JP5623886B2 - 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 obtained by the production method, and a liquid crystal display device including the color filter.

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 reproduction of display devices is emphasized. ing. 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 is further added with an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other components to obtain a colorable composition. A color filter in which a colored pattern of three colors of red, green, and blue is formed on a transparent substrate such as glass by a photolithographic method has been developed and put into practical use. In the green coloring pattern, chlorinated copper phthalocyanine pigment (CI PIGMENT Green 7) and chlorinated brominated copper phthalocyanine pigment (CI PIGMENT Green 36) are generally used from the viewpoint of color tone and fastness. Green pigment is used. In addition, an inkjet coloring composition using a phthalocyanine pigment containing Al as a blue pigment used in a blue coloring pattern has been proposed (for example, see Patent Document 1).

  In recent years, as a green pigment, for the purpose of increasing the saturation (color purity and color density) of the pigment, the central metal is not copper, but a polyhalogenated metal phthalocyanine such as aluminum, titanium, cobalt, nickel, zinc, tin, lead, etc. Pigments have been studied, and various pigments have been proposed for polyhalogenated zinc phthalocyanine pigments (CI Pigment Green 58) having particularly high chroma. 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 °) polyhalogenated copper 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. Has been reported. Further, it has been proposed that a color filter having high transparency and high color purity can be obtained using these pigments (see, for example, Patent Documents 2 to 4).

  On the other hand, the color filter is required to have light resistance because it does not fade or discolor due to light from the backlight. A colored photosensitive composition (see Patent Documents 5 to 7) in which the coloring material itself has been improved in order to improve light resistance, and a colored photosensitive composition to which a compound such as a quencher or a light stabilizer is added (Patent Document 8). 9)), or a colored photosensitive composition in which a polymerizable monomer is improved has been reported.

  As for the improvement of light resistance in a resin composition, a vinyl-based polymer containing a proton-donating atomic group is used as a resin composition capable of suppressing optical deterioration and obtaining high-precision optical characteristics when applied as an optical component. A resin composition containing a combination A and a proton-accepting atomic group produced by polymerizing a radical polymerizable hindered amine compound has been proposed (for example, see Patent Document 10).

  In general, dyes are inferior in light resistance as compared with pigments, and therefore, with respect to dyes, light resistance has been actively improved. However, even with pigments, it is known that light resistance deteriorates when miniaturized to improve brightness. For colored photosensitive compositions using such pigments, high transparency and high color purity are obtained. Although it has been necessary to improve the light resistance while maintaining the characteristics, it has not yet been provided.

JP 2007-291259 A JP 2003-161823 A JP 2007-284592 A JP 2008-24743 A JP 2008-138037 A JP 2009-149777 A JP 2009-215380 A JP 2000-214580 A JP 2004-139050 A JP 2004-155812 A

The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a pattern that is excellent in suppressing chromaticity change in the formed colored film and excellent in solvent resistance, and is a color filter. It is to provide a colored photosensitive composition that can be suitably used for forming a colored pattern.
Another object of the present invention is to use the colored photosensitive composition of the present invention to suppress chromaticity change in a colored film, and have high color purity, high contrast, and good color characteristics. A color filter and a liquid crystal display device including the color filter are provided.

  As a result of intensive studies to solve the above problems, the present inventors solved the above problems by using an azoxy-based oxidizing agent having a specific structure in a colored photosensitive composition using a pigment having a phthalocyanine skeleton. As a result, the present invention has been completed.

That is, the means for solving the above problems are as follows.
<1> (A) a pigment having a phthalocyanine skeleton, (B) a solvent, (C) at least one selected from the group consisting of a polymerizable monomer and a binder resin, (D) a photopolymerization initiator, and (E ) A colored photosensitive composition containing at least an oxidizing agent represented by the following general formula (1).

In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group, an aliphatic oxy group, an aromatic oxy group, or a complex. Represents a group, and R ¹ and R ² may be bonded to each other at a terminal to form a cyclic structure.

<2> The content of the oxidizing agent represented by the general formula (1) (E) is 0.1% by mass or more and 5.0% by mass or less in the total solid content of the colored photosensitive composition <1. > The colored photosensitive composition as described in>.
<3> The colored photosensitive composition according to <1> or <2>, wherein the pigment (A) having a phthalocyanine skeleton contains a metal in its chemical structure.
<4> The colored photosensitive composition according to any one of <1> to <3>, wherein the pigment (A) having a phthalocyanine skeleton is a green pigment.
<5> The pigment (A) having a phthalocyanine skeleton is C.I. I. Pigment green 7, C.I. I. Pigment green 36, and C.I. I. The colored photosensitive composition according to any one of <1> to <4>, which is at least one selected from the group consisting of CI Pigment Green 58.

<6> The oxidant represented by (E) the general formula (1) is the oxidant represented by the following general formula (2), according to any one of the above <1> to <5>. Colored photosensitive composition.

In the general formula (2), R ^{3 to} R ¹² each independently represent a hydrogen atom, a halogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group, an aliphatic oxy group, an aromatic oxy group, or a complex. R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , and R ¹¹ R ¹² may be bonded to each other to independently form a 5-membered ring, a 6-membered ring, or a 7-membered ring.

  <7> A color filter having a colored pattern using the colored photosensitive composition according to any one of <1> to <6>.

<8> A colored photosensitive composition layer is formed by applying the colored photosensitive composition according to any one of <1> to <6> directly or via another layer on a substrate. A method for producing a color filter comprising: a step, exposing the colored curable composition layer through a predetermined mask pattern, and developing and removing an uncured portion with a developer after the exposure.
<9> A liquid crystal display device comprising the color filter according to <7>.

According to the present invention, it is possible to form a pattern with excellent suppression of chromaticity change in the formed colored film and with excellent solvent resistance, and a colored photosensitive composition that can be suitably used for forming a colored pattern of a color filter. Things can be provided.
Further, according to the present invention, by using the colored photosensitive composition of the present invention, a color filter excellent in suppression of chromaticity change, high color purity, high contrast, and good color characteristics, and A liquid crystal display device including a color filter can be provided.

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

[Colored photosensitive composition]
The colored photosensitive composition of the present invention comprises (A) a pigment having a phthalocyanine skeleton, (B) a solvent, (C) at least one selected from the group consisting of a polymerizable monomer and a binder resin, and (D) light. A colored photosensitive composition comprising at least a polymerization initiator and (E) an oxidizing agent represented by the following general formula (1).

In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group, an aliphatic oxy group, an aromatic oxy group, or a complex. Represents a group, and R ¹ and R ² may be bonded to each other at a terminal to form a cyclic structure.

The colored photosensitive composition of the present invention can form a colored film excellent in suppressing chromaticity change by containing the above components, and when applied to the formation of a colored pattern, the development latitude is large, In addition, the solvent resistance is excellent. For this reason, the colored photosensitive composition of the present invention is used for forming a colored pattern such as calafirta, which is one of its preferred applications, so that a colored pattern having a small change in chromaticity and exhibiting a good image display ability is obtained. Can be obtained. In addition, the color filter obtained using the colored photosensitive composition of the present invention is a color filter having high color purity and high contrast and good color characteristics. By using this color filter, a bright and clear color filter is obtained. An image liquid crystal display device can be obtained.
In the present invention, the chromaticity change refers to a color that occurs over time when light and / or heat is applied to a colored photosensitive composition or a color filter having a colored pattern formed using the same. Means a change in degree. In this specification, the chromaticity change refers to a value (ΔE * ab) calculated from chromaticity measured using OSP-SP100 (Olympus Co., Ltd.) for a colored film to be measured. Suppression of the chromaticity change in the colored photosensitive composition can contribute to an improvement in the reliability of a color filter or the like obtained using the colored photosensitive composition.
Hereinafter, the components constituting the colored photosensitive composition of the present invention will be described.

<(A) Pigment having phthalocyanine skeleton>
The pigment in the present invention is preferably a pigment having a phthalocyanine ring in the molecular structure.
The phthalocyanine ring in the phthalocyanine skeleton may be substituted with a halogen atom. Since the phthalocyanine ring has 16 hydrogen atoms in its structure, up to 16 of these hydrogen atoms can be substituted with halogen atoms. These halogen atoms may all be the same or different.

  Further, the number of halogen atom substitutions is preferably 8 or more and 16 or less, and more preferably 10 or more and 16 or less. When the phthalocyanine ring is substituted with a halogen atom, the halogen atom is preferably a halogen atom selected from a chlorine atom and a bromine atom.

  The pigment having a phthalocyanine skeleton in the present invention preferably contains a metal in its chemical structure from the viewpoint of obtaining a color with particularly high luminance. Such a pigment is preferably a phthalocyanine pigment containing a metal at the center of the phthalocyanine ring (hereinafter also referred to as “phthalocyanine pigment” as appropriate).

  When the phthalocyanine pigment is substituted with 8 or more bromine atoms, the phthalocyanine pigment exhibits a yellowish green color with high brightness and is suitable for forming a colored pattern constituting a green pixel portion such as a color filter. In particular, since those having 10 to 16 bromine atoms have higher brightness, they are preferably used in the colored photosensitive composition of the present invention.

  The central metal having a phthalocyanine ring is not particularly limited as long as it can maintain the stability of the coloring material, but copper, aluminum, titanium, cobalt, nickel, zinc, tin, lead, etc. are preferable, and from the viewpoint of saturation. Zinc is preferable.

  The phthalocyanine pigment can be produced by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, or a melting method. More specific production methods are described in detail in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like. Among these, the halogenated zinc phthalocyanine pigment disclosed in Japanese Patent Application Laid-Open No. 2004-70342, which has a simple process, 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 phthalocyanine pigment 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 having excellent dispersibility stability and coloring power, high luminance, 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 primary particles of the phthalocyanine pigment further have an aspect ratio of 1 to 3 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 phthalocyanine pigment having an average primary particle diameter in the range of 10 nm to 100 nm, the phthalocyanine pigment is finely divided. Any method may be used for atomization, but it is preferable to employ a solvent salt milling treatment from the viewpoint that it is possible to easily suppress crystal growth and obtain pigment particles having a relatively small average primary particle diameter.

  The solvent salt milling means kneading and grinding a phthalocyanine pigment, an inorganic salt, and an organic solvent. The phthalocyanine pigment having a large particle diameter may be subjected to solvent salt milling after dry grinding. Specifically, a phthalocyanine pigment, an inorganic salt, and an organic solvent that does not dissolve the phthalocyanine pigment 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 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 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 phthalocyanine pigment in terms of mass.

  As an organic solvent used for solvent salt milling, it is preferable to use an organic solvent capable of suppressing crystal growth, and a water-soluble organic solvent can be suitably used as such an organic solvent. Examples of the organic solvent include diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2 -(Hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene Glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene group It is possible to use a call like.

  The amount of the water-soluble organic solvent used in this case is not particularly limited, but is preferably 0.01 to 5 parts, more preferably 0.8 to 2 parts relative to 1 part of the phthalocyanine pigment in terms of mass. .

  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 phthalocyanine pigment, an inorganic salt, and an organic solvent as main components is obtained. The organic solvent and the inorganic salt are removed from the mixture, and a solid material mainly containing the phthalocyanine pigment is washed and filtered as necessary. Fine phthalocyanine pigment powder can be obtained by drying, grinding and the like.

  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 or the like, it is carried out to break the pigment into powder, and examples thereof include pulverization with a mortar, hammer mill, disk mill, pin mill, jet mill and the like.

  The (A) pigment having a phthalocyanine skeleton in the present invention can be obtained as a phthalocyanine pigment, for example, by the above-described method, but generally available pigments or pigment dispersion products can also be used.

  The pigment (A) having a phthalocyanine skeleton thus obtained has a weak primary particle cohesive force and has a more easily detachable property, so that the covering power is increased and the production of a high-contrast colored film is easy. Become.

  The pigment having a phthalocyanine skeleton in the present invention is preferably a green pigment. Among the green pigments, C.I. I. Pigment green 7, C.I. I. Pigment green 36, and C.I. I. From the viewpoint of brightness and contrast, at least one selected from the group consisting of CI Pigment Green 58 is preferable.

  In the present invention, these phthalocyanine pigments may be used alone, but other halogenated phthalocyanine pigments having different bromination rates or chlorination rates, or brominated phthalocyanines in which the central metal is substituted with another metal. It can be used as a mixture. 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, from the viewpoint of improving the transmittance, (A) a pigment having a phthalocyanine skeleton is combined with another coloring material to prepare the hue of the colored photosensitive composition, and the transmittance is increased. Can be bigger.

  For example, a yellow pigment or an orange pigment may be used in combination with the phthalocyanine green pigment to form a green colored film such as 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.

Specific examples of such pigments include 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 , 174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, and C. 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 a colored film with high transmittance and high contrast can be obtained.

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

  Specific examples of such pigments include C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, especially C.I. I. Pigment Violet 23 is preferable because a colored film with high transmittance and high contrast can be formed.

The average primary particle diameter of the pigment that can be used in combination with these other colorants is preferably in the range of 10 nm to 40 nm because a colored film with high transmittance and high contrast can be formed. More preferably, it is the range of 10 nm-30 nm. In order to make the average primary particle size small and fine, the salt milling method is effective in the same manner as the phthalocyanine pigment, and may be salt milled together with the phthalocyanine pigment or may be separately salt milled.
The average primary particle diameter of pigments that can be used in combination with other colorants can also be determined by observing with SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating the average value. it can.

In the colored photosensitive composition of the present invention, the total amount of the pigment having a phthalocyanine skeleton is preferably 5 to 60% in terms of mass with respect to the total amount excluding the solvent in the colored photosensitive composition of the present invention. 10 to 50% is more preferable, and optimally 15 to 45%.
By setting the content of the pigment having a phthalocyanine skeleton in the above range, for example, when the colored photosensitive composition of the present invention is used for producing a color filter, the color characteristics are excellent, the contrast is high, and the luminance is high. High color filter can be obtained.

~ Pigment dispersion composition ~
In preparing the colored photosensitive composition of the present invention, when a plurality of pigments are used in combination, a pigment dispersion composition in which a pigment having a phthalocyanine skeleton and another pigment are dispersed together or separately in advance. It is a preferable aspect to use.

  The pigment dispersion composition is obtained by dispersing a phthalocyanine pigment and, if necessary, another pigment in a solvent. At this time, a dispersant, a resin, or the like may be added as necessary. Furthermore, other components such as pigment derivatives may be used as necessary.

-Preparation of pigment dispersion composition-
The preparation mode of the pigment dispersion composition in the present invention is not particularly limited. For example, the pigment, the pigment dispersant, and the solvent are mixed with a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, or the like. 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 carrying out fine dispersion treatment with beads, give a strong shearing force using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single or twin screw extruder, etc. It is also possible to carry out the kneading and dispersing process.

For details on kneading and dispersing, see T.W. C. “Paint Flow” by Patton
and Pigment Dispersion "(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 with respect to the total solid (mass) 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 preferably contains at least one dispersant. By containing the 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 types of compounds can be used as the dispersant, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75. , No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc .; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxy Nonionic surfactants such as ethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (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, etc .; a fluorosurfactant such as MegaFac F171, F172, F173 (manufactured by DIC Corporation); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Polymer dispersing agents such as Disperse Aid 9100 (all manufactured by San Nopco); Sols such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 Perth dispersant (made 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 (manufactured by Asahi Denka Co., Ltd.) and Ionette S-20 (manufactured by Sanyo Kasei 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 (by Big Chemie). 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 derivative is a compound in which a part having affinity for the dispersant or a polar group is introduced into the molecular structure. By adsorbing the pigment derivative on the pigment surface and using this as an adsorption point of the dispersant, the pigment can be dispersed as fine particles in the colored photosensitive composition and re-aggregation can be prevented. Therefore, for example, when the colored photosensitive composition of the present invention is used for producing a color filter, a color filter having high contrast and excellent transparency can be obtained.

  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 include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzimidazolone pigments. Etc. In general, pale yellow aromatic polycyclic compounds such as naphthalene-based, anthraquinone-based, triazine-based, and quinoline-based compounds that are not called pigments are also included in the matrix skeleton of pigment derivatives. Examples of the dye derivative 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. Examples of the solvent include 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, and cyclohexanone. , N-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene, and the like, and in order to adjust the melting point, viscosity, and dispersibility of the pigment, A plurality of them can be used in combination.

  The content of the solvent in the pigment dispersion composition can be selected as appropriate. From the viewpoint of handleability in the preparation of the colored photosensitive composition, the solid content concentration including the pigment and the pigment dispersant is 5 to 50% by mass. It is preferable to contain.

  In the preparation of the colored photosensitive composition of the present invention, when the pigment dispersion composition is prepared in advance, the content of the pigment dispersion composition is the pigment based on the total solid content (mass) of the colored photosensitive composition. Is preferably in the range of 5 to 70% by mass, and more preferably in the range of 15 to 60% by mass. When the content of the pigment dispersion composition is within this range, the color density is sufficient and it is effective to ensure excellent color characteristics.

In addition to the pigment described above, a dye may be used in combination with 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 that can be used in the present invention is not particularly limited as long as it is a dye that is soluble in an organic solvent, but when classified according to chemical structure, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine 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 1 20, 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) Solvent>
The colored photosensitive composition of the present invention contains a solvent.

Examples of the solvent include solvents classified into esters, ethers, ketones, aromatic hydrocarbons and the like.
Examples of solvents classified as esters include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters , Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate and 3 -3-oxypropionic acid alkyl esters such as ethyl oxypropionate (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2 - 2-oxypropionic acid alkyl esters such as methyl cypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropion) Propyl acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.

Examples of solvents classified as 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 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 solvents classified as 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.

<(C) At least one selected from polymerizable monomers and binder resins>
The colored photosensitive composition of the present invention contains at least one selected from a polymerizable monomer and a binder resin as a curing component.

(Polymerizable monomer)
The polymerizable monomer applicable to the present invention is not particularly limited as long as it can be polymerized, and can be subjected to addition polymerization of a low molecular compound, dimer, trimer, oligomer, etc. having at least one ethylenic double bond. A compound can be used conveniently.
Examples of the ethylenic compound include unsaturated carboxylic acid, ester of unsaturated carboxylic acid and monohydroxy compound, aliphatic polyhydroxy compound and ester of unsaturated carboxylic acid, aromatic polyhydroxy compound and unsaturated carboxylic acid. Ester, polyisocyanate compound and (meth) acryloyl-containing ester obtained by esterification reaction with unsaturated carboxylic acid and polyvalent carboxylic acid and polyhydric hydroxy compound such as fatty acid polyhydroxy compound and aromatic polyhydroxy compound as described above Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting with a hydroxy compound.

  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, propionate dipentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate,
Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate, captolactone modified dipentaerythritol hexa Examples include (meth) acrylates 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.

  On the other hand, from the viewpoint of development latitude, those having 1 to 3 polymerizable groups in the same molecule are advantageous, and in particular, a compound having both a hydroxyl group and a carboxyl group in the molecule contributes to improvement in developability. large.

In order to achieve both solvent resistance and ITO sputtering suitability and development latitude, a compound having 1 to 2 polymerizable groups in one molecule and a compound having 3 or more polymerizable groups are used in combination. It is also possible.
When a compound having 1 to 2 polymerizable groups in one molecule and a compound having 3 or more polymerizable groups are used in combination, 1 to 2 when the total amount of polymerizable monomers is 100 parts by mass It is preferable to use together the compound which has one polymerizable 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.

-Binder resin-
As the binder resin applicable to the present invention, any polymer compound that is soluble in a solvent can be used. As a preferable binder resin, an alkali-soluble resin is preferable in view of alkali developability by a photolithography method. Moreover, as a linear organic high molecular polymer applied as a binder resin, what has a polymeric group is preferable.

  The alkali-soluble resin can be contained in the preparation stage of the pigment dispersion composition described above. The pigment dispersion composition is divided into both the preparation stage and the preparation stage of the colored photosensitive composition. It can also be included.

  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 carboxylic acid 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 binder resins include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, and JP-A-11-174224. JP-A 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 the other monomer copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, 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, allyl (meth) acrylate, butyl (meth) acrylate, isobutyl ( Examples include meth) acrylate, pentyl (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 CH ₂ ═CR ³¹ R ³² , CH ₂ ═C (R ³¹ ) (COOR ³³ ), allyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate And at least one selected from styrene, 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.

In the colored photosensitive composition of the present invention, the polymerizable monomer and the binder resin are preferably used in combination.
Moreover, the polymerizable monomer and the binder resin may each be used as a single compound or a plurality of compounds may be used in combination.

In the colored photosensitive composition of the present invention, the content of the polymerizable monomer is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, and still more preferably, when the composition is 100% by mass. Is in the range of 15-50% by weight.
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 contained in this composition, More preferably, it is 2-15. It is mass%, Most preferably, it is 3-12 mass%.

  Moreover, when using together a polymerizable monomer and binder resin, as the content ratio, the range of 0.1-10 is preferable by mass ratio (mass of polymerizable monomer / mass of binder resin), 0.4-8 Is more preferable, and the range of 0.5 to 5 is more preferable.

<(D) Photopolymerization initiator>
The colored photosensitive composition of the present invention contains a photopolymerization initiator. As the photopolymerization initiator, known compounds capable of initiating polymerization by light irradiation can be used in a wide range without limitation.

  Known photopolymerization initiators generally used include, for example, camphorquinone, benzophenone, benzophenone derivatives, O-acyl oxime ester compounds, acyl phosphines, acyl phosphine derivatives, acetophenones, acetophenone derivatives, such as 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 benzyldimethyl Ketals, phenyl glyoxalate and derivatives thereof, dimer phenyl glyoxalate, peresters such as benzophenone tetracarboxylic acid peresters (eg European Patent 112 6,541), halomethyltriazines such as 2- [2- (4-methoxy-phenyl) -vinyl] -4,6-bis-trichloromethyl [1,3,5 ] Triazine, 2- (4-methoxy-phenyl) -4,6-bis-trichloromethyl [1, 3, 5] triazine, 2- (3,4-dimethoxy-phenyl) -4,6-bis-trichloromethyl Combined with [1,3,5] triazine, 2-methyl-4,6-bis-trichloromethyl [1,3,5] triazine, hexaarylbisimidazole / co-initiator system, eg 2-mercaptobenzothiazole Ortho-chlorohexaphenyl-bisimidazole; ferrocenium compounds or titanocenes, for example dicyclopentadienyl Bis (2,6-difluoro-3-pyrrolo-phenyl) - titanium; for example, it is also possible to use mixtures of O- acyloxime ester compounds as described in EP GB2,339,571. A boric acid compound can also be used as a co-initiator.

  Among these, as the photopolymerization initiator, an O-acyl oxime ester compound (hereinafter also referred to as an O-acyl oxime initiator) is preferable from the viewpoint of exposure sensitivity.

~ O-acyloxime initiator ~
The O-acyl oxime initiator can be appropriately selected from known initiators such as oxime initiators described in JP-A Nos. 2000-80068 and 2001-233842. Specific examples of such O-acyloxime initiators include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl). -Phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1-one oxime-O-acetate, 1- (4-phenylsulfanyl-phenyl) ) -Butan-1-one oxime-O-acetate and the like. As the O-acyloxime initiator, one kind of compound may be used or two or more kinds of compounds may be used in combination.

  In addition to the above, the compound represented by the following general formula (I) can also be mentioned as a suitable photopolymerization initiator from the viewpoint that a pattern with a good rectangular profile can be obtained with a smaller exposure amount.

  In general formula (I), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In the general formula (I), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group shown below.
That is, as the monovalent nonmetallic atomic group represented by R, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, An alkynyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, a substituent An arylsulfonyl group which may have, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent A phosphinoyl group that may have a substituent, a heterocyclic group that may have a substituent, an alkylthiocarbonyl group that may have a substituent, an arylthiocarbonyl group that may have a substituent, and a substituent. Good dialkylamine Carbonyl group, optionally dialkylaminothiocarbonyl group, or the like may have a substituent.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group , 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitro Enashiru group, and the like.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl, fluorenyl, anthryl, bianthracenyl, teranthraceni Group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexa Examples thereof include a phenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. For example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, perfluoroalkylsulfonyl group, etc. It is done.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Examples thereof include an oxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  The aryloxycarbonyl group which may have a substituent includes a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, and a 4-phenylsulfanylphenyloxycarbonyl group. 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3 -Chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fur B phenyloxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and 4-methoxyphenyloxycarbonyl group.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the alkylthiocarbonyl group which may have a substituent include, for example, methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, Examples thereof include a trifluoromethylthiocarbonyl group.

  Examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethyl. Aminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group Group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group Boniru group, 4-methoxyphenyl thiocarbonyl group.

  Examples of the dialkylaminocarbonyl group that may have a substituent include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.

  Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, and a dibutylaminothiocarbonyl group.

  Among these, from the viewpoint of increasing sensitivity, R is more preferably an acyl group, and specifically, an acetyl group, an ethyloyl group, a propioyl group, a benzoyl group, and a toluyl group are preferable.

  In the general formula (I), the monovalent substituent represented by B may have an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a substituent. It represents a good arylcarbonyl group or an optionally substituted heterocyclic carbonyl group. Among these, a monovalent substituent having the structure shown below is particularly preferable. In the monovalent substituent having the following structure, Y, X, and n have the same meanings as Y, X, and n in General Formula (II) described later, and preferred examples are also the same.

In the general formula (I), the divalent organic group represented by A includes an optionally substituted alkylene having 1 to 12 carbon atoms, an optionally substituted cyclohexylene, and a substituent. The alkynylene which may have is mentioned.
Examples of the substituent that can be introduced into these groups include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p- Aryloxy groups such as tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy groups such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group Group, acyl group such as methacryloyl group and methoxalyl group, alkylsulfanyl group such as methylsulfanyl group and t-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group and p-tolylsulfanyl group, methylamino group, cyclohexane Alkylamino group such as silamino group, dialkylamino group such as dimethylamino group, diethylamino group, morpholino group, piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group, ethyl group, t-butyl group In addition to alkyl groups such as dodecyl group, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, Sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group, Triphenylphenacylphosphoniumyl group And the like.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a t-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

In general formula (I), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent.
Specific examples of the aryl group represented by Ar include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, a 1-pyrenyl group, a 5-naphthacenyl group, 1 -Indenyl, 2-azurenyl, 9-fluorenyl, terphenyl, quarterphenyl, o-, m-, and p-tolyl, xylyl, o-, m-, and p-cumenyl, mesityl Group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group , Teranthracenyl group, quarteranthracenyl group, Traquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, pleadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group , A coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, an obalenyl group, and the like. Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  When the phenyl group has a substituent, examples of the substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and t-butoxy group. Groups, phenoxy groups, aryloxy groups such as p-tolyloxy groups, methylthioxy groups, ethylthioxy groups, alkylthioxy groups such as t-butylthioxy groups, arylthiooxy groups such as phenylthioxy groups and p-tolyloxy groups, methoxycarbonyl Groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups, methoxalyl groups, etc. Group methylsulf Nyl group, alkylsulfanyl group such as t-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, alkylamino group such as methylamino group, cyclohexylamino group, dimethylamino group, diethylamino group, morpholino Group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, alkyl group such as ethyl group, t-butyl group, dodecyl group, hydroxy group, carboxy group, formyl group, mercapto group , Sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group , Li phenyl phenacyl phosphonium Niu mill group, and the like.

  In the general formula (I), the structure of “SAr” formed by Ar and adjacent S is preferably the following structure from the viewpoint of sensitivity.

  The compound represented by the general formula (I) is preferably a compound represented by the following general formula (II).

  In general formula (II), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5.

  R, A and Ar in the general formula (2) have the same meanings as R, A and Ar in the general formula (I), and preferred examples thereof are also the same.

  In the general formula (II), the monovalent substituent represented by X may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Alkenyl group, optionally substituted alkynyl group, optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted alkylthioxy group, substituted An arylthioxy group which may have a group, an acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, a substituent An alkylsulfinyl group that may have, an arylsulfinyl group that may have a substituent, an alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and a substituent May be acyl group, substituted An optionally substituted alkoxycarbonyl group, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, an optionally substituted amino group, and an optionally substituted substituent Examples thereof include a good phosphinoyl group, a heterocyclic group which may have a substituent, and a halogen atom.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitrophena Group, and the like.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl, fluorenyl, anthryl, bianthracenyl, teranthraceni Group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexa Examples include a phenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, and an oberenyl group.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, or a sec-butoxy group. Tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2 -Ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarb Methylpropenylmethyl group, N- methyl -N- benzylaminocarbonyl methyloxy group, a benzyloxy group, and a cyanomethyloxy group.

  The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, Examples include 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group and the like.

  The alkylthioxy group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms. For example, a methylthioxy group, an ethylthioxy group, a propylthioxy group, an isopropylthioxy group, a butylthioxy group, an isobutylthio group. Oxy group, s-butylthioxy group, t-butylthioxy group, pentylthioxy group, isopentylthioxy group, hexylthioxoxy, heptylthioxy group, octylthioxy group, 2-ethylhexylthioxy group, decylthioxy group, dodecylchioxy group Examples thereof include an oxy group, an octadecylthioxy group, and a benzylthioxy group.

  The arylthioxy group which may have a substituent is preferably an arylthioxy group having 6 to 30 carbon atoms, such as a phenylthioxy group, a 1-naphthylthioxy group, a 2-naphthylthioxy group, 2 -Chlorophenylthioxy group, 2-methylphenylthioxy group, 2-methoxyphenylthioxy group, 2-butoxyphenylthioxy group, 3-chlorophenylthioxy group, 3-trifluoromethylphenylthioxy group, 3-cyano Phenylthioxy group, 3-nitrophenylthioxy group, 4-fluorophenylthioxy group, 4-cyanophenylthioxy group, 4-methoxyphenylthioxy group, 4-dimethylaminophenylthioxy group, 4-methylsulfanyl Examples thereof include a phenylthioxy group and a 4-phenylsulfanylphenylthioxy group.

  The acyloxy group which may have a substituent is preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, or trifluoromethylcarbonyloxy. Group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

  The alkylsulfanyl group which may have a substituent is preferably an alkylsulfanyl group having 1 to 20 carbon atoms. For example, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, or a hexylsulfanyl group. Group, cyclohexylsulfanyl group, octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group and the like.

  The arylsulfanyl group which may have a substituent is preferably an arylsulfanyl group having 6 to 30 carbon atoms, such as a phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfuric group Aniru group, 4-dimethylamino-phenylsulfanyl group and the like.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. For example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group and the like.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Oxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4- Phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group Group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group , 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group and the like.

  The carbamoyl group which may have a substituent is preferably a carbamoyl group having 1 to 30 carbon atoms, for example, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, or an N-butylcarbamoyl group. N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2- Chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenyl Carbamoyl group N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like can be mentioned.

  The sulfamoyl group which may have a substituent is preferably a sulfamoyl group having 0 to 30 carbon atoms, for example, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, N, N- Examples thereof include a dialkylsulfamoyl group, an N, N-diarylsulfamoyl group, and an N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like.

The amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N— Examples include sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenyla Group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino Group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenyl Amino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) Amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, morpholino group, 3, - dimethyl morpholino group, and a carbazolyl group.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Furthermore, the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, a substituent An alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylthioxy group that may have a substituent, an arylthioxy group that may have a substituent, and a substituent. An acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, and a substituent. Good arylsulfinyl group, alkylsulfonyl group which may have a substituent, arylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl which may have a substituent Base The carbamoyl group which may have a substituent, the sulfamoyl group which may have a substituent, the amino group which may have a substituent, and the heterocyclic group which may have a substituent may be further substituted. It may be substituted with a group.

  Examples of such a substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and p-tolyloxy group. Aryloxy group, alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy group such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group , Acyl groups such as methoxalyl groups, alkylsulfanyl groups such as methylsulfanyl groups and t-butylsulfanyl groups, arylsulfanyl groups such as phenylsulfanyl groups and p-tolylsulfanyl groups, methylamino groups and cyclohexylamino groups Alkylamino groups such as dimethylamino group, diethylamino group, morpholino group, piperidino group, etc., arylamino groups such as phenylamino group, p-tolylamino group, methyl group, ethyl group, t-butyl group, dodecyl In addition to alkyl groups such as groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, sulfo groups , Mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumumyl group, dimethylsulfoniumumyl group, triphenyl And phenacylphosphoniumyl group .

Among these, X has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy which may have a substituent A group, an arylthioxy group which may have a substituent, and an amino group which may have a substituent are preferable.
Moreover, although n in general formula (II) represents the integer of 0-5, the integer of 0-2 is preferable.

  In the general formula (II), examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “*” represents a bonding position between Y and an adjacent carbon atom in the general formula (II).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  The compound represented by the general formula (I) is preferably a compound represented by the following general formula (III).

  In general formula (III), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5.

  R, X, A, Ar, and n in the general formula (III) have the same meanings as R, X, A, Ar, and n in the general formula (II), and preferred examples are also the same.

  The content of the photopolymerization initiator in the colored photosensitive composition of the present invention is preferably 0.05 to 30% by mass with respect to 100% by mass of the polymerizable compound containing a polymerizable monomer and a binder resin having a polymerizable group. It is more preferable that it is 0.1-20 mass%, and it is more preferable that it is 0.2-10 mass%.

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 sensitizing dye and the initiator to actinic radiation or suppressing inhibition of polymerization 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 Examined Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 51-82102. , JP-A-52-134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure Examples include compounds described in No. 33825, and specific examples include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, and the like.

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

  Other examples of co-sensitizers include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), Japanese Patent Publication No. 55-34414. And a hydrogen compound described in JP-A-6-308727 (eg, trithiane).

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

<(E) Oxidizing agent represented by general formula (1)>
The colored photosensitive composition of the present invention contains an oxidizing agent (oxidizing agent having an azoxy structure) represented by the following general formula (1) as an oxidizing agent.

In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group, an aliphatic oxy group, an aromatic oxy group, or a complex. Represents a group, and R ¹ and R ² may be bonded to each other at a terminal to form a cyclic structure.

  The colored photosensitive composition of the present invention contains an oxidant represented by the general formula (1) as a characteristic component thereof, so that the transparency and color purity of the pigment having a phthalocyanine skeleton are not impaired. In addition to forming a colored film having excellent properties, it is possible to achieve both developability and solvent resistance even when applied to the formation of a colored pattern.

In the case where a colored photosensitive composition containing a pigment having a phthalocyanine skeleton is applied on a substrate after ITO sputtering to form a colored film such as a colored pattern, the present inventors particularly deteriorate the light resistance of the colored film. In particular, when a colored pattern is formed on ITO using a colored photosensitive composition containing a pigment having a phthalocyanine skeleton, the chromaticity represented by the ΔE * ab value over time It was found that the change in chromaticity was large at the center of the coloring pattern and small at the end. Thus, in the colored pattern, the ΔE * ab value indicating the chromaticity change decreases with time, and the chromaticity change at the end of the colored pattern, which is the most contacted site with oxygen, is small during light irradiation. It is considered that the redox reaction occurring in the coloring pattern is related to the deterioration of light resistance.
In the colored photosensitive composition of the present invention, by containing the oxidizing agent represented by the general formula (1), the oxidation-reduction reaction in the colored pattern is most effectively suppressed, and a colored pattern is formed on the ITO. Even in such a case, it is considered that an excellent improvement in light resistance of the colored film has been achieved. In this case, the effect of improving the light resistance by the oxidizing agent represented by the general formula (1) has not been elucidated accurately, but at present, the pigment having a phthalocyanine skeleton and the oxidation which is a material of ITO When tin comes into contact, the tin component discolors due to electron transfer (oxidation-reduction reaction) between the pigment and tin oxide, which is the ITO material, but the oxidizing agent represented by the general formula (1) It is presumed to be caused by obstructing electronic transfer.

Further, the oxidant represented by the general formula (1) has less performance deterioration due to heating compared to other oxidants, and most effectively suppresses the redox reaction that can occur in the colored film during light irradiation. It is estimated to be. This indicates that the colored photosensitive composition of the present invention is particularly significant for use in forming a color pattern of a color filter.
That is, when forming a colored pattern of a color filter with a colored photosensitive composition, as described later, in the colored pattern forming process, heat treatment (post-baking) is performed at a temperature of 100 to 250 ° C. For this reason, the oxidizing agent contained in the colored photosensitive composition is required not to deactivate the oxidizing ability before and after the heat treatment, but in many compounds generally reported as an organic oxidizing agent, Oxidizing ability tends to be deactivated after heat treatment.
On the other hand, since the oxidant represented by the general formula (1) is particularly excellent in heat resistance, the colored photosensitive composition of the present invention is subjected to heat treatment as in the formation of a color filter color pattern. Even when applied to the intended application, deactivation of the oxidizing ability of the oxidizing agent is suppressed. For this reason, the colored photosensitive composition of the present invention can sufficiently exhibit the above-described excellent effects of the present invention when used for producing a color filter which is a preferred application.

The general formula (1) will be described in detail.
In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group, an aliphatic oxy group, an aromatic oxy group, or a complex. R ¹ and R ² may be bonded to each other at the terminal to form a cyclic structure.

Examples of the halogen atom represented by R ¹ and R ² include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferable.

Examples of the aliphatic group represented by R ¹ and R ² include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. Among these, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, or a substituted aralkyl group is preferable, and an alkyl group and a substituted alkyl group are particularly preferable. The aliphatic group may be a cyclic aliphatic group or a chain aliphatic group. The chain aliphatic group may have a branch.

  Examples of the alkyl group include linear, branched, and cyclic alkyl groups, and the number of carbon atoms of the alkyl group is preferably 1 to 30, and more preferably 1 to 10. Examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, cyclohexyl group, cyclopentyl group, neopentyl group, isopropyl group, An isobutyl group etc. are mentioned.

  The preferred range of the number of carbon atoms in the alkyl moiety of the substituted alkyl group and the preferred structure of the alkyl moiety are the same as in the case of the alkyl group.

Examples of the substituent that the substituted alkyl group has include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, fluorine atom, chlorine atom, bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (for example, methoxycarbonyl). Group, ethoxycarbonyl group, benzyloxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, acylaminosulfonyl group having 30 or less carbon atoms, carbon number 30 The following alkoxy groups (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), alkylthio groups having 30 or less carbon atoms (for example, methylthio group, ethylthio group, methylthioethylthioethyl group) ), An aryloxy group having 30 or less carbon atoms (for example, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro group, alkyl group having 30 or less carbon atoms, alkoxycarbonyloxy group, aryl An oxycarbonyloxy group, an acyloxy group having 10 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), an acyl group having 10 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl group (for example, Carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl) Group), aryl having 30 or less carbon atoms (For example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.), substituted amino group (for example, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acylamino) Group), a substituted ureido group, a substituted phosphono group, a heterocyclic group, and the like.
Among these substituents, an electron donating group is preferable from the viewpoint of enhancing the oxidizing ability of the azoxy structure in the general formula (1).

  Examples of the alkenyl group include linear, branched, and cyclic alkenyl groups, and the number of carbon atoms of the alkenyl group is preferably 2 to 10, and more preferably 2 to 5. The alkenyl group may be a substituted alkenyl group having a substituent or an unsubstituted alkenyl group. In the case of a substituted alkenyl group, the preferred range of the number of carbon atoms in the alkenyl moiety and the preferred structure of the alkenyl moiety are the same as in the case of an alkenyl group. Moreover, as a substituent which a substituted alkenyl group has, the substituent similar to the substituent which the said substituted alkyl group has is mentioned.

  Examples of the alkynyl group include linear, branched, and cyclic alkynyl groups. The number of carbon atoms of the alkynyl group is preferably 2 to 30, and more preferably 2 to 10. The alkynyl group may be a substituted alkynyl group having a substituent or an unsubstituted alkynyl group. In the case of a substituted alkynyl group, the preferred range of the number of carbon atoms in the alkynyl moiety and the preferred structure of the alkynyl moiety are the same as in the case of the alkynyl group. Examples of the substituent that the substituted alkynyl group has include the same substituents as the substituent that the substituted alkyl group has.

  Examples of the aralkyl group include linear, branched, and cyclic aralkyl groups. The number of carbon atoms in the aralkyl group is preferably 7 to 30, and more preferably 7 to 15. The aralkyl group may be a substituted aralkyl group having a substituent or an unsubstituted aralkyl group. In the case of a substituted aralkyl group, the preferred range of the number of carbon atoms in the aralkyl moiety and the preferred structure of the aralkyl moiety are the same as in the case of the aralkyl group. Examples of the substituent that the substituted aralkyl group has include the same substituents as the substituent that the substituted alkyl group has.

Examples of the aromatic group represented by R ¹ and R ² include an aryl group and a substituted aryl group. The number of carbon atoms of the aryl group is preferably 6 to 30, and more preferably 6 to 10. Examples of the aryl group include a phenyl group, an α-naphthyl group, and a β-naphthyl group.
The preferred range of the number of carbon atoms in the aryl moiety of the substituted aryl group and the preferred structure of the aryl moiety are the same as those of the aryl group.
Examples of the substituent that the substituted aryl group has include the same substituents as the substituent that the substituted alkyl group has.

The aliphatic oxy group represented by R ¹ and R ² is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a butoxy group, an octyloxy group, and a phenoxyethoxy group. However, it is not limited to these.

As the aromatic oxy group represented by R ¹ and R ² , an aryloxy group having 6 to 30 carbon atoms is preferable, for example, phenoxy group, methylphenyloxy group, chlorophenyloxy group, methoxyphenyloxy group, octyloxyphenyl. An oxy group etc. are mentioned. However, it is not limited to these.

The heterocyclic group represented by R ¹ and R ² is preferably a heterocyclic group containing an N atom, an O atom or an S atom, and examples thereof include a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, and a pyrrolyl group.

  One preferred embodiment of the oxidizing agent represented by the general formula (1) includes an oxidizing agent represented by the following general formula (2) from the viewpoint of the stability and ease of handling of the compound.

In the general formula (2), R ^{3 to} R ¹² each independently represent a hydrogen atom, a halogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group, an aliphatic oxy group, an aromatic oxy group, or a complex. R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , and R ¹¹ R ¹² may be bonded to each other to independently form a 5-membered ring, a 6-membered ring, or a 7-membered ring.

In General Formula (2), the aliphatic group having 1 to 30 carbon atoms represented by R ^{3 to} R ¹² is preferably an aliphatic group represented by R ^{1 or} R ² in General Formula (1). It is synonymous with the C1-C30 aliphatic group mentioned as an example, and its preferable range is also the same.

In general formula (2), as the halogen atom, aromatic group, aliphatic oxy group, aromatic oxy group, and hetero group represented by R ^{3 to} R ¹² , R ¹ and aromatic group represented by R ^2, an aliphatic oxy group, has the same meaning as those described as preferable examples of the aromatic group and heterocyclic group, and preferred ranges are also the same.

In the general formula (2), R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , or As the ring structure that R ¹¹ and R ¹² may form, for example,
The 5-membered ring is a cyclopentane ring, cyclopentene ring, cyclopentanone ring, furan ring, tetrahydrofuran ring, and the 6-membered ring is a cyclohexane ring, cyclohexene ring, cyclohexanone ring, benzene ring, pyridine ring, piperidine ring, 7-membered ring Examples of the ring include a cycloheptane ring, a cycloheptene ring, and a cycloheptanone ring.

  Among the oxidizing agents represented by the general formula (2), those having an electron donating group as a substituent are more preferable from the viewpoint of enhancing the oxidizing ability.

  Specific examples of the oxidizing agent represented by the general formula (1) include azoxybenzene represented by the following structural formula (A), azoxyanisole represented by the following structural formula (B), and the following structural formula (C ), A compound represented by the structural formula (D), and a compound represented by the structural formula (E), but are not limited thereto.

In the colored photosensitive composition of the present invention, the content of the oxidizing agent represented by the general formula (1) is preferably 0.1 to 5.0% by mass with respect to the total solid content of the colored photosensitive composition, It is more preferable that it is 0.2-4.0 mass%, and it is more preferable that it is 0.5-2.0 mass%.
When the content of the oxidant represented by the general formula (1) is in the above range, the effect as an oxidant and the exposure sensitivity become better.

<Additives>
In the colored photosensitive composition of the present invention, various types such as a thermal polymerization initiator, a surfactant, a development accelerator, a thermal polymerization inhibitor, a filler, a dispersant, an ultraviolet absorber, and an anti-aggregation agent are included as necessary. Additives can be included.

<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.

3-40 mass% is suitable for the fluorine content of the fluorine-type surfactant in a coloring photosensitive composition, More preferably, it is 5-30 mass%, Especially preferably, it is 7-25 mass%.
When the fluorine content is within the above range, it is more 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 Co., Ltd.)), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (Co) polymer 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 octyl phenyl ether , Polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (for example, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904 , 150R1 (manufactured by BASF)) and the like; and anionic surfactants such as W004, W005 and W017 (manufactured by Yusho Co., Ltd.).

  The addition amount of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass with respect to the total mass of the pigment dispersion composition or the colored photosensitive composition. is there.

<Alkoxysilane compound>
In the photosensitive resin composition used in the present invention, an alkoxysilane compound, particularly a silane coupling agent, can be used from the viewpoint of improving adhesion to the substrate.
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material, and (meth) acryloyl or phenyl that exhibits affinity by interacting or forming a bond with an organic resin. , Mercapto, epoxy, and aminosilane are preferable, and (meth) acryloylpropyltrimethoxysilane is more preferable among them. Examples of such materials include KBM-303, KBM-402, KBM-403, KBM-502, KBM-503, KBM-802, KBM-803, and KBM-903 (manufactured by Shin-Etsu Chemical Co., Ltd.). Can do.
The addition amount in the case of using a silane coupling agent is preferably in the range of 0.2% by mass to 5.0% by mass in the total solid content in the photosensitive resin composition used in the present invention. More preferably, it is 5 mass%-3.0 mass%.

<Development accelerator>
Further, when the alkali solubility of the uncured part is promoted and the developability of the colored photosensitive composition is further improved, the colored photosensitive composition contains an organic carboxylic acid, preferably a low molecular weight organic compound having a molecular weight of 1000 or less. Carboxylic acid can be added. 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 colored photosensitive composition includes EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperseide 6, polymer dispersants such as Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Various Solsperse dispersants (manufactured by Nippon Lubrizol Co., Ltd.) may be added.

<Other additives>
As other additives, fillers such as glass and alumina; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka) and Ionette S-20 (manufactured by Sanyo Chemical); 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone And an anti-aggregation agent such as sodium polyacrylate.

  The colored photosensitive composition of the present invention comprises (A) a solution or dispersion containing a pigment having a phthalocyanine skeleton, (C) at least one selected from the group consisting of a polymerizable monomer and a binder resin, and (D) photopolymerization. An initiator and (E) an oxidant having the structure of the general formula (1) are contained together with the solvent (B), and prepared by mixing other additives such as a surfactant as necessary. it can.

  The colored photosensitive composition of the present invention can be suitably used for forming a colored pattern of a color filter included in a liquid crystal display device or a solid-state imaging device, and can also be used for photosensitive ink and the like.

[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 colored photosensitive composition of the present invention described above. A photosensitive film is formed by applying the colored photosensitive composition of the present invention directly or through another layer (preferably, coating by a spin coating, slit coating, cast coating, roll coating or the like). The formed photosensitive film is exposed through a predetermined mask pattern, and after exposure, the uncured portion is developed and removed with a developing solution to develop a colored pattern (for example, colored) of each color (for example, three or four colors). By forming the pixel), a color filter can be most preferably manufactured.
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 particularly preferably ultraviolet rays such as g-line, h-line, i-line, and j-line.

  In addition to a general proximity exposure method, an exposure method using a laser light source can also be suitably used. 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 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 matches the photosensitive wavelength of the resist. It is preferable in that it does.

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 (buoy technology), and DF2200G (Dainippon Screen). Manufactured by Hitachi High-Technologies Corporation, etc. 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 an organic solvent, what was enumerated as the above-mentioned solvent which can be used when preparing the colored photosensitive composition of this invention is mentioned.

Examples of alkaline aqueous solutions include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Concentration of an alkaline compound such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001 to 10% by mass, preferably 0.01 to 1 An alkaline aqueous solution dissolved so as to be in 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 μm to 5.0 μm, preferably 0.5 μm to 3.5 μm, Most desirably, the thickness is 1.0 μm 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.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.

  The color filter of the present invention can also be used for a bright and high-definition COA (Color-filter On Array) system. 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 color filter of the present invention is considered to enhance the transparency of the ultraviolet light laser that is the exposure light by selecting the hue and film thickness of the pixels defined by the present invention in addition to the exposure method using the ultraviolet light laser. As a result, the curability of the colored pixel is improved, and a pixel free from chipping, peeling, or twisting can be formed. Therefore, the resistance to the peeling liquid of the colored layer provided directly or indirectly on the TFT substrate is improved. Useful for liquid crystal display devices. 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 by the COA method has a rectangular shape with a side length of about 1 to 15 μm in order to connect the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conduction path such as a through-hole or a U-shaped depression, and the dimension of the conduction path (that is, the length of one side) is particularly preferably 5 μm or less. It is also possible to form a conduction path of 5 μm or less.
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 issue, 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 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.
The average primary particle size measured with a transmission electron microscope (JEM-2010, manufactured by JEOL Ltd.) was 0.065 μm.

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

-Preparation of phthalocyanine pigment dispersion-
In the high-speed disperser “TSC-6H” manufactured by Igarashi Machine Manufacturing Co., Ltd. charged with zirconia beads having a diameter of 0.5 mm, 14.9 parts of the partially brominated zinc phthalocyanine pigment (referred to as PG58) obtained above, Big Chemie Preparation of 7.2 parts of acrylic dispersant “BYK-2001” and 78 parts of PGMEA, and stirring for 8 hours at 2000 rpm to prepare a dispersion of partially brominated zinc halide phthalocyanine pigment (PG58) did.

-Preparation of pigment dispersion containing yellow pigment PY150-
As a pigment, C.I. I. 40 parts (average particle diameter 60 nm) of Pigment Yellow 150 (PY150), 223 parts (22.3 parts in terms of solid content) of a PGMEA 10% by mass solution of the resin (J-1), and a bead mill (zirconia beads 0. 3 mm) to mix and disperse for 3 hours to prepare a pigment dispersion containing yellow pigment PY150.

-Preparation of pigment dispersion containing yellow pigment PY138-
As a pigment, C.I. I. Pigment Yellow 138 (PY138) 40 parts (average particle size 60 nm), PGMEA 10 mass% solution of the resin (J-1) 223 parts (22.3 parts in terms of solid content) mixed solution, beads mill (zirconia beads 0.3 mm ) For 3 hours to prepare a pigment dispersion containing yellow pigment PY138.

-Preparation of pigment dispersion containing green pigment PG36-
As a pigment, C.I. I. Pigment Green 36 (PG36) 40 parts (average particle size 60 nm), resin (J-1) PGMEA 10 wt% solution 200 parts (solid content 20 parts) mixed liquid, beads mill (zirconia beads 0.3 mm) Was mixed and dispersed for 3 hours to prepare a pigment dispersion containing green pigment PG36.
With respect to the obtained dispersion, the average primary particle diameter of the pigment was measured using a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and was 25 nm.

-Preparation of pigment dispersion containing blue pigment PG15: 6-
As a pigment, C.I. I. Pigment Blue 15: 6 (PG15: 6) 40 parts (average particle diameter 60 nm), PGMEA 10 mass% solution of the resin (J-1) 223 parts (solids equivalent 22.3 parts) mixed solution was mixed with beads mill (zirconia). A pigment dispersion containing blue pigment PG15: 6 was prepared by mixing and dispersing for 3 hours using beads 0.3 mm).

-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 1 Subsequently, Compound 1 is synthesized according to the following scheme using Compound B.
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 1 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 1: 36.6 parts of pigment dispersion containing green pigment PG58-Pigment dispersion 2: 12.6 parts of pigment dispersion containing yellow pigment PY150-25.8 parts of solvent (PGMEA)-Solvent (EEP: 3-Ethoxyethylpropionate) 16.7 parts Binder resin (allyl methacrylate-methacrylic acid (copolymerization molar ratio = 8: 2) copolymer, weight average molecular weight 30000) 1.37 parts Aronix M-510 ( Toa Gosei Co., Ltd.) 3.77 parts Photopolymerization initiator: Compound 1 0.94 parts Oxidizing agent: azoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd., listed above as structural formula (A))
1.80 parts ・ Polymerization inhibitor (p-methoxyphenol) 0.0024 parts ・ Surfactant (Fluorine-based surfactant, manufactured by DIC Corporation): Product name MegaFuck F781 0.033 parts ・ Silane coupling Agent (3-methacryloyloxy-trimethoxysilylpropane)
0.32 parts

<Colored pattern formation using colored photosensitive composition>
Using the colored photosensitive composition obtained as described above, a colored pattern was formed on a glass substrate as follows.

-Formation of colored photosensitive composition layer-
The obtained colored photosensitive composition was 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-Tech, LE5565A).

-Development process, baking (post-baking) process-
Thereafter, using a developing device (manufactured by Hitachi High-Technologies Corporation), 1.0% developer (CDK-1 by 1 part by mass) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) The solution was developed with 99 parts by mass of pure water (25 ° C.) at a shower pressure of 0.2 MPa for 60 seconds and washed with pure water.
After sufficiently drying, it was post-baked in an oven at 230 ° C. for 40 minutes.

(Examples 2 to 13, Comparative Examples 1 to 6)
In composition 1 of Example 1, the type of pigment dispersion, the type of oxidizing agent, and the amount added were changed as described in Table 1, and other than that, Examples 2 to 13, And each coloring photosensitive composition of Comparative Examples 1-6 was prepared. Further, a colored pattern was prepared in the same manner as in Example 1 except that the exposure method in the exposure step was changed as described in Table 1 using each of the obtained colored photosensitive compositions.

  The details of the exposure method described as proxy in Table 1 are the exposure method (proximity exposure) applied in the exposure step in Example 1. In Table 1, the details of the exposure method denoted as laser are as follows.

-Exposure process (laser exposure)-
After pre-baking, EGIS (buoy technology, 3rd harmonic wavelength of YAG laser, wavelength 355 nm, pulse width 6 nsec) is used as a laser exposure device, and about 1 mJ / cm ² with respect to the surface of the colored photosensitive resin composition layer. Pulse irradiation was performed 20 times through a photomask.

  Details of the compound (b) and the compound (c) shown in Table 1 are as follows.

<Evaluation>
About each obtained coloring pattern, each item of linearity, a shape, a chip, solvent resistance, and a chromaticity change was evaluated. Evaluation methods and evaluation criteria are shown below.

1. Evaluation of linearity of coloring pattern
The color pattern linearity is evaluated with an optical microscope at 200 times reflection, and the edge portion of the color pattern is photographed, the pixel edge portion is observed in a 5 cm × 5 cm photograph, and evaluated according to the following criteria. did.
-Evaluation criteria-
○: The edge portion of the coloring pattern looks linear Δ: A part of the coloring pattern (not more than 1/4 of the entire length) is jagged,
X: The edge part of the coloring pattern is jagged over 1/4 of the entire length

The edge portion of the coloring pattern is preferably straight.
That is, when the edge portion of the colored pattern becomes jagged due to a residual film, undercut, or the like, when the colored pattern (pixel pattern) of the color filter is formed by the colored photosensitive composition of the present invention, It is necessary to increase the overlap of the black matrix, which widens the width of the black matrix and lowers the aperture ratio. In addition, when the overlap with the black matrix is not large, there is a possibility that a portion that does not have a coloring pattern and is white is formed near the edge of the black matrix. Furthermore, when the edge portion of the colored pattern is jagged, there may be practical problems such as the transparent electrode formed thereon being disconnected and the resistance value being increased.

2. Colored pattern shape, brightness and evaluation of the color The colored pattern shape and the color of the color filter obtained above were photographed with an optical microscope at a reflection of 200 times and the shape and the color of the edge of the colored pattern. Evaluation was made according to the following criteria.
Here, regarding the chip, (A) a shape in which the edge portion disappears in a half-moon shape, and (B) there are cases where it is elongated longer than (A), but the line width becomes discontinuous and narrower than the surroundings and is missing. It was assumed that any one of the recognized shapes was observed. In this evaluation, if even one chip was seen, it was determined that there was a chip.
When chipping occurs, the portion is white and light is lost, which is not preferable for practical use.
The luminance was measured by OSP-SP100: Olympus Corporation.

-Evaluation criteria-
○: (2-1) The shape of the colored pattern is a forward taper or a rectangle, (2-2) there is no chipping, and (2-3) the brightness is high ×: (2-1) to (2-2) above ) Items that do not correspond to at least one item

3. 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 abbreviated 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 is 3 or more, various solvent resistances used for panel processing are insufficient in the production of liquid crystal display devices and the like, which is a practical problem.
Furthermore, the change of the shape with 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-
◯: (3-1) ΔE * ab is 3.0 or less, and (3-2) No change in the shape of the colored pattern ×: The above (3-1) and (3-2) Items that do not correspond to at least one item

4). Evaluation of chromaticity change Evaluation of chromaticity change of each colored pattern should be based on the following evaluation criteria based on the chromaticity change (ΔE * ab) results obtained in heat resistance evaluation and light resistance evaluation. It went by.
-Evaluation criteria-
○: ΔE * ab is 3.0 or less in both of the following heat resistance evaluation and light resistance evaluation ×: In at least one of the following heat resistance evaluation and light resistance evaluation, ΔE * ab is 3. More than 0

4). -(1) Heat resistance evaluation It heated at 230 degreeC for 30 minutes in the convection oven further with respect to the glass substrate which has a coloring pattern after performing post-baking similarly to "3. Evaluation of solvent resistance". The chromaticity of the obtained substrate was measured with OSP-SP100 (manufactured by Olympus Corporation), and ΔE * ab was determined from the chromaticity of the colored pattern before and after heating.
In this evaluation, those having ΔE * ab of 3.0 or less were evaluated as having excellent heat resistance.

4). -(2) Light resistance evaluation ITO sputtering was performed on the glass substrate which has a coloring pattern after performing post-baking similarly to "3. Evaluation of solvent resistance" under the conditions shown in Table 2 below. .
The substrate after ITO sputtering was put into a xenon weather meter “Sx-75”: Suga Test Instruments Co., Ltd., and irradiated for 180 W for 60 hours under conditions of a temperature of 30 ° C., a humidity of 50%, and a black panel temperature of 63 ° C. .
Thereafter, the chromaticity of the substrate was measured with OSP-SP100 (manufactured by Olympus Corporation), and ΔE * ab was determined from the chromaticity of the colored pattern before and after irradiation.
In this evaluation, those having ΔE * ab of 3.0 or less were evaluated as having excellent light resistance.

5. Comprehensive evaluation Based on each evaluation result of said 1-4, comprehensive evaluation was performed by the following references | standards.
○: Each of the evaluation results 1 to 4 is ○ or Δ. ×: Any one of the evaluation results 1 to 4 is ×.

  The above evaluation results are shown in Table 3 below.

As shown in Table 3, each colored pattern (colored film) obtained by using the colored photosensitive composition of the example has excellent linearity, good shape, no chipping, and chromaticity change. The suppression (light resistance and heat resistance) and solvent resistance were also good. On the other hand, each colored pattern obtained using the colored photosensitive compositions of Comparative Examples 1-3, 5, and 6 was inferior in chromaticity change suppression (light resistance and heat resistance).
If the decomposition temperature of the oxidant is lower than in Comparative Examples 3 and 4, it may not be possible to achieve both suppression of chromaticity change and linearity, shape and solvent resistance of the coloring pattern regardless of the amount of addition. Recognize.

  Further, according to the comparison between Example 2 and Example 1, the same good results were obtained in any of the examples, and this is also the case where pattern exposure by a laser exposure machine is applied. It turns out that the outstanding effect of this invention is acquired similarly to the exposure with a mercury lamp.

Claims (9)

(A) a pigment having a phthalocyanine skeleton, (B) a solvent, (C) at least one selected from the group consisting of a polymerizable monomer and a binder resin, (D) a photopolymerization initiator, (E) A colored photosensitive composition comprising at least an oxidizing agent represented by formula (1).


[In General Formula (1), each of R ¹ and R ² independently represents a hydrogen atom, a halogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group, an aliphatic oxy group, an aromatic oxy group, or Represents a heterocyclic group, and R ¹ and R ² may be bonded to each other at a terminal to form a cyclic structure. ]   The content of the oxidizing agent represented by (E) general formula (1) is 0.1% by mass or more and 5.0% by mass or less in the total solid content of the colored photosensitive composition. Colored photosensitive composition.   The colored photosensitive composition according to claim 1 or 2, wherein the pigment (A) having a phthalocyanine skeleton contains a metal in its chemical structure.   The colored photosensitive composition according to any one of claims 1 to 3, wherein the pigment (A) having a phthalocyanine skeleton is a green pigment.   The pigment (A) having a phthalocyanine skeleton is C.I. I. Pigment green 7, C.I. I. Pigment green 36, and C.I. I. The colored photosensitive composition according to any one of claims 1 to 4, which is at least one selected from the group consisting of CI Pigment Green 58. The colored photosensitive composition according to any one of claims 1 to 5, wherein the oxidizing agent represented by the general formula (1) is an oxidizing agent represented by the following general formula (2). object.


[In General Formula (2), R ^{3 to} R ¹² are each independently a hydrogen atom, a halogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group, an aliphatic oxy group, an aromatic oxy group, or Represents a heterocyclic group, R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , and R ¹¹ And R ¹² may be bonded to each other to independently form a 5-membered ring, a 6-membered ring, or a 7-membered ring. ]   The color filter which has a coloring pattern which uses the coloring photosensitive composition of any one of Claims 1-6.   A photosensitive film forming step of forming a photosensitive film by applying the colored photosensitive composition according to any one of claims 1 to 6 directly or via another layer on a substrate, and formation And a colored pattern forming step of forming a colored pattern by sequentially performing pattern exposure and development on the photosensitive film formed.   A liquid crystal display device comprising the color filter according to claim 7.