JP5726462B2 - Colored photosensitive composition, method for producing color filter, color filter, and liquid crystal display device - Google Patents

Description

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

Conventionally, in a small liquid crystal display device such as a mobile phone, a mobile game machine, and a PDA, it is essential to use a backlight light source with a limited electric capacity such as a secondary battery or a dry battery. As the color material of the filter, a color material that is highly transparent and can display a color by transmitting the bright line of the backlight well has been advantageously used.
In recent years, the increase in size of liquid crystal display devices has progressed in applications such as liquid crystal display monitors for personal computers and liquid crystal televisions. In these liquid crystal display devices, there is no restriction on the power supply of the backlight, and the RGB color reproducibility of the display devices is emphasized. Has been. Therefore, in addition to the conventional transparency, the color material of the color filter is required to have higher image quality, that is, improvement in contrast and color purity.

In response to the above requirements, a pigment composition in which the particle diameter of the pigment is further refined, and further an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and other components are used as a colorable composition, which is used for photolithography. For example, a color filter in which a three-color pattern of red, green, and blue is formed on a transparent substrate such as glass has been developed and put to practical use.
Among them, the green coloring pattern is generally chlorinated copper phthalocyanine pigment (CI Pigment Green 7), chlorinated brominated copper phthalocyanine pigment (CI Pigment Green 36), etc. from the viewpoint of color tone and fastness. Green pigment is used.

  In recent years, as a green pigment, a halogenated metal phthalocyanine pigment such as aluminum, titanium, cobalt, nickel, zinc, tin, lead, etc., whose central metal is not copper, for the purpose of increasing the chroma (color purity and color density) of the pigment. (See, for example, Patent Document 1), and various pigments have been proposed for a zinc halide phthalocyanine pigment (CI Pigment Green 58) having a particularly high chroma (for example, Patent Document 2). To 4). For example, detailed studies on the degree of substitution of Br and Cl, a pigment treatment method using a betaine-type surfactant, various crystal forms, etc. have progressed, and in the X-ray diffraction spectrum, the Bragg angle (2θ ± 0.2 °) a copper halide phthalocyanine having a maximum diffraction peak at 26.4 ° or 25.5 ° has high chroma (color purity and color density), is excellent in stability over time, and is useful. It has been reported (for example, see Patent Document 5). Further, it has been proposed that a color filter having high transparency and high color purity can be obtained using these pigments.

  However, halogenated metal phthalocyanine pigments with high brightness, high saturation and high contrast have problems that the particle size is small, the development latitude is narrower than before, and the performance over time becomes unstable when stored as a colored photosensitive composition. There was something to do. In order to improve the temporal stability, it has been proposed to use a thiol compound having a branched structure (see, for example, Patent Document 6). However, the working environment is improved and cured due to higher temporal stability and odor. There is a demand for solvent resistance of the film.

JP 2003-161823 A JP 2007-284592 A JP 2004-70342 A JP 2008-24743 A JP 2009-223288 A JP 2004-264435 A

  The present invention has been made in view of the above-described problems. The object of the present invention is a colored cured film having excellent stability over time in a liquid state, a wide development latitude, no odor problems, and good solvent resistance. It is providing the coloring photosensitive composition which can form. Further, the present invention further provides a color filter having a high color purity and a high contrast color property, a method for producing the color filter, and a color filter using the colored photosensitive composition of the present invention. A liquid crystal display device including a filter is provided.

As a result of intensive studies to solve the above problems, the present inventors have found that the problems of the present invention can be achieved by the following means, and have reached the present invention.
<1> (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 chain transfer agent selected from, and (F) a solvent only containing the (B) colored photosensitive composition polymerizable monomer having an acid group is a carboxyl group-modified polyfunctional acrylate compound.

<2> The colored photosensitive composition according to <1>, wherein the secondary or tertiary aliphatic thiol compound is a monofunctional or bifunctional aliphatic thiol compound.
<3> The colored photosensitive composition according to <1> or <2>, wherein the (D) photopolymerization initiator is a hexaarylbisimidazole compound.
<4> The colored photosensitive composition according to <3>, wherein the (D) photopolymerization initiator further includes two or more kinds including an oxime compound.
<5> The colored photosensitive composition according to any one of <1> to <4>, wherein the (C) binder resin is a resin having an acid group.
<6> The colored photosensitive composition according to any one of <1> to <5>, further comprising (G) a photosensitizer.
<7> The carboxyl group-modified polyfunctional acrylate compound is succinic acid-modified pentaerythritol triacrylate, succinic acid-modified trimethylolpropane triacrylate, succinic acid-modified pentaerythritol tetraacrylate, succinic acid-modified dipentaerythritol pentaacrylate, or succinic acid-modified. dipentaerythritol hexaacrylate, adipic acid-modified pentaerythritol triacrylate, adipic acid-modified trimethylolpropane triacrylate, adipic acid-modified pentaerythritol tetraacrylate, adipic acid-modified dipentaerythritol pentaacrylate and adipic acid-modified dipentaerythritol tetra acrylated DOO at least one selected additive et <1> to colored photosensitive group according to any one of <6> Adult.
<8> The zinc halide phthalocyanine pigment (A) is C.I. I. Pigment green 58, and C.I. I. The colored photosensitive composition according to any one of <1> to <7>, including CI Pigment Yellow 150.

< 9 > A colored layer forming step of applying the colored photosensitive composition according to any one of <1> to < 8 > onto a substrate to form a colored layer, and a pattern-like pattern on the formed colored layer A pattern forming method comprising: an exposure step of curing the exposed region by performing the above exposure; and a developing step of developing and removing an unexposed portion in the colored layer after exposure to form a pattern.

< 10 > The color filter manufactured by the pattern formation method as described in < 9 >.
< 11 > A liquid crystal display device comprising the color filter according to < 10 >.

  According to the present invention, it is possible to provide a colored photosensitive composition that can form a colored cured film having excellent stability over time in a liquid state, wide development latitude, no odor problems, and good solvent resistance. it can. In addition, a color filter having a high color purity and a high contrast and good color characteristics, a method for producing the color filter, and a liquid crystal display device provided with the color filter, comprising the colored photosensitive composition of the present invention. Can be provided.

  Hereinafter, the colored photosensitive composition of the present invention, a color filter using the colored photosensitive composition, and a liquid crystal display device using the color filter will be described in detail.

<Colored photosensitive composition>
The colored photosensitive composition of the present invention comprises (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 chain transfer agent selected from tertiary aliphatic thiol compound, and (F) viewed contains a solvent, a polymerizable monomer having a (B) acid group and wherein the carboxyl group-modified polyfunctional acrylate compound .
Hereinafter, each component which comprises the colored photosensitive composition of this invention is described.

<(A) Halogenated zinc 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, up to 16 of these hydrogen atoms can be substituted with bromine atoms and / or chlorine atoms.
These halogen atoms may all be the same or different.
The number of halogen atom substitutions is preferably 8 or more and 16 or less, more preferably 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 these is preferably a chlorine atom or a bromine atom.

The zinc halide phthalocyanine pigment is substituted with 8 or more bromine atoms, thereby exhibiting a yellowish and light green color, and is suitable for use in a green pixel portion pattern of a color filter.
In particular, those having a bromine atom substitution number of 10 to 16 have higher brightness, and thus are preferably used in the present invention.

The zinc halide phthalocyanine pigment used in the present invention can be produced by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, or a melting method.
As for a more specific production method, the method for producing a zinc halide phthalocyanine pigment disclosed in JP-A-2004-70342 is preferable from the viewpoint of cost.
In addition, in terms of stability, although depending on other additives and the way of assembling the post-process, the crystal-converted zinc halide phthalocyanine pigment disclosed in JP-A-2008-19383 is preferable.
In particular, a resin-coated zinc halide phthalocyanine pigment disclosed in JP-A-2007-320986 is a preferred embodiment for improving dispersibility.

The average primary particle diameter of the halogenated zinc phthalocyanine pigment of the present invention is preferably in the range of 10 nm to 100 nm, more preferably in the range of 10 nm to 40 nm.
By using a phthalocyanine pigment having an average primary particle size in this range, a colored photosensitive composition for a color filter having excellent dispersion stability and coloring power, high brightness, and high contrast can be obtained.

  The average primary particle diameter in the present invention is the longer one of 100 primary particles of a phthalocyanine pigment constituting an aggregate on a two-dimensional image obtained by photographing particles in the field of view with a transmission electron microscope. The average value of the diameter (major axis) and the shorter diameter (minor axis) is obtained and averaged.

When the primary and horizontal aspect ratio of the zinc halide phthalocyanine pigment of the present invention is in the range of 1 to 3, the viscosity characteristics are improved in each application field and the fluidity is further increased.
In order to obtain the aspect ratio, as in the case of obtaining the average particle diameter of the primary particles as described above, the particles in the field of view are photographed with a transmission electron microscope or a scanning electron microscope.
Then, an average value of the longer diameter (major diameter) and the shorter diameter (minor diameter) is obtained for 100 primary particles constituting the aggregate on the two-dimensional image, and the average value is calculated using these values. .

  In obtaining a halogenated zinc phthalocyanine pigment having an average primary particle size in the range of 10 nm to 100 nm, it may be finely divided by any method, but crystal growth can be easily suppressed and the average primary particle size is compared. It is preferable to employ a solvent salt milling treatment in that small pigment particles can be obtained.

The solvent salt milling means kneading and grinding a halogenated zinc phthalocyanine pigment, an inorganic salt, and an organic solvent.
The zinc halide phthalocyanine pigment having a large particle size may be subjected to solvent salt milling after dry grinding.
Specifically, a zinc halide phthalocyanine pigment, an inorganic salt, and an organic solvent that does not dissolve it are charged into a kneader, and kneading and grinding are performed therein.
As a kneader at this time, for example, a kneader, a mix muller, or the like can be used.

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

In obtaining a halogenated zinc phthalocyanine pigment having an average primary particle diameter in the range of 10 nm to 100 nm, it is preferable to increase the ratio of the amount of inorganic salt used to the amount of zinc halide phthalocyanine pigment used in solvent salt milling.
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, an organic solvent capable of suppressing crystal growth is preferably used, and 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 mono Butyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene group Call, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, can be used dipropylene glycol.

  The amount of the water-soluble organic solvent used in this case is not particularly limited, but is preferably 0.01 to 5 parts and 0.8 to 2 parts in terms of mass with respect to 1 part of the halogenated zinc phthalocyanine pigment. More preferred.

  30-150 degreeC is preferable and the temperature at the time of solvent salt milling has more preferable 80-100 degreeC. The solvent salt milling time is preferably 5 to 20 hours, and more preferably 8 to 18 hours.

  In this way, a mixture containing a halogenated zinc phthalocyanine pigment, an inorganic salt, and an organic solvent as main components is obtained. The organic solvent and the inorganic salt are removed from this mixture, and if necessary, a zinc halide phthalocyanine pigment is mainly used. A fine powder of zinc halide phthalocyanine pigment can be obtained by washing, filtering, drying, pulverizing, etc. the solid.

As washing, either water washing or hot water washing can be employed. The number of washings can be repeated in the 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.

Examples of the drying after filtration and washing described above include batch-type or continuous drying in which the pigment is dehydrated and / or desolvated by heating at 80 to 120 ° C. with a heating source installed in a dryer. Examples of the dryer generally include a box dryer, a band dryer, and a spray dryer.
In addition, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle size of the primary particles, but, for example, in the case of drying using a box dryer or a band dryer. When the pigment is in the form of a lamp, etc., it is performed to break the pigment into powder, and examples include pulverization with a mortar, hammer mill, disk mill, pin mill, jet mill, and the like.

  The (A) halogenated zinc phthalocyanine pigment of the present invention can be obtained by, for example, the above-described method, but a generally distributed zinc halide phthalocyanine pigment or pigment dispersion product can also be used.

The (A) halogenated zinc phthalocyanine pigment thus obtained has a weak primary particle agglomeration and is more easily disintegrated, so that the covering power is increased and it is easy to create a high-contrast colored film. Become.
In the present invention, these zinc halide phthalocyanine pigments may be used alone, but other zinc halide phthalocyanine pigments having different bromination rates or chlorination rates, or the central metal is substituted with another metal. It can be used by mixing with brominated phthalocyanine.
By changing the bromination rate and chlorination rate, or changing the central metal, it is expected that the color tone of the pigment will change and that variations in the reproducible hue will increase.

  In the colored photosensitive composition of the present invention, the hue of the colored photosensitive composition can be adjusted and the transmittance can be increased by combining (A) the halogenated zinc phthalocyanine pigment with another color material.

For example, a yellow pigment or an orange pigment may be used in combination with the halogenated zinc phthalocyanine pigment to form a green pixel.
Examples of yellow pigments include disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments, benzimidazolone yellow pigments, nickel azo yellow pigments, diketopyrrolopyrrole orange pigments, Orange pigments such as perinone-based orange pigments can also be used if necessary.

  As a specific example, C.I. I. 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, 17 3, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, and C.I. I. 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, Etc.

Of these, C.I. I. 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, etc. And more preferably C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139.
In particular, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 138, C.I. I. It is preferable to use Pigment Yellow 139 because of high transmittance and high contrast.

  In order to form a blue pixel, a purple pigment may be used in combination with the zinc halide phthalocyanine pigment. Examples of purple pigments include quinacridone purple pigments, oxazine purple pigments, anthraquinone purple pigments, indigoid purple pigments, and xanthene purple pigments.

  As a specific example, C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, especially C.I. I. Pigment Violet 23 is preferable 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.
To make the average primary particle size small and fine, the salt milling method is effective like the zinc halide phthalocyanine pigment, and may be salt milled together with the zinc halide phthalocyanine pigment or separately. May be.
The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.

In the colored photosensitive composition of the present invention, the total amount of the pigment containing the halogenated zinc phthalocyanine pigment is 5 to 60% in terms of mass with respect to the total solid content excluding the solvent in the colored photosensitive composition of the present invention. Preferably, it is 10 to 50%, more preferably 15 to 45%.
By using the addition amount in this range, a color filter having excellent color characteristics, high contrast, and high luminance can be obtained.
The “solid content” of the colored photosensitive resin composition in the present invention includes all components of the colored photosensitive composition excluding the solvent.

<Pigment dispersion composition>
When a plurality of pigments are used in combination in the preparation of the colored photosensitive composition of the present invention, (A) a zinc halide phthalocyanine pigment and other pigments are dispersed together or separately in advance to obtain a pigment dispersion composition. It is a preferred embodiment.
The pigment dispersion composition disperses the pigment and the solvent. At this time, a dispersant, a resin, and the like are added as necessary.
Furthermore, it can comprise using another component as needed, such as a pigment derivative.

-Preparation of pigment dispersion composition-
The preparation mode of the pigment dispersion composition of the present invention is not particularly limited. For example, a pigment, a pigment dispersant, and a solvent are used in a vertical or horizontal sand grinder mill, a pin mill, a slit mill, an ultrasonic disperser, or the like. In addition, it can be obtained by performing fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm.

  Before performing bead dispersion, knead and disperse using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder while applying strong shearing force. It is also possible to perform processing.

  For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

-Pigment concentration-
As content in the pigment dispersion composition of a pigment, 10-60 mass% is preferable in conversion of mass with respect to the total solid content except the solvent of this composition, and 15-50 mass% is more preferable.
When the pigment content is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

-Dispersant-
The pigment dispersion composition contains at least one dispersant.
By containing this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (above, manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene Nonionic surfactants such as oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (above, Yusho Co., Ltd.) Anionic surface activity such as) An amphoteric surfactant having a carboxybetaine structure, an amide betaine structure, a sulfobetaine structure, a hydroxybetaine structure, or the like; a fluorosurfactant such as MegaFac F171, F172, or F173 (manufactured by DIC Corporation); EFKA- 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Ciba Specialty Chemical Co., Ltd.), Disperse aid 6, Disperse aid 8, Disperse aid 15, Disperse Polymer dispersants such as Aid 9100 (San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28 Various Solsperse dispersants such as 00 (manufactured by Nippon Lubrizol Co., Ltd.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (above, manufactured by Asahi Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (above, manufactured by Big Chemie Co., Ltd.).
In addition, acrylic copolymers, oligomers or polymers having polar groups such as N, N-disubstituted amino groups or acidic groups at the molecular ends or side chains, polyurethane resins modified with tertiary amines, and JP2009-52010A And AB type and ABA type block copolymers described in the publication.

  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 derivative-
A pigment derivative is added to the pigment dispersion composition as necessary.
The pigment is dispersed in the colored photosensitive composition as fine particles by adsorbing to the pigment surface a part having affinity with the dispersant or a pigment derivative having a polar group introduced and using this as the adsorption point of the dispersant. Therefore, the reaggregation can be prevented, and it is effective in constructing a color filter having high contrast and excellent transparency.

Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent.
Specific examples of organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoic pigments. Examples include imidazolone pigments. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included.
Examples of pigment derivatives include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 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 total mass of a pigment, and 3-20 mass% is more preferable.
When the content of the pigment derivative is within this range, the dispersion of the pigment dispersion composition can be favorably dispersed and the dispersion stability after dispersion can be improved while keeping the viscosity of the pigment dispersion composition low.
As a result, a colored photosensitive composition having high transmittance and excellent color characteristics can be obtained. Therefore, when the colored photosensitive composition is applied to, for example, a color filter production application, good color characteristics are obtained. And a color filter with high contrast can be obtained.

Furthermore, a polymer compound such as an alkali-soluble resin described later can be added to the pigment dispersion composition.
Polar groups such as acid groups contained in the alkali-soluble resin are considered to be effective for the dispersion of the pigment, and are often effective for the dispersion stability of the pigment dispersion.

-Solvent-
The solvent in the pigment dispersion composition is not particularly limited as long as it is an organic solvent used in a general 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, methyl isobutyl ketone, cyclohexanone, n-propanol , 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene, and the like, and a plurality of these may be used together to adjust the melting point, viscosity, and pigment dispersibility. Is also possible.
Moreover, the (F) solvent used for preparation of the coloring photosensitive composition mentioned later can also be used.

The content of the solvent in the pigment dispersion composition is appropriately selected according to the use of the pigment dispersion composition.
When the pigment dispersion composition is used for the preparation of the colored photosensitive composition described later, from the viewpoint of handleability, the sum of the pigment and the pigment dispersant is based on the total mass excluding the solvent of the pigment dispersion composition. It can contain so that it may become 5-50 mass%.

As content of the pigment dispersion composition in the colored photosensitive composition of this invention, content of a pigment is 5-70 mass% with respect to the mass of the total solid content except the solvent of the colored photosensitive composition. The amount in the range is preferable, and the amount in the range of 15 to 60% by mass is more preferable.
When the content of the pigment dispersion composition is within the above range, the color density is sufficient and effective in securing excellent color characteristics.

In addition to the pigment, a dye may be used in combination as the (A) zinc halide phthalocyanine pigment of the colored photosensitive composition of the present invention. By using the dye together, the contrast of the color filter can be expected to increase.
The dye used in the colored photosensitive composition of the present invention is not particularly limited as long as it is a dye that is soluble in an organic solvent, but when classified by chemical structure, an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinoneimine And dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and derivatives thereof.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Disperse Orange 5, C.I. I. Disperse Red 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Modern Red 7, C.I. I. For example, Modern Yellow 5.

Examples of anthraquinone dyes include C.I. I. Vat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse Red 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Vat Blue 5 and the like are quinoneimine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 etc. are mentioned.

<(B) Polymerizable monomer having an acid group>
The colored photosensitive composition of the present invention contains (B) at least one carboxyl group-modified polyfunctional acrylate compound that is a polymerizable monomer having an acid group as a curable component.
In the present invention, the colored photosensitive composition contains (B) a carboxyl group-modified polyfunctional acrylate compound which is a polymerizable monomer having an acid group.

  By using a polymerizable monomer having an acid group in the structure, development in the unexposed area is promoted, so that the development latitude is greatly improved. Among them, a polymerizable monomer having an acid group such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphoric acid group is particularly preferable because alkali solubility is increased, and the contribution of improving developability and residue control is large. In addition to the effect of imparting alkali solubility of the binder resin (C) described later, the effect of using a polymerizable monomer having an acid group also increases the development latitude in a colored resin composition in which the pigment concentration is increased to improve brightness, A stable color filter can be manufactured.

  Examples of polymerizable monomers containing carboxyl groups include polyfunctional acrylates modified with carboxyl groups in addition to unsaturated fatty acids such as acrylic acid, methacrylic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, and cinnamonic acid. Compounds. Examples of carboxyl group-modified polyfunctional acrylate compounds include succinic acid-modified pentaerythritol triacrylate, succinic acid-modified trimethylolpropane triacrylate, succinic acid-modified pentaerythritol tetraacrylate, succinic acid-modified dipentaerythritol pentaacrylate, and succinic acid-modified dipenta. Erythritol hexaacrylate, adipic acid modified pentaerythritol triacrylate, adipic acid modified trimethylolpropane triacrylate, adipic acid modified pentaerythritol tetraacrylate, adipic acid modified dipentaerythritol pentaacrylate, adipic acid modified dipentaerythritol tetraacrylate, etc. Aronix M-510, Aronix M-520, Aronix T -2349, Aronix TO-2359 (manufactured by Toagosei Co., Ltd.) can be preferably used commercially available compounds such as.

  Examples of the polymerizable monomer containing a phenolic hydroxyl group include p-hydroxystyrene, 3,4-dihydroxystyrene, 3,5-dihydroxystyrene, 2,4,6-trihydroxystyrene, (p-hydroxy) benzyl acrylate, and 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, and the like, preferably salicylic acid-modified dipentaerythritol Hexaacrylate, salicylic acid-modified dipentaerythritol pentaacrylate.

  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. Of these, butylsulfonic acid-modified acrylamide is preferable, and a commercially available compound is ATBS (manufactured by Toagosei Co., Ltd.).

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

  In the colored photosensitive composition of the present invention, a polymerizable monomer having an acid group may be used alone as a polymerizable monomer, or a polymerizable monomer having a plurality of acid groups may be used in combination. Moreover, you may use together 1 or more types of the polymerizable monomer containing an acid group, and the polymerizable monomer which does not have an acid group, respectively. In order to achieve both solvent resistance and ITO sputtering suitability and development latitude, it is preferable to use a polymerizable monomer having no acid group in combination with a polymerizable monomer having an acid group.

(Polymerizable monomer having no acid group)
In the present invention, the polymerizable monomer having no acid group that can be used in combination with the polymerizable monomer having an acid group is not particularly limited as long as it is polymerizable, and is a low molecular compound having at least one ethylenic double bond, dimer Compounds capable of addition polymerization such as isomers, trimers, and oligomers can be suitably used.
Examples of the ethylenic compound include an ester of an unsaturated carboxylic acid and a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, and an unsaturated carboxylic acid. Reaction of ester, polyisocyanate compound and (meth) acryloyl-containing hydroxy compound obtained by esterification reaction of acid with polyhydric carboxylic acid and polyhydric hydroxy compound such as fatty acid polyhydroxy compound and aromatic polyhydroxy compound described above And an ethylenic compound having a urethane skeleton.

  Specific polymerizable monomers can be classified according to the number of polymerizable groups in one molecule as shown below, but are not limited thereto.

(1) Compound having one polymerizable group in one molecule Examples of the compound having one polymerizable group in one molecule include, for example, 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 glycol (meth) Acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, cyanoethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2,2, 2-tetrafluoro Ethyl (meth) acrylate, 1H, 1H, 2H, 2H perfluorodecyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxy Methyl (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 oxide monomethyl ether ( ) Acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified Examples include cresol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, PO-modified nonylphenol (meth) acrylate, and EO-modified-2-ethylhexyl (meth) acrylate.

(2) Compound having two polymerizable groups in one molecule Examples of a compound having two polymerizable groups in one molecule include two (meth) acryloyl groups in the same molecule as the polymerizable group. 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) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) ) Acrylate, tripropylene glycol Di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-hydroxy-1,3-diaacryloxypropane, 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-acryloyloxypropyl methacrylate, dimethylol-tricyclodecane di (meth) acrylate and the like, preferably dimethylol-tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylation Bisf Nord A di (meth) acrylate, and bisphenol A type epoxy resin (meth) acrylic acid modified product.

(3) Compound having three polymerizable groups in one molecule Examples of the compound having three polymerizable groups in one molecule include, for example, trimethylolpropane tri (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid Alkylene oxide modified tri (meth) acrylate, dipentaerythritol propionate tri (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde modified dimethylol group Examples include lopantri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated glycerin triacrylate.

(4) 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 and sorbitol tetra (meth) acrylate. , Ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol propionate tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol Penta (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate, captolactone modified dipentaerythritol hexa (me And urethane acrylates such as UA-306H, UA-306T, and UA-306I manufactured by Kyoeisha Chemical Co., Ltd.

Among these, from the viewpoint of suitably maintaining solvent resistance and ITO sputtering suitability, (meth) acrylate monomers having two or more (meth) acryloyl groups in the same molecule are preferred, and three or more (meth) acryloyl are preferred. A (meth) acrylate monomer having a group is more preferable.
In particular, a (meth) acrylate monomer having 4 or more (meth) acryloyl groups is advantageous. For example, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are preferable in terms of solvent resistance and suitability for ITO sputtering. A mixture of (a mixing ratio in terms of mass is dipentaerythritol pentaacrylate: dipentaerythritol hexaacrylate = 2-4: 8-6) is preferably used.

  When a polymerizable monomer having an acid group and a polymerizable monomer having no acid group are used in combination, the total of the polymerizable monomer having an acid group and the polymerizable monomer having no acid group is 100 parts by mass. It is preferable to use together the polymerizable monomer which has group in the range of 1-50 mass parts, The range of 1-40 mass parts is more preferable, The range of 5-20 mass parts is still more preferable.

  In the colored photosensitive composition of the present invention, the preferred content of the polymerizable monomer in which the polymerizable monomer having an acid group and the polymerizable monomer having no acid group are added is the total content excluding the solvent of the colored photosensitive composition. 5-80 mass% is preferable with respect to solid content, More preferably, it is 10-60 mass%, More preferably, it is the range of 15-50 mass%.

<(C) Binder resin>
As the (C) binder resin applicable to the present invention, any polymer compound that is soluble in a solvent can be used. Each of the binder resins may be used as a single compound or a plurality of compounds may be used in combination. As a preferable binder resin, a resin having an acid group (hereinafter, appropriately referred to as “alkali-soluble resin”) is preferable in view of alkali developability by a photolithography method.

  The alkali-soluble resin can be contained in the preparation stage of the pigment dispersion composition described above, and can be contained separately in both the preparation stage of the pigment dispersion composition and the preparation stage of the colored photosensitive composition. Is possible.

  The alkali-soluble resin is preferably a linear organic polymer having an alkali-soluble polymer having at least one alkali-soluble group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.) More preferably, it is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

For example, a known radical polymerization method can be applied to the production of the alkali-soluble resin.
Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxyl group in the side chain is preferable.
For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxylic acid, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful.
The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Is mentioned.

  Examples of other alkali-soluble resins include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-11-174224, and JP-A-11-174224. Known polymer compounds described in 2000-56118, JP-A 2003-233179, JP-A 2009-52020, and the like can be used.

  Regarding the specific structural unit of the alkali-soluble resin, in particular, a copolymer of (meth) acrylic acid and other monomers copolymerizable therewith can be easily obtained, and adjustment of alkali solubility and the like is easy. Therefore, it is preferably used.

Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

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

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl (meth) acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl (meth) acrylate, polystyrene macromonomer, and polymethyl methacrylate macro. Monomer, 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 of 1 to 5 carbon ^{atoms, R 33} is several alkyl group or C 1 to 8 carbon atoms 6 Represents -12 aralkyl groups. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more.
Other preferred copolymerizable monomers are selected from CH ₂ ═CR ³¹ R ³² , CH ₂ ═C (R ³¹ ) (COOR ³³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably, CH ₂ = CR ³¹ R ³² and / or CH ₂ = C (R ³¹ ) (COOR ³³ ). These R ³¹ , R ³² and R ³³ are as defined above.

  Moreover, as content of binder resin, such as alkali-soluble resin, in a colored photosensitive composition, 1-20 mass% is preferable with respect to the total solid content except the solvent contained in a colored photosensitive composition, More preferably, it is 2-15 mass%, Most preferably, it is 3-12 mass%.

  In addition, as a ratio of the content of the polymerizable monomer having a polymerizable monomer having an acid group and the polymerizable monomer having no acid group and the content of the binder resin, a mass ratio (total weight of polymerizable monomer / binder resin Mass), a range of 0.1 to 10 is preferable, a range of 0.4 to 8 is more preferable, and a range of 0.5 to 5 is more preferable.

<(D) Photopolymerization initiator>
The (D) photopolymerization initiator in the colored photosensitive composition of the present invention is not particularly limited as long as it is a compound that initiates polymerization upon exposure.
(D) As the photopolymerization initiator, for example, camphorquinone, benzophenone, benzophenone derivative, oxime compound, acylphosphine, acylphosphine derivative, acetophenone, acetophenone derivative, hexaarylbisimidazole compound, boric acid compound, etc. can be used. it can.

  Specific examples include α-hydroxycycloalkyl phenyl ketones or 2-hydroxy-2-methyl-1-phenyl-propanone, dialkoxyacetophenones, α-hydroxy- or 4-aroyl-1,3-dioxolanes. Benzoin alkyl ethers and benzyl ketals such as benzyl dimethyl ketal, phenyl glyoxalate and derivatives thereof, dimer phenyl glyoxalate, peresters such as benzophenone tetracarboxylic acid peresters (eg published European patent applications) No. 1,126,541), halomethyltriazines, such as 2- [2- (4-methoxy-phenyl) -vinyl] -4,6-bis-trichloromethyl [1 , 3,5] triazine, 2- (4-methoxy-phen Nyl) -4,6-bis-trichloromethyl [1,3,5] triazine, 2- (3,4-dimethoxy-phenyl) -4,6-bis-trichloromethyl [1,3,5] triazine, 2 -Methyl-4,6-bis-trichloromethyl [1,3,5] triazine, hexaarylbisimidazole / co-initiator system such as ortho-chlorohexaphenyl-bisimidazole in combination with 2-mercaptobenzothiazole; ferrocenium Compounds or titanocenes, such as dicyclopentadienyl-bis (2,6-difluoro-3-pyrrolo-phenyl) titanium; for example O— as described in British Patent 2,339,571 Mixtures with acyloxime ester compounds can also be used. A boric acid compound can also be used as a photopolymerization initiator used in combination.

  In the colored photosensitive composition of the present invention, among the above (D) photopolymerization initiators, it is preferable to use a hexaarylbisimidazole compound. The colored photosensitive composition layer patterned by using a hexaarylbisimidazole compound can exhibit good light resistance.

(Hexaarylbisimidazole compound)
The hexaarylbisimidazole compound is not particularly limited as long as it is a dimer of an imidazole ring substituted with three aryl groups. In particular, a compound represented by the following general formula (1) is preferable, and represented by the general formula (2). More preferred is a compound.

In general formula (1), a plurality of X's each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms, and a plurality of A's independently Represents an alkoxy group having 1 to 12 carbon atoms or —COO—R ⁹ (wherein 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 to 3, and m is an integer of 1 to 3.

In General Formula (2), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 9 carbon atoms. However, two or more of X ¹ , X ² and X ³ do not take a hydrogen atom at the same time.

  Examples of the hexaarylbisimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole and 2,2′-bis (2-chlorophenyl) -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-ethoxycarbonylphenyl) 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-phenoxycarbonylphenyl) bisimidazole, 2,2'-bis (2-methylphenyl) -4,4 ', 5 , 5′-tetrakis (4-methoxycarbonylphenyl) bisimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetra (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-ethoxycarbonylphenyl) bisimidazole, 2,2'-bis (2-phenylphenyl) -4,4 ', 5 Bisimidazole compounds such as 5,5′-tetrakis (4-phenoxycarbonylphenyl) bisimidazole;

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) bis Imidazole

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′-tetra Phenylbisimidazole, 2,2′-bis (2,4,6-tricyanophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole, 2,2′-bis (2,4-dimethylphenyl) ) -4,4 ', 5,5'-tetraf Nilbisimidazole, 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 ' And the like bisimidazole compounds such as 5,5'-tetraphenyl-bis-imidazole.

  Among the above, as a particularly preferable compound, 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, manufactured by Nippon Sebel Hegner), 2,2 ′ -Bis (2-methylphenyl) -4,4 ', 5,5'-tetraphenylbisimidazole (manufactured by Kurokin Kasei)

  The content of the photopolymerization initiator in the colored photosensitive composition of the present invention is the content of a polymerizable monomer (a polymerizable monomer that is a total of a polymerizable monomer having an acid group and a polymerizable monomer having no acid group). When it is 100 mass parts, about 0.05-30 mass% is preferable, it is more preferable that it is 0.1-20 mass%, and it is more preferable that it is 0.2-10 mass%.

Moreover, the ratio of the content when using a photopolymerization initiator having a structure other than the hexaarylbisimidazole compound and the hexaarylbisimidazole compound is hexagonal on a mass basis when the content of the hexaarylbisimidazole compound is 1. The content of the photopolymerization initiator having a structure other than the arylbisimidazole compound is preferably 0.1 or more and 5.0 or less, more preferably 0.2 or more and 3.0 or less, and particularly preferably 0.3 or more and 2.0 or less. preferable.
By setting it as this range, especially light resistance becomes favorable.

<(E) Chain transfer agent>
The colored photosensitive composition of the present invention comprises (E) a chain transfer agent selected from secondary or tertiary aliphatic thiol compounds. The secondary or tertiary aliphatic thiol compound has a hydrogen donating property as a chain transfer agent. In the present invention, the series indicates the number of carbons to which the carbon atom adjacent to the thiol group is bonded.

In general, compounds having similar structures tend to be stabilized by interaction. The phthalocyanine compound has a planar structure, and since there is a density of electron density between the constituent nitrogen atoms and carbon atoms, it has a structure that can be stacked in a direction parallel to the plane and is complementary. Interacts easily with compounds with high or low electron density.
The (A) zinc halide phthalocyanine pigment in the present invention has high brightness, high saturation, and high contrast, but has poor dispersibility and dispersion stability. When a polymerizable monomer having a high acid value is used to ensure alkali developability of the colored photosensitive composition, the colored photosensitive composition is shifted to the acidic side. Thereby, it is considered that the acid-base interaction between the halogenated zinc phthalocyanine pigment and the dispersant is weakened, and the dispersion stable region is biased. In this case, if there is a compound that can easily interact with the halogenated zinc phthalocyanine pigment, the dispersion state becomes unstable due to the interaction between the halogenated zinc phthalocyanine pigment and the dispersant, which may cause aggregation of the pigment. It is considered to be high.

From such a point, when an aromatic thiol compound is used as a chain transfer agent for (A) the halogenated zinc phthalocyanine pigment in the present invention, the halogenated zinc phthalocyanine pigment and the aromatic compound are used due to the effect of the thiol structure and the aromatic ring structure. It is considered that the thiol compound is easily adsorbed on the surface of the halogenated zinc phthalocyanine pigment by the interaction with the group thiol compound. As a result, it is considered that a problem arises in the temporal performance (viscosity, contrast) of the colored photosensitive composition due to aggregation of the halogenated zinc phthalocyanine pigment.
In the present invention, since an aliphatic thiol compound is used, the action caused by the aromatic ring of the thiol compound described above hardly occurs, and a compound having a secondary or tertiary thiol group is used. It is considered that the interaction with the zinc halide phthalocyanine pigment is weak and the function as a chain transfer agent is exhibited without causing aggregation of the halogenated zinc phthalocyanine pigment.

The surface of the halogenated zinc phthalocyanine pigment ensures dispersion stability by adsorbing the dispersant, but since the dispersant is usually a polymer, it adsorbs to all the adsorption points on the surface of the zinc halide phthalocyanine pigment, and the zinc halide. The adsorption point on the surface of the phthalocyanine pigment cannot be deactivated. That is, it is considered that an adsorption point that has not been adsorbed remains on the surface of the zinc halide phthalocyanine pigment, which may cause the pigment to aggregate over a long period of time. However, since a polymerizable monomer having an acid group is used as the polymerizable monomer in the present invention, the monomer having the acid group is adsorbed on the adsorption point of the remaining pigment surface, and the aggregation of the pigment due to the thiol group described above occurs. It is thought that there is not. That is, in order to prevent aggregation of the halogenated zinc phthalocyanine pigment, the surface of the halogenated zinc phthalocyanine pigment is caused 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 considered that the aging performance of the colored photosensitive composition of the present invention was able to prevent deterioration. This is considered to have realized the good color characteristics of the halogenated zinc phthalocyanine pigment.
In the present invention, a secondary or tertiary aliphatic thiol compound exhibits a chain transfer action, and can provide a colored photosensitive composition having excellent sensitivity and good developability.

  Moreover, the thiol compound which has a sulfur atom emits a characteristic odor. It is known that odor is largely related to volatility. However, since aliphatic primary thiol compounds are generally highly volatile, they are not preferred for use as colored photosensitive compositions. Since a secondary or tertiary aliphatic thiol compound is used, there is no problem of odor when using the colored photosensitive composition, and a suitable colored photosensitive composition can be obtained.

  Secondary or tertiary aliphatic thiol compounds include t-butanethiol, octyl-2-mercaptopropionate, octyl-3-mercaptobutyrate, stearyl-2-mercaptopropionate, stearyl-3-mercaptobuty Rate, 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-butanediol bis-2-mercaptopropionate, 1,4-butanediol bis-3-mercaptobutyrate, ethylene glycol bis-2 -Mercaptopropionate, ethylene glycol bis-3-mercaptobutyrate, trimethylolpropane tris-2-mercaptopropionate, trimethylolpropane tris-3-mercaptobutyrate, pentaerythritol tetrakis-2-mercaptopropione DOO, pentaerythritol tetrakis-3-mercapto butyrate, dipentaerythritol pentakis 2-mercaptopropionate, dipentaerythritol pentakis-3-mercapto butyrate, and the like.

  Of these, monofunctional or bifunctional aliphatic thiol compounds are preferable because they have further improved stability over time, and t-butanethiol, octyl-2-mercaptopropionate, octyl-3-mercaptobutyrate, stearyl- 2-mercaptopropionate, stearyl-3-mercaptobutyrate, 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-butanediol bis-2-mercaptopropionate, 1,4-butanediol Bis-3-mercaptobutyrate, ethylene glycol bis-2-mercaptopropionate, and ethylene glycol bis-3-mercaptobutyrate are particularly preferable.

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 aliphatics may be used. Thiol compounds may be used.
The content of the secondary or tertiary aliphatic thiol compound in the colored photosensitive composition of the present invention is 0.2 to 10 mass based on the total solid content excluding the solvent contained in the colored photosensitive composition. % Is preferable, more preferably 0.3 to 8% by mass, and particularly preferably 0.5 to 5% by mass.

Further, the content of the secondary or tertiary aliphatic thiol compound in the colored photosensitive composition with respect to the total amount of the photopolymerization initiator (D) is preferably 5 to 150% by mass, more preferably 10 to 100%. It is mass%, Most preferably, it is 10-50 mass%.
By being in this range, the polymerization when the colored photosensitive composition layer is formed is accelerated, and a good pattern with high sensitivity can be formed.
Further, the content of the secondary or tertiary aliphatic thiol compound in the colored photosensitive composition with respect to the (A) halogenated zinc phthalocyanine pigment is preferably 1 to 10% by mass, more preferably 2 to 8% by mass. %, Particularly preferably 3 to 5% by mass.
By being in this range, the storage stability of the colored photosensitive composition is good.

<(F) Solvent>
The colored photosensitive composition of the present invention contains (F) a solvent.
Examples of the (F) solvent that can be used in the present invention include solvents classified into esters, ethers, ketones, aromatic hydrocarbons and the like.
(F) A solvent can be used also for preparation of an above-described pigment dispersion composition.

  Examples of 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, butyl butyrate, In addition to alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc., 3-oxypropion 3-oxypropionic acid alkyl esters such as methyl acid and ethyl 3-oxypropionate; methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-oxy-2-methylpropionic acid Methyl, 2-o 2-oxypropionic acid alkyl esters such as ethyl -2-methylpropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl Alkoxypropionic acid alkyl esters such as ethyl propionate; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.

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, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether Examples include acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Examples of aromatic hydrocarbons include toluene, xylene, and the like.

Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, Butyl carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
A solvent may be used independently and may be used in combination of 2 or more type.
The content of the solvent (F) in the colored photosensitive composition of the present invention is appropriately determined in consideration of the applicability of the colored photosensitive composition, but in general, the content in the colored photosensitive composition ( F) The content of the solvent is 76% by mass to 88% by mass.

<(G) Photosensitizer>
The colored photosensitive composition of the present invention may further contain (G) a photosensitizer.
(G) As a photosensitizer, a compound having a maximum absorption wavelength at 350 to 450 nm is preferably used.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), Merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium ( For example, in addition to compound groups such as squalium) and benzophenones (for example, 4,4′-diethylaminobenzophenone), JP2007-91806A, JP2008-9323A, and JP20. And compounds described in JP-A-10-49160.

The content ratio (mass ratio) of (D) photopolymerization initiator, (E) secondary or tertiary aliphatic thiol compound, and (G) photosensitizer in the present invention is: photopolymerization initiator / thiol compound / It is preferable that it is photosensitizer = 20-50 / 30-70 / 10-30, and it is photopolymerization initiator / thiol compound / photosensitizer = 30-40 / 40-60 / 10-10-20. More preferably, it is still more preferable that it is photoinitiator / thiol compound / photosensitizer = 35-40 / 50-55 / 10-15.
By using each component at these ratios, the exposure sensitivity for g-line, h-line, and i-line is increased, and a colored pattern with high line width according to the exposure area can be easily obtained.

  In addition, the colored photosensitive composition of the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the photosensitizer and photopolymerization initiator to actinic radiation or suppressing polymerization inhibition of the photopolymerizable compound by oxygen.

  Examples of such co-sensitizers include amines such as MRSander et al., “Journal of Polymer Society”, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 51-82102. Publication, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Research Disclosure 33825 Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like can be mentioned.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), and JP-B-55-34414. Examples thereof include a hydrogen donor described in the publication and a sulfur compound (eg, trithiane) described in JP-A-6-308727.

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

<Additives>
In the colored photosensitive composition of the present invention, if necessary, a radical scavenger, a light stabilizer, a curing aid, a thermal polymerization initiator, a surfactant, an adhesion assistant, a development accelerator, a thermal polymerization inhibitor, Various additives such as a dispersant and other additives (filler, ultraviolet absorber, aggregation inhibitor, etc.) can be contained.

(Radical scavenger)
Various radical scavengers may be added to the present invention in order to improve light resistance. The type of the radical scavenger is not particularly limited, but an azoxy compound and various light stabilizers are preferable from the viewpoints of heat resistance and light resistance. Specific examples of the azoxy compound include azoxybenzene, azoxyanisole, azoxyphenetole, 4,4′-dioctylazoxybenzene and the like.

(Light stabilizer)
Various light stabilizers are also effective in improving light resistance. Although it does not specifically limit about the kind of light stabilizer, From the surface of versatility, a hindered amine type light stabilizer; 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 phenol light stabilizers; for example, pentaerythritol-tetrakis (3- (3 ′, 5′-di-t-butyl-4′-hydro Shifeniru) propionate or the like is preferably used.

  About 0.1-5.0 mass% is preferable with respect to the total solid of a coloring photosensitive composition, and content of the light stabilizer in this invention is 0.2-4.0 mass%. More preferably, it is more preferable that it is 0.5-2.0 mass%. If it is 0.1% by mass or less, the desired light resistance cannot be obtained, and if it is 5.0% by mass or more, the sensitivity decreases, which is not preferable.

(Curing aid)
As a curing aid, a compound having an epoxy ring may be used in order to increase the strength of the formed coating film. The use of a compound having an epoxy ring is preferable because thermal polymerization proceeds, solvent resistance is improved, and ITO sputtering suitability is improved.

The compound having an epoxy ring is a compound having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( In addition to Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (Made by Daicel Chemical) These similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used.

The cresol novolac type includes Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Tohto Kasei), Denacol EM-125, etc. (above, manufactured by Nagase Kasei), Biphenyl type As alicyclic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl, Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT- 302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100, etc. (manufactured by Toto Kasei), Epilon 430, 673. 695, 850S, 4032 (above, manufactured by DIC And the like.
1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Diglycidyl ester, amine type epoxy resins such as Epototo YH-434, YH-434L (manufactured by Nagase Kasei Co., Ltd.), glycidyl ester in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin, and the like can also be used.

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

  About 0.1-5.0 mass% is preferable with respect to the total solid of a coloring photosensitive composition, and content of the hardening adjuvant in this invention is 0.2-4.0 mass%. More preferably, it is more preferable that it is 0.5-2.0 mass%. If it is 0.1% by mass or less, the effect of promoting the curing cannot be obtained, and if it is 5.0% by mass or more, the light resistance is deteriorated, which 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. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

(Surfactant)
The colored photosensitive composition of the present invention is preferably constituted using various surfactants from the viewpoint of improving coatability. The surfactant can improve liquid properties (particularly fluidity) when used as a coating liquid, and can improve the uniformity of coating thickness and liquid-saving properties. That is, the interfacial tension between the substrate and the coating liquid is reduced to improve the wettability to the substrate and the coating property to the substrate is improved, so that a thin film of about several μm is formed with a small amount of liquid. This is also effective in that a film having a uniform thickness with small thickness unevenness can be formed. It is also effective in slit coating that easily causes liquid breakage.

  As the surfactant, various nonionic, cationic and anionic surfactants can be used. Among these, a nonionic surfactant and a fluorosurfactant having a perfluoroalkyl group are preferable.

  The fluorine content of the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. When the fluorine content is within the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F173, F177, F141, F142, F143, F144, R30, and F437 (above, manufactured by DIC Corporation), Fluorard FC430, FC431, FC171 (Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-10 381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), and the like.

  Examples of surfactants other than fluorine-based surfactants include phthalocyanine derivatives (commercial product EFKA-745 (manufactured by Morishita Sangyo)), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) heavy Combined polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, poly Oxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (manufactured by BASF, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, Nonionic surfactants such as 150R1; anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.).

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

(Adhesion aid)
An adhesion assistant can be added to the photosensitive resin composition used in the present invention from the viewpoint of improving adhesion to the substrate. As the adhesion assistant, an alkoxysilane compound, especially a silane coupling agent can be used.
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material as a substrate, and exhibits an affinity by interaction or bond formation with an organic resin (meta) Silane coupling agents having a group such as acryloyl group, phenyl group, secondary or tertiary mercapto group, epoxy group, aminosilane group are preferred, and among them, (meth) acryloylpropyltrimethoxysilane and epoxypropyltrimethoxysilane are preferred. Is more preferable. Examples of such materials include KBM-303, KBM-403, KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.).
In the case of using a silane coupling agent, the addition amount is preferably in the range of 0.2% by mass to 5.0% by mass in the total solid content in the colored photosensitive composition of the present invention, 0.5 The mass% to 3.0 mass% is more preferable.

(Development accelerator)
Further, when the alkali solubility of the uncured portion of the colored photosensitive composition layer is promoted and the developability of the colored photosensitive composition is further improved, a development accelerator is used in the colored photosensitive composition. be able to.
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. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

(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-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like 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;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone;
And an aggregation inhibitor such as sodium polyacrylate.

  The colored photosensitive composition of the present invention comprises the components described above, that is, (A) a zinc halide phthalocyanine pigment, (B) a polymerizable monomer having an acid group, (C) a binder resin, and (D) a photopolymerization initiator. , (E) a secondary or tertiary aliphatic thiol compound, and (F) a solvent (or (G) a sensitizer), and, if necessary, other additives such as a surfactant. It can be prepared by adding and mixing.

<Color filter and manufacturing method thereof>
The color filter of the present invention is produced by forming a colored film (colored pattern) on a substrate such as glass using the above-described colored photosensitive composition of the present invention. A colored layer forming step of applying the colored photosensitive composition of the invention on a substrate to form a colored layer, an exposure step of patternwise exposing the colored layer to form a latent image, and after exposure And a developing step of developing the colored layer to form a colored pattern.

The colored layer is applied to the substrate directly or via another layer. As a method for applying the colored layer, a method such as spin coating, slit coating, cast coating, roll coating, ink jet coating, or transfer is used. It is formed. Each color is formed by exposing the uncolored part (uncured part) with a developer after the exposed colored part is exposed to the formed colored layer through a mask pattern or exposed in a pattern, and the exposed part is cured. A color filter can be produced by forming a colored pattern (for example, three colors or four colors).
Thereby, the color filter used for a liquid crystal display device or a solid-state image sensor has few process difficulties, and can be manufactured with high quality and low cost.

In this case, the radiation used for exposure is preferably an ultraviolet laser in addition to ultraviolet rays such as g-line, h-line, i-line, and j-line.
In addition to the proximity exposure method and the sputtering exposure method, an exposure method using a laser light source can be suitably used as the exposure method.

  In the laser exposure method, an ultraviolet laser is used as a light source. Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Oscillators and amplifiers that produce monochromatic light with stronger coherence and directivity by amplification and oscillation of light waves, utilizing the phenomenon of stimulated emission that occurs in materials with inversion distribution, crystals, glass, liquids, dyes as excitation media, There are gases and the like, and lasers having an oscillation wavelength for known ultraviolet light such as solid laser, liquid laser, gas laser, and semiconductor laser can be used from these media. Among these, a solid laser and a gas laser are preferable from the viewpoint of laser output and oscillation wavelength.

The wavelength of laser exposure that can be used in the present invention is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm. This is preferable in that it matches the photosensitive wavelength of the composition.
Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
The exposure amount of the exposure object ^(pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

  There are no particular restrictions on the exposure apparatus that can be used in the present invention, but commercially available devices include Callisto (buoy technology), EGIS (buy technology), and DF2200G (Dainippon Screen). ) Etc. can be used. Further, devices other than those described above are also preferably used.

  Further, a light emitting diode (LED) and a laser diode (LD) can be used as the active radiation source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. When even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit actinic radiation centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. The actinic radiation source particularly preferred in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength at 340 to 370 m.

  Since the parallelism of the ultraviolet laser is good, pattern exposure can be performed without using a mask at the time of exposure. However, it is more preferable to expose the pattern using a mask because the linearity of the pattern is further increased.

  Drying (pre-baking) of the film with the colored photosensitive composition of the present invention applied (preferably applied) on the substrate is performed under conditions of 10 to 300 seconds in a temperature range of 50 to 140 ° C. using a hot plate, an oven or the like. Can be done.

In development, the uncured part after exposure is eluted in the developer, leaving only the cured part. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Any developer can be used as long as it dissolves the colored photosensitive composition film in the uncured portion while not dissolving the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

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

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned.
In addition, when alkaline aqueous solution is used as a developing solution, generally it wash | cleans (rinse) with water after image development.

After the development, excess developer is washed away, dried, and then generally heated (post-baked) at a temperature of 100 to 250 ° C.
Post-baking is heating after development for complete curing, and is usually performed at about 200 ° C. to 250 ° C. (hard baking). This post-bake treatment is performed continuously or batchwise by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

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

  When the colored photosensitive composition of the present invention is applied to a substrate to form a film, the dry thickness of the film is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm, Most desirably, the thickness is 1.0 to 2.5 μm.

  As the substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like in which a transparent conductive film is attached thereto, a solid-state imaging device, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a plastic substrate. On these substrates, usually, black stripes for isolating each pixel are formed.

The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.
Examples of other layers in the case where the colored photosensitive composition is applied to the substrate via another layer include a gas barrier layer and a solvent resistant layer.

[Liquid Crystal Display]
The color filter of the present invention is particularly suitable as a color filter for a liquid crystal display device. A liquid crystal display device including such a color filter can display a high-quality image.

  For the definition of display devices and explanation of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Device (written by Junaki Ibuki, Industrial Book Co., Ltd.) Issue year)). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

  The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention is a liquid crystal display device with a wide viewing angle such as a horizontal electric field driving method such as IPS, a pixel division method such as MVA, and a liquid crystal display such as STN, TN, VA, OCS, FFS, and R-OCB. It can also be applied to devices.

The color filter of the present invention can also be used for a bright and high-definition COA (Color-filter On Array) type liquid crystal display device. In the case of a COA type liquid crystal display device, the required characteristics for the color filter layer must be the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling solution, in addition to the normal required characteristics as described above.
The colored photosensitive composition of the present invention improves the curability of the colored pixels, and can form pixels that are not chipped, peeled off, or twisted. Therefore, the colored layer provided directly or indirectly on the TFT substrate is particularly resistant to the stripping solution. And is useful for a COA liquid crystal display device. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

Further, the colored layer formed for the COA color filter has a side length of 1 in order to make the ITO electrode disposed on the colored layer and the terminal of the driving TFT substrate below the colored layer conductive. It is necessary to form a conduction path such as a rectangular through hole or a U-shaped depression of about 15 μm, and the dimension of the conduction path (that is, the length of one side) is preferably 5 μm or less. It is also possible to form a conductive path of 5 μm or less by using the colored photosensitive composition.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

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

  Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Have been described.

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 conventionally known three-wavelength tube of a cold cathode tube, but further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

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

-Synthesis of zinc halide phthalocyanine pigments-
Zinc phthalocyanine was produced from phthalodinitrile and zinc chloride.
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, and then the reaction mixture was poured into water to precipitate a partially brominated zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 80 ° C., and dried at 90 ° C. to obtain 2.6 parts of a purified partially brominated zinc phthalocyanine crude pigment.

1 part of this partially brominated zinc phthalocyanine crude pigment, 7 parts of crushed sodium chloride, 1.6 parts of diethylene glycol and 0.09 part of xylene were charged into a double-arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, it was taken out into 100 parts of water at 80 ° C., stirred for 1 hour, and then filtered, washed with hot water, dried and ground to obtain a partially brominated zinc phthalocyanine pigment.
The obtained partially brominated zinc phthalocyanine pigment has an average composition of ZnPcBr ₁₀ Cl ₄ H ₂ (Pc; phthalocyanine) and contains an average of 10 bromines in one molecule, based on a halogen content analysis by mass spectrometry. there were.
In addition, the average value of the primary particle diameter measured with the transmission electron microscope (JEM-2010 by JEOL Co., Ltd.) was 0.065 μm.

-Synthesis of quinophthalone compounds-
Quinophthalone pigment (4,5,6,7-tetrachloro-2- [2- (4,5,6,7-tetrachloro-2,3-dihydro-1,3-dioxo-1H-inden-2-yl ) -8-quinolinyl] -1H-isoindole-1,3 (2H) -dione) (“Pariotol” Yellow K0961HD, manufactured by BSF, Inc.) with stirring, 15 ° C. fuming sulfuric acid (25% (SO ₃ ) was introduced into 130 g. After stirring for 3 hours, it was added onto 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 put into 330 ml of water and neutralized with an aqueous ammonia solution (added aqueous ammonia until pH was 7). 75 g of ammonium chloride was added and stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystals were washed with water and then dried at 80 ° C. to obtain 17 g of an ammonium salt of a sulfonated quinophthalone derivative.
This ammonium salt of the sulfonated quinophthalone derivative was heat-treated at 180 ° C. for 3 hours to obtain 16 g (yield 94%) of the sulfonated quinophthalone derivative (compound 4 having the following structure) from which the ammonium salt had been removed.

  To 10 g of the sulfonated product (Compound 4), 2.2 g of oxalyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 1 ml of N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) were added in chloroform and ice-cooled at 50 ° C. 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 5.0 g of Compound 5, 0.9 g of 6-chloro-1-hexylamine (manufactured by Rare Chemicals) was added in chloroform under ice-cooling, 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, washed with water, and dried under reduced pressure to obtain 4.3 g of a sulfoamidoalkyl 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 4.3 g of Compound 6 and heated in an autoclave at 180 ° C. for 12 hours. After allowing to cool, the crystals were filtered to obtain 3.7 g of a sulfoamidoalkylsulfonic 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 ε-caprolactone and 5 g of titanium (IV) tetrabutoxide were mixed, heated at 160 ° C. for 8 hours, then cooled to room temperature and polyester. Resin (i-1) was obtained.
A synthesis scheme is shown below.

(2) Synthesis of Resin (J-1) Polyethyleneimine (SP-018, number average molecular weight 1,800, manufactured by Nippon Shokubai) 10 g and polyester resin (i-1) 100 g were mixed and heated at 120 ° C. for 3 hours. Intermediate (J-1B) was obtained. Thereafter, the mixture was allowed to cool to 65 ° C., 200 g of propylene glycol methyl ether acetate (hereinafter referred to as PGMEA) containing 3.8 g of succinic anhydride was slowly added and stirred for 2 hours. Then, PGMEA was added and the 10% PGMEA solution of resin (J-1) was obtained. The resin (J-1) has a side chain derived from the polyester resin (i-1) and a carboxyl group derived from succinic anhydride.
A synthesis scheme is shown below.

-Preparation of dispersion composition containing partially brominated zinc phthalocyanine pigment-
11.9 parts of the partially brominated zinc phthalocyanine pigment (hereinafter referred to as PG58), 3.1 parts of Compound 7 as a quinophthalone compound, 9.0 parts of Solsperse 24000GR (manufactured by Nippon Lubrizol Co., Ltd.) as a dispersant, as a solvent After mixing 76 parts of PGMEA, a pigment dispersion composition containing a partially brominated zinc phthalocyanine pigment was obtained by dispersing in a sand grinder mill for 3 hours. When the viscosity of the obtained pigment dispersion composition was measured at a temperature of 23 ° C. with an E-type viscometer RE-85L (manufactured by Toki Sangyo Co., Ltd.), it was very stable and good at 9.2 mPa · s. It was confirmed that excellent dispersion stability was obtained. Storage conditions: 14 days after dispersion (storage temperature 5 ° C)

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

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

-Synthesis of Compound 1 as Photopolymerization Initiator-
(1) Synthesis of Compound A First, Compound A is synthesized according to the following scheme.
Ethylcarbazole (100.0 g, 0.512 mol) is dissolved in 260 ml of chlorobenzene, and after cooling to 0 ° C., aluminum chloride (70.3 g, 0.527 mol) is added. Subsequently, o-tolyl chloride (81.5 g, 0.527 mol) is added dropwise over 40 minutes, the temperature is raised to room temperature, and the mixture is stirred for 3 hours. Next, after cooling to 0 ° C., aluminum chloride (75.1 g, 0.563 mol) is added. 4-Chlorobutyryl chloride (79.4 g, 0.563 mol) is added dropwise over 40 minutes, and the mixture is warmed to room temperature and stirred for 3 hours. A 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 with suction, washed with distilled water and methanol, and recrystallized with acetonitrile to obtain Compound A (yield 164.4 g, yield 77%) having the following structure.

(2) Synthesis of Compound B Next, Compound B is synthesized using Compound A according to the following scheme.
Compound A (20.0 g, 47.9 mmol) is dissolved in 64 ml of THF and 4-chlorobenzenethiol (7.27 g, 50.2 mmol) and sodium iodide (0.7 g, 4.79 mmol) are added. Subsequently, sodium hydroxide (2.0 g, 50.2 mmol) is added to the reaction solution and refluxed for 2 hours. Next, after cooling to 0 ° C., SM-28 (11.1 g, 57.4 mmol) is added dropwise over 20 minutes, and the temperature is raised to room temperature and stirred for 2 hours. Next, after cooling to 0 ° C., isopentyl nitrite (6.73 g, 57.4 mmol) is added dropwise over 20 minutes, the temperature is raised to room temperature, and the mixture is stirred for 3 hours. The reaction solution is diluted with 120 ml of acetone and added dropwise to a 0.1N hydrochloric acid aqueous solution cooled to 0 ° C. The precipitated solid was filtered with suction and washed with distilled water. Subsequently, recrystallization was performed with acetonitrile to obtain Compound B having the following structure (yield: 17.0 g, yield: 64%).

(3) Synthesis of Compound C Subsequently, using Compound B, Compound C as an initiator is synthesized according to the following scheme.
Compound B (18.0 g, 32.4 mmol) was dissolved in 90 ml N-methylpyrrolidone and triethylamine (3.94 g, 38.9 mmol) was added. Next, after cooling to 0 ° C., acetyl chloride (3.05 g, 38.9 mmol) is added dropwise over 20 minutes, and then the temperature is raised 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 subjected to suction filtration, washed with 200 ml of isopropyl alcohol cooled to 0 ° C., dried, and then dried to give compound C having the following structure (yield 19.5 g, yield). 99%).

[Example 1]
<Preparation of colored photosensitive composition>
The components shown in the following composition 1 were mixed with stirring to prepare a colored photosensitive composition of Example 1.
(Composition 1)
Pigment dispersion composition containing PG58 33.0 parts Pigment dispersion composition containing PY150 15.2 parts Solvent (PGMEA) 20.1 parts 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: Aronix M-520 (manufactured by Toagosei Co., Ltd.) 4.43 parts, photopolymerization initiator: 2-chlorophenyl-4,5-bisphenyl Imidazole dimer (B-CIM, manufactured by Hodogaya Chemical Co., Ltd.) 0.14 parts Photopolymerization initiator: IRGACURE OXE01 (Ciba Specialty Chemicals Co., Ltd., following structure)
1.47 parts Aliphatic thiol compound: Karenz MT-BD1 (butanediol bis (3-mercaptobutyrate, Showa Denko KK) 0.19 parts Photosensitizer: Compound 8 (the following structure) 042 parts Surfactant (Fluorosurfactant, DIC's MegaFuck F781-F 0.033 parts

IRGACURE OXE-01

<Formation of colored pattern using colored photosensitive composition>
-Formation of colored photosensitive composition layer-
The obtained colored photosensitive composition was slit applied to a glass substrate (Corning Millennium, 0.7 mm thickness). Specifically, coating was performed at a coating speed of 120 mm / second by adjusting the interval between the slit nozzle and the substrate and the discharge amount so that the thickness of the colored composition layer after post-baking was about 2.4 μm.
-Pre-baking process-
Next, the colored photosensitive composition layer was dried with a vacuum dryer until the degree of vacuum reached 66 Pa, and then heated (prebaked) at 90 ° C. for 120 seconds using a hot plate.
-Exposure process (proximity exposure)-
After the pre-bake treatment, exposure was performed at 40 mJ / cm ² using a proximity exposure machine (manufactured by Hitachi High-Technologies Corporation, LE5565A).
-Development process, baking (post-baking) process-
Thereafter, using a developing device (manufactured by Hitachi High-Technologies Corporation), 1.0 part of a potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) (1 part of CDK-1), The solution was developed for 60 seconds with 99 parts of pure water diluted at 25 ° C. and a shower pressure of 0.2 MPa, and washed with pure water.
After sufficiently drying, it was post-baked in an oven at 230 ° C. for 40 minutes.

(Examples 2-12, Comparative Examples 1-8)
In composition 1 of Example 1, the types of the pigment dispersion composition, polymerizable monomer, photopolymerization initiator, and chain transfer agent (aliphatic thiol compound) were changed as shown in Table 1; In the same manner, colored photosensitive compositions of Examples 2 to 12 and Comparative Examples 1 to 8 were prepared.
Using each of the obtained colored photosensitive compositions, a colored pattern was prepared in the same manner as in Example 1 except that the exposure method in the exposure process was changed as shown in Table 1.

In Table 1, the pigment dispersion composition is a pigment dispersion composition indicated by the name of the pigment.
The details of the exposure method described as “proxy” in Table 1 are the exposure methods (proximity exposure) applied in the exposure process in the first embodiment. The details of the exposure method denoted as “laser” are as follows.
-Exposure process (laser exposure)-
After pre-baking, EGIS (buoy technology Co., Ltd., third harmonic wavelength of YAG laser, wavelength 355 nm, pulse width 6 nsec) is used as a laser exposure apparatus, and a pulse of about 1 mJ / cm ² is applied to the surface of the photosensitive resin composition layer. Irradiation was performed 20 times through a photomask.

In Table 1, the structures of DPHA and Karenz MT-PE1 are shown below.
DPHA: Nippon Kayaku dipentaerythritol hexaacrylate Karenz MT-PE1: Showa Denko K.K., pentaerythritol tetrakis (3-mercaptobutyrate)
In Table 1, OXE-01 is IRGACURE OXE-01.

<Evaluation>
Each colored photosensitive composition and colored pattern obtained were evaluated for each item of stability over time, odor, developability, and solvent resistance. 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 from the viewpoint of liquid viscosity stability and contrast stability. The liquid viscosity stability was evaluated by the change in the viscosity of the liquid before and after the colored photosensitive composition was stored at 40 ° C. for 7 days.
Contrast stability was determined by applying a colored photosensitive composition with a thickness of 2.3 μm on a substrate before and after standing still for 7 days under a thermal condition of 40 ° C., and changing the rate of change from the contrast value of each substrate. It was evaluated by calculating.
E-type viscometer RE-85L (manufactured by Toki Sangyo Co., Ltd.) was used for viscosity measurement, and BM-5 (Topcon Co., Ltd.) was used for contrast measurement.
-Evaluation criteria-
(Circle): Before and after thermostating stationary preservation | save, on the basis of the value before stationary (1) Viscosity change rate is less than 10%, and (2) Contrast change rate is less than 10%.
X: What does not correspond to any one or more of said (1) and (2).

  The viscosity change rate over time and the contrast change rate over time of the colored photosensitive composition are preferably within 10% based on the values before storage at rest. When the above items change remarkably with time, in the case of forming a color filter color pattern (pixel pattern) with the colored photosensitive composition of the present invention, production stability cannot be obtained, and it is suitable for production of a color filter. Absent.

2. Evaluation of Odor Evaluation of odor was performed by sensory evaluation at 23 ° C. according to the following criteria by dropping 1 ml of the colored photosensitive composition on a petri dish. If the odor is tight, it is not only unpleasant, but it is necessary to reinforce equipment such as exhaust, which is not preferable in practice.
-Evaluation criteria-
○: The number of people who felt uncomfortable in the odor sensory evaluation of 10 people was 0 to 3 people.
X: The number of people who felt uncomfortable in the odor sensory evaluation of 10 people was 4 or more.

3. Evaluation of developability The development latitude and solubility of the developer when the glass substrate after the exposure process was developed under the above conditions were evaluated. If the development latitude is narrow, the development stability in the production process cannot be obtained, which is not preferable. Further, if the developer solubility is poor, film removal and peeling occur at the time of development, causing a residue and process contamination, which causes a problem.
The obtained results were evaluated according to the following evaluation criteria. The break point is the time (in seconds) that the unexposed part of the colored photosensitive composition dissolves and peels off during the development process, and the break point means that the unexposed part of the colored photosensitive composition dissolves and peels off during the development process. It is the moment of peeling.
-Evaluation criteria-
○: (1) No peeling of the colored pattern for 80 seconds or more from the break point, and (2) No peeling or peeling of the colored layer in the developer during the break.
X: What does not correspond to any one or more of said (1) and (2).

4). Evaluation of solvent resistance The glass substrate on which the colored pattern after the development process was formed was post-baked at 230 ° C. for 30 minutes in a convection oven. The chromaticity of the obtained substrate after baking was measured with OSP-SP100: Olympus Corporation and immersed in N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”) at 23 ° C. for 30 minutes. ΔE ^* ab was determined from the chromaticity of the colored pattern before and after immersion. The chromaticity was measured by OSP-SP100: Olympus Corporation.
When ΔE ^* ab exceeds 3, the solvent resistance of various chemicals used for panel processing is insufficient in the production of a liquid crystal display device and the like, which is a practical problem.
Furthermore, the change in the shape of the colored pattern before and after immersion in NMP was observed by optical microscope observation.
The obtained results were evaluated according to the following evaluation criteria.
-Evaluation criteria-
◯: (1) ΔE ^* ab is 3.0 or less, and (2) No change in the colored pattern shape is observed.
X: What does not correspond to any one or more of said (1) and (2).

  As shown in Table 2, the colored photosensitive compositions of the examples were excellent in stability over time, had no unpleasant odor, and had good solvent resistance. On the other hand, the colored photosensitive compositions of Comparative Examples 1 to 4 had a large change in performance before and after aging and were inferior in stability. Further, the colored photosensitive composition of Comparative Example 5 has a problem in that the development latitude is narrow. The colored photosensitive compositions of Comparative Examples 6 to 8 had a strong odor due to the thiol compound and were not practical.

  In addition, according to the comparison between Example 2 and Example 1, the colored pattern (colored film) formed in any of the examples has the same good results regarding the solvent resistance. It can also be seen that, when pattern exposure by a laser exposure machine is applied, the excellent effects of the present invention can be obtained as in the case of exposure by a high-pressure mercury lamp.

Claims (11)

  (A) a halogenated zinc 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. A colored photosensitive composition comprising a chain transfer agent and (F) a solvent, wherein the polymerizable monomer (B) having an acid group is a carboxyl group-modified polyfunctional acrylate compound.   The colored photosensitive composition according to claim 1, wherein the secondary or tertiary aliphatic thiol compound is a monofunctional or bifunctional aliphatic thiol compound.   The colored photosensitive composition according to claim 1 or 2, wherein the (D) photopolymerization initiator is a hexaarylbisimidazole compound.   The colored photosensitive composition according to claim 3, wherein the (D) photopolymerization initiator further includes two or more kinds including an oxime compound.   The colored photosensitive composition according to any one of claims 1 to 4, wherein the binder resin (C) is a resin having an acid group.   Furthermore, (G) The coloring photosensitive composition of any one of Claims 1-5 containing a photosensitizer. The carboxyl group-modified polyfunctional acrylate compound is succinic acid modified pentaerythritol triacrylate, succinic acid modified trimethylolpropane triacrylate, succinic acid modified pentaerythritol tetraacrylate, succinic acid modified dipentaerythritol pentaacrylate, succinic acid modified dipentaerythritol. hexaacrylate, adipic acid-modified pentaerythritol triacrylate, adipic acid-modified trimethylolpropane triacrylate, adipic acid-modified pentaerythritol tetraacrylate, or we choose adipic acid-modified dipentaerythritol pentaacrylate and adipic acid-modified dipentaerythritol tetra acrylated DOO The colored photosensitive composition according to any one of claims 1 to 6, wherein the colored photosensitive composition is one or more kinds. .   The (A) halogenated zinc phthalocyanine pigment is C.I. I. Pigment green 58, and C.I. I. The colored photosensitive composition according to any one of claims 1 to 7, comprising CI Pigment Yellow 150. A colored layer forming step of forming the colored layer by applying the colored photosensitive composition according to any one of claims 1 to 8 on a substrate;
An exposure step of curing the exposed area by pattern-like exposure to the formed colored layer;
Development step of developing and removing unexposed portions in the colored layer after exposure to form a pattern;
A pattern forming method including:   A color filter manufactured by the pattern forming method according to claim 9.   A liquid crystal display device comprising the color filter according to claim 10.