JP5371507B2 - Colored photosensitive composition, color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive composition useful for colored pattern formation in a color filter for forming a colored pattern with excellent curability even at high pigment concentration, giving a high development latitude, and preventing pattern defects in development, to provide a color filter having good color properties such as high color purity and high contrast, and to provide a liquid crystal display device of a high-luminance clear image. <P>SOLUTION: The colored photosensitive composition includes a zinc halide phthalocyanine pigment (A), a yellow pigment (B), polymerizable compounds (C), a binder resin (D), and a photopolymerization initiator (E). The polymerizable compounds (C) includes a polymerizable compound (C-1) having two polymerizable groups in one molecule and a polymerizable compound (C-2) having 5-6 polymerizable groups in one molecule, while a content of the polymerizable compound (C-1) having two polymerizable groups in one molecule is 15-40 mass% based on the total amount of the polymerizable compounds. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a colored photosensitive composition, a color filter produced using the same, and a liquid crystal display device including the color filter.

  Color filters are indispensable components for liquid crystal displays. The liquid crystal display is compact compared to the CRT as a display device, and can save power, and has become more than equivalent in terms of performance due to technological advancement. Therefore, TV screens, personal computer screens, and other display devices It is being replaced by CRT.

In recent years, the development of liquid crystal displays has been expanded from the use of personal computers and monitors having a relatively small screen area to TV applications that require a large screen and high image quality.
In TV applications, higher image quality, that is, improvement in contrast and color purity is required compared to conventional monitor applications. In order to improve contrast, a finer particle size of a colorant (such as an organic pigment) used in a colored photosensitive composition used for forming a color filter is required. Moreover, the higher thing is calculated | required as content rate of the coloring agent (organic pigment) which occupies in solid content of this colored photosensitive composition for color purity improvement.

  In response to the above-mentioned requirements, the pigment dispersion composition in which the pigment having a finer particle diameter of the pigment is dispersed is further colored with an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other components. A photosensitive composition is used, and a color filter is obtained using the composition by a photolithography method or the like.

  If the pigment becomes finer and the pigment content becomes high, when an image pattern is formed by the photolithographic method, the pattern may be missing in the development process, the stability of the pattern size may be impaired, or a residue may be generated during development. Or the curability is inferior, and there has been a problem that a large amount of exposure is required. For TV applications, it is particularly required to provide a color filter at a low cost. However, the above-described problems centered on the development process have been required to be improved because the yield is lowered and the productivity is deteriorated.

In order to solve the above problems, many attempts have been made to improve the sensitivity by improving the photopolymerization initiator used in the colored photosensitive composition for a color filter (see, for example, Patent Documents 1 and 2). Attempts to improve sensitivity by improving photopolymerizable monomers have also been proposed (see Patent Document 3). Furthermore, by defining the average double bond equivalent in the organic compound formed by adding the binder resin and polymerizable monomer in the colored photosensitive composition, and by specifying the molecular weight of the binder resin, a forward taper shape is formed by firing. The technique to do is disclosed (refer patent document 4).
However, these techniques are inferior in productivity in the exposure process and the development process and cannot secure sufficient productivity.

  On the other hand, in order to improve the color characteristics of the color filter, C.I. I. When using a copper halide phthalocyanine such as CI Pigment Green 36, it is necessary to increase the pigment concentration in the colored photosensitive composition. After forming a colored photosensitive layer containing the colored photosensitive composition on the substrate, exposure is performed. When developing and forming pixels, the latitude during development is narrow, and the pixel shape after development may be inversely tapered.

It has been proposed that a color filter with high brightness, high transmittance, and high color purity can be obtained using a green pigment other than a halogenated copper phthalocyanine (phthalocyanine having a central metal other than copper) (for example, a patent) Reference 5)), phthalocyanine having a central metal other than copper is poor in stability during dispersion and over time, so a large amount of binder is required at the time of dispersion, and the development latitude of the colored photosensitive composition is narrow, indicating Unevenness may occur in the device.
Non-patent document 1 details zinc halide phthalocyanine, which is a kind of phthalocyanine having a central metal other than copper.

JP-A-6-289611 Japanese Patent Laid-Open No. 9-80225 JP 2004-163917 A JP 2007-93811 A JP 2008-122478 A

DIC Technical Review, 10, 46 (2004)

This invention makes it a subject to achieve the following objectives.
That is, the object of the present invention is that when forming a colored pattern, even when the pigment concentration is high, the formed colored pattern is excellent in curability, has a large development latitude, and further, pattern chipping during development is suppressed. It is to obtain a colored photosensitive composition useful for forming a colored pattern of a color filter.
Furthermore, a further object of the present invention is to obtain a color filter having high color purity and high color characteristics by using the colored photosensitive composition, and further using this color filter. An object of the present invention is to obtain a liquid crystal display device with high brightness and clear images.

Means for solving the above problems are as follows.
<1> (A) a halogenated zinc phthalocyanine pigment, (B) a yellow pigment, (C) a polymerizable compound, (D) a binder resin, and (E) a photopolymerization initiator, includes a (C-1) a polymerizable compound having two polymerizable groups in one molecule, a polymerizable compound having 5 to 6 polymerizable groups in (C-2) 1 molecule, said (C -1) A polymerizable compound having two polymerizable groups in one molecule is composed of compounds represented by the following general formula (1), general formula (2), general formula (6) and general formula (7). The polymerizable compound selected from the group, and the content of the polymerizable compound (C-1) having two polymerizable groups in one molecule is (C-1) 2 polymerizable groups in one molecule. Colored photosensitivity ranging from 15% by weight to 40% by weight with respect to the total amount of the polymerizable compound having 1 and the polymerizable compound (C-2) having 5 to 6 polymerizable groups in one molecule. Sex composition.

In General Formula (1), Y ¹ and Y ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. p and q are integers of 1 to 20, and p + q is an integer of 2 to 30.

In General Formula (2), Y ¹ and Y ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A represents a linking group shown below. r and s are integers of 1 to 20, and r + s is an integer of 2 to 30.

In General Formula (6), Y ¹ and Y ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and B represents a linking group shown below. m is an integer of 1-3. When m is 2 or 3, the plurality of B contained therein may be the same as or different from each other.

In General Formula (7), Y ¹ and Y ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

<2> The colored photosensitive material according to <1>, wherein the polymerizable group of the polymerizable compound (C-2) having 5 to 6 polymerizable groups in one molecule is a (meth) acryloyl group or a vinyl ether group. Sex composition.
< 3 > The colored photosensitive composition according to <1> or < 2>, wherein the (A) halogenated zinc phthalocyanine pigment is a compound represented by the following general formula (a).

In the general formula (a), X ^{21 to} X ³⁶ each independently represent a hydrogen atom, a chlorine atom or a bromine atom. However, 8 or more of X ^{21 to} X ³⁶ are chlorine atoms or bromine atoms.

< 4 > The yellow pigment (B) is C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 138, C.I. I. The colored photosensitive composition according to any one of <1> to < 3 >, which is any pigment of Pigment Yellow 139.

< 5 > The colored photosensitive composition according to any one of <1> to < 4 >, wherein the (E) photopolymerization initiator is a compound represented by the following general formula (I).

In general formula (I), R ^{1 to} R ¹⁴ are each independently any one of a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a carboxyl group, an aromatic group, and an aliphatic group. However, the aromatic group and the aliphatic group may include a structure selected from a branched structure and an alicyclic structure, from an ether bond, an ester bond, an amino bond, an amide bond, a thioether bond, and an unsaturated bond. One or more selected may be present, and one or more selected from a hydroxyl group, an amino group, a carboxyl group, a halogen atom, and an aromatic group may be included at the terminal of the group.

< 6 > The colored photosensitive composition according to any one of <1> to < 5 >, further comprising (F) a compound having an epoxy ring.
< 7 > The colored photosensitive composition according to any one of <1> to < 6 >, which is for a color filter.

< 8 > A color filter having a colored pattern formed on the substrate using the colored photosensitive composition according to any one of <1> to < 7 >.
< 9 > A liquid crystal display device comprising the color filter according to < 8 >.

In the present invention, (C) as the polymerizable compound, (C-1) a polymerizable compound having two polymerizable groups in one molecule, and (C-2) 5 to 6 polymerizable groups in one molecule. And (C-1) a polymerizable compound having two polymerizable groups in one molecule is represented by the general formula (1), the general formula (2), the general formula (6) and the general formula The polymerizable compound selected from the group consisting of compounds represented by formula (7), and the content of the polymerizable compound (C-1) having two polymerizable groups in one molecule is (C- 1) 15% by mass relative to the total content of the polymerizable compound having two polymerizable groups in one molecule and (C-2) the polymerizable compound having 5 to 6 polymerizable groups in one molecule To 40% by mass, moderately bifunctional compounds are present in the polymerizable compound having 5 to 6 polymerizable groups, and are hardened by irradiation with ultraviolet rays or the like. When a film is formed, this cured film has moderate flexibility and excellent adhesion to the substrate. Therefore, in the development process, exposure is performed while maintaining the alkali developability of the colored photosensitive composition itself. It is presumed that only the cured film in the part is difficult to peel off and a wide development latitude is developed.
At this onset bright, (C-1) before following general formula (1), the general formula (2), the general formula (6) and the general formula (7) with a polymerizable selected from the group consisting of compounds represented By using the compound, since the permeability of the developer is suppressed by the cross-linked bisphenol skeleton and the like in the exposed portion, it is presumed that the effect is remarkable in combination with the adhesion to the substrate.
However, the effect of developing the wide development latitude of the present invention is seen with the halogenated zinc phthalocyanine pigment and is not seen with Pigment Green 36, but the reason is not clear.

According to the present invention, when a colored pattern is formed, a color filter having excellent curability of the formed colored pattern, a large development latitude, and suppressing pattern chipping during development even at a high pigment concentration. A colored photosensitive composition useful for forming a colored pattern can be obtained.
In addition, by using the colored photosensitive composition, a color filter having high color purity and high contrast and good color characteristics can be obtained, and further, using this color filter, a liquid crystal of a clear image with high luminance can be obtained. A display device can be obtained.

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

<Colored photosensitive composition>
The colored photosensitive composition of the present invention comprises at least (A) a zinc halide phthalocyanine pigment, (B) a yellow pigment, (C) a polymerizable compound, (D) a binder resin, and (E) a photopolymerization initiator, The polymerizable compound (C) has (C-1) a polymerizable compound having two polymerizable groups in one molecule and (C-2) a polymerizable compound having 5 to 6 polymerizable groups in one molecule. And (C-1) a polymerizable compound having two polymerizable groups in one molecule is represented by the general formula (1), the general formula (2), the general formula (6), and the general formula (7). ) And a content of the polymerizable compound having two polymerizable groups in one molecule (C-1) is (C-1) 1. 15% by mass relative to the total amount of the polymerizable compound having two polymerizable groups in the molecule and the polymerizable compound (C-2) having 5 to 6 polymerizable groups in one molecule? A colored photosensitive composition in the range of 40 wt%.
Hereinafter, each component which comprises the colored photosensitive composition of this invention is explained in full detail.

<(A) Halogenated zinc phthalocyanine pigment>
Generally, since the halogenated zinc phthalocyanine pigment has 16 hydrogen atoms in the phthalocyanine ring, up to 16 of these hydrogen atoms can be substituted with bromine atoms and / or chlorine atoms. These halogen atoms may all be the same or different. When the number of substituents is constant, green becomes darker in the order of bromine atom> chlorine atom. When these hydrogen atoms are substituted with bromine atoms, for example, chlorine atoms, the number of bromine atoms is 0 to 16, the number of chlorine atoms is 0 to 16, and the number of hydrogen atoms is 0 to 16, in theory. A total of 136 types of substitution products can be produced. However, at this time, at least one of the 16 is a halogen atom. The number of halogen atom substitutions is preferably 8 or more and 16 or less, more preferably 12 or more and 16 or less, from the viewpoint of obtaining a green color with high luminance.

In the present invention, the (A) halogenated zinc phthalocyanine pigment is a general term for zinc halide phthalosinine represented by the following general formula (a), and X ^{21 to} X ³⁶ are each independently a hydrogen atom, chlorine atom, or bromine. It is an atom, and at least one of these represents a pigment that is a chlorine atom or a bromine atom.
In the present invention, zinc halide phthalocyanine in which at least 8 or more of X ^{21 to} X ^{36 in} the general formula (a) are chlorine atoms or bromine atoms is preferable.

In the general formula (a), X ^{21 to} X ³⁶ each independently represent a hydrogen atom, a chlorine atom, or a bromine atom, and at least one of these is a chlorine atom or a bromine atom.

In the above-described zinc halide phthalocyanine, when eight or more of X ^{21 to} X ³⁶ are substituted with bromine atoms, yellowish, bright green color is exhibited, and the color filter is used for the green pixel portion pattern. Is optimal. In the present invention, zinc phthalocyanine substituted with 8 or more bromine atoms is most preferred. The number of bromine atoms substituted is more preferably 10-14.

  The average composition of the halogenated zinc phthalocyanine pigment can be easily determined from mass spectrometry based on mass spectroscopy and halogen content analysis by flask combustion ion chromatography.

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

  In the present invention, the average primary particle diameter is obtained by photographing particles in a field of view with a transmission electron microscope and measuring 100 primary particles of a zinc halide phthalocyanine pigment constituting an aggregate on a two-dimensional image. The weighted arithmetic mean values of the longer diameter (major axis) and the shorter diameter (minor axis) are obtained and averaged.

  In obtaining a halogenated zinc phthalocyanine pigment having an average primary particle size in the range of 10 nm to 40 nm, it may be finely divided by any method, but crystal growth can be easily suppressed and comparison of average primary particle sizes is possible. It is preferable to employ a solvent salt milling treatment in that small pigment particles can be obtained.

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

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

  In obtaining a halogenated zinc phthalocyanine pigment having an average primary particle diameter in the range of 10 nm to 40 nm, it is preferable to increase the ratio of the amount of inorganic salt used to the amount of zinc halide phthalocyanine pigment used in solvent salt milling. That is, the amount of the inorganic salt used is preferably 5 to 20 parts, more preferably 7 to 15 parts, based on 1 part of the zinc halide phthalocyanine pigment in terms of mass.

  As the organic solvent, an organic solvent capable of suppressing crystal growth is preferably used, and as such an organic solvent, a water-soluble organic solvent can be suitably used. For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene Glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene group Call, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, can be used dipropylene glycol.

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

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

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

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

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

  Thus, a powder of a halogenated zinc phthalocyanine pigment is obtained. The (A) halogenated zinc phthalocyanine pigment used in the present invention has weaker primary particle agglomeration force than conventional copper halide phthalocyanine pigments, and has a property that is easier to unravel. Therefore, the colored photosensitive composition of the present invention has a high contrast.

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

  The zinc halide phthalocyanine pigment of the present invention having an average primary particle size in the range of 10 nm to 40 nm can be obtained, for example, by the above-described method, but can also be purchased from DIC Corporation.

<(B) Yellow pigment>

In the colored photosensitive composition of the present invention, (A) a halogenated zinc phthalocyanine pigment is used with (B) a yellow pigment to adjust the hue of the colored photosensitive composition and increase the transmittance. A conventionally known yellow pigment can be used as such a yellow pigment.
Examples of yellow pigments include disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments, benzimidazolone yellow pigments, nickel azo yellow pigments, diketopyrrolopyrrole orange pigments, Orange pigments such as perinone-based orange pigments can also be used if necessary.

As a specific example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 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 CI Pigment Yellow 139 because of its high transmittance and high contrast.

The average primary particle diameter of these pigments is preferably in the range of 10 nm to 40 nm because of high transmittance and high contrast. More preferably, it is the range of 10 nm-30 nm. To make the average primary particle size small and fine, the salt milling method is effective like the zinc halide phthalocyanine, and may be salt milled together with the zinc halide phthalocyanine pigment or separately. Also good.
The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating a weighted arithmetic average value.

The use ratio of (A) the halogenated zinc phthalocyanine pigment and (B) the yellow pigment is preferably 10 to 200 parts by weight of the yellow pigment with respect to 100 parts of the halogenated zinc phthalocyanine pigment in terms of mass. More preferably, it is 20-100 parts.
If the said mass ratio is this range, the light transmittance will be large and color purity can be made high.

  In the colored photosensitive composition of the present invention, the total amount of the pigment containing the halogenated zinc phthalocyanine pigment is 5 to 60% in terms of mass with respect to the total amount excluding the solvent in the colored photosensitive composition of the present invention. Is more preferable, 10 to 50% is more preferable, and optimally 15 to 45%. By using the addition amount in this range, a color filter having excellent color characteristics, high contrast, and high luminance can be obtained.

<Pigment dispersion composition>
In preparation of the colored photosensitive composition of the present invention, it is preferable that (A) a zinc halide phthalocyanine pigment and (B) a yellow pigment are dispersed together or separately in advance to prepare a pigment dispersion composition. is there.
The pigment dispersion composition disperses the pigment and the solvent. At this time, a dispersant, a resin, and the like are added as necessary. Furthermore, it can comprise using another component as needed, such as a pigment derivative.

-Preparation of pigment dispersion composition-
The preparation mode of the pigment dispersion composition of the present invention is not particularly limited. For example, the pigment, the pigment dispersant, and the solvent are mixed using 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 performing bead dispersion, knead and disperse using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder while applying strong shearing force. It is also possible to perform processing.

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

-Pigment concentration-
As content in the pigment dispersion composition of a pigment, 10-60 mass% is preferable 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 contains at least one dispersant. By containing this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yusho Co., Ltd.) Anionic surfactants such as 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. Disperse aid 9100 (all manufactured by San Nopco) and other polymer dispersants; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L12 , P-123 (manufactured by Asahi Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by Big Chemie Co., Ltd.). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

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

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

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of 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 mass of a pigment, and 3-20 mass% is more preferable. When the content is within the above range, the dispersion can be favorably performed while the viscosity is kept low, the dispersion stability after dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

  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-
Examples of the solvent in the pigment dispersion composition 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, Mention may be made of solvents such as methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene and xylene.

  The content of the solvent in the pigment dispersion composition is appropriately selected according to the use of the pigment dispersion composition. When the pigment dispersion composition is used for the preparation of a colored photosensitive composition to be described later, from the viewpoint of handleability, it should be contained so that the solid content concentration including the pigment and the pigment dispersant is 5 to 50% by mass. Can do.

<Colored photosensitive composition>
The colored photosensitive composition of the present invention comprises (A) a halogenated zinc phthalocyanine pigment, (B) a yellow pigment, (C) a polymerizable compound, (D) a binder resin, and (E) a photopolymerization initiator, (C) The polymerizable compound is (C-1) a polymerizable compound having two polymerizable groups in one molecule, and (C-2) a polymerizable compound having 5 to 6 polymerizable groups in one molecule. Including. The (C-1) polymerizable compound having two polymerizable groups in one molecule is a compound represented by general formula (1), general formula (2), general formula (6), or general formula (7). A polymerizable compound selected from the group consisting of:

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

<(C-1) polymerizable compound selected from the group consisting of compounds represented by general formula (1), general formula (2), general formula (6) and general formula (7) >
Hereinafter, in this specification, (C-1) a polymerizable compound selected from the group consisting of compounds represented by general formula (1), general formula (2), general formula (6) and general formula (7) is provided. As appropriate, (C-1) is referred to as a polymerizable compound having two polymerizable groups in one molecule.
(C-1) The polymerizable compound having two polymerizable groups in one molecule is preferably a compound containing two (meth) acryloyl groups or vinyl ether groups in the same molecule as the polymerizable group.
In the present specification, the acryloyl group and the methacryloyl group are collectively referred to as a (meth) acryloyl group. In addition, acrylate and methacrylate are collectively referred to as (meth) acrylate.

  Specific examples of the compound having two (meth) acryloyl groups in the same molecule include 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-diacryloxyp Bread, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, bis (acryloyloxyethyl) ether of bisphenol A, bisphenol (Meth) acrylic acid modified product of type A epoxy resin, 3-methylpentanediol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dimethylol-tricyclodecane di (meth) acrylate, etc. , Preferably dimethylol-tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, (meth) acrylic acid modified product of bisphenol A type epoxy resin, and the like. . Specific examples of the compound having two (meth) acryloyl groups in the same molecule include the compounds described below.

  Specific examples of the compound having two vinyl ether groups in the same molecule include 1,3-cyclohexyldiol divinyl ether, neopentyl glycol divinyl ether, bisphenol A type divinyl ether, and the like.

Among these, a (meth) acrylate monomer having two (meth) acryloyl groups in the same molecule is preferable from the viewpoint of suitably maintaining solvent resistance and ITO sputtering suitability in the subsequent step.
Of these compounds, (C-1) (meth) acrylate monomers that are more preferred as polymerizable compounds having two polymerizable groups in one molecule are the following general formulas (4) and (5). .

In General Formula (4) and General Formula (5), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents a hydrogen atom, a methyl group, or an ethyl group. X ^{1 to} X ⁴ each independently represents a hydrogen atom, a methyl group, a phenyl group, or a halogen atom, and Y represents —C (CH ₃ ) ₂ —, —CH ₂ —, —S—, —SO ₂ —. Or a group represented by the following structural formulas (3) and (8). a, b, c, and d each independently represents an integer of 0 to 20;

In the compound represented by the general formula (4) or the general formula (5), from the viewpoints of sensitivity and developability, R ²¹ is a hydrogen atom, R ²² is a hydrogen atom, X ^{1 to} X ⁴ are hydrogen atoms, Y Is —C (CH ₃ ) ₂ —, —CH ₂ —, or —S—, and a, b, c, and d are preferably integers of 0 to 10. Further, R ²¹ is a hydrogen atom, R ²² is a hydrogen atom, X ^{1 to} X ⁴ are hydrogen atoms, Y is —C (CH ₃ ) ₂ —, a, b, c, and d are integers of 0 to 5. Is more preferable.

  The compounds represented by the general formula (4) and the general formula (5) can be produced by a known method. Moreover, as a compound marketed, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30, A-B1206PE, A-BPEF A-BPFL-16E (manufactured by Shin-Nakamura Chemical Co., Ltd.), M-208, BAEPS (manufactured by Toagosei Chemical Co., Ltd.), HBPE-4 (manufactured by Daiichi Chemical Pharmaceutical Co., Ltd.), and the like.

For example, the commercial product ABE-300 is a diacrylate represented by the above formula (4), in which R ²¹ : hydrogen atom, R ²² : hydrogen atom, X ^{1 to} X ⁴ : hydrogen atom, Y: −. C (CH ₃ ) ₂ −, a = 0, d = 0, b + c = 3. The structural formula of the commercial product ABE-300 is shown below.

  As the polymerizable compound having two polymerizable groups in one molecule (C-1) in the present invention, a compound represented by the following general formula (1), a compound represented by the general formula (2), The compound represented by the general formula (6) and the compound represented by the general formula (7) can obtain a wide development latitude, and when used as a color filter, the solvent resistance and the ITO sputtering suitability are suitably maintained. Particularly preferred from the viewpoint. Particularly preferred are compounds represented by general formula (1) and general formula (2).

In General Formula (1), Y ¹ and Y ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More specifically, Y ¹ and Y ² each independently represent a hydrogen atom, a methyl group, or an ethyl group, and are preferably a hydrogen atom or a methyl group from the viewpoint of increasing sensitivity.
p and q are integers of 1 to 20, and p + q is an integer of 2 to 30. The range of p + q from 10 to 30 is preferable from the viewpoint of developability, and the range of 15 to 25 is most preferable.
Such a compound is also available as a commercial product, for example, Shin Nakamura Chemical Co., Ltd. NK ester A-BPE-4, A-BPE-10, A-BPE-20, A-BPE-30. . A-BPE-20 is preferable from the viewpoint of development latitude, which is the subject of the present invention, and A-BPE-4 is preferable from the viewpoint of tapering the shape of the pixel end after post-baking.

In General Formula (2), Y ¹ and Y ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. r and s are integers of 1 to 20, and r + s is an integer of 2 to 30. A represents a linking group shown below.

Y ¹ and Y ² are preferably a hydrogen atom or a methyl group from the viewpoint of sensitivity. From the viewpoint of developability, A is a skeleton obtained by removing OH groups at both ends from bisphenol F or bisphenol S. Preferably, r and s are preferably integers of 1 to 5, and (r + s) is preferably in the range of 5 to 20.
Specific compounds include the following compounds.

In General Formula (6), Y ¹ and Y ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. B represents a linking group shown below, and m is an integer of 1 to 3. When m is 2 or 3, the plurality of B contained therein may be the same as or different from each other.

Y ¹ and Y ² are preferably a hydrogen atom or a methyl group from the viewpoint of sensitivity. From the viewpoint of developability, A is obtained by removing OH groups at both ends from bisphenol A, bisphenol F, or bisphenol S. It is preferably a skeleton, and m is preferably an integer of 1 or 2.
Specific compounds include the following compounds.

In General Formula (7), Y ¹ and Y ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Y ¹ and Y ² are preferably a hydrogen atom or a methyl group from the viewpoint of sensitivity.
Specific compounds include the following compounds.

<(C-2) Polymerizable compound having 5 to 6 polymerizable groups in one molecule>
(C-2) As the polymerizable compound having 5 to 6 polymerizable groups in one molecule, (meth) acrylate having 5 to 6 (meth) acryloyl groups in the same molecule is preferably used. . Examples of the (meth) acrylate having 5 to 6 (meth) acryloyl groups in the same molecule include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol penta (meth) acrylate, and sorbitol hexa Urethane acrylates such as (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, captolactone-modified dipentaerythritol hexa (meth) acrylate, UA-306H, UA-306T, UA-306I manufactured by Kyoeisha Chemical Co., Ltd. Preferably, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are mentioned. Among these, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are preferable from the viewpoint of solvent resistance and suitability for ITO sputtering, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio in terms of mass) Is most preferably a mixture of dipentaerythritol pentaacrylate: dipentaerythritol hexaacrylate = 2-4: 8-6) from the viewpoint of solvent resistance and suitability for ITO sputtering.

The content of the polymerizable compound having two polymerizable groups in one molecule (C-1) in the colored photosensitive composition is 1 to 1 when the solid content of the colored photosensitive composition is 100 parts by mass. A range of 40 parts by weight is preferable because pattern development is less likely to occur during development, and developability is good. Moreover, the range of 1-20 mass parts is further more preferable.
(C-2) The content of the polymerizable compound having 5 to 6 polymerizable groups in one molecule in the colored photosensitive composition is, when the solid content of the colored photosensitive composition is 100 parts by mass, A range of 10 to 60 parts by mass is preferable because pattern blurring hardly occurs during development and developability is good. Moreover, the range of 15-50 mass parts is further more preferable.

  The content of the polymerizable compound (C-1) having two polymerizable groups in one molecule is as follows: (C-1) the polymerizable compound having two polymerizable groups in one molecule and (C-2) ) When the total mass of the polymerizable compound having 5 to 6 polymerizable groups in one molecule is 100% by mass, it needs to be in the range of 15% by mass to 40% by mass. That is, by including the predetermined amount of the bifunctional compound with respect to the 5-6 functional polymerizable compound, both curability, flexibility of the formed film, and adhesion to the substrate are compatible. By setting the content ratio of the bifunctional compound in the range of 20% by mass to 30% by mass, the development latitude is further improved, which is preferable.

Furthermore, in the colored photosensitive composition of the present invention, (C) as a polymerizable compound, (C-1) a polymerizable compound having two polymerizable groups in one molecule and (C-2) polymerized in one molecule. Polymerizable compounds other than the polymerizable compound having 5 to 6 functional groups can also be used as long as the effects of the present invention are not impaired.
Examples of these polymerizable compounds include the following compounds.

  Compound having one polymerizable group in one molecule: hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) ) Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate , 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (meth) ) Acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) Acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H perfluorodecyl (meth) acrylate, 4-butylphenyl ( (Meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate Glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyalkyl (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, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate Rate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, Oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2 -Methacryloyloxytyl succinic acid, 2-methacryloyloxy Hexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (Meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified cresol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, PO-modified nonylphenol (meth) acrylate, EO-modified-2-ethylhexyl (meth) acrylate, etc. Can be mentioned. Dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate,

  Compounds having three polymerizable groups in one molecule: for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (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 tri (meth) acrylate propionate, tri ((Meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) a Relate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin triacrylate,

Compound having 4 polymerizable groups in one molecule: for example, pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, Ethoxylated pentaerythritol tetra (meth) acrylate and the like can also be used.
The content of these other polymerizable compounds is preferably about 0 to 20 mass percent with respect to the content of all polymerizable compounds contained in the colored photosensitive composition.

<(D) Binder resin>
The colored photosensitive composition of the present invention contains (D) a binder resin. As the binder resin, any polymer compound that is soluble in a solvent can be used. However, as a preferable binder resin, an alkali-soluble resin is preferable in view of alkali developability by a photolithography method.

Alkali-soluble resins can be contained in the stage of adjusting the pigment dispersion composition, and can be added separately in both the stage of adjusting the pigment dispersion composition and the stage of adjusting the colored photosensitive composition. It is.
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are 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 said linear organic high molecular polymer, the polymer which has carboxylic acid in a 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.

  Of 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.

  As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable.

  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, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, and cyclohexyl acrylate.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl (meth) acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl (meth) acrylate, polystyrene macromonomer, and polymethyl methacrylate macro. Monomer, CH ₂ = CR ³¹ R ³² [wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. ^{_{], CH 2 = C (R 31}} ) (COOR 33) ^{[wherein, R 31} represents a hydrogen atom or an alkyl group of 1 to 5 carbon ^{atoms, R 33} is several alkyl group or C 1 to 8 carbon atoms 6 Represents -12 aralkyl groups. ], Etc. can be mentioned.

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

  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 of this composition, More preferably, it is 2-15 mass%, Especially preferably, it is 3-12 mass%.

<(E) Photopolymerization initiator>
The colored photosensitive composition of the present invention contains at least one photopolymerization initiator.
Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Isoactive halogen compounds, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in each specification such as US Pat. No. 4,318,791 and European Patent Publication No. EP88050A, benzophenones described in US Pat. No. 4,199,420 Aromatic ketone compounds such as thiols, (thio) xanthones or acridine compounds described in French Patent No. 2456541, compounds such as coumarins or lophine dimers described in JP-A-10-62986, JP-A Sulphonium organoboron described in JP-A-8-015521 Body, etc., etc. can be mentioned.

  Among them, as the photopolymerization initiator, acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, triazine series, halomethyloxadiazole series, acridine series, coumarin series, lophine dimers series, A biimidazole type is preferred.

Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and p-dimethylaminoacetophenone. Preferable examples include 4'-isopropyl-2-hydroxy-2-methyl-propiophenone.
Preferable examples of the ketal photopolymerization initiator include benzyldimethyl ketal and benzyl-β-methoxyethyl acetal.

  Examples of the benzophenone-based photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, 1-hydroxy- Cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone A preferred example is 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl. -S-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl -S-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl -2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s- Liazine, 4-Benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (Chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine and the like can be preferably exemplified.

Examples of the halomethyloxadiazole-based photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1, 3,4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3 Preferred examples include 1,4-oxodiazole.
Preferred examples of the acridine-based photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the coumarin-based photopolymerization initiator include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-(( Preferred examples include s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like. .

Examples of the lophine dimer-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. And 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like.
Preferable examples of the biimidazole-based photopolymerization initiator include 2-mercaptobenzimidazole and 2,2′-benzothiazolyl disulfide.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

As a photoinitiator which can be used for this invention, it is not limited to the above photoinitiator, Another well-known thing can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, the triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, And benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516.
Moreover, these photoinitiators can also be used together.

Among the photopolymerization initiators described above, compounds represented by the following general formula (I), 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, It is preferable to use at least one of 4 ′-(bisdiethylamino) benzophenone and a compound represented by E-1 below.
In particular, the use of the compound represented by the general formula (I) is most preferable from the viewpoint of forming a suitable pixel by suppressing surface roughness.

In general formula (I), R ^{1 to} R ¹⁴ are each independently any one of a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a carboxyl group, an aromatic group, and an aliphatic group. However, the aromatic group and the aliphatic group may include a structure selected from a branched structure and an alicyclic structure, from an ether bond, an ester bond, an amino bond, an amide bond, a thioether bond, and an unsaturated bond. One or more selected may be present, and one or more selected from a hydroxyl group, an amino group, a carboxyl group, a halogen atom, and an aromatic group may be included at the terminal of the group.

In general formula (I), by making one or two or more R ^{1 to} R ¹⁴ a halogen atom, the cleavage reactivity of the compound of general formula (I) can be increased, and the sensitivity is further improved. Can be made. Examples of the halogen atom include Br and Cl.

Moreover, the absorption spectrum of the compound of general formula (I) by making one or two or more R < ¹ > -R < ¹⁴ > into any of a hydroxyl group, an amino group, a carboxyl group, an aromatic group, or an aliphatic group. The absorption wavelength characteristics can be adjusted in accordance with the irradiation wavelength.
These aromatic groups or aliphatic groups may have a substituent, or may have a structure other than hydrocarbon in the middle of the group.

The aromatic group is preferably an aromatic group having 5 to 20 carbon atoms, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, or a group containing a heteroatom other than a hydrocarbon such as a pyridyl group. Also mentioned.
As an aliphatic group, a C1-C10 aliphatic group is preferable, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl. In addition to aliphatic hydrocarbon groups such as a group, an alkyl group such as an n-hexyl group, and an unsaturated hydrocarbon group such as an alkenyl group, groups containing hetero atoms other than hydrocarbons are also included.

  The photopolymerization initiator represented by the general formula (I) has high sensitivity, and by using this photopolymerization initiator, the sensitivity of the colored photosensitive composition is dramatically improved, so that the reaction proceeds efficiently, As a result, it can be sufficiently cured even with a smaller exposure amount than usual. In addition, by using this photopolymerization initiator, a pattern with extremely high line width stability against development can be formed, so that a highly productive color filter can be produced.

  Such an improvement in sensitivity and line width stability is particularly remarkable in exposure in the presence of oxygen. Since the photopolymerization initiator of the general formula (I) is less susceptible to reaction inhibition by oxygen, the polymerization reaction proceeds rapidly even in the presence of oxygen. Therefore, when forming a coating film using the colored photosensitive composition of the present invention, it is necessary to apply an oxygen blocking film on the coating film surface before exposure or to expose the coating film in a nitrogen atmosphere. Therefore, the complexity and cost of the process can be avoided.

Of the compounds represented by the above formula (I), compounds in which R ^{2 to} R ¹¹ are hydrogen atoms are preferable, and examples of the compound in which R ^{2 to} R ¹¹ are hydrogen atoms include R ¹ , R ¹² , The compound whose R <^13> , R < ¹⁴ > is a C1-C3 aliphatic group is preferable.
Furthermore, in the general formula (I), R ^{2 to} R ¹¹ are hydrogen atoms, R ¹ is a methyl group, R ¹² is an ethyl group, R ¹³ is a methyl group, and R ¹⁴ is a methyl group. The compound 1 can generate radicals efficiently by exposure.

  As the photopolymerization initiator of E-1, for example, a commercial product such as CGI242 (manufactured by Ciba Specialty Chemicals) can be used.

  (C-1) When the polymerizable group of the polymerizable compound having two polymerizable groups in one molecule is a vinyl ether group, a known photoacid generator useful for cationic polymerization is used as a photopolymerization initiator. The combined use is more useful from the viewpoint of maintaining high sensitivity. Specific examples of the photoacid generator include the aforementioned trihalomethyltriazine-based initiators and onium salts such as iodonium salts and sulfonium salts. These onium salts are commercially available products such as Cyracure-UVI-6990, UVI-6974 (manufactured by Dow Chemical Co., Ltd.), Adekaoptomer SP-150, SP-152, SP-170, SP-172 (manufactured by Asahi Denka ( Co., Ltd.), photoinitiator 2074 (manufactured by Rhodia Co., Ltd.), Irgacure 250 (manufactured by Ciba Specialty Chemical Co., Ltd.), CI-5102 (manufactured by Nippon Soda Co., Ltd.), and the like.

(E) The compounding quantity of a photoinitiator is the range of 0.5-40 mass parts normally with respect to 100 mass parts of total solids in a coloring photosensitive composition, Preferably it is 1-20 mass parts. It is a range.
As content of the photoinitiator in a coloring photosensitive composition, 0.1-15.0 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5-10.0. % By mass. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.
When using a photo-acid generator together as a polymerization initiator, 1-30 mass% is preferable with respect to the whole quantity of a photoinitiator, More preferably, it is 5-20 mass%.

  The colored photosensitive composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization initiator (radical initiator) and increasing the photosensitive wavelength. The sensitizer that can be used in the present invention is preferably a sensitizer that sensitizes a radical initiator by an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

  The content of the sensitizer is preferably in the range of 0.1 to 30% by mass and preferably in the range of 1 to 20% by mass with respect to the total solid content of the colored photosensitive composition from the viewpoints of sensitivity and storage stability. Is more preferable, and the range of 2 to 15% by mass is still more preferable.

  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 Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 51-82102. Publication, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Research Disclosure 33825 Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like can be mentioned.

  Other examples of co-sensitizers include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142773, and JP-A-56. And the like. Specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene. Etc.

  Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Examples thereof include donors and sulfur compounds described in JP-A-6-308727 (eg, trithian etc.).

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

<Solvent>
In general, the colored photosensitive composition of the present invention can be suitably prepared using a solvent together with the above components.

  Examples of the solvent include esters such as 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, and lactic acid. Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate and ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-oxypropionic acid 2-oxypropionic acid alkyl esters such as til, ethyl 2-oxypropionate, and propyl 2-oxypropionate (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy 2-methyl methyl propionate), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl Ether acetate, propylene glycol propyl ether acetate, etc .;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Aromatic hydrocarbons such as toluene, xylene and the like can be mentioned.

Of these, 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.

<Other ingredients>
In the colored photosensitive composition of the present invention, if necessary, a fluorine-based organic compound, a thermal polymerization inhibitor, a colorant, a photopolymerization initiator, other fillers, a polymer compound other than an alkali-soluble resin, and a surfactant. Further, various additives such as an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.

<Fluorine organic compounds>
By containing a fluorinated organic compound, the liquid properties (particularly fluidity) of the coating liquid can be improved, and the uniformity of the coating thickness and the liquid-saving property can be improved. 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.

  3-40 mass% is suitable for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. When the fluorine content is within the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorinated organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, Dainippon Ink and Chemicals, Inc.) Manufactured), FLORARD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).

Fluorine-based organic compounds are particularly effective in preventing coating unevenness and thickness unevenness when, for example, a coating film to be formed is thinned. It is also effective in slit coating that easily causes liquid breakage.
The addition amount of the fluorinated organic compound 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. It is.

<(F) Compound having an epoxy ring>
The colored photosensitive composition of the present invention preferably uses (F) a compound having an epoxy ring as a thermal polymerization component in order to increase the strength of the formed coating film. Use of a compound having an epoxy ring is preferred because solvent resistance is improved and ITO sputtering suitability is improved.

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

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

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

<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 composed of various surfactants from the viewpoint of improving coatability, and various nonionic, cationic, and anionic surfactants can be used. Among these, a nonionic surfactant and a fluorosurfactant having a perfluoroalkyl group are preferable.
Specific examples of the fluorosurfactant include MIC Corporation's MegaFac (registered trademark) series and 3M Fluorard (registered trademark) series.

  In addition to the above, in the colored photosensitive composition, as specific examples of additives, fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid Copolymers, acidic cellulose derivatives, polymers having hydroxyl groups, acid anhydrides added, alcohol-soluble nylons, alkali-soluble resins such as phenoxy resins formed from bisphenol A and epichlorohydrin; , Anionic surfactants, specifically phthalocyanine derivatives (commercial product EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) Polymer Polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.);

  Examples of other additives include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, Sorbitan fatty acid ester (nonionic surfactants such as Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 manufactured by BASF; W004, W005, W017 Anionic surfactants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, E Polymer dispersing agents such as KA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco); Solsperse 3000, 5000 , 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc., various Solsperse dispersants (manufactured by Geneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei); 2- (3-t-butyl-5-methyl-2- Hydroxyphenyl) -5-chlorobenzoto Examples thereof include ultraviolet absorbers such as riazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

  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.

  The colored photosensitive composition of the present invention contains an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator (preferably together with a solvent) in the pigment dispersion composition of the present invention described above, and is necessary for this. Accordingly, it can be prepared by mixing an additive such as a surfactant.

<Color filter and manufacturing method thereof>
The color filter of the present invention is produced by forming a colored film (colored pattern) on a substrate such as glass using the above-described colored photosensitive composition of the present invention. The colored photosensitive composition of the invention is applied to the substrate directly or via another layer (preferably, applied by a coating method such as spin coating, slit coating, cast coating, roll coating) to form a photosensitive film. Then, 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, a colored pixel) (for example, a colored pixel). The 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 the exposure method using a laser light source in the present invention, an ultraviolet laser is used as the light source. Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Oscillators and amplifiers that produce monochromatic light with 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 (buy technology), and DF2200G (Dainippon Screen). In addition, devices other than those described above are also preferably used.

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

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

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

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

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

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

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

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

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

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

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

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

-Synthesis of zinc halide phthalocyanine pigments-
Zinc phthalocyanine was produced from phthalodinitrile and zinc chloride.
Halogenation was performed by mixing 3.1 parts of sulfuryl chloride, 3.7 parts of anhydrous aluminum chloride, 0.46 parts of sodium chloride and 1 part of zinc phthalocyanine at 40 ° C., and dropping 2.2 parts of bromine. The mixture was reacted at 80 ° C. for 15 hours, and then the reaction mixture was poured into water to precipitate a partially brominated zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 80 ° C., and dried at 90 ° C. to obtain 2.6 parts of a purified partially brominated zinc phthalocyanine crude pigment.

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

(Synthesis Example 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, and then cooled to room temperature. A polyester resin (i-1) was obtained.
The scheme is shown below.

(Synthesis Example 2) Synthesis of Resin (J-1) Polyethyleneimine (SP-018, number average molecular weight 1,800, manufactured by Nippon Shokubai) 10 g and polyester resin (i-1) 100 g were mixed, and 120 ° C. for 3 hours. The intermediate (J-1B) was obtained by heating. 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 dispersion of green pigment zinc halide phthalocyanine-
14.9 parts of the partially brominated zinc phthalocyanine pigment (referred to as PG58) obtained above in the high-speed disperser “TSC-6H” manufactured by Igarashi Machinery Manufacturing Co., Ltd. charged with zirconia beads having a diameter of 0.5 mm, acrylic system manufactured by Big Chemie Dispersing agent "BYK-2001" 7.2 parts and 78 parts of PGMEA were charged and stirred at 2000 rpm for 8 hours to prepare a dispersion of partially brominated zinc halide phthalocyanine pigment (PG58).

-Preparation of dispersion of 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.

-Preparation of dispersion of 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 The pigment dispersion was prepared by mixing and dispersing for 3 hours.

-Preparation of dispersion of green pigment PG36-
As a pigment, C.I. I. A mixed liquid consisting of 40 parts of pigment green 36 (PG36) (average particle diameter 60 nm) and 200 parts of resin (i-1) (20 parts in terms of solid content) was mixed for 3 hours using a bead mill (zirconia beads 0.3 mm). Dispersed to prepare a pigment dispersion. With respect to the pigment 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 found to be 25 nm.

Example 1
A colored photosensitive composition having the following composition 1 was prepared.
In addition, the conditions of the gel permeation chromatography method (GPC) measurement which calculates | requires a weight average molecular weight and a number average molecular weight are as follows.
Column used: TSKgel MultiporeHXL-M
(Porous polydisperse type linear column) manufactured by Tosoh Eluent: THF
Flow rate: 1.0 ml / min
Temperature: 40 ° C
Detection condition: RI
System: High-speed GPC equipment set (Tosoh HLC-8220)

(Composition 1)
-Green pigment PG58 dispersion 26.1 parts-Yellow pigment PY150 dispersion 14.3 parts-Binder resin (benzyl methacrylate-acrylic acid (= copolymerization molar ratio 6: 4) copolymer, weight average molecular weight 9000) 2.8 parts. A polymerizable monomer having two polymerizable groups in one molecule (A-BPE-20, 2,2-bis [4- (acryloyloxy-polyethoxy) phenyl] propane manufactured by Shin-Nakamura Chemical Co., Ltd.), Ethoxy is 17 in m + n) 0.94 parts. Polymerizable monomer having 5 to 6 polymerizable groups in one molecule (product name: KAYARAD DPHA, dipentaerythritol hexaacrylate and dipentaerythritol penta 7: 3 (mass ratio) mixture with acrylate 2.64 parts. Photopolymerization initiator (compound E-2 having the following structure) 1.02 parts. Epoxy Compound having a ring (1,2-epoxy-4- (2-oxolanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl-1-butanol, EHPE-3150 manufactured by Daicel Chemical Industries) 0.480 parts, polymerization prohibited Agent (p-methoxyphenol) 0.0018 parts-Surfactant (Fluorine-based surfactant, trade name Megafac F781-F 0.0334 parts manufactured by DIC Corporation-Silane coupling agent (3-methacryloyloxy-trimethoxy Silylpropane) 0.320 parts, solvent (PGMEA) 51.42 parts

(Examples 2-7, Comparative Examples 1-5)
In composition 1, the pigment dispersion, the polymerizable monomer having 2 polymerizable groups in one molecule, and the polymerizable monomer having 5 to 6 polymerizable groups in one molecule were changed as shown in Table 1, and the others In the same manner as in Example 1, the colored photosensitive compositions of Examples 2 to 7 and Comparative Examples 1 to 5 were prepared.
In Table 1, the ◯ marks in the column of pigment dispersion indicate the pigment dispersion used. In addition, as a polymerizable compound, (C) a polymerizable monomer having two polymerizable groups in one molecule (bifunctional monomer) and (D) a polymerizable monomer having five to six polymerizable groups in one molecule (5 , 6 functional monomer) and the total mass was the same as in Example 1. The numerical values in Table 1 represent the ratio of each polymerizable monomer to the polymerizable compound.
In Table 1, A-BPE-10 means A-BPE-10, [2,2-bis [4- (acryloyloxy-polyethoxy) phenyl] propane, ethoxy is 10 in m + n] manufactured by Shin-Nakamura Chemical Co., Ltd. is there.

-Colored composition layer formation-
The obtained colored photosensitive composition was applied to a glass substrate (Corning Millennium 0.7 mm thick). 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.

-Colored layer pre-baking step, colored layer exposure step-
Next, after drying until the degree of vacuum reaches 66 Pa in a vacuum drying apparatus, using a hot plate, heating (prebaking treatment) at 100 ° C. for 120 seconds, and then a proximity exposure machine (manufactured by Hitachi High-Tech, LE5565A) was exposed at 60 mJ / cm ² .

-Colored layer development process, colored layer 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 shower pressure was set to 0.2 MPa with 99 parts by mass of pure water diluted at 25 ° C., the development time was developed in 10-second increments between 10 and 110 seconds, and washed with pure water.

The substrate with a development time of every 10 seconds was observed with an optical microscope, and the development status was evaluated. In Table 2, the lower limit of the development time is the lower limit number of seconds of usable development time, and the non-pixel portion cannot be removed in a time shorter than this time. The upper limit of the development time is the upper limit of the usable development time in seconds. If the time is longer than this time, the pixel is missing or dropped out. Since the development time is preferably 80 seconds or less because of the limitation of the process (tact time), it was evaluated up to 80 seconds. The development latitude indicates the difference in the number of seconds between the development time upper limit and the development time lower limit.
Next, it was baked in an oven at 220 ° C. for 30 minutes.

-Evaluation of pattern linearity-
Using an optical microscope, the edge portion of the pixel pattern was photographed and evaluated at 200 times reflection. Observe the pixel edge part in a 5cm x 5cm photo, and "good" if the pixel edge part looks straight, part of the pixel edge part (within 1/3 of the total length) Non-linear but not jagged, “slightly good”, pixel edge part exceeding 1/3 of the total length, or part (1/1 of the total length) (4 or less) was defined as “slightly bad”, and “bad” when the pixel edge portion was more than ¼ of the entire length.
The edge portion of the pixel pattern is preferably linear. If the edge portion of the pixel pattern becomes jagged due to a residual film, undercut, or the like, it is necessary to make a large overlap with the black matrix, which widens the width of the black matrix and lowers the aperture ratio. Further, when the overlap with the black matrix is not large, there is a possibility that a white portion without a colored layer is formed near the edge of the black matrix. Furthermore, when the edge portion of the pixel pattern is jagged, there is a problem that the transparent electrode formed thereon is disconnected and the resistance value is increased.

−Evaluation of bites−
Using an optical microscope, the edge portion of the pixel pattern was photographed and evaluated at 200 times reflection. The edge of the pixel is observed in a 5cm x 5cm photo, and it becomes a chipped shape (usually a half-moon-shaped edge part. Depending on the case, it may be even longer, but the line width from the periphery. Is discontinuously thinned and is recognized as missing), it is evaluated that there is a chip.
When chipping occurs, the portion is white and light is lost, which is not preferable.

The criteria for determination in Table 2 are shown below.
◯: “◯” indicates that the development latitude is wide (50 seconds or longer), the linearity of the pattern is slightly better or higher, and the luminance is high.
X: The case where any one or more of the above “◯” does not correspond was defined as “x”.

From Table 2, (C) a polymerizable monomer having 2 polymerizable groups in one molecule and (D) a polymerizable monomer having 5 to 6 polymerizable groups in one molecule are used in combination. In Examples 1 to 7, in which the composition ratio was within the range of the present invention, the development latitude was large and the linearity of the pattern was also good. In contrast, (C) Comparative Example 1 not using a polymerizable monomer having two polymerizable groups in one molecule, (C) a polymerizable monomer having two polymerizable groups in one molecule, and (D) In Comparative Examples 2 and 3 in which the composition ratio with the polymerizable monomer having 5 to 6 polymerizable groups in one molecule is outside the scope of the present invention, the development latitude is small and the linearity of the pattern is poor. there were. In Comparative Examples 4 and 5 using Pigment Green 36 which has been widely used as a green pigment which is outside the scope of the present invention, the Y value which is an index of luminance was as low as 58.5 (the present invention was 60.5). . Further, in the system using the conventional pigment Pigment Green 36, when the polymerizable monomer composition is changed to the polymerizable monomer composition of the present invention, chipping occurs earlier, so the development latitude is rather narrow.
Here, the Y value was calculated by measuring the substrate after baking with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100) and having a C light source field of 2 degrees.

(Example 8)
A colored photosensitive composition was prepared with the following composition 2.
(Composition 2)
-Green pigment PG58 dispersion 26.1 parts-Yellow pigment PY150 dispersion 14.3 parts-Binder resin (benzyl methacrylate-acrylic acid (= copolymerization molar ratio 6: 4) copolymer, weight average molecular weight 9000) 2.35 parts. A polymerizable monomer having two polymerizable groups in one molecule (A-BPE-20, 2,2-bis [4- (acryloyloxy-polyethoxy) phenyl] propane manufactured by Shin-Nakamura Chemical Co., Ltd.), Ethoxy is 17 in m + n) 0.94 parts. Polymerizable monomer having 5 to 6 polymerizable groups in one molecule (product name: KAYARAD DPHA, dipentaerythritol hexaacrylate and dipentaerythritol penta 7: 3 (mass ratio) mixture with acrylate 3.76 parts. Photopolymerization initiator (same polymerization initiator E-2 as composition 1) 0.94 parts Polymerization inhibitor (p-methoxyphenol) 0.0018 parts ・ surfactant (fluorine-based surfactant, trade name Megafac F781-F 0.0334 parts manufactured by DIC Corporation ・ silane coupling agent (3-methacryloyloxy- (Trimethoxysilylpropane) 0.320 parts, solvent (PGMEA) 51.42 parts

  Using the obtained colored photosensitive composition, a colored layer was formed in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. As a result, the pattern linearity was good and the development time (sec) was a latitude. Was 70 seconds (lower limit of 10 seconds, upper limit of 80 seconds), high brightness, no lack, and corresponded to the determination ○.

(Examples 9 to 17, Comparative Examples 6 to 10)
In composition 2, the pigment dispersion, the polymerizable monomer having two polymerizable groups in one molecule, and the polymerizable monomer having 5 to 6 polymerizable groups in one molecule were changed as shown in Table 3, and the others In the same manner as in Example 8, the colored photosensitive compositions of Examples 9 to 17 and Comparative Examples 6 to 10 were prepared.
In Table 3, the ◯ marks in the column of pigment dispersion indicate the pigment dispersion used. Further, M-1 to M-8 in the column of the type of polymerizable monomer (bifunctional monomer) having two polymerizable groups in one molecule are compounds represented by the following structure. As a polymerizable compound, a polymerizable monomer having two polymerizable groups in one molecule (bifunctional monomer) and a polymerizable monomer having five to six polymerizable groups in one molecule (5, 6 functional monomers) The total amount was the same mass as in Example 8. The numerical values in Table 3 represent the mass ratio of each polymerizable monomer compound to the total amount of polymerizable compounds.
Table 4 shows the results of forming a colored layer and performing the same evaluation in the same manner as in Example 1 using the obtained composition.

From Table 4, Example 8 where the polymerizable monomer having two polymerizable groups in one molecule (C) corresponds to the general formula (1), (C) Polymerization having two polymerizable groups in one molecule Examples 13, 14 and 15 using M-5, M-6, and M-7 corresponding to general formula (2), (C) having two polymerizable groups in one molecule Examples 9, 10, 11, and 12 using M-1, M-2, M-3, and M-4 corresponding to the general formula (6) as the polymerizable monomer, and (C) in one molecule In Example 16, in which M-8 corresponding to the general formula (7) was used as the polymerizable monomer having two polymerizable groups, development latitude was large and the linearity of the pattern was good. In Example 17 using PY138 as the yellow pigment, the development latitude was large and the linearity of the pattern was good.
On the other hand, (C) Comparative Example 6 not using a polymerizable monomer having two polymerizable groups in one molecule, Comparative Examples 7 and 8 not using a pigment, and a green color outside the scope of the present invention In Comparative Example 9 using Pigment Green 36 as the pigment, the development latitude was narrow and the linearity of the pattern was poor. In particular, in Comparative Example 9 using Pigment Green 36, chipping occurred during development from a short development time.

  A colored layer was formed using the colored photosensitive composition of Example 8 so that the y value on the CIE chromaticity diagram was 0.585, and the luminance (Y value) was measured to be 60. On the other hand, a colored layer was formed using the colored photosensitive composition of Comparative Example 10 so that the y value on the CIE chromaticity diagram was 0.585, and the luminance (Y value) measured was 58. Example 8 was found to have better brightness than Comparative Example 10.

(Example 18)
A colored photosensitive composition was prepared with the following composition 3.
(Composition 3)
-Green pigment PG58 dispersion 26.1 parts-Yellow pigment PY150 dispersion 14.3 parts-Binder resin (benzyl methacrylate-acrylic acid (= copolymerization molar ratio 6: 4) copolymer, weight average molecular weight 9000) 2.35 parts · polymerizable monomer having two polymerizable groups in one molecule (polymerizable compound M-10 having the following structure) 0.94 parts · polymerizability having 5 to 6 polymerizable groups in one molecule Monomer (made by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA, 7: 3 (mass ratio) mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, 3.76 parts, photopolymerization initiator (the same polymerization start as composition 1) Agent E-2) 0.75 part-Photopolymerization initiator (Syracure UV-6990 (manufactured by Dow Chemical Company), polymerization initiator E-3 having the following structure) 0.19 part Polymerization inhibitor (p-methoxyphenol) 0.0018 parts-Surfactant (Fluorine-based surfactant, manufactured by DIC Corporation, Megafac F781-F 0.0334 parts-Silane coupling agent (3-methacryloyloxy- (Trimethoxysilylpropane) 0.320 parts, solvent (PGMEA) 51.42 parts

  Formation of a colored layer and the same evaluation were performed using the obtained composition in the same manner as in Example 1. As a result, the pattern linearity was good, and the development time (sec) latitude was 60 seconds (lower limit 20 seconds, The upper limit was 80 seconds), the luminance was high (60 was obtained by extrapolating the Y value at which the y value was 0.585), and there was no blurring, which was equivalent to the determination ◯.

When half of the binder resin in Composition 3 was replaced with the following resin and evaluated, the same effect was obtained in the above evaluation items. Furthermore, when the surface roughness (Ra) of the two samples was evaluated using AFM, the sample that was 4 nm in the sample before the replacement was 2 nm in the sample after the replacement, which was good.
Alkali-soluble resin: copolymer of allyl methacrylate and methacrylic acid (= 80/20 [molar ratio]) Weight average molecular weight = 35,000

(Example 19)
When the same evaluation was performed except that the exposure process was changed to the following using the composition of Example 8, the same good results as Example 8 were obtained. From this result, it was found that the excellent effect of the present invention can be obtained by pattern exposure using a laser exposure machine as well as exposure using a high-pressure mercury lamp.
(Exposure process)
Using EGIS (buoy technology Co., Ltd., YAG laser third harmonic wavelength 355 nm, pulse width 6 nsec) as a laser exposure device, pulse irradiation of about 1 mJ / cm ² was performed 20 times on the surface of the photosensitive resin composition layer. I went through a photomask.

[Production of color filters]
1. Formation of colored photosensitive composition layer The green colored photosensitive composition of Example 1 was slit-coated on a glass substrate provided with a black matrix of 550 mm × 650 mm under the following conditions, followed by vacuum drying (66 Pa) and pre-baking ( prebake) (80 ° C., 160 seconds) to form a green colored photosensitive composition coating film (colored photosensitive composition layer).

(Slit application conditions)
Opening gap at the tip of the coating head: 100 μm
Coating speed: 150 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C

2. Exposure, Development Then, the green coloring photosensitive composition layer was exposed in the pattern form at 60 mJ / cm < ² > using the proximity exposure machine (Hitachi High Technology company make, LE5565A). The entire surface of the colored photosensitive composition layer after the exposure was washed with a 1.0% aqueous solution (25 ° C.) of an inorganic developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) at a shower pressure of 0. Development was performed at 2 MPa (setting) for 60 seconds.

3. Heat treatment After that, pure water was sprayed onto the colored photosensitive composition layer in a shower to wash away the developer, and then heated in an oven at 220 ° C. for 1 hour (post-baking).

4). After that, a colored pattern is formed with a blue colored photosensitive composition (the following B-1 composition), and further a colored pattern is formed with a red colored photosensitive composition (the following C-1 composition). Then, ITO is vapor-deposited, a spacer is formed using a photopolymerizable composition (CSP-3210L; manufactured by FUJIFILM Electronics Materials Co., Ltd.), and a color filter having green, red, and blue coloring patterns on the substrate Got.

(B-1 composition)
Blue pigment dispersion (described below) 246.2 parts Alkali-soluble resin: copolymer of benzyl methacrylate and methacrylic acid (= 70/30 [molar ratio]) Weight average molecular weight = 8,000 (45 mass%) 2.08 parts of a propylene glycol monomethyl ether solution having a concentration) Alkali-soluble resin: copolymer of allyl methacrylate and methacrylic acid (= 80/20 [molar ratio]) Weight average molecular weight = 35,000 (45% by mass concentration) Propylene glycol monomethyl ether solution) 18.7 parts Polymerizable compound: Nippon Kayaku Co., Ltd. DPHA 20 parts Polymerization initiator: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5 '-Tetraphenylbiimidazole 3 parts, polymerization initiator: Ciba Specialty Chemicals oxime initiator OXE-3 3 parts, multifunctional Epoxy compound: DIC Corporation, Epicron 695 5 parts, diethylaminobenzophenone 0.5 part, N-phenylmercaptobenzimidazole 0.5 part, surfactant: (Structure 1 below) 1.0 part, solvent (propylene glycol) 400 parts of methyl ether acetate / ethyl ethoxypropionate = 8/2)

(C-1 composition)
Red pigment dispersion (described below) 246.2 parts Alkali-soluble resin: copolymer of benzyl methacrylate and methacrylic acid (= 70/30 [molar ratio]) Weight average molecular weight = 8,000 (45% by mass) 2.08 parts of a propylene glycol monomethyl ether solution having a concentration) Alkali-soluble resin: copolymer of allyl methacrylate and methacrylic acid (= 80/20 [molar ratio]) Weight average molecular weight = 35,000 (45% by mass concentration) Propylene glycol monomethyl ether solution) 18.7 parts Polymerizable compound: Nippon Kayaku Co., Ltd. DPHA 20 parts Polymerization initiator: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5 '-Tetraphenylbiimidazole 3 parts, polymerization initiator: Ciba Specialty Chemicals oxime initiator OXE-3 3 parts, multifunctional Epoxy compound: DIC Corporation, Epicron 695 5 parts, diethylaminobenzophenone 0.5 part, N-phenylmercaptobenzimidazole 0.5 part, surfactant: (Structure 1 below) 1.0 part, solvent (propylene glycol) 400 parts of monomethyl ether acetate / ethyl ethoxypropionate = 8/2)

The above B-1 compositions, and blue pigment dispersion was used in C-1 composition, and red pigment dispersion as follows.
First, a coated pigment was prepared as follows.

(Preparation of coated pigment 1)
50 g of pigment (CI Pigment Red254, CROMOPHTAL RED BP manufactured by Ciba Specialty Chemicals), 500 g of sodium chloride, 20 g of the above-described polymer 1 solution, and 100 g of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) made of stainless steel. Kneaded for 9 hours. Next, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to prepare coated pigment 1.

(Preparation of coated pigment 2)
In the adjustment of the coating pigment 1, C.I. I. Pigment Blue 15: 6 (HELIOGEN Blue L6700F manufactured by BASF) was used, and Polymer 2 was used in place of Polymer 1, and the same procedure as in Preparation of Covered Pigment 1 was performed, except that Covered Pigment 2 was prepared.

(Preparation of red pigment dispersion)
With a composition of Dispersic byk161 (manufactured by BYK Chemie) 7.0 parts as a dispersant and 200 parts of solvent: propylene glycol methyl ether acetate with respect to 35 parts of the pigment equivalent of the coated pigment 1, the number of revolutions was 3, using a homogenizer. 3,000 rpm, mixed for 3 hours to prepare a mixed solution, and further dispersed for 6 hours with a bead disperser Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) using 0.1 mmφ zirconia beads. It was.

(Preparation of blue pigment dispersion)
A blue pigment dispersion was obtained in the same manner as the preparation of the red pigment dispersion except that the coated pigment 1 was changed to the coated pigment 2.

Claims (9)

(A) a halogenated zinc phthalocyanine pigment, (B) a yellow pigment, (C) a polymerizable compound, (D) a binder resin, and (E) a photopolymerization initiator, wherein the (C) polymerizable compound is (C -1) a polymerizable compound having two polymerizable groups in one molecule, and (C-2) a polymerizable compound having 5 to 6 polymerizable groups in one molecule, the (C-1) The polymerizable compound having two polymerizable groups in one molecule is selected from the group consisting of compounds represented by the following general formula (1), general formula (2), general formula (6) and general formula (7). And the content of the polymerizable compound having two polymerizable groups in one molecule of (C-1) is (C-1) polymerization having two polymerizable groups in one molecule. Colored photosensitive composition in a range of 15% to 40% by weight based on the total amount of the polymerizable compound and (C-2) a polymerizable compound having 5 to 6 polymerizable groups in one molecule .


In General Formula (1), Y ¹ and Y ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. p and q are integers of 1 to 20, and p + q is an integer of 2 to 30.


In General Formula (2), Y ¹ and Y ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A represents a linking group shown below. r and s are integers of 1 to 20, and r + s is an integer of 2 to 30.




In General Formula (6), Y ¹ and Y ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and B represents a linking group shown below. m is an integer of 1-3. When m is 2 or 3, the plurality of B contained therein may be the same as or different from each other.




In General Formula (7), Y ¹ and Y ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Polymerizable group before SL (C-2) 5 to polymerizable compound having six polymerizable groups in one molecule, the colored photosensitive composition of claim 1 which is (meth) acryloyl groups or vinyl ether groups, object. The colored photosensitive composition according to claim 1 or 2, wherein the (A) halogenated zinc phthalocyanine pigment is a compound represented by the following general formula (a).


In the general formula (a), X ^{21 to} X ³⁶ each independently represent a hydrogen atom, a chlorine atom or a bromine atom. However, 8 or more of X ^{21 to} X ³⁶ are chlorine atoms or bromine atoms. The (B) yellow pigment is C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 138, and C.I. I. The colored photosensitive composition according to any one of claims 1 to 3 , comprising one or more pigments selected from CI Pigment Yellow 139. The colored photosensitive composition according to any one of claims 1 to 4 , wherein the (E) photopolymerization initiator includes a compound represented by the following general formula (I).


In general formula (I), R ^{1 to} R ¹⁴ are each independently any one of a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a carboxyl group, an aromatic group, and an aliphatic group. However, the aromatic group and the aliphatic group may include a structure selected from a branched structure and an alicyclic structure, from an ether bond, an ester bond, an amino bond, an amide bond, a thioether bond, and an unsaturated bond. One or more selected may be present, and one or more selected from a hydroxyl group, an amino group, a carboxyl group, a halogen atom, and an aromatic group may be included at the terminal of the group. The colored photosensitive composition according to any one of claims 1 to 5 , further comprising (F) a compound having an epoxy ring. The colored photosensitive composition according to any one of claims 1 to 6 , which is used for a color filter. On a substrate, a color filter having a colored pattern formed by using the colored photosensitive composition as claimed in any one of claims 7. A liquid crystal display device comprising the color filter according to claim 8 .