. In order to make solvent resistance, ITO sputter | compatibility, and image development latitude compatible, it is preferable to use together the polymerizable monomer which does not have an acidic radical other than the polymerizable monomer which has an acidic radical.

(Polymerizable Monomer Having No Acidic Group)

In the present invention, the polymerizable monomer having no acid group which can be used in combination with the acidic group is not particularly limited as long as it is polymerizable, and has a low molecular compound, dimer, trimer, and oligomer having at least one ethylenic double bond. Addition polymerizable compounds, such as these, can be used suitably.

As an ethylenic compound, For example, ester of an unsaturated carboxylic acid and a monohydroxy compound, ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, and unsaturated carboxylic acid Urethane which reacted the ester obtained by esterification of polyhydric hydroxy compounds, such as a carboxylic acid and the above-mentioned fatty acid polyhydroxy compound, an aromatic polyhydroxy compound, a polyisocyanate compound, and the (meth) acryloyl containing hydroxy compound And ethylenic compounds having a skeleton.

Although a specific polymerizable monomer can be classified and enumerated by the number of polymerizable groups in 1 molecule as shown below, it is not limited to this.

(1) a compound having one polymerizable group in one molecule

As an example of the compound which has one polymerizable group in 1 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, butoxy Ethyl (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) acrylate, 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-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyethylene jade Seed monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, 2-hydroxy-3-phenoxy Cypropyl (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 (meta) It may include methacrylate and so on.

(2) a compound having two polymerizable groups in one molecule

As an example of the compound which has two polymerizable groups in 1 molecule, the compound which has two (meth) acryloyl groups in the same molecule as a polymerizable group is mentioned, For example, ethylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylic Rate, 1,6-hexanediol di (meth) acrylate, neopentylglycol 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 (acryloyloxyethyl) ether of bisphenol A, (meth) acrylic acid modified product of bisphenol A type epoxy resin, 3-methylpentanediol di (meth) acrylate, 2-hydroxy-3-acrylo Iloxypropyl methacrylate, dimethylol tricyclodecane di (meth) acrylate, etc. are mentioned, Preferably dimethylol- tricyclodecane di (meth) acrylate and neopentyl glycol di (meth) acrylate are mentioned. And (meth) acrylic acid modified substances of ethoxylated bisphenol A di (meth) acrylate and bisphenol A type epoxy resins.

(3) a compound having three polymerizable groups in one molecule

As an example of the compound which has three polymerizable groups in 1 molecule, the alkylene oxide modified tri (meth) acrylate of trimethylol propane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, and trimethylol propane, for example. , Pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate , Propionic acid dipentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate And propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin triacrylate, and the like. .

(4) a compound having four or more polymerizable groups in one molecule

Examples of the compound having four or more polymerizable groups in one molecule include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and propionic acid dipentaerythritol tetra ( Meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylic Alkylene oxide modified hexa (meth) acrylate of phosphazene, captolactone modified dipentaerythritol hexa (meth) acrylate, Kyoeisha Chemical Industry Co., Ltd. And urethane acrylates such as UA-306H, UA-306T, and UA-306I of the product.

Among these, from the viewpoint of suitably maintaining solvent resistance and ITO sputterability, a (meth) acrylate monomer having two or more (meth) acryloyl groups in the same molecule is preferable, and three or more (meth) acryloyl groups The (meth) acrylate monomer which has is more preferable.

In particular, a (meth) acrylate monomer having four or more (meth) acryloyl groups is advantageous, and for example, dipentaerythritol pentaacrylate and dipentaerythritol hexa acrylate are preferable in view of solvent resistance and ITO sputter aptitude. A mixture of these mixtures (mixing ratio in terms of mass, dipentaerythritol pentaacrylate: dipentaerythritol hexaacrylate = 2 to 4: 8 to 6) is suitably used.

When using together the polymeric monomer which has an acidic radical, and the polymeric monomer which does not have an acidic radical, when the sum total of the polymeric monomer which has an acidic radical, and the polymeric monomer which does not have an acidic radical is 100 mass parts, It is preferable to use together in the range of -50 mass parts, The range of 1-40 mass parts is more preferable, The range of 5-20 mass parts is further more preferable.

In the coloring photosensitive composition of this invention, 5-80 mass% is preferable with respect to the total solid except the solvent of a coloring photosensitive composition, as for preferable content of the polymerizable monomer which totaled the polymerizable monomer which has an acidic radical, and the polymerizable monomer which does not have an acidic radical, More preferably, it is 10-60 mass%, More preferably, it is the range of 15-50 mass%.

<(C) Binder Resin>

As (C) binder resin applicable to this invention, any can be used as long as it is a high molecular compound soluble in a solvent. The binder resin may be used as a single compound or may use a plurality of compounds in combination. As preferable binder resin, in consideration of alkali developability by the port lithography method, a resin having an acid group (hereinafter, appropriately referred to as "alkali-soluble resin") is preferable.

Alkali-soluble resin can also be contained in the preparation step of the said pigment dispersion composition, and can also be divided and contained in both the preparation step of a pigment dispersion composition and the preparation step of a coloring photosensitive composition.

As alkali-soluble resin, it is a linear organic polymer polymer, The 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.) is preferable, More preferably, it is soluble and weak alkali in an organic solvent. It is developable by an aqueous solution.

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 temperature, pressure, the kind and amount of the radical initiator, the kind of the solvent, and the like when preparing the alkali-soluble resin in the radical polymerization method can be easily set by those skilled in the art, and the conditions can also be determined experimentally.

As a linear organic high molecular polymer applied as alkali-soluble resin, the polymer which has a carboxyl group 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 No. 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 Japanese Patent Application Publication No. 59-71048; and The acid cellulose derivative which has a carboxylic acid in a side chain, what 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.

In these, the multicomponent copolymer which consists of a benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / other monomer is especially suitable.

In addition, what copolymerized methacrylic acid 2-hydroxyethyl etc. can also be mentioned as a useful thing.

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 / polymethylmethacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxy Ethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer; and the like.

As other alkali-soluble resins, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 11 The well-known high molecular compounds of -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 since it is easy to adjust alkali solubility, it is used suitably.

Examples of the other monomer copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds, and the like.

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, etc. Can be mentioned.

As said vinyl compound, styrene, (alpha) -methylstyrene, vinyltoluene, glycidyl (meth) acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl (meth) acrylate, for example , 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 Aralkyl group); and the like.

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 ). Among these, R ³¹ , R ³² and R ³³ have the same meanings as described above.

Moreover, 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 except the solvent contained in a coloring photosensitive composition, More preferably, it is 2-15 mass%. Especially preferably, it is 3-12 mass%.

In addition, as a ratio of content of the polymerizable monomer which totaled the polymerizable monomer which has an acidic radical, and the polymerizable monomer which does not have an acidic radical, and binder resin, it is 0.1-10 in mass ratio (total mass of a polymeric monomer / mass of binder resin). Is preferable, the range of 0.4-8 is more preferable, and the range of 0.5-5 is still more preferable.

<(D) Photoinitiator>

(D) The photoinitiator in the coloring photosensitive composition of this invention will not be specifically limited if it is a compound which starts superposition | polymerization by exposure.

(D) As a photoinitiator, a camphor quinone, a benzophenone, a benzophenone derivative, an oxime compound, an acyl phosphine, an acyl phosphine derivative, an acetophenone, an acetophenone derivative, a hexaarylbisimidazole compound, a boric acid compound, etc. are mentioned, for example. Can be used.

Specific examples include α-hydroxycycloalkylphenylketones or 2-hydroxy-2-methyl-1-phenyl-propane, dialkoxyacetophenones, α-hydroxy- or 4-aloyl-1,3-dioxolane Benzoin alkyl ethers and benzyl ketals such as benzyl dimethyl ketal, glyoxalic acid phenyl and derivatives thereof, dimer glyoxalic acid phenyl, peresters such as benzophenone tetracarboxylic acid peresters (e.g. For example, as described in European Patent Application Publication No. 1,126,541), halomethyltriazines, for example 2- [2- (4-methoxy-phenyl) -vinyl) -4,6-bis-trichloro Methyl [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, hexaarylbisimime Dazole / co-initiator system, for example 2-mercaptobenzo Ortho in combination with azole-hexahydro-chloro-phenyl-bis-imidazole; Ferrocenium compounds or titanocenes such as dicyclopentadienyl-bis (2,6-difluoro-3-pyrrolo-phenyl) titanium; For example, mixtures with O-acyl oxime ester compounds such as those described in the specification of British Patent 2,339,571 may be used. A boric acid compound can also be used as a combined photoinitiator.

In the coloring photosensitive composition of this invention, it is preferable to use the hexaaryl bisimidazole compound in the said (D) photoinitiator. The patterned colored photosensitive composition layer by using the hexaarylbisimidazole compound can exhibit good light resistance.

(Hexaarylbisimidazole compound)

The hexaarylbisimidazole compound may be any dimer of an imidazole ring substituted with three aryl groups, but a compound represented by the following general formula (1) is particularly preferable, and a compound represented by the general formula (2) is more preferred. desirable.

In General Formula (1), X in which there are a plurality is independently a hydrogen atom, a halogen atom, a cyano group, a C1-C4 alkyl group, or a C6-C9 aryl group, and A with several is each independently C1-C12 Alkoxy groups or -COO-R ⁹ , provided that R ⁹ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms. n is an integer of 1-3, and m is an integer of 1-3.

In General formula (2), X <^1> , X <^2> and X <^3> respectively independently represent a hydrogen atom, a halogen atom, a cyano group, a C1-C4 alkyl group, or a C6-C9 aryl group. However, two or more of X ¹ , X ² and X ³ do not simultaneously take hydrogen atoms.

Examples of the hexaarylbisimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole and 2,2'-bis (2-chloro Phenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5 ' Tetrakis (4-phenoxycarbonylphenyl) bisimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonyl Phenyl) bisimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) bisimidazole, 2,2' -Bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) bisimidazole, 2,2'-bis (2,4, 6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) bisimidazole, 2,2'-bis (2-cyanophenyl) -4,4' , 5,5'-tetrakis (4-ethoxycarbonylphenyl) bisimidazole, 2,2'-bis (2-cyanophenyl) -4,4 ', 5,5'-tetrakis (4- Phenoxycarbonyl Phenyl) bisimidazole, 2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) bisimidazole, 2,2'-bis ( 2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) bisimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5 '-Tetrakis (4-phenoxycarbonylphenyl) bisimidazole, 2,2'-bis (2-ethylphenyl) -4,4', 5,5'-tetrakis (4-methoxycarbonylphenyl ) Bisimidazole, 2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) bisimidazole, 2,2'-bis ( 2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) bisimidazole, 2,2'-bis (2-phenylphenyl) -4,4', 5 , 5'-tetrakis (4-methoxycarbonylphenyl) bisimidazole, 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycar Bisimidazoles such as carbonylphenyl) bisimidazole and 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) bisimidazole compound ;

2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra- (p-methoxyphenyl) bisimidazole, 2,2'-bis (o-chlorophenyl) -4 , 4 ', 5,5'-tetra- (m-methoxyphenyl) bisimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra- (3, 4-dimethoxyphenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra- (4-methoxyphenyl) bisimidazole, 2,2' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra- (3,4-dimethoxyphenyl) bisimidazole

2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4 , 4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2, 2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4-dicyanophenyl) -4 , 4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4,6-tricyanophenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2 , 2'-bis (2,4-dimethylphenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4,6-trimethylphenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4-diethylphenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2,2'- Bis (2,4,6-triethylphenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4-diphenylphenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4,6-triphenylphenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'- Bis (2- Fluorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (o-fluorophenyl) -4,4', 5,5'-tetraphenylbisimidazole Bisimidazole type compounds, such as these, etc. are mentioned.

Among the above, particularly preferred compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole (B-CIM, manufactured by Hodogaya Chemical Co., Ltd.), 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra- (3,4-dimethoxyphenyl) bisimidazole (HABI1311 from Nihon SiberHegner), 2,2'- Bis (2-methylphenyl) -4,4 ', 5,5'-tetraphenylbisimidazole (manufactured by Kurogane Kasei Co., Ltd.).

Content of the photoinitiator in the coloring photosensitive composition of this invention is 0.05? When content of the polymerizable monomer (polymerizable monomer which totaled the polymerizable monomer which has an acidic radical, and the polymerizable monomer which does not have an acidic radical) is 100 mass parts. About 30 mass% is preferable, It is more preferable that it is 0.1-20 mass%, It is more preferable that it is 0.2-10 mass%.

In addition, the ratio of content when using together the photoinitiator of structures other than a hexaaryl bisimidazole compound and a hexaaryl bisimidazole compound is hexaaryl bisimimi on a mass basis, when content of a hexaaryl bisimidazole compound is 1; 0.1 or more and 5.0 or less are preferable, as for content of photoinitiators of structures other than a diazole compound, 0.2 or more and 3.0 or less are more preferable, 0.3 or more and 2.0 or less are especially preferable.

By setting it as this range, especially light resistance becomes favorable.

<(E) Chain Transfer Agent>

The coloring photosensitive composition of this invention is characterized by including the chain transfer agent chosen from the (E) secondary or tertiary aliphatic thiol compound. Secondary or tertiary aliphatic thiol compounds have hydrogen donors as chain transfer agents. In the present invention, the water supply refers to the number of carbons to which carbon atoms adjacent to the thiol group are bonded.

In general, compounds having similar structures tend to be stabilized by interaction. The phthalocyanine compound has a planar structure, and because there is an electron density thick salt between the constituent nitrogen atoms and carbon atoms, the phthalocyanine compound has a structure stackable in parallel with respect to the plane, and complementary electron density thick salt It is easy to interact with the compound.

The zinc halide phthalocyanine pigment (A) in the present invention has high brightness, high saturation and high contrast, but has poor dispersibility and dispersion stability. In order to ensure the alkali developability of a coloring photosensitive composition, when a high acid value polymerizable monomer is used, a coloring photosensitive composition shifts to the acidic side. Thereby, it is thought that the acidic group interaction between a zinc halide phthalocyanine pigment and a dispersing agent becomes weak and a dispersion stable region is ubiquitous. In this case, when a compound which is easy to interact with the zinc halide phthalocyanine pigment is present, it is considered that the interaction between the zinc halide phthalocyanine pigment and the dispersant causes the dispersion state to become unstable, resulting in high aggregation of the pigment.

From this point of view, when an aromatic thiol compound is used as the chain transfer agent for the (A) zinc halide phthalocyanine pigment in the present invention, the effect of the structure and the aromatic ring structure of the thiol is used between the halogenated zinc phthalocyanine pigment and the aromatic thiol compound. It is thought that a thiol compound becomes easy to adsorb | suck to the surface of a halogenated zinc phthalocyanine pigment by interaction. As a result, it is thought that a problem arises with time-lapse performance (viscosity and contrast) of a colored photosensitive composition by aggregation of a zinc halide phthalocyanine pigment.

In the present invention, since an aliphatic thiol compound is used, the action due to the aromatic ring of the thiol compound is hardly generated, and since a compound having a secondary or tertiary thiol group is used, the interaction between the thiol compound and the halogenated zinc phthalocyanine pigment It is considered that the action is not so weak that aggregation of the halogenated zinc phthalocyanine pigment does not occur, so that the function as a chain transfer agent can be exhibited without regret.

Although the surface of the zinc halide phthalocyanine pigment has secured dispersion stability by adsorbing the dispersing agent, since the dispersing agent is usually a polymer, the surface of the halogenated zinc phthalocyanine pigment cannot be adsorbed to all the adsorption points of the surface of the zinc halide phthalocyanine pigment to deactivate the surface adsorption point of the halogenated zinc phthalocyanine pigment. That is, the adsorption point which has not been adsorbed is considered to remain on the surface of the zinc halide phthalocyanine pigment, which may cause the pigment to aggregate over time. However, in this invention, since the polymerizable monomer which has an acidic radical is used as a polymerizable monomer, it is thought that the monomer which has this acidic radical adsorb | sucks to the adsorption point of the remaining pigment surface, and the aggregation of the pigment by the thiol group mentioned above does not arise. . That is, to prevent aggregation of the zinc halide phthalocyanine pigment, the surface of the zinc phthalocyanine pigment of the present invention is formed by the synergistic effect of the secondary or tertiary aliphatic thiol compound selected in the present invention and the polymerizable monomer having an acid group. It is thought that the deterioration of performance over time could be prevented. It is thought that the favorable color characteristic which zinc halide phthalocyanine pigment has by this was implement | achieved.

Moreover, in this invention, the secondary or tertiary aliphatic thiol compound showed the chain transfer effect, was excellent in the sensitivity, and was able to provide the coloring photosensitive composition with favorable developability.

In addition, thiol compounds having a sulfur atom give off a characteristic odor. Odor is known to be highly related to volatility, but in general, aliphatic primary thiol compounds are not preferred for use as colored photosensitive compositions because of their high volatility, and in the present invention, secondary or tertiary aliphatic thiol compounds are used. Since it used, there was no problem of a bad smell when using a colored photosensitive composition, and the suitable colored photosensitive composition was obtained.

As the secondary or tertiary aliphatic thiol compound, t-butanethiol, octyl-2-mercaptopropionate, octyl-3-mercaptobutylate, stearyl-2-mercaptopropionate, stearyl-3- Mercaptobutylate, 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-butanediolbis-2-mercaptopropionate, 1,4-butanediolbis-3-mercaptobutylate, Ethylene glycol bis-2-mercaptopropionate, ethylene glycol bis-3- mercaptobutylate, trimethylol propane tris-2- mercapto propionate, trimethylol propane tris-3- mercapto butyrate, pentaerythritol Tetrakis-2-mercaptopropionate, pentaerythritol tetrakis-3-mercaptobutylate, dipentaerythritol pentakis-2-mercaptopropionate, dipentaerythritol pentakis-3-mercaptobutylate, etc. Can be mentioned.

Among these, mono- or bi-functional aliphatic thiol compounds are preferred because they have better stability over time, and are preferable, such as t-butanethiol, octyl-2-mercaptopropionate, octyl-3- mercaptobutylate, stearyl- 2-mercaptopropionate, stearyl-3-mercaptobutylate, 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-butanediolbis-2-mercaptopropionate, 1 , 4-butanediolbis-3-mercaptobutylate, ethylene glycol bis-2-mercaptopropionate and ethylene glycol bis-3-mercaptobutylate are particularly preferred.

In the colored photosensitive composition of the present invention, a secondary or tertiary aliphatic thiol compound may be used alone as a chain transfer agent, or two or more secondary or tertiary aliphatic thiol compounds may be used.

As for content of the secondary or tertiary aliphatic thiol compound in the coloring photosensitive composition of this invention, 0.2-10 mass% is preferable with respect to the total solid except the solvent contained in a coloring photosensitive composition, More preferably, 0.3-8 It is mass%, Especially preferably, it is 0.5-5 mass%.

Moreover, as for content with respect to the total amount of (D) photoinitiator of the secondary or tertiary aliphatic thiol compound in a coloring photosensitive composition, 5-150 mass% is preferable on a mass basis, More preferably, it is 10-100 mass%. It is especially preferably 10-50 mass%.

By being in this range, superposition | polymerization at the time of setting it as a coloring photosensitive composition layer is accelerated | stimulated, high sensitivity can form a favorable pattern.

Moreover, as for content with respect to (A) zinc halide halogenated phthalocyanine pigment of the secondary or tertiary aliphatic thiol compound in a coloring photosensitive composition, 1-10 mass% is preferable on a mass basis, More preferably, it is 2-8 mass%. Especially preferably, it is 3-5 mass%.

The storage stability of a coloring photosensitive composition is favorable by being in this range.

<(F) solvent>

The coloring photosensitive composition of this invention contains the (F) solvent.

Examples of the solvent (F) usable in the present invention include solvents classified into esters, ethers, ketones, aromatic hydrocarbons, and the like.

(F) A solvent can also be used for preparation of the said pigment dispersion composition.

Examples of the esters used as the solvent (F) include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate and butyl butyrate In addition to alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetic acid, ethyl oxyacetic acid, butyl butyl acetate, methyl methoxyacetate, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, etc. 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionic acid, methyl 2-oxy-2-methyl propionate and ethyl 2-oxy-2-methyl propionate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2 Alkoxypropionic acid alkyl esters such as methyl ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

Examples of ethers include, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, di Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like.

As an example of ketones, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. are mentioned, for example.

As an example of aromatic hydrocarbons, toluene, xylene, etc. are mentioned, for example.

Of these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexa Paddy, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether acetate and the like are suitable.

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

Although content of the (F) solvent in the coloring photosensitive composition of this invention can be suitably determined considering the applicability | paintability of a coloring photosensitive composition, etc., generally content of the (F) solvent in a coloring photosensitive composition is 76 mass%-88 mass%. to be.

<(G) photosensitizer>

The colored photosensitive composition of this invention may contain (G) photosensitizer further.

(G) As a photosensitizer, the compound which has the maximum absorption wavelength in 350-450 nm is used suitably.

For example, polynuclear aromatics (e.g. pyrene, perylene, triphenylene), xanthenes (e.g. fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (e.g. For example, thiacarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue) , Acridines (e.g., acridine orange, chloroflavin, acriflavin), anthraquinones (e.g., anthraquinones), squarias (e.g., squarias), benzophenones In addition to the group of compounds, such as (4,4'- diethylamino benzophenone), it is described in Unexamined-Japanese-Patent No. 2007-91806, Unexamined-Japanese-Patent No. 2008-9323, 2010-49160. The compound can be mentioned.

Content ratio (mass ratio) of the (D) photoinitiator, (E) secondary or tertiary aliphatic thiol compound, and (G) photosensitizer in this invention is a photoinitiator / thiol compound / photosensitizer = 20? It is preferable that it is 50/30-70/10-30, It is more preferable that it is a photoinitiator / thiol compound / photosensitizer = 30-40/40-60/10-20, A photoinitiator / thiol compound / photosensitizer It is more preferable that it is = 35-40 / 50 * 55 / 10-15.

By using each component in these ratios, the exposure sensitivity with respect to g line | wire, h line | wire, and i line | wire becomes high, and it becomes easy to obtain the coloring pattern of the line width with high precision according to an exposure area | region.

Moreover, it is also preferable that the coloring photosensitive composition of this invention contains a sensitizer. In the present invention, the sensitizer has an effect of further improving the sensitivity of the photosensitizer and the photopolymerization initiator to the active radiation or suppressing the inhibition of polymerization of the photopolymerizable compound by oxygen.

Examples of such sensitizers include amines such as M.R. Sander et al. Journal of Polymer Society, Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication The compound of Unexamined-Japanese-Patent No. 59-138205, Unexamined-Japanese-Patent No. 60-84305, Unexamined-Japanese-Patent No. 62-18537, Unexamined-Japanese-Patent No. 64-33104, Research Disclosure 33825, etc. are mentioned, Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, etc. are mentioned.

As another example of a sensitizer, an amino acid compound (e.g., N-phenylglycine, etc.), an organometallic compound (e.g., tributyl tin acetate, etc.) described in JP-A-48-42965, JP-A-55-34414 And hydrogen compounds described in Japanese Patent Application Laid-Open No. 6-308727 (for example, trithiane).

The content of the co-sensitizer is preferably in the range of 0.1 to 30% by mass and preferably in the range of 1 to 25% by mass with respect to the mass of the total solid of the photosensitive composition from the viewpoint of the improvement of the curing rate due to the balance of polymerization growth rate and chain transfer. Is more preferable, and the range of 0.5-20 mass% is still more preferable.

<Additive>

In the colored photosensitive composition of the present invention, if necessary, radical scavengers, light stabilizers, curing aids, thermal polymerization initiators, surfactants, adhesion aids, development accelerators, thermal polymerization inhibitors, dispersants, other additives (fillers, ultraviolet absorbers, anti-aggregation agents, etc.). May contain various additives.

(Radical scavenger)

You may add various radical trapping agents to this invention for the improvement of light resistance. Although the kind of radical scavenging agent is not specifically limited, Azinc clock compound and various light stabilizers are preferable from a heat resistance and light resistance viewpoint. Azoxy benzene, azoxy cyanisole, azoxyphenitol, 4,4'- dioctyl azoxy benzene, etc. are mentioned as an example of a cyan clock compound.

(Light stabilizer)

Various light stabilizer effects are exerted to improve light resistance. Although it does not specifically limit about the kind of light stabilizer, Hindered amine light stabilizer from a general-purpose viewpoint; For example bis (2,2,6,6-tetramethyl-4-piperidyl) adipate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2, 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-tetraacrylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-tetraacrylate, hindered phenolic light stabilizer; For example, pentaerythritol-tetrakis (3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate and the like are suitably used.

As for content of the light stabilizer 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%, It is still more preferable that it is 0.5-2.0 mass%. If it is 0.1 mass% or less, desired light resistance will not be obtained, and if it is 5.0 mass% or more, a sensitivity will decrease and it is unpreferable.

(Hardening preparation)

In order to raise the intensity | strength of the coating film formed as a hardening adjuvant, you may use the compound which has an epoxy ring. Thermal polymerization advances by using the compound which has an epoxy ring, and solvent tolerance improves or ITO sputter suitability improves, and it is preferable.

As a compound which has an epoxy ring, it is a compound which has 2 or more epoxy rings in a molecule | numerator, such as a bisphenol A type, a cresol novolak type, a biphenyl type, and an alicyclic epoxy compound.

For example, as bisphenol A, Epo Tohto YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, XX-1059, YDF-8170, YDF-17 0 (Above, Tohto Kasei Co., Ltd.), DENACOL EX-1101, EX-1102, EX-1103 (more, Nagase ChemteX Corporation product), PLACCEL GL-61, GL-62, G101, G102 (more , Daicel Chemical Industries, Ltd.), and similar bisphenol F type and bisphenol S type are also mentioned. Moreover, epoxy acrylates, such as Ebecryl 3700, 3701, 600 (above, Daicel-UCB Co. Ltd. product), can also be used.

As the cresol novolak type, Epo Tohto YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Tohto Kasei Co., Ltd.), DENACOL EM-125, etc. (above, Tohto Kasei Co., Ltd.) and the alicyclic epoxy compound such as 3,5,3 ', 5'-tetramethyl-4,4'-diglycidyl biphenyl as the biphenyl type, CELLOXIDE 2021, 2081, 2083, 2085 , EPOLEAD GT-301, GT-302, GT-401, GT-403, EHPE-3150 (from Daicel Chemical Industries, Ltd.), SAN TOHTO ST-3000, ST-4000, ST-5080, ST-5100 And the like (above, manufactured by Tohto Kasei Co., Ltd.), Epiclon 430, 673, 695, 850S, 4032 (above, manufactured by DIC Corporation), and the like.

1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyl tris (hydroxyethyl) isocyanurate, o Phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and other amine epoxy resins, Epo Tohto YH-434 and YH-434L (above, manufactured by Tohto Kasei Co., Ltd.) and bisphenol A epoxy resins. Glycidyl ester etc. which modified | denatured dimer acid in a skeleton can also be used.

Among these, "molecular weight / number of epoxy rings" is preferably 100 or more, more preferably 130 to 500. If the "molecular weight / number of epoxy rings" is small, the curability is high, the shrinkage during curing is large, and if too large, the curability is insufficient, resulting in insufficient reliability or poor flatness.

Specific preferred compounds include Epo Tohto YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701 (above, manufactured by Tohto Kasei Co., Ltd.), PLACCEL GL-61, GL-62, 3,5 , 3 ', 5'-tetramethyl-4,4' diglycidylbiphenyl, CELLOXIDE 2021, 2081, EPOLEAD GT-302, GT-403, EHPE-3150 (above, Daicel Chemical Industries, Ltd.) Can be mentioned.

As for content of the hardening adjuvant 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%, It is more preferable that it is 0.5-2.0 mass%. If it is 0.1 mass% or less, the hardening promoting effect will not be acquired, but in 5.0 mass% or more, light resistance deteriorates and it is a problem.

(Thermal polymerization initiator)

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. As the peroxide compounds, ketone peroxide, peroxy ketal, and hydroper are mentioned. Oxide, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxydicarbonate, etc. are mentioned.

(Surfactants)

It is preferable to comprise in the coloring photosensitive composition of this invention using various surfactant from a viewpoint of improving applicability | paintability. Liquid characteristics (especially fluidity) at the time of using a surfactant as a coating liquid can be improved, and the uniformity and liquid saving of coating thickness 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 film having a uniform thickness with a small thickness unevenness is obtained. It is effective in that formation is possible. Moreover, it is effective also in slit application which is easy to produce liquid saving.

As surfactant, various surfactant of nonionic, cationic, and anionic type can be used. Especially, the fluorine-type surfactant which is a nonionic surfactant and has a perfluoroalkyl group 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 a fluorine type surfactant, MEGAFACE F171, copper F172, copper F173, copper F177, copper F141, copper F142, copper F143, copper F144, copper R30, copper F437 (above, DIC Corporation), FLORAD FC430, copper FC431 , East FC171 (above, Sumitomo 3M Ltd. product), SURFLON S-382, East SC-101, East SC-103, East SC-104, East SC-105, East SC1068, East SC-381, East SC-383 , S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), and the like.

Examples of surfactants other than fluorine-based include phthalocyanine derivatives (commercially available EFKA-745 (manufactured by Morishita Sangyo KK)), organosiloxane polymer KP341341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), (meth) acrylic acid-based (co) polymers Polyflow No. 75, No. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusu 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 Esters (nonionic surfactants such as Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 from BASF; W004, W005, W017 (Yusho Co., Ltd. product), and the like.

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

(Adherence preparation)

An adhesive adjuvant can be added to the photosensitive resin composition used for this invention from a viewpoint of improving adhesiveness with a board | substrate. As an adhesion | attachment adjuvant, an alkoxy silane compound and the (in particular) silane coupling agent can be used especially.

The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group chemically bondable with the inorganic material serving as the substrate, and forms a (meth) acryloyl group, a phenyl group, which exhibits affinity by forming an interaction or bond with an organic resin. The silane coupling agent which has groups, such as a secondary or tertiary mercapto group, an epoxy group, and an aminosilane group, is preferable, and it is more preferable that it is (meth) acryloylpropyl trimethoxysilane and epoxypropyl trimethoxysilane among these. As such a material, KBM-303, KBM-403, KBM-503 (above Shin-Etsu Chemical Industry Co., Ltd. product) is mentioned.

As addition amount at the time of using a silane coupling agent, it is preferable that it is the range of 0.2 mass%-5.0 mass% in all solid content in the coloring photosensitive composition of this invention, and 0.5 mass%-3.0 mass% are more preferable.

(Developing accelerator)

Moreover, when promoting alkali solubility of the uncured part of a coloring photosensitive composition layer, and aiming at further improving developability of a coloring photosensitive composition, a developing accelerator can be used for a coloring photosensitive composition.

As such a development accelerator, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is preferable. 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, suberic acid, azelaic acid, sebacic acid, brasilic acid, 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; And other carboxylic acids such as phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildeacetic acid, coumalic acid and umbelic acid. Can be.

(Thermal polymerization inhibitor)

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, Benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butyl phenol), 2-mercaptobenzoimidazole Etc. are useful.

(Dispersant)

In addition to the above, the pigment dispersant described in the section of the pigment dispersion composition can be added to the colored photosensitive composition.

(Other additives)

Fillers such as glass and alumina;

Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone;

And aggregation inhibitors such as sodium polyacrylate.

The coloring photosensitive composition of this invention is each component mentioned above, namely (A) zinc-halogenated phthalocyanine pigment, the polymerizable monomer which has the (B) acidic group, (C) binder resin, (D) photoinitiator, (E) secondary, or It contains a tertiary aliphatic thiol compound, (F) solvent, (or (G) sensitizer), and can also prepare by adding and mixing other additives, such as surfactant, as needed.

<Color filter and manufacturing method thereof>

The color filter of this invention is produced by forming the colored film (coloring pattern) on the board | substrates, such as glass, using the coloring photosensitive composition of the said invention, For example, apply | coating the coloring photosensitive composition of this invention on a board | substrate. And a color layer forming step of forming a colored layer, an exposure step of forming a latent image by exposing the colored layer in a pattern form, and a developing step of developing the colored layer after exposure to form a colored pattern. Is manufactured by.

Although a colored layer is provided directly to a board | substrate or through another layer, As a method of providing a colored layer, it is formed by methods, such as a rotary coating, a slit coating, cast coating, roll coating, inkjet coating, or a transfer. The colored layer formed is exposed through a mask pattern or exposed in a pattern to cure the exposed part, and then the unexposed part (uncured part) is developed and removed with a developer to form a colored pattern of each color (for example, three or four colors). By doing this, a color filter can be produced.

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

At this time, as radiation used for exposure, an ultraviolet laser etc. other than ultraviolet rays, such as g line | wire, h line | wire, i line | wire, and j line | wire, are preferable.

Moreover, as an exposure system, the exposure system using a laser light source can also be used suitably besides the proximity exposure system and the sputter exposure system.

In the laser exposure method, an ultraviolet light laser is used as the light source. Laser is the acronym for English Light Amplification by Stimulated Emission of Radiation. 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, a laser having an oscillation wavelength can be used for known ultraviolet light such as a solid laser, a liquid laser, a gas laser, or a semiconductor laser. 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 of the laser exposure 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 which is the wavelength of the range of 300 nm-360 nm is the photosensitive wavelength of a coloring photosensitive composition. It is preferable at the point to correspond to.

Specifically, the third harmonic (355 nm) of the Nd: YAG laser of the 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 suitably 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 productivity of pattern formation that an exposure amount is this 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 Mfg. Co. , Ltd.) and the like. Moreover, the apparatus of that excepting the above is also used suitably.

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. Nichia Corporation, for example, markets purple LEDs with a extraction spectrum of wavelengths between 365 nm and 420 nm. When even shorter wavelengths are needed, US Pat. No. 6,084,250 discloses LEDs capable of emitting active radiation centered between 300 nm and 370 nm. In addition, other ultraviolet LEDs are 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, pattern exposure can be performed without using a mask at the time of exposure. However, when exposing a pattern using a mask, since the linearity of a pattern becomes further high, it 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 development, the uncured part after exposure is eluted with a developing solution so that only the 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 the developing solution, any one can be used as long as it dissolves the film of the colored photosensitive composition in the uncured portion and does not dissolve the cured portion. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used.

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

As said alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl The concentration of the alkaline compound such as ammonium 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 melt | 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 post-development heating for making hardening complete, and it normally heats about 200 degreeC-250 degreeC (hard baking). 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 become said condition.

By repeating the above operation sequentially for each color in accordance with the desired number of colors, a color filter formed by forming a cured film in which a plurality of colors are colored can be produced.

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

Examples of the substrate include alkali-free glass, soda glass, pyrex (registered trademark) glass, quartz glass, and photoelectric conversion element substrates used for solid-state imaging devices, etc. For example, a silicon substrate etc. and a plastic substrate are mentioned. On these substrates, black stripes are usually formed to isolate each pixel.

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.

[LCD]

The color filter of this invention is especially suitable 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.

The definition of the display device and the description of each display device are described in, for example, "Electronic display device" by Teru Sasaki, Kogyo Chosakai Publishing, Inc. 1990), "Display device (by Ibuki Sumiaki, Sangyo-Tosho 1989) Issuance). In addition, the liquid crystal display device is described, for example in "next-generation liquid crystal display technology (Tatsuo Uchida editing, Kogyo Chosakai Publishing, Inc. 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 the present invention is particularly effective for a color TFT type liquid crystal display device. 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 is also applied to a liquid crystal display device having an enlarged viewing angle such as a lateral electric field drive method such as IPS, a pixel division method such as MVA, or a liquid crystal display device such as STN, TN, VA, OCS, FFS, and R-OCB. can do.

In addition, the color filter of the present invention can be provided in a liquid crystal display device of a bright and high precision Color-filter On Array (COA) method. In the COA type liquid crystal display device, the required characteristics for the color filter layer are 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 colored photosensitive composition of the present invention can improve the curability of the colored pixel to form a pixel without missing, peeling, or misdirection, so that especially the peeling liquid resistance of the colored layer formed directly or indirectly on the TFT substrate is reduced. It is improved and useful also for a COA type liquid crystal display device. 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 for the COA color filter, a rectangular through hole 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 driving substrate below the colored layer. Alternatively, it is necessary to form a conductive path such as a U-shaped recess, and the dimension (that is, the length of one side) of the conductive path is preferably 5 µm or less. It is also possible to form a conductive path of.

These image display methods are described, for example, on page 43 of "EL, PDP, LCD display technology and the latest trends in the market" (Research Study Division, Toray Research Center, Inc. 2001).

In addition to the color filter of the present invention, the liquid crystal display of the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle guarantee film, and the like. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members.

For these members, for example, the '94 liquid crystal display peripheral materials and the chemical market (Kenta Shima, CMC Publishing Co., Ltd. 1994), the 2003 liquid crystal related market and future prospects (the lower volume) ( Omote Ryokichi, issued by Fuji Chimera Research Institute Inc. 2003).

Backlights are described in SID meeting Digest 1380 (2005) (A. Konno et al), pages 18-24 (Shima Yasuhiro), and pages 25-30 (Yagi Takaaki) of the December 2005 issue of the 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 the luminance is increased by using a red, green, and blue LED light source (RGB-LED) as a backlight. A liquid crystal display device having high color reproducibility with high color purity can be further provided.

Example

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

Synthesis of halogenated zinc 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 crude pigment.

1 part of this partial zinc bromide phthalocyanine crude pigment, 7 parts of crushed sodium chloride, 1.6 parts of diethylene glycol, and 0.09 parts of xylene were added to a double arm kneader and kneaded at 100 ° C for 6 hours. After kneading, the mixture was taken out in 100 parts of water at 80 ° C, and stirred for 1 hour to obtain a partially zinc bromide phthalocyanine pigment obtained by filtration, warm water washing, drying and pulverization.

The obtained partial zinc bromide phthalocyanine pigment was ZnPcBr ₁₀ Cl ₄ H ₂ (Pc; phthalocyanine) from halogen content analysis by mass spectrometry, and contained an average of ₁₀ bromines in one molecule.

In addition, the average value of the primary particle diameter measured with the transmission electron microscope (JEOL Co. Ltd. product, JEM-2010) 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 K0961 HD from BASF) fuming sulfuric acid (25% SO) at 15 ° C. with stirring ₃ ) It put in 130g. After stirring for 3 hours, it was added to 250 g of ice. After standing for 30 minutes, the resulting suspension was filtered and the resulting 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 ammonia chloride was added, the mixture was stirred at 80 ° C for 30 minutes, and the precipitate deposited was filtered at 60 ° C. The obtained wet crystal was washed with water, and then dried at 80 ° C. to obtain 17 g of an ammonium salt of quinophthalone derivative sulfonate.

The ammonium salt of this quinophthalone derivative sulfonate was heat-treated at 180 degreeC for 3 hours, and 16g (yield 94%) of quinophthalone derivative sulfonates (compound 4 of the following structure) from which ammonium salt was removed were obtained.

To 10 g of sulfonate (Compound 4) was added 2.2 g of oxalyl chloride (from Wako Pure Chemical Industries, Ltd.) and 1 ml of N, N-dimethylformamide (from Wako Pure Chemical Industries, Ltd.) under ice-cooling in chloroform, It stirred at 50 degreeC for 2 hours. 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 a sulfonic acid chloride compound (compound 5 having the following structure). (Yield 72%)

To 55.0 g of compound, 0.9 g of 6-chloro-1-hexylamine (manufactured by Rare Chemicals) was added under ice cooling in chloroform, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was added to 150 ml of water, and the precipitated crystals were filtered off, washed with water and dried under reduced pressure to obtain 4.3 g of a sulfoamide alkyl chloride compound (compound 6 having the following structure). (Yield 76%)

An excess amount of water and anhydrous sodium sulfite (manufactured by KANTO CHEMICAL CO., INC.) Was added to 64.3 g of the compound, and the mixture was heated at 180 ° C for 12 hours in an autoclave. After allowing to cool, the crystals were filtered to obtain 3.7 g of a sulfoamide alkyl sulfonic acid compound (Compound 7 having the following structure). (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-018, number average molecular weight 1,800, product of NIPPON SHOKUBAI CO., LTD.) And 100 g of polyester resin (i-1) are mixed and heated at 120 ° C. for 3 hours to give an intermediate (J-1B). Got it. Then, it cooled to 65 degreeC, 200g of propylene glycol monomethyl ether acetate (henceforth PGMEA) containing 3.8g of succinic anhydride was added slowly, 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 a Dispersion Composition Containing Partial Zinc Bromide Phthalocyanine Pigment

After the partial zinc bromide phthalocyanine pigment (hereinafter referred to as PG58, 11.9 parts, 73.1 parts of a compound as a quinophthalone compound, 9.0 parts of SOLSPERSE 24000GR (manufactured by Lubrizol Japan Limited) as a dispersant, 76 parts of PGMEA as a solvent, and then sand grinder mill The pigment dispersion composition containing the partially zinc bromide phthalocyanine pigment was obtained by disperse | distributing for 3 hours.The viscosity of the obtained pigment dispersion composition was measured at the temperature of 23 degreeC with E-type viscosity meter RE-85L (made by TOKI SANGYO CO., LTD.). It was confirmed that it was very stable at 9.2 mPa · s and good dispersion stability was obtained Storage conditions: 14 days after dispersion (preservation temperature 5 ° C.)

Preparation of Dispersion Composition Containing Yellow Pigment PY150-

As a pigment, a mixture of 40 parts of CI Pigment Yellow 150 (average primary particle diameter 60 nm) (hereinafter referred to as PY150) and 223 parts of PGMEA 10% solution of the resin (J-1) (22.3 parts in terms of solid content) is a bead mill. (Zirconia beads 0.3 mm) was mixed and dispersed for 3 hours to prepare a dispersion composition containing the yellow pigment PY150.

Preparation of Dispersion Composition Containing Yellow Pigment PY138-

A mixture of 40 parts of CI Pigment Yellow 138 (average primary particle diameter 60 nm) (hereinafter referred to as PY138) as a pigment and 223 parts of a PGMEA 10% solution of the resin (J-1) (22.3 parts in terms of solid content) was mixed with a bead mill ( Zirconia beads 0.3 mm) were mixed and dispersed for 3 hours to prepare a dispersion composition containing the yellow pigment PY138.

Synthesis of Compound 1 as a Photopolymerization Initiator

(1) Synthesis of Compound A

First, compound A is 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. Subsequently, o-tolyl chloride (81.5 g, 0.527 mol) 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 dripped over 40 minutes, it warms up to room temperature, and it 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 ° C., and the reaction solution is added dropwise. The precipitated solid was filtered off with suction, washed with distilled water and methanol, and recrystallized with acetonitrile to obtain Compound A (amount 164.4 g, yield 77%) having the following structure.

(2) Synthesis of Compound B

Next, using Compound A, Compound B is synthesized according to the following scheme.

Compound A (20.0 g, 47.9 mmol) was dissolved in 64 ml of THF, and 4-chlorobenzenethiol (7.27 g, 50.2 mmol) and sodium iodide (0.7 g, 4.79 mmol) were added. Then, sodium hydroxide (2.0 g, 50.2 mmol) is added to the reaction solution, and the mixture is refluxed for 2 hours. Then, after cooling to 0 degreeC, SM-28 (11.1g, 57.4mmol) is dripped over 20 minutes, it warms up to room temperature and stirred for 2 hours. Then, after cooling to 0 degreeC, nitrous acid isopentyl (6.73 g, 57.4 mmol) 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 filtered off with suction and washed with distilled water. Subsequently, it recrystallized with acetonitrile and the compound B (amount 17.0g, yield 64%) of the following structure was obtained.

(3) Synthesis of Compound C

Subsequently, the compound C which is an initiator is 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. Then, after cooling to 0 degreeC, acetyl chloride (3.05g, 38.9mmol) is dripped over 20 minutes, Then, it warms up to room temperature and stirred for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0 ° C., and the precipitated solid was suction filtered and washed with 200 ml of isopropyl alcohol cooled to 0 ° C., dried, and then Compound C (amount 19.5 g, yield 99%) )

Example 1

<Preparation of a colored photosensitive composition>

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

(Composition 1)

33.0 parts of pigment dispersion composition comprising PG58

15.2 parts of a pigment dispersion composition comprising PY150

Solvent (PGMEA) part 20.1

Solvent (3-ethoxyethyl propionate) 24.6 parts

Binder resin (allyl methacrylate-methacrylic acid (= copolymerization molar ratio 8: 2)

      Copolymer, weight average molecular weight 30000) 0.78 parts

Polymerizable monomer: 4.43 parts of ARONIX M-520 (manufactured by Toagosei Co., Ltd.)

Photoinitiator: 2-chlorophenyl-4,5-bisphenylimidazole dimer

0.14 parts (B-CIM, Hodogaya Chemical Co., Ltd. product)

Photoinitiator: 1.47 parts of IRGACURE OXE01 (Ciba Specialty Chemicals product, structure below)

Aliphatic thiol compound: Karenz MT-BD1 (butanediol bis (3-mercaptobutyrate, manufactured by Showa Denko K.K.) 0.19 parts

Photosensitizer: compound 8 (following structure) 0.042 parts

Surfactants (Fluorinated surfactants, manufactured by DIC Corporation, MEGAFACE F781-F)

                                                           0.033 part

IRGACURE OXE-01

<Formation of a Colored Pattern Using a Colored Photosensitive Composition>

Formation of Colored Photosensitive Composition Layer

The obtained colored photosensitive composition was applied to a glass substrate (Corning Incorporated, Millennium, 0.7 mm thick). Specifically, the interval between the slit nozzle and the substrate and the discharge amount were adjusted so that the film thickness of the colored composition layer after postbaking was about 2.4 µm, and the coating speed was applied at a coating speed of 120 mm / second.

Prebaking Process

Then, the colored photosensitive composition layer was dried in a vacuum drying apparatus until the degree of vacuum reached 66 Pa, and then heated (prebaked) 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 LE5565A by Hitachi High-Technologies Corporation).

Development Process, Baking (Post Baking) Process

After that, a 1.0% developer (1 part of CDK-1 and 99 parts of pure water) of the potassium hydroxide developer CDK-1 (manufactured by Fujifilm Electronics Materials Co., Ltd.) was developed using a developing apparatus (manufactured by Hitachi High-Technologies Corporation). The diluted solution, 25 ° C) was developed for 60 seconds at a shower pressure of 0.2 MPa, and washed with pure water.

After drying sufficiently, it was post-baked for 40 minutes in 230 degreeC oven.

(Examples 2-12, Comparative Examples 1-8)

In the composition 1 of Example 1, the kind of pigment dispersion composition, a polymerizable monomer, a photoinitiator, and a chain transfer agent (aliphatic thiol compound) was changed as shown in Table 1, except the same as that of Example 1 Each colored photosensitive composition of Examples 2-12 and Comparative Examples 1-8 was prepared.

Using the obtained coloring photosensitive composition, the coloring pattern was produced like Example 1 except having changed the exposure system in an exposure process as shown in Table 1.

In Table 1, a pigment dispersion composition is a pigment dispersion composition shown by the name of a pigment.

In addition, the detail of the exposure system described as "proxy" in Table 1 is the exposure system (proxy exposure) applied by the exposure process in Example 1. FIG. In addition, the detail of the exposure system described with "laser" 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. product, YAG laser's third high frequency wavelength 355 nm, pulse width 6 nsec) as the laser exposure apparatus. Was performed 20 times through a photomask.

In Table 1, the structures of DPHA and Karenz MT-PE1 are shown below.

DPHA: Nippon Kayaku Co., Ltd. Product of dipentaerythritol hexaacrylate

Karenz MT-PE1: Showa Denko K.K. Pentaerythritol tetrakis (3-mercaptobutyrate) of the product

In Table 1, OXE-01 is IRGACURE OXE-01.

<Evaluation>

About each obtained coloring photosensitive composition and coloring pattern, it evaluated about each item of stability, odor, developability, and solvent resistance with time. Evaluation methods and evaluation criteria are shown below. The obtained evaluation results are collectively shown in Table 2.

1. Evaluation of stability over time

The stability over time was evaluated in terms of liquid viscosity stability and contrast stability.

Liquid viscosity stability was evaluated by the viscosity change of the liquid before and after leaving a colored photosensitive composition fixed for 7 days under 40 degreeC thermostat conditions.

Contrast stability was evaluated by apply | coating the coloring photosensitive composition before and after 7 days standing still at 40 degreeC thermostat on the board | substrate with thickness of 2.3 micrometers, respectively, and calculating a change rate from the contrast value of each board | substrate.

E-type viscometer RE-85L (made by TOKI SANGYO CO., LTD.) For viscosity measurement, and BM-5 (made by TOPCON CORPORATION) was used for contrast measurement.

-Evaluation standard-

(Circle): (1) The viscosity change rate is less than 10%, and (2) The contrast change rate is less than 10% on the basis of the value of a political warfare before and after political preservation in thermostat conditions.

X: It does not correspond to any one or more of said (1) and (2).

It is preferable that the viscosity change rate with time and the contrast change rate with time of a coloring photosensitive composition are 10% or less on the basis of the value before stationary storage. If the above items are remarkably changed over time, in the case of forming the color pattern (pixel pattern) of the color filter by the coloring photosensitive composition of the present invention, production stability is not obtained and is not suitable for the production of the color filter.

2. Evaluation of odor

Evaluation of the odor was carried out by dropwise adding 1 ml of the colored photosensitive composition to Shaale, and by sensory evaluation at 23 ° C. according to the following criteria. If the odor is severe, not only it is unpleasant, but also necessitates the need for reinforcement of facilities such as exhaust, which is not preferable in practice.

-Evaluation standard-

(Circle): The number of people who felt unpleasant in 10 odor sensory evaluations is 0-3.

X: The number of people who felt unpleasant in ten odor sensory evaluations is four or more.

3. Evaluation of developability

The development latitude and the developer solubility were evaluated when the glass substrate after the completion of the exposure step was developed under the above conditions. If the developing latitude is narrow, developing stability in the manufacturing process is not obtained, which is not preferable. In addition, lack of developer solubility causes film removal and peeling during development, which causes residue and process contamination, which is a problem.

About the obtained result, it evaluated by the following evaluation criteria. A breakpoint is the time (seconds) in which the unexposed part of a coloring photosensitive composition melt | dissolves and peels off in a developing process, and is a moment when the unexposed part of a coloring photosensitive composition dissolves and peels in a break shi developing process.

-Evaluation standard-

(Circle): (1) There is no peeling of a coloring pattern from a break point for 80 sec or more, and (2) The film | membrane of peeling and peeling of a colored layer is not seen in a developing solution at the time of a break.

X: It does not correspond to any one or more of said (1) and (2).

4. 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 board | substrate after baking was measured by OSP-SP100: Olympus Corporation, and it immersed in 23 degreeC x 30 minutes with N-methyl- 2-pyrrolidone (henceforth "NMP"), and the coloring pattern before and behind immersion ΔE * ab was determined from the chromaticity. Chromaticity was measured by OSP-SP100: Olympus Corporation.

When ΔE * ab exceeds 3, solvent resistance in various chemical liquids used for panel processing is insufficient in the production of a liquid crystal display device and the like, which becomes a problem in practical use.

In addition, the change of the shape of 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-

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

X: It does not correspond to any one or more of said (1) and (2).

As shown in Table 2, the coloring photosensitive composition of an Example was excellent in stability with time, there was no unpleasant odor, and was also favorable about solvent resistance. On the other hand, the colored photosensitive composition of Comparative Examples 1-4 had a large change in performance before and after aging and deteriorated in stability. Moreover, the coloring photosensitive composition of the comparative example 5 had a problem because the developing latitude was narrow. The colored photosensitive composition of Comparative Examples 6-8 was bad in odor due to the thiol compound and could not withstand practical use.

In addition, according to the contrast between Example 2 and Example 1, all of the colored patterns (colored films) formed in the examples have the same favorable results with respect to solvent resistance, and this is obtained when pattern exposure with a laser exposure machine is applied. It can also be seen that the excellent effects of the present invention can be obtained in the same manner as in the exposure with a high pressure mercury lamp.

Claims (8)

A chain transfer agent selected from (A) a zinc halide phthalocyanine pigment, (B) a polymerizable monomer having an acid group, (C) a binder resin, (D) a photopolymerization initiator, (E) a secondary or tertiary aliphatic thiol compound, and ( F) The coloring photosensitive composition containing a solvent. The method of claim 1,
The secondary or tertiary aliphatic thiol compound is a monofunctional or bifunctional aliphatic thiol compound, characterized in that the coloring photosensitive composition. The method of claim 1,
The said (D) photoinitiator is a hexaarylbisimidazole compound, The coloring photosensitive composition characterized by the above-mentioned. The method of claim 1,
The said (C) binder resin is resin which has an acidic radical, The coloring photosensitive composition characterized by the above-mentioned. The method of claim 1,
(G) The coloring photosensitive composition further containing a photosensitizer. The colored layer formation process of providing the coloring photosensitive composition of any one of Claims 1-5 on a board | substrate, and forming a colored layer;
An exposure step of hardening an exposure area by performing exposure in a pattern form to the formed colored layer; And
And a developing step of developing and removing the unexposed part in the colored layer after the exposure to form a pattern. It is manufactured by the pattern formation method of Claim 6. The color filter characterized by the above-mentioned. A liquid crystal display device comprising the color filter according to claim 7.