JP2010175878A - Color photosensitive composition, color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color photosensitive composition exhibiting a high developing rate and a large development latitude and preventing chipping in a pattern even when the composition has a high pigment concentration; to obtain a color filter having favorable color characteristics of high color purity and high contrast, and high productivity by using the above color photosensitive composition; and to provide a liquid crystal display device displaying a sharp image with high luminance by using the color filter. <P>SOLUTION: The color photosensitive composition contains (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 has a hydroxyl group and a double bond density of 9.6 meq/g to 11.5 meq/g. <P>COPYRIGHT: (C)2010,JPO&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, cannot secure sufficient productivity, and therefore cannot reduce the price of the color filter.

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.
In order to improve the development latitude described above, a polymerizable compound into which a hydroxy group has been introduced has also been proposed (see Patent Document 6), but it is still insufficient.

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 JP-A-8-327813 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 to form a colored pattern with a high development speed, a large development latitude, excellent curability of the formed colored pattern, and lack of pattern at the time of development even at a high pigment concentration. Is to obtain a colored photosensitive composition useful for forming a colored pattern of a color filter.
Another object of the present invention is to obtain a color filter having high color purity, high contrast, good color characteristics, and high productivity by using the colored photosensitive composition. An object of the present invention is to obtain a liquid crystal display device having a high brightness and a clear image using a color filter.

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, (C-1) A colored photosensitive composition comprising a polymerizable compound having a hydroxy group and having a double bond density in the range of 9.6 meq / g to 11.5 meq / g.

<2> 3 to 8 polymerizable compounds having a (C-1) hydroxy group and having a double bond density in the range of 9.6 meq / g to 11.5 meq / g The colored photosensitive composition according to <1>, which is a polymerizable compound having a polymerizable group.

<3> A colored photosensitive composition having a polymerizable compound having a hydroxy group (C-1) and having a double bond density in the range of 9.6 meq / g to 11.5 meq / g. The colored photosensitive composition according to <1> or <2>, which is 40% by mass or more of the content of all polymerizable compounds contained in.

<4> The colored photosensitive composition according to any one of <1> to <3>, wherein the (A) halogenated zinc phthalocyanine pigment is a compound represented by the following general formula (a).

In general formula (a), X ^{21 to} X ³⁶ are each independently 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.

<5> The (B) yellow pigment is C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 138, and C.I. I. The colored photosensitive composition according to any one of <1> to <4>, comprising at least one selected from CI Pigment Yellow 139.

<6> The colored photosensitive composition according to any one of <1> to <5>, 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.

<7> The colored photosensitive composition according to any one of <1> to <6>, further including (F) a compound having an epoxy ring.
<8> The colored photosensitive composition according to any one of <1> to <7>, which is for a color filter.

<9> A color filter having a colored pattern formed using the colored photosensitive composition according to any one of <1> to <8> on a substrate.
<10> A liquid crystal display device comprising the color filter according to <9>.

  In the present invention, when a polymerizable compound having a hydroxy group and a specific amount of a double bond in the molecule is used for the colored photosensitive composition, the development speed is high in the development step and the development latitude is increased. This is because the polymerizable compound has a hydroxy group, so that the permeability of the developer in the non-exposed part of the colored photosensitive composition layer is increased and the development speed is increased. A high-density cross-linking structure is formed by bonding, and the adhesion to the substrate is strengthened by the hydrogen bonding action caused by the hydroxy group, and as a result, the development resistance of the exposed area and the good developability of the unexposed area are improved. At the same time, it is estimated that the development latitude has increased.

According to the present invention, when forming a colored pattern, even at a high pigment concentration, the developing speed is fast, the developing latitude is large, the formed colored pattern is excellent in curability, and pattern loss during development is suppressed. A colored photosensitive composition useful for forming a colored pattern of a color filter can be obtained.
Furthermore, by using the colored photosensitive composition, it is possible to obtain a color filter with high color purity, high contrast, good color characteristics, and high productivity. A liquid crystal display device with a high and clear image 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 (A) a halogenated zinc phthalocyanine, (B) a yellow pigment, (C-1) a polymerizable compound having a hydroxy group and a specific amount of double bonds in the molecule, (D ) A binder resin, and (E) a photopolymerization initiator.
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 X21 to X36 are substituted with bromine atoms, it exhibits a yellowish and light green color and is optimal for use in the color filter green pixel part pattern. is there. 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, the halogenated zinc phthalocyanine pigment disclosed in Japanese Patent Application Laid-Open No. 2004-70342, which has a simple process, is preferable from the viewpoint of cost. In addition, in terms of stability, although depending on other additives and the way of assembling the post-process, the crystal-converted zinc halide phthalocyanine pigment disclosed in JP-A-2008-19383 is preferable. In particular, a resin-coated zinc halide phthalocyanine pigment disclosed in JP-A-2007-320986 is a preferred embodiment for improving dispersibility.

  The 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 average value of the longer diameter (major axis) and the shorter diameter (minor axis) is 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 size 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 described above, it is preferable to use an organic solvent capable of suppressing crystal growth, as described above, and a water-soluble organic solvent can be suitably used as such an organic solvent, for example, diethylene glycol, glycerin, ethylene glycol. , Propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propano Le, dipropylene glycol, 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 carried out to break the pigment into powder, and examples thereof include pulverization with a mortar, hammer mill, disk mill, pin mill, jet mill and the like.

  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-mentioned method, but can also be purchased from Dainippon Ink and Chemicals, Inc.

<(B) Yellow pigment>

In the colored photosensitive composition of the present invention, the hue of the colored photosensitive composition is adjusted by using (B) a yellow pigment in (A) the halogenated zinc phthalocyanine pigment to 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 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 an 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 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162 , 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (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, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the 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 zinc halide phthalocyanine pigment and (B) a yellow pigment, a pigment dispersion composition containing (C) a polymerizable compound, (D) a binder resin, and (E ) A photopolymerization initiator is included, and the polymerizable compound (C) has (C-1) a hydroxy group, and its double bond density is in a range of 9.6 meq / g or more and 11.5 meq / g or less. It is a preferred embodiment that it contains a polymerizable compound.

  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.

<Polymerizable compound having (C-1) hydroxy group and having a double bond density in the range of 9.6 meq / g to 11.5 meq / g>
The colored photosensitive composition of the present invention is a polymerizable compound (hereinafter referred to as (C-1) having a hydroxy group in the molecule and having a double bond density of 9.6 meq / g or more and 11.5 meq / g or less. Also referred to as “specific polymerizable compound”).
The specific polymerizable compound (C-1) that can be used in the present invention has one hydroxy group in the molecule and has a double bond density of 9.6 meq / g or more and 11.5 meq / g or less. .
By using a colored photosensitive composition having a specific polymerizable compound, when the formed colored photosensitive composition layer is exposed and developed, an increase in the line width or deterioration of the pattern shape observed in the past is observed. Therefore, both the line width and the pattern shape can be achieved. Furthermore, there is an effect that an unexposed part is quickly removed by development (break time).
The bonding position in the molecule of the hydroxy group possessed by the polyfunctional monomer in the present invention is not particularly limited.

The double bond density in the present invention needs to be within the above range in order to achieve the effects of the present invention, but from the viewpoints of sensitivity, pattern shape, fine adjustment of line width, and improvement of resolution, unsaturated per molecule. It is necessary to set the group content to a specific value, that is, the double bond density needs to be 9.6 meq / g or more and 11.5 meq / g or less. This double bond density is preferably 10.0 meq / g or more and 11.5 meq / g or less, more preferably 10.2 meq / g or more and 11.5 meq / g or less, and particularly preferably 10.5 meq / g. It is 11.5 meq / g or less.
Here, “double bond density (meq / g)” in the present invention refers to the number of milliequivalents (meq) of double bonds per polyfunctional monomer (1 g). For example, since the compound A-1 has a molecular weight of 298.29 and a double bond of 3000 meq, the double bond density is 10.1 (3000 (meq) /298.29 (g)).

The specific polymerizable compound in the present invention may have the hydroxy group and have a double bond density in the specific range, but from the viewpoint of pattern shape, line width, and resolution, it is preferably trifunctional or higher. 3 to 8 functionals are more preferable, 3 to 6 functionals are more preferable, and 3 and 4 functionals are particularly preferable.
By making the specific polymerizable compound in the present invention trifunctional or more, it is preferable because the pattern forming property is excellent and the pattern is less likely to be chipped or peeled off.

  Specific examples of the specific polymerizable compound in the invention include the following, but are not limited thereto. The mixing ratio of Compound A-14 is a mass ratio.

  As the specific polymerizable compound in the present invention, a commercially available product may be used, or a suitably synthesized compound may be used.

The content of the specific polymerizable compound in the present invention is preferably in the range of 1% by mass to 90% by mass in the solid content of the colored photosensitive composition of the present invention, and is preferably 5% by mass to 80% by mass. Is more preferable, and it is still more preferable that it is the range of 10 mass% or more and 70 mass% or less.
In particular, when the colored photosensitive composition of the present invention is used for forming a colored pattern of a color filter, the content is preferably in the range of 5% by mass to 50% by mass, and more preferably 7% by mass to 40%. The range is more preferably in the range of mass% or less, and still more preferably in the range of 10 mass% or more and 35 mass% or less.

The specific polymerizable compound in the present invention may be used alone or in combination of two or more. However, in order to increase the strength of the image portion, that is, the cured film, different functional numbers and different polymerizable groups are used. Use of the polymerizable compound in combination is effective in controlling both sensitivity and strength.
Examples of the polymerizable compound having a different functional number / different polymerizable group include polymerizable compounds other than the specific polymerizable compound in the present invention.

<Other polymerizable compounds>
As preferred examples of other polymerizable compounds having different functional numbers and different polymerizable groups, (meth) acrylic monomers having 5 or more (meth) acryloyl groups in the same molecule are preferably used. Examples of the (meth) acrylic monomer having 5 or more (meth) acryloyl groups in the same molecule include dipentaerythritol hexa (meth) acrylate and UA-306H, UA-306T, UA-306I manufactured by Kyoeisha Chemical Co., Ltd. Urethane acrylates such as dipentaerythritol hexaacrylate are preferable. Among these, dipentaerythritol hexaacrylate is preferable from the viewpoint of solvent resistance and suitability for ITO sputtering.

  When the other polymerizable compound is used in combination, the addition ratio of the specific polymerizable compound is preferably 40% by mass or more, more preferably 60% by mass or more, and more preferably 65% by mass or more with respect to the total mass of all polymerizable compounds. Is particularly preferred. When it is 40% by mass or more, preferable results can be obtained from the viewpoint of development latitude, sensitivity, and dura strength.

<(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. is at least one, 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 (E) 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, compounds such as (thio) xanthones or acridine compounds described in French Patent 2,456,741, compounds such as coumarins or lophine dimers described in JP-A-10-62986, 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 the compounds described in the following [Chemical Formula 11] and [Chemical Formula 12].
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. By using this photopolymerization initiator, the sensitivity of the colored photosensitive composition is dramatically improved, and 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 to be generated can generate radicals efficiently by exposure.

  As the photopolymerization initiator having the above structure, for example, a commercially available product such as CGI242 (manufactured by Ciba Specialty Chemicals) can be used.

(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.

  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, and a polymer compound other than an alkali-soluble resin, a surface activity Various additives such as an agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent 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.

<Compound having epoxy ring>
The colored photosensitive composition of the present invention preferably uses 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.

The compound having an epoxy ring is a compound having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( In addition to Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (Nagase Chemical 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.

Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (manufactured by Tohto Kasei), Denacol EM-125, etc. (manufactured by Nagase Kasei), and 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, ceroxide 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 the MegaFac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc., and the Fluorad (registered trademark) series manufactured by 3M.

  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 esters (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 Zeneca); 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, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and 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 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.

  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). Resin (J-1) has a side chain derived from polyester (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.

(Comparative Example 1)
A colored photosensitive composition having the following composition 1 was prepared.
(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, polymerizable compound (product name: KAYARAD DPHA, 7: 3 (mass ratio) mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd. 3.58 parts, photopolymerization initiator (The following compound) 1.02 parts-Compound having an epoxy ring (1,2-epoxy-4- (2-oxolanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl 1-butanol), manufactured by Daicel Chemical Industries, Ltd. EHPE- 3150) 0.480 parts, polymerization inhibitor (p-methoxyphenol) 0.0018 parts, surface activity (Fluorine-containing surface active agent, DIC Corporation, trade name Megafac F781-F)
0.0334 parts ・ Silane coupling agent (3-methacryloyloxy-trimethoxysilylpropane)
0.320 parts / solvent (PGMEA) 51.34 parts

光重合開始剤

Photopolymerization initiator

In composition 1, the pigment dispersion and the polymerizable compound were changed as shown in Table 1, and the other components were the same as in Comparative Example 1, and the respective colored photosensitive compositions of Examples 1 to 6 and Comparative Examples 2 to 6 were used. I adjusted things.
In Table 1, the ◯ marks in the column of pigment dispersion indicate the pigment dispersion used. Moreover, about the polymeric compound, the addition amount was shown in Table 1 by "mass part", and the double bond density of the specific polymeric compound used was written together in Table 1 in the unit of "meq / g". The DPHA of the polymerizable compound is Nippon Kayaku Co., Ltd. product name: KAYARAD DPHA shown in Composition 1 of Comparative Example 1, and is another polymerizable compound not included in the specific polymerizable compound of the present invention.

-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.

-Evaluation of developability-
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 of usable development time in seconds, 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. In addition, 80 seconds or less is preferable because of process (tact time) restrictions. The development latitude indicates a difference in the number of seconds between the upper limit of the development time and the lower limit of the development time.

-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 photograph, "good" if the pixel edge part looks linear, part of the pixel edge part (within 1/3 of the total length) is not linear Is not slightly jagged, “slightly good”, pixel edge part is more than 1/3 of the entire length and not linear, or part (less than 1/4 of the total length) is jagged The case where the pixel edge portion is “slightly bad” and the pixel edge portion which is more than ¼ of the entire length is made “bad”.
The edge portion of the pixel pattern is preferably linear. If the edge of the pixel pattern becomes jagged due to residual film, undercuts, etc., it is necessary to increase the overlap with the black matrix. I will lower it. Further, when the overlap with the black matrix is not increased, there is a possibility that a portion that does not have a colored layer and is white is formed near the edge of the black matrix. Further, 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 Y value (luminance)-
The substrate after post-baking was measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100) and calculated as a result of a C light source field of view of 2 degrees.
The Y value (luminance) of Examples 1 to 5 using PG58 and PY150 is 60.5, and the Y value (luminance) of Comparative Examples 5 and 6 using PG36 and PY150 is 58. It was low at .5.

The criteria for determination in Table 2 are shown below.
○: The development latitude was wide (50 seconds or more), the linearity of the pattern was “slightly good” or higher, and the Y value (luminance) was high, “◯”.
X: The case where any one or more of the above-mentioned items did not correspond was defined as “x”.

From Table 2, Examples 1 to 6 using the specific polymerizable compound of the present invention had large development latitude and good pattern linearity. On the other hand, Comparative Examples 1 to 4 which did not use the specific polymerizable compound of the present invention had a small development latitude and could not be judged.
In Comparative Examples 5 and 6 using PG36 as a green pigment which is outside the scope of the present invention, the Y value (luminance) is low, and in Comparative Example 5 which is different from Example 1 only in the type of green pigment, chipping in development occurs earlier. The development latitude has become narrower. The colored photosensitive composition of the present invention exhibits an effect when combined with PG58, and the development latitude is widened. However, the interaction with PG36 is poor, and a sufficient function cannot be exhibited due to phase separation in the colored layer. Therefore, it is estimated that the development latitude is narrowed.

Claims (10)

  (A) a halogenated zinc phthalocyanine pigment, (B) a yellow pigment, (C) a polymerizable compound, (D) a binder resin, and (E) a photopolymerization initiator, wherein (C) the polymerizable compound is (C -1) A colored photosensitive composition comprising a polymerizable compound having a hydroxy group and having a double bond density in the range of 9.6 meq / g to 11.5 meq / g.   The polymerizable compound having a hydroxy group (C-1) and having a double bond density in the range of 9.6 meq / g to 11.5 meq / g has 3 to 8 polymerizable compounds in the molecule. The colored photosensitive composition according to claim 1, which is a polymerizable compound having a group.   The colored photosensitive composition contains the polymerizable compound having a hydroxyl group (C-1) and having a double bond density in the range of 9.6 meq / g to 11.5 meq / g. The colored photosensitive composition according to claim 1, wherein the content is 40% by mass or more of the content of all polymerizable compounds. The colored photosensitive composition according to any one of claims 1 to 3, wherein the (A) halogenated zinc phthalocyanine pigment is a compound represented by the following general formula (a).

In general formula (a), X ^{21 to} X ³⁶ are each independently 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 138, and C.I. I. The colored photosensitive composition according to any one of claims 1 to 4, comprising at least one selected from CI Pigment Yellow 139. The colored photosensitive composition according to any one of claims 1 to 5, 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.   The colored photosensitive composition according to any one of claims 1 to 6, further comprising (F) a compound having an epoxy ring.   The colored photosensitive composition according to any one of claims 1 to 7, which is used for a color filter.   The color filter which has a coloring pattern which uses the coloring photosensitive composition of any one of Claims 1-8 on a base material.   A liquid crystal display device comprising the color filter according to claim 9.