KR101511202B1 - Processed pigment, pigment dispersion composition, photocurable composition, color filter, and method of manufacturing color filter - Google Patents

Abstract

The present invention relates to a process for producing a pigment composition, which comprises a process for producing a pigment, which comprises treating a pigment with a polymer compound having a basic nitrogen atom, a pigment dispersion composition obtained by dispersing the pigment in an organic solvent, a photocurable composition comprising the pigment dispersion composition, a polymerizable compound and a photopolymerization initiator , A color filter having a colored region formed by using the photo-curable composition, and a method of manufacturing the same.

A pigment dispersion composition, a photocurable composition, a color filter

Description

FIELD OF THE INVENTION [0001] The present invention relates to a process for producing a pigment, a pigment dispersion composition, a photocurable composition, a color filter, and a method of manufacturing a color filter,

The present invention relates to a process pigment, a pigment dispersion composition, a photocurable composition, a color filter, and a process for producing a color filter. More specifically, the present invention relates to a process for producing a pigment, which comprises a process pigment which is excellent in dispersibility and dispersion stability and which can be preferably used in a wide range of paints, printing inks and color filters, a pigment dispersion composition obtained by dispersing the above- , A color filter having a colored region formed by the photo-curable composition, and a method of manufacturing the same.

The color filter includes a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a photo-curable composition containing a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components, and is used by photolithography, Thereby forming a colored pattern.

In recent years, the color filter tends to be used not only as a monitor but also as a television (TV) in a liquid crystal display device (LCD) application. In accordance with the tendency of this application to be widened, color filters are required to have high color characteristics in terms of chromaticity, contrast, and the like. In addition, color filters for use in image sensors (solid-state image pickup devices) are also required to have high color characteristics, such as reduction in color unevenness and improvement in color resolution.

With respect to the above-mentioned requirement, it is required to disperse the pigment contained in the photo-curing composition in a finer state (good dispersibility) and disperse it in a stable state (good dispersion stability). In the case where the dispersibility of the pigment is insufficient, there is a problem that fringes (irregularities of the edge portion) and surface irregularities are formed in the colored pixels formed by the photolithography method, and a large amount of development residue (residue) There is a problem in that the chromaticity and dimensional accuracy of the color filter are deteriorated and the contrast is remarkably deteriorated. Further, when the dispersion stability of the pigment is insufficient, various problems are likely to occur in each step of the production of the color filter. Particularly, there arises a problem that the uniformity of the film thickness of the coating film is lowered in the coating process of the photocurable composition, the sensitivity is lowered in the exposure process, and the alkali solubility is lowered in the developing process. In addition, when the dispersion stability of the pigment is poor, there is also a problem that the components of the photocurable composition undergo agglomeration over time, the viscosity increases, and the pot life becomes extremely short. In order to improve the color characteristics such as the contrast of the color filter, it is effective to make the particle diameter of the pigment finer. However, since the surface area of the pigment particles becomes larger when the particle diameter of the pigment is made smaller, the cohesive force between the pigment particles becomes stronger, It is often difficult to achieve both performance and dispersion stability.

The following are known for improving the fineness and dispersibility of pigment particles.

In general, fine pulverization of primary particles of a pigment is well known as a method of mechanically kneading a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent which does not substantially dissolve the inorganic salt in a kneader or the like (salt milling method). In this method, first, a mixture of primary particles of the obtained fine pigment is poured into water and stirred with a mixer or the like to form a slurry. Subsequently, this slurry is filtered, washed with water and dried to obtain a fine pigment as a secondary aggregate, which is an agglomerate of primary particles of the pigment. Further, dispersion is carried out by a general dispersing machine such as a sand mill or a ball mill, and a secondary aggregate which is an agglomerate of the primary particles of the pigment is loosened to obtain a dispersion in a state close to primary particles.

However, when the primary particles of the pigment are made finer, they tend to agglomerate, and aggregates (secondary agglomerates) are likely to be formed when the slurry is made into a slurry or dried. Further, as the primary particles of the pigment become finer, strong secondary aggregation tends to occur. Therefore, it is generally very difficult to re-disperse the finely divided pigment into the primary particles. A color filter formed using a dispersion containing a large amount of secondary agglomerates has a problem that light scattering is large, contrast is remarkably lowered or color density unevenness occurs, so that the pigment dispersion composition is not aggregated and the primary particles are stably dispersed And it is preferable that it is easy to handle.

For the purpose of suppressing strong secondary agglomeration of the finely pulverized pigment, pigments are treated by adding a rosin or a rosin derivative or a water-insoluble monomer or oligomer, respectively, in the salt milling step, and a pigment A technique of obtaining a high color filter has been proposed (see, for example, Japanese Patent No. 3130217 and Japanese Patent Application Laid-Open No. 2004-233727).

It is also possible to provide a pigment dispersion composition, a photo-curable composition, a photocurable composition, and the like which can form a colored pattern for a color filter having a high dispersion stability and a high contrast by using a polymer compound having a heterocyclic ring as a dispersant in a dispersion process of the pigment during the dispersion step, And a technique for obtaining a color filter have been proposed (see, for example, Japanese Patent Application Laid-Open No. 2003-26950).

However, according to these methods, it is not possible to cope with a demand for contrast in a market that is even higher, and a higher dispersibility and dispersion stability in a fine pigment have been desired.

In addition, in recent years, there has been a demand for a color filter having not only contrast but also high luminance. As a method for obtaining a high-luminance and high-contrast color filter, there has been proposed a method of using polyhalogenated zinc phthalocyanine instead of conventional CI Pigment Green 36 or CI Pigment Green 7 in a green pixel portion (see, for example, 2004-70342, and JP-A-2008-19383).

SUMMARY OF THE INVENTION The present invention has as its object to achieve the following objects.

That is, a first object of the present invention is to provide a processed pigment capable of inhibiting the formation of secondary agglomerates to be dispersed in the state of primary particles, and capable of stably maintaining the state of primary particles even after dispersion .

It is a second object of the present invention to provide a pigment dispersion composition containing the above-mentioned processed pigment and excellent in dispersibility and dispersion stability of the above-mentioned processed pigment, and a pigment dispersion composition containing such a pigment dispersion composition and capable of forming a colored cured film excellent in contrast And to provide a photocurable composition.

A third object of the present invention is to provide a color filter formed using the photo-curing composition and having a high color density and excellent color characteristics with low color density unevenness, and a method for producing the same.

Means for solving the above problems are as follows.

≪ 1 > A treated pigment obtained by coating a pigment with a polymer compound having a basic nitrogen atom.

<2> A processed pigment according to <1>, wherein the polymer compound having a basic nitrogen atom is at least one kind of polymer compound selected from the following (1) to (4).

(1) a poly (alkyleneimine) having an alkylene group having 2 to 6 carbon atoms;

(2) Polyallylamine

(3) Polyvinylamine

(4) A polymer compound having at least one monomer component selected from (meth) acrylic acid esters having a basic nitrogen atom in the ester moiety, vinyl pyridine, and aminostyrene.

<3> A processed pigment according to <1> or <2>, wherein the average primary particle diameter is in the range of 5 nm to 25 nm.

<4> A processed pigment according to any one of <1> to <3>, wherein the pigment is a pigment containing polyhalogenated zinc phthalocyanine.

<5> A processed pigment according to any one of <1> to <4>, wherein the polymer compound having a basic nitrogen atom has an oligomer chain or polymer chain having a number average molecular weight of 500 to 1,000,000 in the side chain.

<6> A processed pigment according to <5>, wherein the oligomer chain or polymer chain contained in the polymer compound having a basic nitrogen atom is polycaprolactone.

&Lt; 7 > A pigment dispersion composition obtained by dispersing a treated pigment described in any one of <1> to <6> in an organic solvent.

<8> The pigment dispersion composition according to <7>, further comprising a pigment dispersant.

<9> A photocurable composition comprising the pigment dispersion composition according to <7> or <8>, a polymerizable compound, and a photopolymerization initiator.

&Lt; 10 > A color filter having a colored region formed using the photo-curable composition according to any one of the items < 10 >.

<11> A process for forming a photosensitive film by applying the photocurable composition described in <9> directly or through another layer on a substrate to form a photosensitive film, and a step of forming a colored region by sequentially performing pattern exposure and development on the formed photosensitive film And forming a color filter on the color filter.

Another preferred form of the processed pigment of the present invention is as follows.

<12> A treated pigment according to any one of <1> to <6>, wherein the glassy polymer has a glassy content of 30% by mass or less of a polymer compound having a basic nitrogen atom when washed with 1-methoxy-2-propanol.

<13> A processed pigment according to any one of <1> to <6> and <12>, which is produced by adding a polymer compound having a basic nitrogen atom in a process of micronizing a pigment.

<14> A treated pigment according to any one of <1> to <6>, <13> and <14>, wherein the polymer having a basic nitrogen atom has a weight average molecular weight of 1,000 to 100,000.

The &quot; amount of glass &quot; in the above &lt; 12 &gt; means the amount of the surface treatment agent (the polymer compound having a basic nitrogen atom in the present invention) eluted in the solvent by immersing the processed pigment in 1-methoxy- Divided by the amount of surface treatment agent used.

The present invention relates to a processed pigment coated with a polymer compound having a basic nitrogen atom and its application. By using such a treated pigment, it is possible to obtain a pigment having excellent dispersibility and dispersion stability and a high contrast, It is possible to obtain a pigment dispersion composition and a color filter which are less soluble.

That is, when the polymer compound having a basic nitrogen atom of the present invention is used for pigment treatment, it is considered that the generation of secondary aggregates, which are aggregates of the primary particles of the pigment, can be effectively inhibited or the cohesion of the secondary aggregates can be effectively weakened . Therefore, it is possible to obtain a dispersion in a state close to primary particles in the dispersion step, and to obtain a color filter with high contrast and a color filter with small color density unevenness.

Further, the pigment dispersion composition containing the processed pigment of the present invention, to which the polyhalogenated zinc phthalocyanine is applied as a pigment, can be produced by using the photo-curable composition comprising the pigment dispersion composition while maintaining excellent dispersibility and dispersion stability A color filter having better brightness and contrast can be obtained.

Although the action of the present invention is not clear, it is considered that the polymer compound used for coating has a basic nitrogen atom in its molecular structure, and that the above structure and pigment have strong electrostatic interaction, and that strong intermolecular force , The polymeric compound is strongly adsorbed to the pigment primary particles and the polymeric compound coated even when slurry, filtration and washing are not desorbed, so that it is considered that the primary particles of the pigment are effectively prevented from agglomerating each other.

In the present invention, such a feature is that the pigment is coated with a polymer compound having a basic nitrogen atom to form a processed pigment, and it is particularly effective to carry out the coating at the same time as the step of finely grinding the primary particles of the pigment. That is, as compared with the method of stabilizing dispersion by adsorbing a graft polymer compound containing a heterocycle in the dispersion step after the micronization step as in the above-described Japanese Patent Application Laid-Open No. 2003-26950, A polymer compound having a basic nitrogen atom according to the present invention is adsorbed by a strong electrostatic action on the new interface of the pigment and a strong coating layer of the polymer compound is formed so that a processed pigment having a higher dispersion stability can be obtained . That is, in the present invention, even if the processed pigment is washed with an organic solvent that dissolves the polymer compound, most of the coated polymer compound is not released. On the other hand, in the pigment disclosed in Japanese Patent Application Laid-Open No. 2003-26950, most of the polymer compound as a dispersant is desorbed from the pigment, so that the finely divided pigment becomes easy to flocculate, and high dispersion stability can not be obtained.

Further, the color filter using the processed pigment of the present invention coated with the polymer compound having a basic nitrogen atom can solve the problem that the color filter layer is blurred under high temperature and high humidity, and that the color filter is blurred when the color filter is manufactured. Such a problem is considered to be a phenomenon in which fine pigment particles in the color filter aggregate and grow as crystals, and it tends to occur as the primary particles of the pigment become finer. The processed pigment of the present invention coated with a polymer compound having a basic nitrogen atom is effective in effectively suppressing the aggregation of the pigment particles in the color filter because the polymer compound having a basic nitrogen atom is strongly adsorbed on the fine pigment I think.

In addition, the color filter using the processed pigment of the present invention, which has been coated with the polymer compound having a basic nitrogen atom, has excellent voltage retention of liquid crystal. The lowering of the voltage holding ratio of the liquid crystal is likely to occur when the metal ion concentration in the color filter is high. This is an easy problem to occur especially when the pigment is made fine by the salt milling method because the inorganic salt (ions) used in the salt milling process is adsorbed on the pigment particles in the salt milling process, Or from the pigment particles after forming the liquid crystal display element. The finer the primary particles of the pigment, the more easily the ionic compound is contained, making it difficult to remove it by washing with water and filtering. The processed pigment of the present invention, which has been coated with a polymer compound having a basic nitrogen atom, can effectively inhibit the dissolution of ions in the dispersion process or the color filter because the polymer compound is strongly adsorbed on the fine pigment for the reasons described above do.

The photocurable composition using the processed pigment of the present invention, which has been coated with a polymer compound having a basic nitrogen atom, has an advantage that precipitates are not easily generated in the developing solution in a developing process when applied to the production of a color filter. The precipitate is often an aggregate of pigment particles. It is considered that the precipitation is a phenomenon in which the pigment dispersant dispersed by the dispersant is desorbed by the alkali developing solution and the fine pigment particles aggregate to grow crystal and precipitate. In the processed pigment of the present invention, since the polymer compound is strongly adsorbed on the fine pigment, the polymer compound is not desorbed even by the alkali developer, and it is considered that the precipitate is hardly generated in the developer.

On the other hand, when the polymer compound having a heterocyclic ring disclosed in Japanese Patent Application Laid-Open No. 2003-26950 is used as a pigment dispersant in a dispersing process, since the adsorption to the pigment is insufficient, these effects can not be sufficiently exhibited. It does not lead to improvement.

(Effects of the Invention)

According to the present invention, it is possible to provide a processed pigment capable of suppressing the formation of secondary agglomerates to be dispersed in the state of primary particles and stably maintaining the state of primary particles even after dispersion.

According to the present invention, there is also provided a pigment dispersion composition containing the above-mentioned processed pigment and excellent in the dispersibility and dispersion stability of the above-mentioned processed pigment, and a pigment dispersion composition containing such a pigment dispersion composition and capable of forming a cured film having excellent contrast Composition can be provided.

Further, according to the present invention, it is possible to provide a color filter formed using the photo-curable composition and having a colored region having a high contrast and a small color density unevenness and excellent color characteristics, and a method for producing the same.

Hereinafter, the processed pigment, pigment dispersion composition, photocurable composition, color filter, and manufacturing method of the present invention will be described in detail.

[Process pigment]

The treated pigment of the present invention is a processed pigment obtained by coating a pigment with a polymer compound having a basic nitrogen atom.

The average primary particle diameter of the processed pigment of the present invention is preferably 100 nm or less, more preferably 30 nm or less, in consideration of the handling property of the pigment dispersion composition obtained by dispersing the above-mentioned processed pigment and the photo- And most preferably from 5 nm to 25 nm. When the particle diameter is within the above range, it is effective to form a color filter having a high transmittance, a good color characteristic and a high contrast.

The average primary particle diameter is obtained by observing with SEM or TEM and counting 100 particle sizes in a portion where particles are not aggregated and calculating an average value.

One of the preferred forms of the processed pigment of the present invention is a mixture of i) a pigment, ii) a water-soluble inorganic salt, iii) a small amount of a water-soluble organic solvent which does not substantially dissolve ii), iv) a polymer compound having a basic nitrogen atom, (This process is referred to as salt milling), the mixture after the kneading is put into water and stirred with a high-speed mixer or the like to obtain a slurry, and the obtained slurry is filtered and washed with water Followed by a drying step.

By such a production method, the processed pigment of the present invention, which is fine and excellent in dispersibility and dispersion stability with little agglomeration of the pigment upon drying, is obtained.

The above manufacturing method will be described in more detail.

Firstly, a small amount of iii) water-soluble organic solvent is added as a wetting agent to a mixture of i) an organic pigment and ii) a water-soluble inorganic salt, and the resultant mixture is strongly kneaded with a kneader or the like, and then this mixture is put into water and stirred with a high- To prepare a slurry.

Subsequently, this slurry is filtered, washed with water and dried if necessary, to obtain a pigment which is finely coated with a polymer compound having a basic nitrogen atom.

When the obtained processed pigment is dispersed in an oil-based varnish, the treated pigment (referred to as a filter cake) before drying can be dispersed in the oil-based varnish while removing water by a method generally called flashing. When the obtained processed pigment is dispersed in a varnish of water, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.

In the present invention, by using a resin which is at least partially soluble in iii) a water-soluble organic solvent, that is, iv) a polymer compound having a basic nitrogen atom at the time of salt milling, fine, and the surface thereof is iv) a polymer compound having a basic nitrogen atom A processed pigment with less agglomeration of the coated pigment during drying is obtained.

Further, iv) timing of adding the polymer compound having a basic nitrogen atom may be added all at the beginning of the salt milling process or may be added in divided portions.

As a method for preventing dry agglomeration, an alkali-soluble resin dissolved in an aqueous alkaline solution is added to the slurry, stirred and mixed sufficiently, and neutralized with an acidic aqueous solution such as hydrochloric acid or sulfuric acid to deposit the resin on the pigment, Or by adding an aqueous solution of a water-soluble multivalent metal salt such as barium chloride to precipitate the resin and deposit it on the pigment, thereby preventing dry agglomeration.

[i] Pigment]

In the working pigment of the present invention, conventionally known various inorganic pigments or organic pigments can be appropriately selected and used as a pigment to be coated with a polymer compound having a basic nitrogen atom.

Considering that the processed pigment of the present invention is preferably used for forming the coloring region of the color filter and that the color filter is preferably high in transmittance, the pigment is preferably an organic pigment, .

The particle diameter of the pigment is selected in consideration of the particle diameter of the processed pigment.

Specific examples of the inorganic pigments include metal oxides such as metal oxides and metal complex salts such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, And composite oxides of the above metals.

As the organic pigment, for example,

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: , 81: 2, 81: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12,13,14,15,16,17,18,20,24,31,32,34,35,35,136 , 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97 , 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139 , 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179 , 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214,

CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 ,

C. I. Pigment Green 7, 10, 36, 37,

CI Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, Thing, 80

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,

C. I. Pigment Brown 25, 28,

C. I. Pigment Black 1, 7, etc. can be listed.

Among these pigments, the following pigments can be preferably used. However, the present invention is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

C. I. Pigment Orange 36, 71,

C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C. I. Pigment Violet 19, 23, 32,

C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

C. I. Pigment Green 7, 36, 37;

C. I. Pigment Black 1, 7

<Polyhalogenated zinc phthalocyanine>

One of the preferred forms of organic pigments is polyhalogenated zinc phthalocyanine.

The polyhalogenated zinc phthalocyanine may be used alone, or the polyhalogenated zinc phthalocyanine may be used in combination with conventionally known organic pigments.

Generally, zinc phthalocyanine has 16 hydrogen atoms in the phthalocyanine ring. Therefore, up to 16 of these hydrogen atoms can be substituted with a halogen atom. For example, when these hydrogen atoms are substituted with a bromine atom and / or a chlorine atom, the number of bromine atoms is 0 to 16, the number of chlorine atoms is 0 to 16, the number of hydrogen atoms is 0 to 16, The total number of atoms becomes 1 or more, and in theory, a total of 136 kinds of substituents can be produced.

As the polyhalogenated zinc phthalocyanine in the present invention, it is preferable that 8 to 16 of the 16 substitutable hydrogen atoms in the phthalocyanine ring are substituted, more preferably 12 to 16 substituents. The halogen atom to be substituted for the phthalocyanine ring includes a bromine atom, a chlorine atom, a fluorine atom, and an iodine atom, more preferably a bromine atom or a chlorine atom, and more preferably a bromine atom. The halogen atoms to be substituted may be the same or different.

When the number of substituents of the halogen atom substituted on the phthalocyanine ring is constant, the zinc phthalocyanine substituted with the bromine atom becomes darker than the zinc phthalocyanine substituted with the chlorine atom.

As such polyhalogenated zinc phthalocyanine, a compound represented by the following general formula (1) is preferable.

In the general formula (1), X ¹ to X ¹⁶ each independently represent a chlorine atom, a bromine atom, or a hydrogen atom. Provided that at least eight of X ¹ to X ¹⁶ are chlorine atom or bromine atom.

Herein, polyhalogenated zinc phthalocyanine is a yellowish colored light-emitting green that contains at least 8 bromine atoms and is most suitable for use in a green pixel portion of a color filter. In the present invention, a polyhalogenated zinc phthalocyanine containing 8 or more bromine atoms is referred to as &quot; polybrominated zinc phthalocyanine &quot;. This polybrominated zinc phthalocyanine is preferable as the polyhalogenated zinc phthalocyanine in the present invention.

More preferably, the polybrominated zinc phthalocyanine has 8 to 16 bromine atoms, more preferably 12 to 16 bromine atoms.

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

The polyhalogenated zinc phthalocyanine can be produced by a known production method such as, for example, a chlorosulfonic acid method, a halogenated phthalonitrile method, a melting method and the like. More specific manufacturing methods are described in detail in Japanese Patent Application Laid-Open Nos. 2008-19383, 2007-320986, and 2004-70342. The production methods described in these documents can also be applied to the present invention.

The polyhalogenated zinc phthalocyanine preferably has an average primary particle diameter of 10 nm to 40 nm, more preferably 10 nm to 35 nm, and still more preferably 15 nm to 35 nm.

A pigment dispersion composition having excellent dispersibility, dispersion stability and tinting ability can be obtained by using the treated pigment of the present invention obtained by using polyhalogenated zinc phthalocyanine having an average primary particle diameter in the above range, By using the harmful composition, it is possible to obtain a color filter having a pixel portion having high luminance and high contrast.

The average primary particle diameter in the present invention means that the particles in the visual field are photographed with a transmission electron microscope and the diameter of the long side of the 100 polyhalogenated zinc phthalocyanine primary particles constituting the aggregate on the two- (Long diameter) and the short side diameter (short diameter), respectively, and averages them.

With respect to obtaining polyhalogenated zinc phthalocyanine having an average primary particle diameter of 10 nm to 40 nm, any method may be used to form the particles, but it is possible to obtain pigment particles which can easily suppress crystal growth and have a relatively small average particle diameter It is preferable to employ a solvent salt milling method.

This solvent salt milling means kneading and polishing polyhalogenated zinc phthalocyanine, inorganic salt and organic solvent. The polyhalogenated zinc phthalocyanine having a large particle size may be subjected to solvent salt milling after dry-grinding in advance. More specifically, a polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent that does not dissolve the zinc salt are put into a kneader, and kneading is performed in the kneader. As the kneading machine at this time, for example, nippers or mix maras can be used.

As inorganic salts used in solvent salt milling using polyhalogenated zinc phthalocyanine, water-soluble inorganic salts are preferable, and examples of the water-soluble inorganic salts include inorganic salts such as sodium chloride, potassium chloride and sodium sulfate. It is more preferable to use an inorganic salt having an average particle diameter of 0.5 to 50 mu m. Such an inorganic salt is easily obtained by pulverizing a general inorganic salt.

For obtaining polyhalogenated zinc phthalocyanine having an average primary particle diameter of 10 nm to 40 nm, it is desirable to increase the amount of inorganic salt used relative to the amount of polyhalogenated zinc phthalocyanine used in solvent salt milling. That is, the amount of the inorganic salt to be used is preferably 5 to 20 parts, more preferably 7 to 15 parts, in terms of mass, based on 1 part of the polyhalogenated zinc phthalocyanine.

Polyhalogenated zinc phthalocyanine having an average primary particle diameter of 10 nm to 40 nm can be obtained by, for example, the above-mentioned salt milling, but it is also possible to purchase a commercially available product from DIC Corporation as a FASTGEN GREEN series.

These organic pigments may be used alone or in combination of various ones in order to increase color purity. Specific examples of combinations of organic pigments are shown below.

Examples of the red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them and a disazo yellow pigment, isoindoline yellow pigment, quinophthalone yellow pigment or peryl Based red pigment, anthraquinone-based red pigment, diketopyrrolopyrrole-based red pigment, and the like can be used. Examples of the anthraquinone pigments include CI Pigment Red 177, the perylene pigments include CI Pigment Red 155 and CI Pigment Red 224, the diketopyrrolopyrrole pigments include CI Pigment Red 254, In view of reproducibility, a mixture with CI Pigment Yellow 83, CI Pigment Yellow 139 or CI Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. When the ratio is 100: 4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and the color purity can not be increased in some cases. When the ratio is 100: 81 or more, the coloring power may be lowered. Particularly, the mass ratio is most preferably in the range of 100: 10 to 100: 65. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

As the green pigment, a halogenated phthalocyanine pigment may be used singly or in combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment. For example, a mixture of C. I. Pigment Green 7, 36, 37 and C. I. Pigment Yellow 83, C. I. Pigment Yellow 138, C. I. Pigment Yellow 139, C. I. Pigment Yellow 150, C. I. Pigment Yellow 180 or C. I. Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 to 450 nm, and the color purity may not be increased. On the other hand, if the ratio exceeds 100: 200, the dominant wavelength becomes near the long wavelength and the deviation from the NTSC target color may become large. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

When the halogenated phthalocyanine-based pigment to be used is the above-described polyhalogenated zinc phthalocyanine, the color filter obtained by applying to the processed pigment of the present invention has a pixel portion having high luminance and high contrast. When polyhalogenated zinc phthalocyanine is used, it is preferable to use it in combination with C.I. Pigment Yellow 150 from the viewpoint of obtaining a desirable color and high brightness as a color filter.

As the blue pigment, phthalocyanine pigments may be used singly or in combination with a dioxadine purple pigment. As a particularly preferable example, a mixture of C. I. Pigment Blue 15: 6 and C. I. Pigment Violet 23 can be listed.

The mass ratio of the blue pigment to the purple pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

In addition, carbon black, graphite, titanium black, iron oxide, and titanium oxide may be used alone or as a mixture, and a combination of carbon black and titanium black is preferable as a pigment preferable for use in a black matrix.

The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60 from the viewpoint of dispersion stability.

[ii) Water-soluble inorganic salt]

The water-soluble inorganic salt is not particularly limited as long as it is an inorganic salt dissolved in water, and for example, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used. In terms of price, it is preferable to use sodium chloride or sodium sulfate.

The amount of the water-soluble inorganic salt used in the salt milling is preferably 1 to 30 times by mass, particularly preferably 5 to 25 times by mass, of the organic pigment in terms of treatment efficiency and production efficiency. The larger the ratio of the amount of the water-soluble inorganic salt to the organic pigment, the higher the fineness efficiency but the smaller the throughput of the pigment.

Here, the water-solubility in the water-soluble inorganic salt means that the water-soluble inorganic salt is dissolved in water at 20 ° C in an amount of 1% by mass or more.

[iii] a small amount of a water-soluble organic solvent which does not substantially dissolve ii)

The water-soluble organic solvent is not particularly limited as long as it functions to wet pigments such as organic pigments and water-soluble inorganic salts, dissolves in water (miscible), and does not substantially dissolve the inorganic salt used. However, at the time of salt milling, the temperature rises and the solvent easily evaporates. Therefore, from the viewpoint of safety, the water-soluble organic solvent is preferably a high boiling solvent having a boiling point of 120 ° C or higher.

Examples of the water-soluble organic solvent include organic solvents such as 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monoethyl Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy- , Dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol.

The amount of the water-soluble organic solvent to be added is preferably 5% by mass to 50% by mass based on the water-soluble inorganic salt, more preferably 10% by mass to 40% by mass with respect to the water-soluble inorganic salt, % To 35% by mass. If the addition amount of the water-soluble organic solvent is less than 5% by mass, uniform kneading becomes difficult and the distribution of particle size becomes large, which is not preferable. If the addition amount of the water-soluble organic solvent is 50% by mass or more, the kneading composition becomes too soft, and it becomes difficult to impart shearing to the kneading composition, so that a sufficient fineness effect can not be obtained.

iii) The water-soluble organic solvent may be added all at the beginning of the salt milling process or may be added in divided portions. The water-soluble organic solvent may be used alone, or two or more kinds may be used in combination.

[iv] Polymer compound having a basic nitrogen atom]

The polymer compound having a basic nitrogen atom (hereinafter referred to as a "specific polymer compound" as appropriate) is not particularly limited as long as it has a basic nitrogen atom in its molecular structure.

Herein, a basic nitrogen atom refers to a nitrogen atom which is bonded to only a carbon atom and is in an unoxidized state and has one lone electron pair.

The specific polymer compound is preferably at least one kind of polymer compound selected from the following (1) to (4).

(1) a poly (alkyleneimine) having an alkylene group having 2 to 6 carbon atoms;

(2) Polyallylamine

(3) Polyvinylamine

(4) a polymer compound comprising a constituent unit derived from at least one monomer selected from (meth) acrylic acid ester, vinylpyridine, and aminostyrene having a basic nitrogen atom in the ester moiety

Specific polymer compounds can be further classified into two types of linear polymers and graft-type polymers from their structures.

Herein, the linear polymer in the present invention means a linear polymer having a basic nitrogen atom in the polymer chain, but it is also preferred that the linear polymer of the same linear polymer is cross- Are included in the chain polymer.

The graft polymer in the present invention means a polymer chain having a basic nitrogen atom and a polymer chain other than the polymer chain graft-bonded to each other.

From the viewpoint of maintaining the processed pigment in the state of primary particles and effectively suppressing the generation of the secondary agglomerates, the specific polymer compound is preferably a linear polymer. From the viewpoint of effectively weakening the cohesive force of the secondary aggregate in the dispersion step in the preparation of the pigment dispersion composition, the specific polymer compound is preferably a graft polymer.

<Linear Polymer>

When the specific polymer compound is a linear polymer, the polymer compound may be a polymer compound selected from poly (alkyleneimine), polyallylamine, and polyvinylamine having an alkylene group having 2 to 6 carbon atoms, or a polymer compound selected from basic nitrogen Is a polymer compound containing a constituent unit derived from at least one monomer selected from (meth) acrylic acid ester having an atom, vinylpyridine, and aminostyrene, and has a linear polymer structure.

Poly (alkyleneimine) (hereinafter referred to as &quot; poly (lower alkyleneimine) &quot; as appropriate) having an alkylene group having 2 to 6 carbon atoms may be in the form of a chain or may have a mesh-like structure.

As the poly (lower alkyleneimine), a polymer compound containing a repeating unit represented by the following general formula (I-1) is suitably listed.

In the general formula (I-1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group. a represents an integer of 1 to 5; * Represents a connection between repeating units. X represents a hydrogen atom, a monovalent organic group, or a group containing a functional group having a pKa of 14 or less. Examples of the monovalent organic group represented by X include an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a carboxyl group which may be substituted, a hydroxyl group which may be substituted, and the like.

The polymer compound having a repeating unit represented by the general formula (I-1) has, in addition to the repeating unit represented by the general formula (I-1), a repeating unit represented by the following general formula (I-2) May be included. By using such repeating units in combination, the dispersion performance of the processed pigment can be further improved.

In the general formula ^{(I-2) R 1,} R 2, a, and * is R ^1, R ^2, a, and a * and copper in the formula (I-1). X 'represents a halogen atom.

In the general formulas (I-1) and (I-2), it is particularly preferable that R ¹ and R ² are hydrogen atoms. Also, a is preferably 2 from the viewpoint of raw material availability.

In the formulas (I-1) and (I-1 '), R ¹ and R ² are particularly preferably hydrogen atoms.

The polymer compound containing a repeating unit represented by the general formula (I-1) may further contain, as a copolymer component, other repeating units other than the repeating units represented by the general formulas (I-1) and (I-2) Examples of such a repeating unit include repeating units of a lower alkyleneimine containing a primary or tertiary amino group, and the like. The nitrogen atom in the lower alkyleneimine repeating unit may be bonded with a functional group having a pKa of 14 or less represented by X. [

When X in the general formula (I-1) represents a functional group having a pKa of 14 or less, the structure and the like are not particularly limited as far as the physical properties satisfy this condition, and the pKa satisfies the above range by a known functional group Are listed.

Specific examples of the functional group represented by X include a carboxylic acid group (pKa: about 3 to 5), a sulfonic acid group (pKa: about -3 to -2), -COCH ₂ CO- (pKa : About 8 to 10), -COCH ₂ CN (pKa: about 8 to 11), -CONHCO-, a phenolic hydroxyl group, -R _F CH ₂ OH or - (R _F ) ₂ CHOH (R _F represents a perfluoroalkyl group (PKa: about 3 to 5), a sulfonic acid group (pKa: about 3 to about 2), and a sulfonamide group (pKa: about 9 to 11) ), -COCH ₂ CO- (pKa: about 8 to 10), and the carboxylic acid group is particularly preferable for ease of introduction.

Specific examples of the poly (lower alkyleneimine) include polyethyleneimine, polypropyleneimine, and the like. SP-003, SP-012, SP-018, SP-200, and SP-1000 (available from NIPPON SHOKUBAI CO., LTD.) May be used as the poly (lower alkyleneimine). , LTD.) Are listed.

As the polyallylamine, a polymer compound having a repeating unit represented by the following formula (II-1) is preferably exemplified.

In the general formula (II-1), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group. * And X are synonymous with * and X in the general formula (I-1).

The polymer compound having a repeating unit represented by the general formula (II-1) may further contain, as a copolymerization component, a repeating unit represented by the following general formula (II-2) in addition to the repeating unit represented by the general formula (II- Maybe. By using such repeating units in combination, the dispersion performance of the processed pigment can be further improved.

General formula (II-2) of the ^{R 3, R 4, R 5} , R 6, and * is in the formula ^{(II-1) R 3,} R 4, R 5, R 6, and a * and agree . X 'corresponds to X' in the general formula (I-2).

In the general formulas (II-1) and (II-2), R ³ , R ⁴ , R ⁵ and R ⁶ are preferably hydrogen atoms from the viewpoint of availability of raw materials.

The polymer compound having a repeating unit represented by the general formula (II-1) may further contain, as a copolymerization component, other repeating units other than the repeating units represented by the general formulas (II-1) and (II-2) .

PAA-05, PAA-08, PAA-15, PAA-15C, PAA-25, PAA-H-10C, PAA-05, PAA- 1112, and PAA-U5000 (manufactured by Nitto Boseki Co., Ltd.).

As the polyvinylamine, a polymer compound having a repeating unit represented by the following general formula (III-1) is preferably exemplified.

In the general formula (III-1), R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, or an alkyl group. * And X are synonymous with * and X in the general formula (I-1).

The polymer compound having a repeating unit represented by the general formula (III-1) may further contain, as a copolymerization component, a repeating unit represented by the following general formula (III-2) in addition to the repeating unit represented by the general formula (III- Maybe. By using such repeating units in combination, the dispersion performance of the processed pigment can be further improved.

In the general formula ^{(III-2) R 7,} R 8 , and * is R ^7, R ^8, and - with consent of the general formula (II-1). X 'corresponds to X' in the general formula (I-2).

In the general formulas (III-1) and (III-2), R ⁷ and R ⁸ are preferably hydrogen atoms from the viewpoint of availability of the starting materials.

The polymer compound having a repeating unit represented by the general formula (III-1) may further contain other repeating units other than the repeating units represented by the general formulas (III-1) and (III-2) as copolymer components.

In general, polyvinylamine is a method of hydrolyzing all or part of a polymer or copolymer of an N-vinylcarboxylic acid amide in the presence of an acid or an alkali, as described in JP-A-2-222404, As described in JP-A-6-122712, the monomer aqueous solution can be synthesized by a method of carrying out polymerization using an azo-based initiator in an organic solvent or an aqueous solvent.

The above poly (lower alkyleneimine), polyallylamine and polyvinylamine may be those in which the organic group is further substituted from the viewpoint of improving solubility in a solvent during salt milling. Specific examples of the organic group include an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a carboxyl group which may be substituted, a hydroxyl group which may be substituted, and the like. These organic groups may be introduced by reacting a low molecular compound such as a carboxylic acid chloride, an acid anhydride, or a lactone. The substituent may be one kind or two or more kinds.

The polymer compound comprising a constituent unit derived from at least one monomer selected from (meth) acrylic acid ester, vinylpyridine and aminostyrene having a basic nitrogen atom in the ester moiety is preferably a homopolymer containing only the constituent unit derived from the monomer The copolymer may be a copolymer or a copolymer having a constituent unit derived from a monomer other than the monomer.

Specific examples of the (meth) acrylic acid ester having a basic nitrogen atom in the ester moiety include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) (Meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (Meth) acrylate, di (dimethylaminopropyl) ureidoethyl (meth) acrylate and di (diethylaminopropyl) ureidoethyl (meth) acrylate.

Examples of the monomer other than the above that can be copolymerized with (meth) acrylic acid ester, vinyl pyridine and / or aminostyrene having a basic nitrogen atom in the ester moiety are, for example, methyl (meth) acrylate, ethyl (Meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl , Benzyl (meth) acrylate, styrene, and the like.

The monomers other than the above may be monomers having an acid group. Specific examples of the monomer having an acid group include (meth) acrylic acid, succinic anhydride adduct of hydroxy (meth) acrylate, 1,2-cyclohexylcarboxylic acid anhydride of hydroxy Cyclohexylcarboxylic acid anhydride adduct of hydroxy (meth) acrylate, 1,2-cyclohexenecarboxylic acid anhydride adduct of hydroxy (meth) acrylate, hydroxy (meth) Phthalic acid anhydride adduct of lauric acid, and the like.

By using the monomer having such an acid group, when the pigment dispersion composition containing the processed pigment of the present invention is applied to a photo-curable composition applied to the production of a color filter or the like, the developing ability of the unexposed portion is excellent.

When the specific polymer compound is a polymer compound comprising a constituent unit derived from a monomer of at least one monomer selected from (meth) acrylic acid ester, vinylpyridine and aminostyrene having a basic nitrogen atom in the ester moiety, the monomer may be a specific polymer It is preferably contained in the compound in an amount of 30% by mass to 100% by mass, more preferably 30% by mass to 80% by mass.

Specific examples of specific polymer compounds classified as linear polymers are listed below, but the present invention is not limited thereto. The molecular weight of the polymer compound shown below has a weight average molecular weight (Mw) in the range of 1,000 to 100,000 and a number average molecular weight (Mn) in the range of 400 to 50,000.

It is a specific polymer compound having 100% by mass of the repeating unit. When the content of the repeating unit having a basic nitrogen atom is A and the content of the other repeating units is B, it is preferable that the ratio (A / B) is A / B = 10 / 90% by mass to 90/10% by mass.

When the content of the repeating unit having a basic nitrogen atom is A and the content of the other repeating units is B, the ratio (A / B) is 10/90 mass% To 60/40% by mass.

&Lt; graft type polymer &

When the specific polymer compound is a graft polymer, the polymer compound preferably has an oligomer chain or polymer chain having a number average molecular weight of 500 to 1,000,000 in the side chain. The oligomer chain or polymer chain is preferably polycaprolactone from the viewpoint of obtaining good dispersibility.

The number average molecular weight of oligomer chain or polymer chain can be measured by polystyrene conversion value by GPC method.

Hereinafter, the specific polymer compound which is a graft-type polymer will be described in more detail.

As a specific polymer compound which is a graft polymer, a particularly preferred form is a polymer compound (hereinafter referred to as &quot; graft polymer (1) &quot;) comprising a poly (lower alkyleneimine), a polyallylamine or a polyvinylamine and an oligomer chain or a polymer chain, (Hereinafter also referred to as &quot; polymeric oligomer (hereinafter also referred to as &quot; polymeric oligomer &quot;) and at least one monomer selected from (meth) acrylic acid esters having a basic nitrogen atom in the ester moiety, vinylpyridine and aminostyrene , "Graft-type polymer (2)").

The poly (lower alkyleneimine), polyallylamine and polyvinylamine constituting the graft polymer 1 may be obtained by reacting the poly (lower alkyleneimine), polyallylamine and polyvinylamine described above as the preferred examples of the linear polymer same.

In the graft polymer (1), oligomer chains or polymer chains that can be bonded to poly (lower alkyleneimine), polyallylamine or polyvinylamine are preferably polyester, and from the viewpoint of obtaining good dispersibility, poly More preferred is caprolactone.

As a method of synthesizing the graft polymer 1, for example, the methods described in JP-A-2007-63472 and JP-A-9-176511 can be applied.

Preferable examples of the graft-type polymer (1) include compounds containing repeating units represented by the following general formulas (I-1) and (I-3).

In the formulas (I-1) and (I-3), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group. a represents an integer of 1 to 5; * Represents a connection between repeating units. X represents a hydrogen atom, a monovalent organic group, or a group containing a functional group having a pKa of 14 or less. Examples of the monovalent organic group represented by X include an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a carboxyl group which may be substituted, and a hydroxyl group which may be substituted. And Y represents an oligomer chain or polymer chain having a number average molecular weight of 500 to 1,000,000.

The compound containing a repeating unit represented by the general formula (I-1) and (I-3) is preferably a repeating unit represented by the general formula (I-3) in addition to the repeating unit represented by the general formula (I- 4) as a copolymerization component.

In the general formula ^{(I-4) R 1,} R 2, a and * is R ^1, R ^2, a and a * and copper in the formula (I-1). Y 'represents an oligomer chain or polymer chain having a number average molecular weight of 500 to 1,000,000 having an anionic group. The repeating unit represented by the general formula (I-3) can be formed by reacting a resin having a primary or secondary amino group in the main chain portion with an amine to react with an oligomer or polymer having a salt-forming group.

In the general formulas (I-1), (I-3) and (I-4), it is particularly preferable that R ¹ and R ² are hydrogen atoms. Also, a is preferably 2 from the viewpoint of raw material availability.

The compound containing the repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-3) is a repeating unit represented by the general formula (I-1), the general formula (I- May further contain other repeating units in addition to the repeating unit as a copolymerization component. Examples of such repeating units include repeating lower alkyleneimines containing a primary or tertiary amino group. The nitrogen atom in the lower alkyleneimine repeating unit may further include a group represented by X, Y or Y '. Resins containing both a repeating unit bonded with a group represented by X in this backbone structure and a repeating unit bonded with Y are also included in the specific resin of the present invention.

As another preferable example of the graft-type polymer (1), there are listed compounds containing repeating units represented by the following general formulas (II-1) and (II-3).

In the general formulas (II-1) and (II-3), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group. *, X and Y are synonymous with *, X and Y in the general formulas (I-1) and (I-3).

The compound containing the repeating unit represented by the general formula (II-1) and the repeating unit represented by the formula (II-3) is preferably a repeating unit represented by the general formula (II-1) It is preferable to further contain a repeating unit represented by the following general formula (II-4) as a copolymerization component. When such a repeating unit is used in combination, dispersion performance is further improved when the resin is used as a fine particle dispersing agent such as pigment.

In the general formula ^{(II-4) R 3,} R 4, R 5, R 6 and * is ^{R 3, R 4, R 5} , R 6 and * and agreed in the formula (II-1). Y 'is synonymous with Y' in the general formula (I-4).

In the general formulas (II-1), (II-3) and (II-4), R ³ , R ⁴ , R ⁵ and R ⁶ are preferably hydrogen atoms from the viewpoint of availability of raw materials.

The polymer compound having the repeating units represented by the general formulas (II-1) and (II-3) can be obtained by repeating the repeating units other than the repeating units represented by the general formulas (II-1), (II- Unit as a copolymerization component.

As another preferred example of the graft-type polymer (1), there are listed compounds containing repeating units represented by the following general formulas (III-1) and (III-3).

In the formulas (III-1) and (III-3), R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom or an alkyl group. * Represents a connection between repeating units. X and Y are synonymous with X and Y in the general formulas (I-1) and (I-3).

The compound containing a repeating unit represented by the general formula (III-1) and (III-3) is preferably a repeating unit represented by the general formula (III-1) May further contain, as a copolymerization component, a repeating unit represented by the following general formula (III-4).

In the general formula ^{(III-4) R 7,} R 8 , and * is R ^7, R ^8, and - with consent of the general formula (III-1). Y 'is synonymous with Y' in the general formula (I-4).

In the general formulas (III-1), (III-3) and (III-4), R ⁷ and R ⁸ are preferably hydrogen atoms from the viewpoint of availability of raw materials.

The polymer compound having a repeating unit represented by the general formulas (III-1) and (III-3) can be obtained by repeating a repeating unit other than the repeating units represented by the general formulas (III-1), (III- Unit as a copolymerization component.

Examples of the graft polymer 1 include commercially available products such as Solsperse 24000GR, 28000, 32000 and 38500 (trade names: The Lubrizol Corporation), Ajisper-PB711, PN411, PA111, PB821 and PB822 (Manufactured by Ajinomoto Fine-Techno Co., Inc.), EFKA 4047, 4050 (trade name: EFKA Additives Japan Inc.), Disperbyk-161, 162, 167, 168 (trade name: BYK Japan KK).

(Meth) acrylic acid ester, vinylpyridine and aminostyrene having a basic nitrogen atom in the ester moiety, which is a monomer capable of constituting the graft polymer (2), in the description of the case where the polymer compound having a basic nitrogen atom is a linear polymer It is the same as the listed monomers. In addition, monomers other than the above-mentioned monomers copolymerizable with these monomers can be preferably used as optional monomers which can constitute the graft-type polymer (2).

The polymerizable oligomer (macromonomer) which is preferably used as a monomer capable of constituting the graft-type polymer (2) is an oligomer having a carbon-carbon double bond at the terminal, and specifically includes polystyrene, polyethylene oxide, polypropylene oxide Poly (meth) acrylic acid ester, polycaprolactone, and the like. As the polymerizable oligomer (macromonomer), those having polycaprolactone are preferable from the viewpoint of obtaining good dispersibility.

As a method for synthesizing a polymerizable oligomer (macromonomer), the methods described in the respective publications of Japanese Patent Publication No. 9-507255, Japanese Patent Publication No. 2001-518530, Japanese Patent Application Publication No. 2005-298401, and Japanese Patent Publication No. 2006-521442 are listed do. Further, a method in which caprolactone is linked to the hydroxy (meth) acrylate disclosed in Japanese Patent Application Laid-Open No. 2007-63461 or a method in which caprolactone is linked to the hydroxy (meth) acrylate described in Japanese Patent Application Publication No. 2003-531001 Followed by reaction with an acid chloride.

The polymerizable oligomer (macromonomer) capable of constituting the graft-type polymer (2) is also available as a commercial product. Examples of such polymerizable oligomers (macromonomers) include monomethacryloylated polymethyl methacrylate oligomer (Mn = 6,000, trade name: AA-6, manufactured by TOAGOSEI CO., LTD.) Having a radical polymerized oligomer, Terminal methacryloylated poly-n-butyl acrylate oligomer (Mn = 6,000, trade name: AB-6, manufactured by TOAGOSEI CO., LTD.), One end methacryloylated polystyrene oligomer AS-6, TOAGOSEI CO., LTD.). Further, ε-caprolactone 2-adduct of hydroxymethylmethacrylate having an oligomer composed of polycaprolactone having a terminal hydroxyl group (trade name: Placcel FM2D, produced by DAICEL CHEMICAL INDUSTRIES, LTD.), Hydroxymethylmethacryl (Trade name: Placcel FM3, produced by DAICEL CHEMICAL INDUSTRIES, LTD.), Ε-caprolactone 3-moles adduct of propylene glycol monomethyl ether acetate (Trade name: Placcel FA2D, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) Of ε-caprolactone of hydroxymethyl acrylate, ε-caprolactone 10-mol adduct of hydroxymethyl acrylate : Placcel FA10L, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.).

The graft-type polymer (2) can be produced by a general radical polymerization method. In general, suspension polymerization or solution polymerization is used.

Examples of the solvent used for synthesizing the graft polymer (2) include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol mono Propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene, , Ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.

In the radical polymerization, a radical polymerization initiator can be used. In addition, chain transfer agents (e.g., 2-mercaptoethanol and dodecyl mercaptan) can be used.

Specific examples of specific polymer compounds classified as graft polymers are listed below, but the present invention is not limited thereto. The molecular weight of the polymer compound shown below has a weight average molecular weight (Mw) in the range of 1,000 to 100,000 and a number average molecular weight (Mn) in the range of 400 to 50,000.

When the content of the repeating unit having a basic nitrogen atom is A and the content of other repeating units having a polymer chain in the side chain is B, the ratio (A / B) is A / B = 10 / 90 mass% to 70/30 mass%.

In each of the above embodiments, the content of the repeating unit having a basic nitrogen atom is A, the content of another repeating unit having a polymer chain in the side chain is B and the content of other repeating units having a polymer chain in the side chain is C (A / B / C) is in the range of A / B / C = 10/10/80 mass% to 60/10 / 30 mass%.

When the specific polymer compound has a copolymer unit derived from a monomer having an acid group, the content of the copolymer unit derived from the monomer having an acid group is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 30 mgKOH / 100 mgKOH / g, more preferably 50 mgKOH / g to 80 mgKOH / g.

That is, when the pigment dispersion composition containing the processed pigment of the present invention is applied to the photocurable composition, the content of the polymerized units derived from the monomer having an acid group is preferably 50 mgKOH / g Or more. When the acid value is not less than 200 mgKOH / g, agglomeration between the acid groups becomes strong, so that agglomeration occurs between the processed pigments and the dispersibility deteriorates, which is not preferable. The content of the copolymer unit derived from the monomer having an acid group is preferably within the above range in order to effectively inhibit the generation of secondary aggregates, which are agglomerates of the primary particles of the pigment, or effectively weaken the cohesion of the secondary agglomerates.

The specific polymer compound contributes to a good dispersibility when dispersed in the presence of the acidic dispersant, which is a pigment coated with the above-mentioned polymer compound, and therefore can be preferably used in combination with the acidic dispersant.

In addition, the specific polymer compound can adjust the basicity, hydrophilicity and molecular weight of the polymer compound to suitably adjust the ease of coating on the pigment and the dispersion stability.

From the above viewpoint, as the polymer compound having a basic nitrogen atom, among the above-mentioned specific polymer compounds, a polymer compound containing a structural unit derived from a (meth) acrylic acid ester having a basic nitrogen atom, such as poly (lower alkyleneimine) .

The specific molecular weight of the specific polymer compound preferably has a weight average molecular weight (Mw) in the range of 1,000 to 100,000 and a number average molecular weight (Mn) in the range of 400 to 50,000. It is more preferable that the weight average molecular weight (Mw) is in the range of 5,000 to 50,000 and the number average molecular weight (Mn) is in the range of 2,000 to 30,000. It is most preferable that the weight average molecular weight (Mw) is in the range of 8,000 to 30,000 and the number average molecular weight (Mn) is in the range of 4,000 to 12,000.

That is, the weight average molecular weight (Mw) of the specific polymer compound is preferably 1,000 or more from the viewpoints of effectively suppressing the generation of secondary aggregates, which are agglomerates of the primary particles of the pigment, or effectively weakening the cohesion of the secondary agglomerates. From the viewpoint of developability when a color filter is produced by the photo-curable composition containing the processed pigment of the present invention, the weight average molecular weight (Mw) of the specific polymer compound is preferably 100,000 or less.

In the processed pigment of the present invention, the content ratio of i) the pigment and iv) the specific polymer compound is preferably 1: 0.01 to 1: 2, more preferably 1: 0.05 to 1: 1, and more preferably from 1: 0.1 to 1: 0.6.

When producing the processed pigment of the present invention, other polymer compounds other than the above-mentioned specific polymer compound may be used at the same time, if necessary. A modified natural resin, a synthetic resin, a water-soluble organic solvent, a water-soluble organic solvent, a water-soluble organic solvent, and a water-soluble organic solvent, which are solid at room temperature, insoluble in water, Synthetic resins modified from natural resins, and the like are used.

When a dried processed pigment is obtained, the other polymer compound is preferably solid at room temperature.

Examples of the natural resin include rosin, and modified natural resins include rosin derivatives, fibrin derivatives, rubber derivatives, protein derivatives, and oligomers thereof. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of the synthetic resin modified with a natural resin include a rosin-modified maleic resin and a rosin-modified phenolic resin.

Examples of the synthetic resin include polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate .

The treated pigment of the present invention is characterized in that i) the pigment particles such as organic pigments are coated with a specific polymer compound, iv) the polymer compound is strongly coated on part or all of the surface of the pigment particles to achieve the effect of the present invention And is different from a case where a general polymer dispersant is adsorbed on a pigment. This covered state can be confirmed by measuring the amount of the polymer compound (free ratio) in the cleaning with the organic solvent shown below. In other words, most of the polymer compounds, which are adsorbed only to the pigment, are removed by cleaning with an organic solvent, specifically, 65% or more. However, in the case of the processed pigment surface-coated as in the present invention, , 30% or less.

The glass amount of the polymer compound of the working pigment in the present invention is calculated by washing the treated pigment with 1-methoxy-2-propanol. Specifically, 10 g of the processed pigment is added to 100 ml of 1-methoxy-2-propanol and shaken at room temperature for 3 hours in a shaker. Then, the pigment is settled in a centrifuge at 80,000 rpm for 8 hours to obtain the solids content of the supernatant portion by the drying method. The mass of the polymer compound liberated from the pigment is determined from the amount of the solid component, and the free ratio (%) is calculated from the ratio of the mass of the polymer compound used in the initial treatment.

The free ratio of the processed pigment such as commercially available products can be measured by the following method.

That is, the entire processed pigment is dissolved with a solvent (for example, dimethylsulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.) dissolving the pigment, and then separated from the organic solvent using the difference in solubility between the polymer and the pigment, Mass of the polymer compound used in the initial treatment &quot;. Separately, the treated pigment is washed with 1-methoxy-2-propanol, and the amount of the obtained glass is divided by the "mass of the polymer compound used in the initial treatment" to obtain the glass ratio (%).

The smaller the free ratio, the higher the coating rate on the pigment, and the better the dispersibility and the dispersion stability. The preferred range of the free rate is 30% or less, more preferably 20% or less, and most preferably 15% or less. Ideally it is 0%.

The treated pigment of the present invention is a processed pigment excellent in dispersibility and dispersion stability because it is not advantageous even when the pigment surface is strongly coated with a specific polymer compound and immersed in an organic solvent, and its application range is wide. Particularly, it is useful for the preparation of the pigment dispersion composition described later.

[Pigment dispersion composition]

Next, the pigment dispersion composition of the present invention using the above-mentioned processed pigment of the present invention will be described.

The pigment dispersion composition of the present invention is obtained by dispersing the above-mentioned processed pigment of the present invention in an organic solvent.

In the case of dispersing the processed pigment of the present invention in an organic solvent, it is also a preferable form to use a pigment derivative and a dispersant as necessary.

[Organic solvents]

The organic solvent in the pigment dispersion composition of the present invention is not particularly limited as long as it is an organic solvent and can be appropriately selected from known ones. Examples thereof include 1-methoxy-2-propyl acetate, 1-methoxy- (Poly) alkylene glycol monoalkyl (meth) acrylate such as 2-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether and ethylene glycol monoethyl ether Ethers and their acetic acid esters; Acetic acid esters such as ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate and i-butyl acetate; Aromatic hydrocarbons such as benzene, toluene and xylene; Ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; And alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin. These may be used singly or in combination of two or more kinds. Among them, alkylene glycol monoalkyl ethers, and their acetic acid esters, acetic acid esters, methyl ethyl ketone and the like are preferable.

The content of the organic solvent in the pigment dispersion composition is appropriately selected depending on the use of the pigment dispersion composition and the like. When the pigment-dispersed composition is used for the preparation of a photo-curable composition described later, it may contain a solid content concentration of 5 to 50% by mass in terms of handleability, including a processed pigment and the like.

[Pigment Derivative]

In the pigment dispersion composition of the present invention, a pigment derivative is added as required.

The processed pigment can be dispersed as fine particles in the pigment dispersion composition by adsorbing the pigment derivative having the affinity with the dispersant or the pigment derivative having the polar group introduced thereon to the surface of the processed pigment and using this as the adsorption point of the dispersant, Aggregation can be prevented.

Specifically, the pigment derivative is a compound in which an organic pigment is used as a parent skeleton and an acid group, a basic group or an aromatic group is introduced as a substituent into the side chain. Specific examples of the organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindolin pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoimidazolone pigments, Pigments, and the like. In general, pale yellow aromatic polycyclic compounds such as naphthalene-based, anthraquinone-based, triazine-based, and quinoline-based compounds which are not called pigments are also included. Examples of the pigment derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810 Those described in JP-A-11-199796, JP-A-2005-234478, JP-A-2003-240938, and JP-A-2001-356210 can be used.

The content of the pigment derivative in the pigment dispersion composition is preferably from 1 to 30 mass%, more preferably from 3 to 20 mass%, based on the mass of the pigment. When the content of the pigment derivative is within the above range, dispersion can be favorably performed while suppressing the viscosity to be low, and dispersion stability after dispersion can be improved.

By applying this pigment dispersion composition to the production of a color filter, a color filter having high transmittance, excellent color characteristics, and high contrast can be obtained.

[Dispersant]

To the pigment dispersing composition of the present invention, conventionally known dispersing agents such as pigment dispersing agents and surfactants may be added for the purpose of further improving the dispersibility of the processed pigment.

Examples of known dispersants (pigment dispersants) include polymer dispersants such as polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) , (Meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates], and polyoxyethylene alkylphosphoric acid esters, polyoxyethylene alkylamines, alkanolamines, pigment derivatives, and the like.

Polymeric dispersants can be further divided into linear polymers, end-modified polymers, graft-type polymers, and block-type polymers from the structure.

The polymer dispersant is adsorbed on the surface of the pigment to prevent re-aggregation. Therefore, a terminal modified polymer having an anchor portion on the surface of the pigment, a graft polymer, and a block polymer can be exemplified as preferable structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

In the dispersion step, the polymer dispersant is adsorbed on the surface of the pigment to prevent re-aggregation. Therefore, block type polymers, graft type polymers, and terminal modified polymers having anchor sites on the surface of the pigment can be listed as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

(Graft type polymer)

The graft polymer is not particularly limited, but a compound obtained by reacting a polyalkyleneimine and a polyester compound described in JP-A-54-37082 and JP-A-61-174939, Compounds in which the amino group of the side chain of the polyallylamine described in JP-A-169821 is modified with a polyester, polyester polyol addition polyurethane described in JP 60-166318 A, and the like are preferably listed, Grafted polymers comprising a polymerizable oligomer (hereinafter referred to as a macromonomer) as a copolymerization component, such as those described in JP-A-9-171253 and Macromolecule Chemistry and Industry (IPC Publishing, 1989) In addition, graft polymers having an organic dye moiety described in JP-A-2003-238837 are preferable in terms of being adsorbed on the pigment and imparting a good dispersibility.

The branch portion of the graft-type polymer is preferably a polystyrene, polyethylene oxide, polypropylene oxide, poly (meth) acrylate, polycaprolactone or the like, but more preferably a graft polymer having a polycaprolactone chain.

Solsperse 32000, Solsperse 38500, Solsperse 39000, Solsperse 55000 (manufactured by The Lubrizol Corporation), Disperbyk-161, Disperbyk-171, Disperbyk-174 (above, BYK Japan KK Products) can be listed.

(Terminal modified polymer)

Examples of the terminal modified polymer include polymers described in JP-A-9-77994, JP-A-2002-273191, JP-A-2007-277514, JP-A-2007-140487, A polymer having a functional group at the terminal thereof.

(Block type polymer)

The block type polymer is not particularly limited, but block type polymers comprising a pigment adsorption block and a block that is not adsorbed to the pigment are listed.

The monomers constituting the pigment adsorption block are not particularly limited, and for example, monomers having a functional group capable of adsorbing to the pigment are listed. Specifically, a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, a monomer having a basic nitrogen atom, and the like can be exemplified.

Examples of the monomer having an organic dye structure or a heterocyclic structure include an organic dye skeleton and a maleimide derivative described in JP-A-2003-238837.

A commercially available block type polymer may be used. Specific examples thereof include Disperbyk-2000, Disperbyk-2001 (manufactured by BYK Japan K K), EFKA 4330 and EFKA 4340 (manufactured by EFKA Additives Japan Inc.).

- Preparation of pigment dispersion composition -

The pigment dispersion composition of the present invention can be prepared by mixing and dispersing the mixture using various mixers and dispersers.

The mixing and dispersing step is preferably composed of a kneading dispersion followed by a non-dispersion treatment, but it is also possible to omit the kneading dispersion.

Specifically, the pigment dispersion composition of the present invention can be produced, for example, by mixing the processed pigment of the present invention, the organic solvent and optional components (pigment derivative, dispersant, etc.) used as needed in a sand or a horizontal type sand grinder, pin mill, slit mill , An ultrasonic dispersing machine or the like, and then performing micro-dispersion treatment with beads made of glass, zirconium oxide or the like having a particle diameter of 0.01 mm to 1 mm.

Further, before fine dispersion by beads is carried out, two rolls, three rolls, a ball mill, a trommel, a dispenser, a kneader, a coneizer, a homogenizer, a blender, a single shaft or a biaxial extruder, It is also possible to carry out the kneading dispersion treatment.

Further, details of kneading and dispersing are described in T. C. Patton, "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, Inc. 1964).

[Photocurable composition]

The photocurable composition of the present invention preferably contains the above-described pigment dispersion composition of the present invention, a polymerizable compound and a photopolymerization initiator, and further contains an alkali-soluble resin, and may contain other components as required.

The photocurable composition of the present invention is preferably used in the photocurable composition used in the production of a color filter. Hereinafter, each component contained in the photocurable composition of the present invention will be described in detail.

[Pigment dispersion composition]

The photocurable composition of the present invention comprises at least one kind of the pigment dispersion composition of the present invention. Details of the pigment dispersion composition of the present invention constituting the photocurable composition are as described above.

The content of the pigment dispersion composition in the photocurable composition of the present invention is preferably such that the content of the pigment to be treated is in the range of 5 mass% to 70 mass% relative to the total solid content (mass) of the photocurable composition, more preferably 15 mass% By mass to 60% by mass. When the content of the pigment dispersion composition is within this range, the color density is sufficient and it is also effective in securing excellent color characteristics.

[Polymerizable compound]

The photocurable composition of the present invention contains at least one polymerizable compound.

As the polymerizable compound usable in the present invention, a compound having at least one ethylenically unsaturated group capable of addition polymerization and having a boiling point of 100 DEG C or higher at normal pressure is preferable, and among these, an acrylate compound having four or more functions is more preferable.

(Meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. Examples of the compound having at least one addition polymerizable ethylenic unsaturated group and having a boiling point of at least 100 ° C at normal pressure include polyethylene glycol mono Monofunctional acrylate or methacrylate such as acrylate; (Meth) acrylates such as polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to an alcohol, poly (meth) acrylate of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708, Japanese Patent Publication 50-6034, JP-A-51-37193, JP-A-48-64183, JP-A- Polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resin with (meth) acrylic acid, epoxy acrylates and the like, as disclosed in JP-B-49-43191 and JP-A-52-30490 Can be listed.

Also, 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers.

Further, in Japanese Patent Application Laid-Open No. 10-62986, it is also possible to add ethylene oxide or propylene oxide to the above polyfunctional alcohol represented by general formulas (1) and (2) together with specific examples thereof and then to (meth) Compounds can also be used.

Among them, a structure in which dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate, and acryloyl group of these are interposed between ethylene glycol and propylene glycol residue is preferable. These oligomer types can also be used.

The polymerizable compound may be used singly or in combination of two or more.

The content of the polymerizable compound in the photo-curable composition is preferably from 3 to 55 parts by mass, more preferably from 10 to 50 parts by mass, based on 100 parts by mass of the total solid content of the composition. When the content of the polymerizable compound is within the above range, the curing reaction can be sufficiently performed.

[Photopolymerization initiator]

Examples of the photopolymerization initiator include halomethyloxadiazole described in Japanese Patent Application Laid-Open No. 57-6096, halomethyl-s-aminophenol disclosed in Japanese Patent Publication No. 59-1281, Japanese Patent Application Laid-open No. 53-133428, Aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in each specification such as US Patent USP-4318791, EP-88050A, and the like, as disclosed in U.S. Patent No. USP-4199420 (Thio) xanthones or acridine compounds described in Fr-2456741, compounds such as coumarins or ropin dyes described in JP-A No. 10-62986, compounds such as Japanese Patent And sulfonium organic boron complexes such as disclosed in JP-A-8-015521.

The photopolymerization initiator may be at least one selected from the group consisting of acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, triazine, halomethyloxadiazole, acridine, coumarin, , Oxime ester type and the like are preferable.

Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl- Acetophenone, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, and the like.

As the ketal-based photopolymerization initiator, for example, benzyldimethyl ketal, benzyl- beta -methoxyethyl acetal and the like can be preferably exemplified.

Examples of the benzophenone-based photopolymerization initiator include benzophenone, 4,4'- (bisdimethylamino) benzophenone, 4,4 '- (bisdiethylamino) benzophenone, 4,4'-dichlorobenzophenone, Cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1.

Examples of the benzoin or benzoyl photopolymerization initiator include benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl benzoate, and the like.

Examples of the xanton-based photopolymerization initiator include diethyl thioxanthone, diisopropyl thioxanthone, monoisopropyl thioxanthone, and chlorothioxanthone.

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

Examples of the halomethyloxadiazole photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostiryl) 4-oxodiazole, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, 1,3,4-oxadiazole, and the like can be preferably exemplified.

Examples of the acridine photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

Examples of the coumarinite photopolymerization initiator include 3-methyl-5-amino- ((s-triazin-2-yl) amino) 3-phenylcoumarin, 3-butyl-5-dimethylamino- ((s-triazin-2-yl) amino) -3-phenyl coumarin and the like are preferably enumerated .

Examples of the phosphineimide-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5- Dimerolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, and the like can be preferably exemplified.

As the imidazole-based photopolymerization initiator, for example, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide and the like can be preferably exemplified.

In addition to the above, there may be mentioned 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4'- (benzmercapto) benzoyl- -Trimethylphenylcarbonyl-diphenylphosphonyloxide, hexafluorophosphorothio-trialkylphenylphosphonium salt, and the like.

The present invention is not limited to the photopolymerization initiator described above, and other known ones can be used. For example, bisphenol polyketol aldonyl compounds described in U.S. Patent No. 2,367,660, α-carbonyl compounds described in U.S. Patent Nos. 2,367,661 and 2,367,670, acyloin ethers described in U.S. Patent No. 2,448,828 , Aromatic acyloin compounds substituted with alpha -hydrocarbons described in U.S. Patent No. 2,722,512, polynuclear quinone compounds described in U.S. Patent Nos. 3,046,127 and 2,951,758, triallylimine compounds described in U.S. Patent No. 3,549,367 Benzothiazole compound / trihalomethyl-s-triazine compound described in Japanese Patent Publication No. 51-48516, JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and JP-A 2000-66385.

These photopolymerization initiators may also be used in combination.

The content of the photopolymerization initiator in the photocurable composition is preferably from 0.1 to 10.0% by mass, more preferably from 0.5 to 5.0% by mass, based on the total solid content of the composition. When the content of the photopolymerization initiator is within the above range, it is possible to form a film with good strength by progressing the polymerization reaction well.

[Alkali-soluble resin]

The alkali-soluble resin is preferably a linear organic polymer and is a group which promotes the solubility of at least one alkali in a molecule (preferably an acrylic copolymer, a molecule having a styrenic copolymer as a main chain) (for example, a carboxyl group, a phosphoric acid group, And the like). Of these, more preferably, it is soluble in an organic solvent and can be developed by a weakly alkaline aqueous solution.

The alkali-soluble resin can be produced, for example, by a known radical polymerization method. Polymerization conditions such as the temperature, pressure, kind and amount of the radical initiator and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art and can be determined experimentally .

As the above-mentioned linear organic polymer, a polymer having a carboxylic acid in its side chain is preferable. For example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Laid-Open Patent Publication No. 59-53836, Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like, as described in each publication of Japanese Patent Application Laid-Open No. 59-71048, An acidic cellulose derivative having a carboxylic acid in its side chain, an acid anhydride added to a polymer having a hydroxyl group, and the like, and a polymer having a (meth) acryloyl group in its side chain.

Among these, a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid copolymer or benzyl (meth) acrylate / (meth) acrylic acid / other monomer is preferable.

In addition to these, copolymers of 2-hydroxyethyl methacrylate and the like are also listed as useful. The polymers may be used in any amount and mixed.

In addition to the above, there may be mentioned 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A No. 7-140654, 2-hydroxy- Acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxy Ethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like.

As specific constituent units of the alkali-soluble resin, copolymers of (meth) acrylic acid and other monomers copolymerizable therewith are preferable. Here, (meth) acrylic acid is a generic name including acrylic acid and methacrylic acid, and similarly, (meth) acrylate is also collectively referred to as acrylate and methacrylate.

Examples of the other monomer copolymerizable with the (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, (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, Acrylate, cyclohexyl (meth) acrylate, and the like.

Examples of the vinyl compound include styrene,? -Methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate _{^{macromonomer, CH 2 = CR 1 R 2}} , CH 2 = C (R 1) (COOR 3) [ where, R ¹ is a hydrogen atom or a C 1 -C 5 alkyl group, R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms.

These copolymerizable other monomers may be used singly or in combination of two or more. Preferred other copolymerizable monomers are at least one member selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate, Particularly preferably, CH ₂ = CR ¹ R ² and / or CH ₂ = C (R ¹ ) (COOR ³ ).

The content of the alkali-soluble resin in the photocurable composition is preferably from 1 to 15% by mass, more preferably from 2 to 12% by mass, and particularly preferably from 3 to 10% by mass, based on the total solid content of the composition.

[solvent]

The photocurable composition of the present invention can be preferably prepared by using the above-mentioned respective components and a solvent together.

Examples of the solvent include esters such as ethyl acetate, isobutyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-oxypropionic acid alkyl esters such as ethyl oxypropionate; Methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, Methoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy- Ethyl propionate, methyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2- Ethyl 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 and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene and xylene.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like.

The solvent may be used alone or in combination of two or more.

[Other ingredients]

The photo-curing composition of the present invention may contain, if necessary, a fluorine-containing organic compound, a thermal polymerization initiator, a thermopolymerization component, a thermal polymerization inhibitor, a colorant, a photopolymerization initiator and other fillers, a polymer compound other than the alkali- Antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like.

&Lt; Fluorine organic compound &

By containing the fluorine-based organic compound, it is possible to improve the liquid property (in particular, fluidity) when the coating liquid is used, and it is possible to improve uniformity of coating thickness and liquid saving. That is, since the interfacial tension between the substrate and the coating liquid is lowered, the hygroscopicity to the substrate is improved to improve the coating property on the substrate, so that even when a thin film of about several micrometers is formed with a small amount of liquid, It is effective in that a film can be formed.

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

Examples of the fluorinated organic compounds include Megafac F171, Megafac F173, Megafac F173, Megafac F147, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437 Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1061, Surflon SC-381, Surflon SC-383 (manufactured by Sumitomo 3M Ltd.) Surflon S393, Surflon KH-40 (manufactured by ASAHI GLASS CO., LTD.), And the like.

As the fluorine-containing organic compound, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, the main chain and the side chain can be preferably used. Specific examples of the commercially available products include Megafac F142D, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F183, Megafac 780, Megafac 781, Megafac R30, Megafac R08, Megafac F- Fluorad FC-430, Fluorad FC-431, Novec FC-4430 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG 7105, 7000, 950 (product of DIC Corporation), Fluorad FC- Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-101, Surflon S-112, Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S- Surflon SC-105, Surflon SC-106 (manufactured by ASAHI GLASS CO., LTD.), Eftop EF351, Eftop 352, Eftop 801 and Eftop 802 (manufactured by JEMCO Coopoerations Co., Ltd.).

The fluorine-based organic compound is particularly effective for preventing uneven application and thickness irregularity when the coating film is made thin. In addition, it is also effective in applying a slit which tends to cause a sag.

The amount of the fluorine-based organic compound to be added is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the photocurable composition.

<Thermal polymerization initiator>

It is also effective to include a thermal polymerization initiator in the photocurable composition of the present invention. Examples of the thermal polymerization initiator include various azo-based compounds and peroxide-based compounds, and azo-based compounds may include azobis-based compounds. Examples of the peroxide-based compounds include ketone peroxide, peroxyketal, Peroxides, dialkyl peroxides, diacyl peroxides, peroxy esters, peroxydicarbonates, and the like.

&Lt; Thermal polymerization component >

It is also effective to incorporate a thermally polymerizable component in the photocurable composition of the present invention. If necessary, an epoxy compound may be added to increase the strength of the coating film. The epoxy compound is a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolak type, biphenyl type, and alicyclic epoxy compound. Examples of the bisphenol A type include EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF- Placcel GL-61, GL-62, G101, and G102 (manufactured by Tohto Kasei Co., Ltd.), Denacol EX-1101, EX-1102 and EX- (Manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.), And bisphenol F type and bisphenol S type similar to these. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel UCB Co., Ltd.) can also be used. Examples of the cresol novolak type include EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703 and YDPN-704 (manufactured by Tohto Kasei Co., Ltd.), Denacol EM- 3,5,3 ', 5'-tetramethyl-4,4'-diglycidylbiphenyl as the biphenyl type, and Seroxide 2021, 2081, 2083, 2085, Epolead ST-5000, ST-5100 (or more), GT-301, GT-302, GT-401, GT-403, EHPE- Manufactured by Tohto Kasei Co., Ltd.). Also, there may be mentioned 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyl tris (hydroxyethyl) isocyanurate, o - EPOTOHTO YH-434, YH-434L which are amine type epoxy resins, glycidyl esters obtained by modifying dimer acid in the skeleton of bisphenol A type epoxy resin, and the like can also be used .

<Surfactant>

The photocurable composition of the present invention is preferably composed of various surfactants from the viewpoint of improving the applicability. In addition to the above-mentioned fluorochemical surfactants, various nonionic, cationic and anionic surfactants can be used . Above all, a fluorine-based surfactant or a nonionic surfactant having a perfluoroalkyl group as the nonionic surfactant is preferable.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and the like A nonionic surfactant is particularly preferred. Specific examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether and polyoxyethylene nonyl phenyl ether; Polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, ethylene diamine polyoxyethylene-polyoxypropylene condensates, and the like, such as polyoxyethylene dialkyl esters such as polyoxyethylene distearate and polyoxyethylene distearate, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, Ionic surfactants, which are commercially available from Kao Corporation, NOF CORPORATION, TAKEMOTO OIL & FAT Co., Ltd., ADEKA CORPORATION, SANYO KASEI CO., LTD. And the like can be appropriately used. In addition to the above, the above-described dispersion system can be used.

In addition to the above, various additives may be added to the photo-curable composition. Specific examples of the additives include an ultraviolet absorber such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, an antifogging agent such as sodium polyacrylate, Fillers such as; Itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, acidic anhydrides added to polymers having hydroxyl groups, alcohol-soluble nylons, bisphenol A and epichlorohydrin And an alkali-soluble resin such as a phenoxy resin.

When accelerating the alkali solubility of the uncured portion and further improving the developability of the pigment dispersion composition, it is possible to add an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less, to the pigment dispersion composition have. Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capric acid, diethylacetic acid, enantic acid and caprylic acid; There may be mentioned oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, , Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and canononic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemellitic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, merromatic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydroatrophic acid, hydroxycarboxylic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamidic acetic acid, cumaric acid and umbaric acid.

<Thermal polymerization inhibitor>

In the photo-curable composition of the present invention, it is preferable to further add a thermal polymerization inhibitor in addition to the above, and examples thereof include hydroquinone, p-methoxyphenol, di-t-butyl- (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl- Mercaptobenzimidazole and the like are useful.

Since the photocurable composition of the present invention includes the pigment dispersion composition (pigment dispersion composition of the present invention) comprising the processed pigment of the present invention, the dispersibility of the processed pigment is excellent and the color characteristic is also excellent.

Therefore, it is preferable to use it for forming a colored region of a color filter in which a good color characteristic is required.

<Color filter>

The color filter of the present invention is characterized by having a colored region formed on the substrate by the photocurable composition of the present invention.

Here, the colored region includes both a coloring pattern (pixel portion) of three or four colors and a black matrix.

Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method.

A method of manufacturing the color filter of the present invention will be described.

First, the photocurable composition of the present invention is applied to the substrate directly or through another layer (preferably, applied by spin coating, slit coating, smoothing coating, roll coating, etc.) ) (Coating step). Thereafter, the formed film is exposed through a predetermined mask pattern (exposure step). After exposure, the uncured portions of the coated film are developed and removed with a developer (developing step). Through these steps, a coloring pattern composed of pixels of each color (three colors or four colors) is formed to obtain a color filter.

According to this method, the color filter used in the liquid crystal display element or the solid-state image pickup element can be manufactured with low difficulty in process, high quality, and low cost.

Hereinafter, each step will be described in detail.

[Application step]

First, the substrate used in the coating step will be described.

As the substrate used for the color filter of the present invention, for example, an alkali-free glass, a soda glass, a Pyrex (registered trademark) glass, a quartz glass, and a film obtained by attaching a transparent conductive film thereto, A photoelectric conversion element substrate to be used, for example, a silicon substrate or a plastic substrate is enumerated.

On these substrates, a black matrix for isolating each pixel is formed, or a transparent resin layer may be formed for facilitating adhesion.

It is also preferable that the plastic substrate has a gas barrier layer and / or a solvent-resistant layer on its surface.

(Hereinafter referred to as &quot; TFT type liquid crystal driving substrate &quot;) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed is used, and on this driving substrate A colored pattern can be formed by using the photo-curable composition of the present invention, and a color filter can be produced.

Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, and the like. These substrates may be subjected to a suitable pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition or the like, if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of a TFT type liquid crystal driving substrate can be used.

In the coating step, the method of applying the photocurable composition of the present invention to a substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter referred to as a slit nozzle application Law) is desirable.

In the slit nozzle coating method, the slit-end spin coating method and the spinless coating method have different conditions depending on the size of the application substrate. For example, a fifth-generation glass substrate (1100 mm x 1250 mm) is formed by a spinless coating method, Sec, the amount of the photo-curable composition to be discharged from the slit nozzle is usually 500 to 2000 / / sec, preferably 800 to 1500 / / sec, and the application speed is usually 50 to 300 mm / Second, preferably 100 mm / second to 200 mm / second.

The solid content of the photocurable composition used in the application step is usually 10% to 20%, preferably 13% to 18%.

When a coating film of the photocurable composition of the present invention is formed on a substrate, the thickness of the coating film (after the pre-baking treatment) is generally 0.3 탆 to 5.0 탆, preferably 0.5 탆 to 4.0 탆, 0.5 탆 to 3.0 탆.

In the case of a color filter for a solid-state imaging device, the thickness of the coating film (after pre-baking) is preferably in the range of 0.5 mu m to 5.0 mu m.

In the coating step, prebaking treatment is usually carried out after application. If necessary, a vacuum treatment may be performed before prebaking.

Vacuum drying conditions are usually about 0.1 torr to 1.0 torr, preferably about 0.2 torr to 0.5 torr.

The prebaking treatment can be carried out in a temperature range of 50 占 폚 to 140 占 폚, preferably 70 占 폚 to 110 占 폚, for 10 seconds to 300 seconds by using a hot plate, an oven or the like. The pre-baking treatment may be combined with a high-frequency treatment. High frequency processing can be used alone.

[Exposure step]

In the exposure step, exposure is performed to a coating film formed of the photocurable composition formed as described above through a predetermined mask pattern.

As the radiation used in exposure, ultraviolet rays such as g line, h line, i line and j line are particularly preferable.

When a color filter for a liquid crystal display device is manufactured, exposure using h-line or i-line is preferably used by a proximity photolithography machine or a mirror projection exposure machine.

In manufacturing a color filter for a solid-state imaging device, it is preferable to use i-line mainly in a stepper exposure apparatus.

Further, when manufacturing a color filter using a TFT-type liquid crystal driving substrate, a photomask used for forming a through hole or a U-shaped pit is formed in addition to a pattern for forming a pixel (coloring pattern) Is used.

[Development process]

In the developing step, the uncured portion of the coated film after exposure is eluted into the developing solution so that only the hardened powder remains on the substrate.

The developing temperature is usually 20 ° C to 30 ° C, and the developing time is 20 seconds to 90 seconds.

Any developer may be used as long as it dissolves the coating film of the photocurable composition in the un-cured portion and does not dissolve the cured portion.

Concretely, a combination of various organic solvents or an alkaline aqueous solution can be used.

As the organic solvent to be used for development, the above-mentioned solvents which can be used in preparing the photocurable composition of the present invention are listed.

The alkaline aqueous solution includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, An alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo- [5,4,0] -7-undecene in an amount of 0.001 to 10% Preferably 0.01% by mass to 1% by mass, based on the total amount of the aqueous solution.

To the alkaline aqueous solution, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added.

The developing method may be a dipping method, a shower method, a spray method, or the like, and a swing method, a spin method, an ultrasonic method, or the like may be combined with the developing method. It is also possible to wet the surface to be developed with water or the like before coming into contact with the developing solution to prevent development unevenness. Further, the substrate may be inclined and developed.

When manufacturing a color filter for a solid-state imaging device, a paddle phenomenon is also used.

After the developing treatment, the drying is carried out through a rinsing treatment in which excess developer is removed, and then heat treatment (post baking) is performed to complete the curing.

The rinse treatment is usually carried out with pure water, but pure water is used in the final cleaning for saving the liquid, and pure water is used at the beginning of the cleaning, or the substrate is tilted or the ultrasonic irradiation is used in combination It is also good.

After the rinsing treatment, water is removed and dried, and then heat treatment is usually performed at about 200 ° C to 250 ° C.

This heating treatment (post-baking) can be carried out continuously or batchwise by using a heating means such as a hot plate, a convection oven (hot-air circulation type drier), or a high-frequency heater so that the coated film after development becomes the above-

By repeating the above steps sequentially for each color in accordance with the desired number of colors, it is possible to produce a color filter in which colored cured films (colored patterns) of a plurality of colors are formed.

The color filter of the present invention can be preferably used for a solid-state image pickup device or a liquid crystal display device because of its high contrast, small color density unevenness, and good color characteristics.

The use of the photo-curable composition of the present invention has been mainly described with respect to its application to a coloring pattern of a color filter, but it can also be applied to the formation of a black matrix which isolates a coloring pattern (pixel) constituting a color filter.

The black matrix on the substrate can be formed by using a photo-curing composition containing a working pigment of a black pigment such as carbon black or titanium black, passing through each step of coating, exposure and development, and then post baking if necessary have.

&Lt; Liquid crystal display element, solid state image pickup element &

The color filter of the present invention can be applied as a color filter having a liquid crystal display element or a solid-state image pickup element. More specifically, for example, an orientation film is formed on the inner surface side of a color filter, and a liquid crystal display element is obtained by sealing and sealing the space portion with the liquid crystal opposite to the electrode substrate. Further, for example, by forming a color filter on the light receiving element, a solid-state image pickup element can be obtained.

Example

Hereinafter, the present invention will be described more concretely with reference to Examples, but the present invention is not limited to the following Examples unless they depart from the spirit of the present invention. Unless otherwise specified, &quot; part &quot; is based on mass.

(Synthesis of Specific Polymer Compound and Comparative Polymer Compound)

&Lt; Synthesis Example 1: Synthesis of Polymer Compound 1 >

50.0 g of dimethylaminoethyl methacrylate, 50.0 g of methyl methacrylate, and 233.3 g of 1-methoxy-2-propanol were introduced into a nitrogen-purged three-necked flask and stirred with a stirrer (SHINTO Scientific Co., Ltd., Motor), and the mixture was heated while flowing nitrogen into the flask, and the temperature was raised to 90 캜. To this was added 6.0 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C for 2 hours. After 2 hours, 6.0 g of V-65 was further added, and the mixture was heated and stirred for 3 hours to obtain a 30 mass% solution of Polymer Compound 1 as a specific polymer compound.

The weight average molecular weight of Polymer Compound 1 thus obtained was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance and found to be 2.0,000.

&Lt; Synthesis Example 2: Synthesis of Polymer Compound 2 >

50.0 g of vinylpyridine, 50.0 g of styrene and 233.3 g of 1-methoxy-2-propanol were introduced into a nitrogen-purged three-necked flask, stirred with a stirrer (SHINTO Scientific Co., Ltd., Sreeen Motor) And heated to 90 캜. To this was added 3.9 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C for 2 hours. After 2 hours, 3.9 g of V-65 was further added, and the mixture was heated and stirred for 3 hours to obtain a 30 mass% solution of Polymer Compound 2 as a specific polymer compound.

The weight average molecular weight of the obtained polymer compound was measured by gel permeation chromatography (GPC) using polystyrene as a standard material and found to be 2.5 thousands.

&Lt; Synthesis Examples 3 to 7: Synthesis of Polymer Compound 3 to 7, Polymer Compound C1 >

Polymer compounds 3 to 7 as specific polymer compounds and polymer compound C1 as a comparative polymer compound were obtained in the same manner as in polymer compound 1 except that the monomer used in the synthesis of the polymer compound 1 was changed to the composition (wt% Synthesis was carried out in the same manner.

The following Table 1 shows the monomers constituting the polymer compounds 1 to 7 and the polymer compound C1, the composition (wt%) thereof, and the weight average molecular weights (Mw) of the resulting polymer compounds.

Polymer Compound Number Composition of polymer compound
(weight%)
Mw
Polymer Compound 1 DMEAMA
50 MMA
50
-
20,000
Polymer compound 2 VyPy
50 St
50
-
25,000
Polymer compound 3 ASt
50 BzMA
50
-
18,000
Polymer compound 4 DMEAMA
30 HEMA
30 MMA
40
22,000
Polymer Compound 5 DMEAMA
40 AAEM
50 MAA
10
19,000
Polymer compound 6 DMEAMA
20 MMA
70 MAA
10
20,000
Polymer compound 7 DMEAMA
30 AA-6
60 MMA
10
28,000
Polymer Compound C1 BzMA
50 MAA
20 MMA
30
20,000

In Table 1, DMEAMA is dimethylaminoethyl methacrylate, MAA is methacrylic acid, MMA is methyl methacrylate, BzMA is benzyl methacrylate, HEMA is 2-hydroxyethyl methacrylate, AAEM is acetoacetate ethyl methacrylate Acrylate, styrene is styrene, VyPy is vinylpyridine, ASt is p-aminostyrene, and AA-6 is one-end methacryloylated polymethyl methacrylate oligomer (Mn = 6,000, manufactured by TOAGOSEI CO., LTD.).

&Lt; Synthesis Example 8: Synthesis of Polymer Compound 8 >

100 g of polyethyleneimine (SP-018, number average molecular weight 1,800, manufactured by NIPPON SHOKUBAI CO., LTD.) And 40 g of acetic anhydride were added to 326 g of 1-methoxy-2-propanol and stirred at 120 DEG C for 2 hours to obtain Polymer 8 Of a 30% by mass solution.

&Lt; Synthesis Example 9: Synthesis of Polymer Compound 9 >

According to the method described in Example 1 of Japanese Patent Application Laid-Open No. 2003-531001, Polymer Compound 10 in which condensation of caprolactone 10-moles adduct of 2-butyloctanoic acid and polyethyleneimine was obtained. The solvent was a 30 mass% solution of 1-methoxy-2-propanol.

(Synthesis Example 10: Synthesis of Polymer Compound 10)

(PAA-03, number average molecular weight: 3,000, manufactured by Nitto Boseki Co., Ltd., Japan) in accordance with the method described in Example 1 of Japanese Patent Application Laid-Open No. 2003-531001 and a caprolactone adduct of 2-butyloctanoic acid . The polymer compound 10 as a condensation product was obtained. The solvent was a 30 mass% solution of 1-methoxy-2-propanol.

The polymer compounds 1 to 6 and 8 are specific polymer compounds corresponding to the polymer consisting of repeating units having the nitrogen atom, and the polymer compounds 7, 9 and 10 are specific polymer compounds corresponding to the graft polymer.

[Examples 1-1 to 1-35, Comparative Examples 1-1 to 1-12]

&Lt; Production of a pigment for processing &

50 g of the pigment described in Table 2, 500 g of sodium chloride, 25 g of a specific polymer compound or a 30% solution of a comparative polymer compound and 100 g of diethylene glycol were charged into a stainless steel first gallon kneader (product of INOUE MANUFACTURING CO., LTD.), Kneaded for 9 hours. Subsequently, the mixture was poured into about 3 liters of water, stirred for about 1 hour with a high-speed mixer, and then filtered and washed with water to remove sodium chloride and solvent (diethylene glycol), followed by drying to obtain a polymer And the respective processed pigments of Comparative Examples were obtained.

(Measurement of Diameter of Primary Particle of Pigment)

The primary particle size of the processed pigment was obtained by observing the obtained processed pigment with a transmission electron microscope (TEM).

(Evaluation of coating degree of pigment)

10 g of the obtained processed pigment was added to 100 mL of 1-methoxy-2-propanol and shaken for 3 hours at room temperature on a shaker. The pigment was then settled over a period of 8 hours at 80,000 rpm with a centrifuge. The solids content of the supernatant portion was determined by the drying method. The amount of the polymer compound liberated from the pigment was determined, and the free ratio (%) was calculated from the ratio with the polymer compound used in the treatment. The smaller the free ratio, the higher the degree of coating of the polymer compound with the pigment.

Processed pigment
number
Polymer compound
number
Pigment The average primary of the treated pigment
Particle diameter
Free rate
(%) Example 1-1 R-1 One PR 254 25 nm 3 Examples 1-2 R-2 2 PR 254 25 nm 5 Example 1-3 R-3 3 PR 254 25 nm 7 Examples 1-4 R-4 4 PR 254 25 nm 4 Examples 1-5 R-5 5 PR 254 25 nm 3 Examples 1-6 R-6 6 PR 254 25 nm 4 Examples 1-7 R-7 7 PR 254 25 nm 12 Examples 1-8 R-8 8 PR 254 25 nm 5 Examples 1-9 R-9 9 PR 254 25 nm 10 Example 1-10 R-10 10 PR 254 25 nm 8 Example 1-11 R-11 11 PR 254 25 nm 10 Comparative Example 1-1 R-12 C1 PR 254 25 nm 80 Comparative Example 1-2 R-13 C2 PR 254 25 nm 50 Comparative Example 1-3 R-14 none PR 254 25 nm -

Examples 1-12 L-1 One PR 177 20 nm 8 Examples 1-13 L-2 2 PR 177 20 nm 5 Examples 1-14 L-3 6 PR 177 20 nm 9 Examples 1-15 L-4 8 PR 177 20 nm 8 Comparative Example 1-4 L-5 C1 PR 177 20 nm 82 Comparative Example 1-5 L-6 none PR 177 20 nm -

Examples 1-16 G-1 One PG 36 25 nm 8 Examples 1-17 G-2 3 PG 36 25 nm 5 Example 1-18 G-3 4 PG 36 25 nm 7 Example 1-19 G-4 9 PG 36 25 nm 15 Comparative Example 1-6 G-5 C1 PG 36 25 nm 80 Comparative Example 1-7 G-6 none PG 36 - -

Examples 1-20 Y-1 2 PY 150 20 nm 5 Examples 1-21 Y-2 3 PY 150 20 nm 8 Examples 1-22 Y-3 7 PY 150 20 nm 17 Examples 1-23 Y-4 8 PY 150 20 nm 8 Comparative Example 1-8 Y-5 C1 PY 150 20 nm 75 Comparative Example 1-9 Y-6 none PY 150 - -

Examples 1-24 B-1 2 PB 15: 6 15 nm 10 Examples 1-25 B-2 3 PB 15: 6 15 nm 8 Examples 1-26 B-3 7 PB 15: 6 15 nm 25 Examples 1-27 B-4 8 PB 15: 6 15 nm 8 Comparative Example 1-10 B-5 C1 PB 15: 6 15 nm 90

Examples 1-28 V-1 One PV 23 23nm 6 Examples 1-29 V-2 2 PV 23 23nm 8 Examples 1-30 V-3 7 PV 23 23nm 25 Examples 1-31 V-4 8 PV 23 23nm 5 Comparative Example 1-11 V-5 C1 PV 23 23nm 85

Example 1-32
G-7
One Polybrominated zinc Pc
25 nm
5
Examples 1-33
G-8
3 Polybrominated zinc Pc
25 nm
4
Examples 1-34
G-9
8 Polybrominated zinc Pc
25 nm
8
Example 1-35
G-10
9 Polybrominated zinc Pc
25 nm
12
Comparative Example 1-12
G-11
C1 Polybrominated zinc Pc
25 nm
80

Details of the compounds shown in Table 2 are as follows.

<Pigment>

PR 254: C. I. Pigment Red 254

PR 177: C. I. Pigment Red 177

PG 36: C. I. Pigment Green 36

PY 150: C. I. Pigment Yellow 150

PB 15: 6: C. I. Pigment Blue 15: 6

PV 23: C. I. Pigment Violet 23

Polybrominated zinc Pc: ZnPcBr ₁₀ Cl ₄ H ₂ (Pc: phthalocyanine)

&Lt; Polymer compound &

Polymer Compound 1 to 11, C1: Specific polymer compound obtained in the above Synthesis Example and Comparative Polymer Compound

Polymer compound C2: Polyurethane dispersant (Product name: Disperbyk-167, BYK Japan K K)

[Examples 2-1 to 2-4, Comparative Example 2-1]

&Lt; Preparation of pigment dispersion composition >

The components of the following composition (1) were mixed and stirred with a homogenizer at 3,000 rpm for 3 hours and mixed to prepare a mixed solution containing the pigment.

[Composition (1)]

- 95 parts of the processed pigment (each of the processed pigments shown in Table 3)

(With 82.7 parts in Comparative Example 2-1).

5 parts of pigment derivative A having the following structure

Dispersant The amount described in Table 3

(30% 1-methoxy-2-propyl acetate solution of the dispersant shown in Table 3)

- 750 parts of 1-methoxy-2-propyl acetate

Then, the mixed solution obtained above was subjected to dispersion treatment for 6 hours with a bead disperser dispromat (product of GETZMANN) using 0.3 mm? Zirconium oxide beads. Thereafter, dispersion treatment was further carried out at a flow rate of 500 g / min under a pressure of 2,000 kg / cm 3 using a high-pressure disperser NANO-3000-10 (manufactured by NIPPON BEE CHEMICAL CO., LTD. This dispersion treatment was repeated ten times to obtain a pigment dispersion composition.

&Lt; Evaluation of Pigment Dispersion Composition >

Each of the obtained pigment dispersion compositions was subjected to the following evaluations. The results are shown in Table 3.

(1) Measurement and evaluation of viscosity

For each of the obtained pigment dispersion compositions, viscosity η1 of the pigment dispersion composition immediately after dispersion and viscosity η2 of the pigment dispersion composition after one week at room temperature after dispersion were measured using an E-type viscometer to evaluate the degree of thickening. Here, the lower viscosity indicates that the increase in the viscosity due to the dispersing agent is suppressed, and the dispersibility and the dispersion stability of the pigment are good.

(2) Measurement and evaluation of contrast

Each of the obtained pigment dispersion compositions was coated on a glass substrate, and a sample was produced so that the thickness of the coated film after drying was 1 占 퐉. A substrate coated between two polarizing plates was arranged so that the brightness of the polarizing plate at the time of parallelism and the brightness at the time of the parallelism were measured (BM-5 TOPCON CORPORATION), and the contrast was obtained as the brightness at the time of parallelism / straightness. The high contrast indicates that the transmittance, that is, the tinting strength, is high because the pigment is uniformly dispersed in a state where the pigment is highly refined.

Processed pigment
Dispersant Initial viscosity
(mPa 占 퐏) Aging viscosity
(mPa 占 퐏)
Contrast Example 2-1 R-1 D-1 18 21 2200 Example 2-2 R-2 D-1 20 25 2500 Example 2-3 R-6 D-1 15 17 2300 Examples 2-4 R-8 D-1 18 20 2600 Comparative Example 2-1 R-13 D-1 50 100 1500

Details of the dispersant D-1 in Table 3 are as follows.

D-1: Polymer having a BzMA / A-1 / MAA of 20/65/15 (mass ratio), a weight average molecular weight of 2.3 million, an acid value of 100 mgKOH / g

As shown in Table 3, it can be seen that the pigment dispersion composition of the examples has a high contrast, a small initial viscosity, and a small viscosity increase with time in comparison with the pigment dispersion composition of the comparative example.

[Examples 2-5 to 2-11 and Comparative Examples 2-2 to 2-4]

&Lt; Preparation of pigment dispersion composition >

The components of the following composition (2) were mixed and stirred with a homogenizer at 3,000 rpm for 3 hours and mixed to prepare a mixed solution containing the pigment.

[Composition (2)]

ㆍ Processed pigment (each of the processed pigments described in Table 4) 100 parts

(Provided that Comparative Examples 2-2 and 2-3 were 82.7 parts).

Dispersant The amounts listed in Table 4

(30% 1-methoxy-2-propyl acetate solution of the dispersant described in Table 4)

- 750 parts of 1-methoxy-2-propyl acetate

Then, the mixed solution obtained above was dispersed for 6 hours in a bead dispersing machine dispenser (GETZMANN product) using 0.3 mm diameter zirconium oxide beads. Thereafter, a high pressure disperser NANO-3000-10 (NIPPON BEE CHEMICAL CO Ltd.) was further subjected to dispersion treatment at a flow rate of 500 g / min under a pressure of 2,000 kg / cm 3. This dispersion treatment was repeated ten times to obtain a pigment dispersion composition.

&Lt; Evaluation of Pigment Dispersion Composition >

The obtained pigment dispersion composition was evaluated in the following manner.

The evaluation method and evaluation criteria are the same as those for the pigment dispersion composition of Example 2-1. The results are shown in Table 4.

(1) Measurement and evaluation of viscosity

(2) Measurement and evaluation of contrast

Processed pigment
Dispersant Initial viscosity
(mPa 占 퐏) Aging viscosity
(mPa 占 퐏)
Contrast Example 2-5 G-2 D-1 32 34 7800 Examples 2-6 G-3 D-1 33 35 7700 Examples 2-7 G-4 D-1 30 32 7500 Examples 2-8 G-7 D-1 34 36 10000 Examples 2-9 G-8 D-1 34 36 10500 Examples 2-10 G-9 D-1 32 35 10000 Examples 2-11 G-10 D-1 30 31 11000 Comparative Example 2-2 G-5 D-1 45 65 5500 Comparative Example 2-3 G-6 D-1 45 65 5000 Comparative Example 2-4 G-11 D-1 45 60 9000

The dispersant D-1 in Table 4 is a dispersant such as the dispersant D-1 described in Table 3 above.

As shown in Table 4, it can be seen that the pigment-dispersed composition of the examples has a high contrast, a small initial viscosity, and a small viscosity increase over time in comparison with the pigment dispersion composition of the comparative example.

[Examples 3-1 to 3-9, Comparative Examples 3-1 to 3-2]

&Lt; Preparation of pigment dispersion composition >

The components of the following composition (3) were mixed and stirred with a homogenizer at 3,000 rpm for 3 hours and mixed to prepare a mixed solution containing the pigment.

[Composition (3)]

ㆍ Processed pigment (processed pigment described in Table 5): 110 parts

ㆍ Dispersant 250 parts

(30% 1-methoxy-2-propyl acetate solution of the dispersing agent shown in Table 5)

20 parts of pigment derivative B of the following structure

- 750 parts of 1-methoxy-2-propyl acetate

Then, the mixed solution obtained above was dispersed for 6 hours in a bead dispersing machine dispenser (GETZMANN product) using 0.3 mm diameter zirconium oxide beads. Thereafter, a high pressure disperser NANO-3000-10 (NIPPON BEE CHEMICAL CO , LTD.) Under the pressure of 2000 kg / cm &lt; 3 &gt; at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain the respective pigment dispersion compositions (DG-1 to DG-11, DY-1 to DY-6) shown in Table 5 below.

Pigment dispersion composition Kinds Processed pigment Dispersant DG-1 G-2 D-1 - DG-2 G-1 D-1 - DG-3 G-3 D-1 - DG-4 G-4 D-1 D-2 DG-5 G-5 D-1 - DG-6 G-6 D-1 - DG-7 G-7 D-1 - DG-8 G-8 D-1 - DG-9 G-9 D-1 D-2 DG-10 G-10 D-1 - DG-11 G-11 D-1 - DY-1 Y-2 D-1 - DY-2 Y-3 D-1 - DY-3 Y-3 D-1 - DY-4 Y-4 D-1 D-2 DY-5 Y-5 D-1 - DY-6 Y-6 D-1 -

The dispersant D-1 in Table 5 is a dispersant such as the dispersant D-1 described in Table 3 above. Details of the dispersant D-2 are as follows.

D-2: "Solsperse 24000" manufactured by The Lubrizol Corporation

&Lt; Preparation of photocurable composition >

The following photo-curable composition was prepared using each pigment dispersion composition obtained above.

Pigment dispersion composition A (pigment dispersion composition described in column A of Table 6) 2000 parts

Pigment dispersion composition B (pigment dispersion composition described in column B of Table 6) 1000 parts

KAYARAD DPHA (photopolymerizable compound, manufactured by NIPPON KAYAKU Co., Ltd.) 120 parts

50 parts of 4- [o-bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine (photopolymerization initiator)

Copolymer of benzyl methacrylate / methacrylic acid (= 75/35 [mass ratio])

Propylene glycol monomethyl ether acetate solution (solid content 30%) (weight average molecular weight: 10,000) (alkali-soluble resin) 300 parts

Methoxy-2-propyl acetate (solvent) 390 parts

&Lt; Fabrication of color filter using photocurable composition >

The obtained photo-curable composition (color resist solution) was coated on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) with a slit to a thickness of 1.75 μm and dried in a 90 ° C. oven for 60 seconds (prebaked). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm 2 (roughness 20 mW / cm 2), and the exposed coating film was subjected to showering for 60 seconds in an aqueous 1% solution of alkali developer CDK-1 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) . After stopping, pure water was sprayed in a shower, and the developing solution was washed and shed. Then, the coated film having been exposed and developed as described above was heat-treated (post-baked) in an oven at 220 캜 for one hour to form a colored pattern (colored resin film) for the color filter on the glass substrate, Substrate (color filter) was produced.

&Lt; Evaluation of color filter &

The obtained color filter substrate (color filter) was evaluated for contrast as follows. The results are shown in Table 6.

(1) Contrast

A polarizing plate was provided on the colored resin film of the color filter substrate obtained above, and a colored resin film was sandwiched therebetween. The luminance at the time of orthogonality with the parallel luminance of the polarizing plate was measured using BM-5, A value obtained by dividing the luminance by the luminance at the time of orthogonality (= luminance in parallel / luminance in orthogonal) is used as an index for evaluating the contrast. The larger the value, the higher the contrast.

Pigment dispersion composition
Contrast A B Example 3-1 DG-1 DY-1 7000 Example 3-2 DG-2 DY-2 6800 Example 3-3 DG-3 DY-3 6800 Example 3-4 DG-4 DY-4 7200 Example 3-5 DG-5 DY-5 7000 Examples 3-6 DG-7 DY-1 10000 Examples 3-7 DG-8 DY-2 10500 Examples 3-8 DG-9 DY-3 10000 Examples 3-9 DG-10 DY-4 11000 Comparative Example 3-1 DG-6 DY-6 4500 Comparative Example 3-2 DG-11 DY-6 9000

As shown in Table 6, it can be seen that the color filter of the embodiment has a high contrast in comparison with the color filter of the comparative example.

Hereinafter, an example in which a photo-curable composition is prepared for forming a color filter for a solid-state image sensor will be described.

[Examples 4-1 to 4-4, Comparative Example 4-1]

<B1. Preparation of resist solution>

The following composition was mixed and dissolved to prepare a resist solution.

[Composition of resist solution]

Propylene glycol monomethyl ether acetate 19.20 parts

(PGMEA: solvent)

ㆍ Ethyl lactate 36.67 parts

- Resin (benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer

40% PGMEA solution having a weight average molecular weight (Mw ratio = 60/22/18, weight average molecular weight: 15,000, number average molecular weight: 8,000)

- Ethylenically unsaturated double bond-containing compound

(Dipentaerythole hexaacrylate) 12.20 parts

Polymerization inhibitor (p-methoxyphenol) 0.0061 part

ㆍ Fluorine-based surfactant (F-475, manufactured by DIC Corporation) 0.83 part

Photopolymerization initiator (trihalomethyltriazine based photopolymerization initiator) 0.586 part

(TAZ-107, manufactured by Midori Kagaku Co., Ltd.)

B2. Fabrication of silicon substrate with undercoat layer &gt;

The 6-inch silicon wafer was heated in an oven at 200 占 폚 for 30 minutes. Subsequently, the resist solution was coated on the silicon wafer so that the dry film thickness became 1.5 占 퐉 and heated and dried in an oven at 220 占 폚 for one hour to form an undercoat layer, thereby obtaining a silicon wafer substrate having an undercoat layer formed thereon.

<B3. Preparation of pigment dispersion composition >

The pigment dispersion composition was prepared by dispersing in the same manner as in Examples 3-6 to 3-9 and Comparative Example 3-2.

<B4. Preparation of photocurable composition (coating liquid) >

Each of the pigment dispersion compositions obtained above was stirred and mixed to have the following compositional ratio to prepare a photocurable composition solution.

Colorant (the above pigment dispersion) 600 parts

Photopolymerization initiator (oxime-based photopolymerization initiator)

(CGI-124, manufactured by Ciba Specialty Chemicals Co., Ltd.) 30 parts

ㆍ TO-1382 (manufactured by TOAGOSEI CO., LTD.) 25 parts

30 parts of dipentaerythole hexaacrylate

Solvent (PGMEA) 900 parts

ㆍ Substrate adherent (3-methacryloxypropyltrimethoxysilane) 1 part

<B5. Fabrication and Evaluation of Color Filter Using Photocurable Composition>

(1) Evaluation of pattern formation property

The photo-curable composition prepared as described above was applied on the undercoat layer of the silicon wafer on which the undercoat layer obtained in the above B2. Was formed to form a colored layer (coating film). Then, a heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 캜 so that the dried film thickness of the coated film became 0.5 탆.

Subsequently, the pattern was exposed at various exposure amounts of 50 to 1200 mJ / cm 2 through an island pattern mask of 2 탆 square at a wavelength of 365 nm using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.).

Thereafter, the silicon wafer substrate having the irradiated coated film formed thereon was placed on a horizontal rotary table of a spin-shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and a CD-2000 (FUJIFILM Electronic Materials Co. , Ltd.) at 23 DEG C for 60 seconds to form a colored pattern on a silicon wafer substrate.

The silicon wafer having the colored pattern formed thereon is fixed to the horizontal rotary table by a vacuum chucking method, and the silicon wafer substrate is rotated at a rotation speed of 50 rpm by a rotary device, pure water is supplied from the nozzle to the shower Followed by rinsing, followed by spray drying.

The pattern formability was evaluated by observing the cross-sectional shape of the colored pattern formed as described above. The cross-sectional shape of the pattern is preferably a rectangular shape, and reverse tapering is not preferable.

The results are shown in Table 7.

(3) Evaluation of storage stability of photocurable composition

After the photo-curing composition (coating liquid) prepared in the above B4. Was stored at room temperature for one month, the viscosity of the liquid was measured and evaluated according to the following criteria. The results are shown in Table 7.

-Evaluation standard-

?: No increase in viscosity was observed.

B: Viscosity increase of not less than 5% and less than 10% was confirmed.

X: Viscosity increase of 10% or more was confirmed.

(4) Evaluation of color unevenness

The color unevenness was evaluated based on the ratio of the pixels having an error from the average within ± 5% to the total number of pixels by analyzing the luminance distribution by the following method. The evaluation criteria are as follows.

A method of measuring the luminance distribution will be described. First, a photo-curable composition was applied on an undercoat layer of a glass plate on which an undercoat layer obtained in the same manner as in B2. Above was formed to form a colored layer (coating film). A heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 캜 so that the dried film thickness of the coating film was 0.7 탆. An image obtained by photographing the luminance distribution of the coated glass plate with a microscope MX-50 (manufactured by OLYMPUS CORPORATION) was analyzed.

The results are shown in Table 7.

-Evaluation standard-

&Amp; cir &amp;: More than 99% of the pixels having an error from the average within 5%

?: 95% or more and less than 99% of the pixels in which the error from the average is within ± 5%

X: A pixel whose error from the average is within ± 5% is less than 95% of the total number of pixels

Pigment dispersion composition preservation
stability
Color stain pattern
Formability A B Example 4-1 DG-7 DY-1 ○ ○ ○ Example 4-2 DG-8 DY-2 ○ ○ ○ Example 4-3 DG-9 DY-3 ○ ○ ○ Example 4-4 DG-10 DY-4 ○ ○ ○ Comparative Example 4-1 DG-11 DY-6 × × ×

From the results shown in Table 7, it was found that the photo-curing composition using the working pigment of the examples had excellent storage stability in the solution state even when used for forming a color filter for use in a solid-state imaging device. When a colored pattern is formed on a support using this photo-curable composition, a color filter excellent in developability and excellent in both cross-sectional shape of pattern and color irregularity is obtained in comparison with the comparative example .

From these results, the photo-curing composition containing the working pigment of the examples shows that, even in the case of producing a color filter for use in a solid-state imaging device, excellent pattern forming property can be realized as in the case of producing a color filter for use in a liquid crystal display element Could know.

Claims (11)

A processed pigment characterized by comprising a pigment coated with a graft polymer having at least one kind of basic nitrogen atom selected from the following (1) to (4). (1) a poly (alkyleneimine) having an oligomer chain or a polymer chain having a number average molecular weight of 500 to 1,000,000 in the side chain and having an alkylene group having 2 to 6 carbon atoms, (2) an oligomer chain having a number average molecular weight of 500 to 1,000,000 or a polyallylamine having a polymer chain in the side chain (3) an oligomer chain having a number average molecular weight of 500 to 1,000,000 or a polyvinyl amine having a polymer chain in the side chain (4) an oligomer chain or polymer containing a constitutional unit derived from at least one monomer selected from (meth) acrylic acid esters having a basic nitrogen atom in the ester moiety, vinylpyridine and aminostyrene, and having a number average molecular weight of 500 to 1,000,000 Polymer compound having a chain in its side chain The method according to claim 1, Wherein the oligomer chain or polymer chain having a number average molecular weight of 500 to 1,000,000 is polycaprolactone. The method according to claim 1, Wherein the average primary particle diameter is in the range of 5 nm to 25 nm. The method according to claim 1, Wherein the pigment is a pigment comprising polyhalogenated zinc phthalocyanine. A pigment dispersion composition characterized by dispersing the treated pigment according to any one of claims 1 to 4 in an organic solvent. 6. The method of claim 5, A pigment dispersion composition, further comprising a pigment dispersant. A photocurable composition comprising the pigment dispersion composition according to claim 5, a polymerizable compound, and a photopolymerization initiator. A color filter having a colored region formed by using the photo-curable composition according to Claim 7. A step of forming a photosensitive film by applying the photo-curable composition according to claim 7 directly or through another layer to a substrate, and a step of forming a colored area by sequentially performing pattern exposure and development on the formed photosensitive film Wherein the color filter comprises a plurality of color filters. The method according to claim 6, The pigment dispersant may be at least one selected from the group consisting of polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin Wherein the pigment dispersion composition is at least one selected from the group consisting of polyoxyethylene alkyl phosphates, polyoxyethylene alkyl phosphates, polyoxyethylene alkyl amines, alkanolamines and pigment derivatives. 8. The method of claim 7, Wherein the photopolymerization initiator is an oxime-based photopolymerization initiator.