KR20100027952A - Processed pigment, pigment dispersion composition, photocurable composition, color filter, and method of manufacturing color filter - Google Patents

Abstract

PURPOSE: A processed pigment is provided to disperse the pigment in a first particle form by suppressing the formation of a second aggregate and to stably maintain the state of the first particles after dispersion. CONSTITUTION: A processed pigment is formed by coating a polymer compound having basic nitrogen atoms. The polymer compound having basic nitrogen atoms is at least one kind of polymer compound selected from the followings: poly(alkyleneimine) with C2~6 alkylene groups; polyallylamine; polyvinylamine; and at least one kind of monomer selected from (meth)acrylic acid ester with a basic nitrogen atom to an ester portion, vinyl pyridine, and aminostyrene.

Description

Processed pigments, pigment dispersion compositions, photocurable compositions, color filters, and methods for producing color filters {PROCESSED PIGMENT, PIGMENT DISPERSION COMPOSITION, PHOTOCURABLE COMPOSITION, COLOR FILTER, AND METHOD OF MANUFACTURING COLOR FILTER}

The present invention relates to process pigments, pigment dispersion compositions, photocurable compositions, color filters, and methods for producing color filters. More specifically, the present invention is excellent in dispersibility and dispersion stability process pigments that can be preferably used in a wide range of coatings, printing inks, color filters, etc., pigment dispersion composition obtained by dispersing the process pigment, the pigment dispersion composition It relates to a photocurable composition comprising a, a color filter having a colored region formed by the photocurable composition and a method for producing the same.

The color filter comprises a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components to form a photocurable composition. The color filter is used by a photolithography method, an inkjet method, or the like. It is manufactured by forming a coloring pattern.

In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display devices (LCDs). In accordance with the tendency of this application expansion, the color filter is requesting high color characteristic in chromaticity, contrast, etc. Moreover, also in the color filter for image sensor (solid-state image sensor) use, high color characteristics, such as reduction of a color nonuniformity and improvement of color resolution, are calculated | required.

In response to the above demands, it is desired to disperse the pigment contained in the photocurable composition in a finer state (good dispersibility) and to disperse in a stable state (good dispersion stability). If the dispersibility of the pigment is insufficient, the color filter manufactured due to the occurrence of fringes (uneven edges) or surface irregularities in the colored pixels formed by the photolithography method, or a large amount of developing residues (residues) on the substrate. There is a problem that the chromaticity and the dimensional accuracy of the resin deteriorate or the contrast deteriorates remarkably. In addition, when the dispersion stability of the pigment is insufficient, various problems are likely to occur in each step of producing the color filter. In particular, in the application | coating process of a photocurable composition, the uniformity of the film thickness of a coating film falls, the sensitivity in an exposure process, or the problem of alkali solubility in a developing process falls easily. Moreover, when the dispersion stability of a pigment is bad, there also exists a problem that the component in a photocurable composition aggregates with time, viscosity rises, and pot life becomes extremely short. It is effective to refine the particle diameter of the pigment to improve the color characteristics such as the contrast of the color filter.However, when the particle diameter of the pigment is reduced, the surface area of the pigment particle is increased, so that the cohesion force between the pigment particles is increased, and the pigment is dispersed at a high level. Comparing performance and dispersion stability is often difficult.

The following are known about the refinement | miniaturization of a pigment particle and the improvement of dispersibility.

In general, the fineness of the primary particles of the pigment is well known 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 (salt milling method). In this method, first, a mixture of primary particles of the obtained fine pigment is introduced into water, stirred with a mixer or the like to form a slurry. Subsequently, a fine pigment is obtained as a secondary aggregate which is an aggregate of the primary particle of a pigment by filtering, washing with water, and drying this slurry. Furthermore, it disperse | distributes with general dispersers, such as a sand mill and a ball mill, and dissolves the secondary aggregate which is an aggregate of the primary particle of a pigment, and obtains the dispersion of the state near a primary particle.

However, when the primary particles of the pigment are made finer, the aggregates tend to aggregate, and aggregates (secondary aggregates) tend to be formed when the slurry is used or when dried. In addition, as the primary particles of the pigment become finer, strong secondary aggregation tends to occur. Therefore, it is generally very difficult to redistribute the refined pigment into primary particles. The color filter formed by using a dispersion containing a large number of secondary agglomerates has a large scattering of light, a marked decrease in contrast, or a color density nonuniformity, so that the pigment particles do not aggregate and stably disperse the primary particles. It is preferable that it is preferable and it is a property which is easy to handle.

For the purpose of suppressing strong secondary aggregation of this finely pigmented pigment, a rosin or a rosin derivative or a water-insoluble monomer or oligomer is added at the time of the salt milling process to treat the pigment, and the contrast is increased using the dispersion of the pigment. The technique of obtaining a high color filter is proposed (for example, refer Unexamined-Japanese-Patent No. 3130217, Unexamined-Japanese-Patent No. 2004-233727).

In addition, the pigment dispersion composition, the photocurable composition which use the high molecular compound which has a heterocycle at the time of a dispersion process as a dispersing agent in the pigment dispersion process, and are excellent in dispersion stability and can form the coloring pattern for color filters of high contrast, And techniques for obtaining color filters have also been proposed (see, for example, Japanese Patent Laid-Open No. 2003-26950).

However, these methods cannot cope with ever-increasing demands of contrast in the market, and more advanced dispersibility and dispersion stability in fine pigments have been desired.

In recent years, color filters having high luminance as well as contrast are demanded. As a method for obtaining a high brightness and high contrast color filter, a method of using polyhalogenated zinc phthalocyanine in place of conventional CI Pigment Green 36 or CI Pigment Green 7 has been proposed in the green pixel portion (for example, Japanese Patent Laid-Open). 2004-70342, Japanese Patent Laid-Open No. 2008-19383).

An object of the present invention is to achieve the following object.

That is, the 1st objective of this invention is to provide the processed pigment which can suppress formation of a secondary aggregate, disperse | distribute to the state of a primary particle, and can maintain the state of a primary particle stably after dispersion. .

Moreover, the 2nd objective of this invention is the pigment dispersion composition which contains the said process pigment and was excellent in the dispersibility and dispersion stability of the said process pigment, and such a pigment dispersion composition, and can form the colored cured film excellent in contrast. It is providing a photocurable composition.

Further, a third object of the present invention is to provide a color filter which is formed using the photocurable composition, has a high contrast, has small color density unevenness, and has a color region excellent in color characteristics, and a method of manufacturing the same.

Means for solving the above problems are as follows.

Processed pigment formed by coating a pigment with a high molecular compound which has <1> basic nitrogen atom.

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

(1) poly (alkyleneimines) having alkylene groups of 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, vinylpyridine, and aminostyrene.

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

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

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

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

<7> Pigment dispersion composition formed by disperse | distributing the process pigment in any one of <1>-<6> in an organic solvent.

<8> The pigment dispersion composition of <7> which further contains a pigment dispersant.

<9> Photocurable composition containing the pigment dispersion composition, polymeric compound, and photoinitiator as described in <7> or <8>.

<10> Color filter which has a coloring area | region formed using the photocurable composition as described in <10>.

<11> A process of forming a photosensitive film by applying the photocurable composition as described in <9> on a board | substrate directly or through another layer, and forming a colored area | region by performing pattern exposure and image development to the formed photosensitive film sequentially. Method of manufacturing a color filter comprising a.

Other preferable forms of the process pigment of this invention are as follows.

<12> The processed pigment according to any one of <1> to <6>, wherein the free amount of the polymer compound having a basic nitrogen atom when washed with 1-methoxy-2-propanol is 30% by mass or less.

<13> The processed pigment according to any one of <1> to <6> and <12>, which is prepared by adding a polymer compound having the basic nitrogen atom in a pigment miniaturization step.

<14> The processed pigment according to any one of <1> to <6>, <13> and <14>, wherein the weight average molecular weight of the polymer compound having a basic nitrogen atom is in the range of 1,000 to 100,000.

In addition, the "free amount" in said <12> means the quantity of the surface treating agent (high molecular compound which has a basic nitrogen atom in this invention) immersed in the solvent by immersing a processing pigment in 1-methoxy- 2-propanol which is a solvent. % By mass divided by the amount of surface treatment agent used.

The present invention relates to a processed pigment coated with a high molecular compound having a basic nitrogen atom and its application, and by using the processed pigment, dispersibility and dispersion stability are superior to those of the conventional one, and contrast is higher, and color density is uneven. A few pigment dispersion compositions and color filters can be obtained.

That is, when the high molecular compound which has a basic nitrogen atom of this invention is used for a pigment process, it is thought that the production | generation of the secondary aggregate which is an aggregate of the primary particle of a pigment can be effectively suppressed, or the cohesion force of a secondary aggregate can be effectively weakened. . Therefore, in the dispersion | distribution process, the dispersion of the state near a primary particle can be obtained, and the color filter with high contrast and the color filter with little color density nonuniformity can be obtained.

In addition, the pigment dispersion composition comprising the process pigment of the present invention to which the polyhalogenated zinc phthalocyanine is applied as a pigment can be used to prepare a color filter using the photocurable composition comprising the pigment dispersion composition while maintaining excellent dispersibility and dispersion stability. In this case, a color filter having better brightness and contrast can be obtained.

Although the action of the present invention is not clear, the polymer compound used for coating has a basic nitrogen atom in its molecular structure, and the structure and the pigment have a strong electrostatic interaction, and a strong intermolecular force by the polymer compound. It is considered that the polymer compound is strongly adsorbed to the pigment primary particles, and the coated polymer compound is not desorbed even during slurry, filtration, and washing with water, so that aggregation of the primary particles of the pigment is effectively suppressed.

In this invention, it is one of the characteristics that the pigment is coat | covered with the high molecular compound which has a basic nitrogen atom in this way, and it is one of the characteristics, and it is especially effective to perform coating | coating simultaneously with the process of refining the primary particle of a pigment. That is, as in Japanese Patent Application Laid-Open No. 2003-26950, in comparison with a method of stabilizing dispersion by adsorbing a graft polymer compound containing a heterocycle in the dispersion step after the miniaturization step, the surface activity resulting from the miniaturization is high. Since the polymer compound having a basic nitrogen atom in the present invention is adsorbed by a strong electrostatic action on the new interface of the pigment and forms a firm coating layer of the polymer compound, a processed pigment having higher dispersion stability can be obtained. It is thought to be. That is, in this invention, even if the pigment after processing is wash | cleaned with the organic solvent which melt | dissolves a high molecular compound, the coated high molecular compound is not liberated. On the other hand, in the pigment in JP-A-2003-26950, when the organic solvent is washed, most of the high molecular compound as the dispersant desorbs from the pigment, and thus the micronized pigment tends to aggregate and high dispersion stability is not obtained.

Furthermore, the color filter using the process pigment of this invention coated with the high molecular compound which has a basic nitrogen atom can also solve the problem that a color filter layer becomes cloudy under high temperature and high humidity, and the problem that it becomes cloudy at the time of color filter manufacture. Such a problem is considered to occur when fine pigment particles in a color filter agglomerate and crystal grow, and the smaller the primary particles of the pigment, the more likely to occur. The processing pigment of the present invention coated with a polymer compound having a basic nitrogen atom is because the polymer compound having a basic nitrogen atom is strongly adsorbed to the fine pigment, and thus is effective in suppressing agglomeration between pigment particles even in a color filter. I think.

Moreover, the color filter using the process pigment of this invention coated with the high molecular compound which has a basic nitrogen atom is excellent in the voltage retention of a liquid crystal. The decrease in the voltage retention of the liquid crystal is likely to occur when the metal ion concentration in the color filter is high. This is particularly a problem that occurs when the pigment is refined using the salt milling method, but the reason is that the inorganic salt (ion) used in the salt milling process is adsorbed onto the pigment particles in the salt milling process, and thus, the dispersion process and the color filter manufacturing process. Or it is considered that it is eluted from pigment particle after forming a liquid crystal display element. The finer the primary particles of the pigment, the easier it is to contain the ionic compound, and the more difficult it is to remove in water washing and filtration. The processed pigment of the present invention coated with a high molecular compound having a basic nitrogen atom is considered to be because the high molecular compound is strongly adsorbed to the fine pigment for the above-mentioned reason, so that the dissolution of ions in the dispersing process or the color filter can be effectively suppressed. do.

Moreover, the photocurable composition using the process pigment of this invention coated with the high molecular compound which has a basic nitrogen atom has the advantage that it is hard to generate | occur | produce a precipitate in a developing solution in the developing process, when applied to manufacture a color filter. Precipitates are often aggregates of pigment particles. Precipitation is considered to be a phenomenon in which the pigment dispersion dispersed by the dispersant desorbs the dispersant by an alkaline developer, and fine pigment particles aggregate to crystal grow and precipitate. In the processing pigment of the present invention, since the polymer compound is strongly adsorbed to the fine pigment, the polymer compound is not desorbed even by the alkaline developer, and it is considered that precipitates are less likely to occur in the developer.

On the other hand, when the polymer compound having a heterocycle disclosed in Japanese Patent Application Laid-Open No. 2003-26950 is used as a pigment dispersant in the dispersing process, since the adsorption to the pigment is insufficient, these effects cannot be sufficiently expressed, and therefore their performance It does not lead to improvement.

(Effects of the Invention)

ADVANTAGE OF THE INVENTION According to this invention, the process pigment which can suppress formation of a secondary aggregate and disperse | distribute in the state of a primary particle, and can maintain the state of a primary particle stably after dispersion can be provided.

Moreover, according to this invention, the pigment | dye dispersion composition which contains the said process pigment, and is excellent in the dispersibility and dispersion stability of the said process pigment, and such a pigment dispersion composition, and can be formed the photocurable which can form the colored cured film excellent in contrast. A composition can be provided.

Moreover, according to this invention, the color filter which is formed using the said photocurable composition, has a high contrast, little color density nonuniformity, and has the coloring area excellent in color characteristics, and its manufacturing method can be provided.

Below, the process pigment, pigment dispersion composition, photocurable composition, color filter, and its manufacturing method of this invention are demonstrated in detail.

[Process Pigment]

The process pigment of this invention is a process pigment formed by coating a pigment with the high molecular compound which has a basic nitrogen atom.

As an average primary particle diameter of the process pigment of this invention, when handling property of the pigment dispersion composition which disperse | distributes the said process pigment, and the photocurable composition containing this, 100 nm or less is preferable, 30 nm or less is more preferable, 5 nm-25 nm are the most preferable. If the particle diameter is within the above range, the transmittance is high, the color characteristics are good, and it is effective to form a high contrast color filter.

The average primary particle diameter is observed by SEM or TEM, and is calculated | required by measuring 100 particle sizes in the part which particle | grains are not aggregated, and calculating an average value.

One preferred form of the process pigment of the invention is a kneader by mixing i) a pigment, ii) a water soluble inorganic salt, iii) a small amount of a water soluble organic solvent that does not substantially dissolve ii), and iv) a polymer compound having a basic nitrogen atom. The process of mechanically kneading with the like (this process is referred to as salt milling), the mixture after the kneading is introduced into water, stirred with a high speed mixer or the like to form a slurry, and the resulting slurry is filtered and washed with water if necessary. According to the drying process.

By this manufacturing method, the processed pigment of this invention which is fine and is excellent in the dispersibility and dispersion stability with little aggregation of the pigment at the time of drying is obtained.

The above production method will be described in more detail.

First, a small amount of iii) water-soluble organic solvent is added to the mixture of i) organic pigment and ii) water-soluble inorganic salt as a wetting agent and kneaded vigorously with a kneader or the like, and then the mixture is added to water and stirred with a high speed mixer or the like. To make a slurry.

Subsequently, this slurry is filtered, washed with water, and dried as necessary to obtain a pigment which is refined and coated with a high molecular compound having a basic nitrogen atom.

In addition, in the case where the obtained processed pigment is dispersed and used in an oily varnish, it is also possible to disperse the treated pigment (called a filtration cake) before drying in an oily varnish while removing water by a method generally called flashing. In addition, when disperse | distributing the obtained process pigment to an aqueous varnish, a process pigment does not need to be dried and a filter cake can be disperse | distributed to a varnish as it is.

In the present invention, when salt milling, iii) a polymer compound which is at least partially soluble in a water-soluble organic solvent, that is, iv) a polymer compound having a basic nitrogen atom, the polymer compound is fine and has a surface of iv) a basic nitrogen atom. Processed pigments with little aggregation of the pigments at the time of coating drying are obtained.

In addition, iv) timing of adding the high molecular compound which has a basic nitrogen atom may be added all at the beginning of a salt milling process, and may be added separately.

In addition, as a method of preventing dry aggregation, an alkali-soluble resin dissolved in an alkaline aqueous solution is added to the slurry, and the mixture is sufficiently stirred and mixed, and then neutralized with an acidic aqueous solution such as hydrochloric acid or sulfuric acid to deposit the resin on the pigment, or calcium chloride. Alternatively, it is also possible to prevent dry agglomeration by adding an aqueous solution of a water-soluble polyvalent metal salt such as barium chloride to precipitate the resin and deposit it on the pigment.

[i) pigments]

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

As a pigment, when the processed pigment of this invention is used suitably for formation of the coloring area of a color filter, and it is preferable that a color filter has a high transmittance | permeability, etc., an organic pigment is preferable and the thing with a small particle diameter is used as much as possible. It is desirable to.

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

Examples of the inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, And complex oxides of the above metals.

As said organic pigment, for example,

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 , 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 , 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: 1, 36 , 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97 , 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139 , 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 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 substituents of CI Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 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 and the like.

Among these, the following can be mentioned as a pigment which can be used preferably. However, in this invention, it 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 preferred form of organic pigment is polyhalogenated zinc phthalocyanine.

The polyhalogenated zinc phthalocyanine may be used alone or in combination of a polyhalogenated zinc phthalocyanine and a conventionally known organic pigment.

In general, zinc phthalocyanine has 16 hydrogen atoms in the phthalocyanine ring. Therefore, up to 16 of these hydrogen atoms can be substituted with halogen atoms. For example, when these hydrogen atoms are replaced with a bromine atom and / or a chlorine atom, the bromine atom number is 0-16, the chlorine atom number is 0-16, the hydrogen atom number is 0-16, and the bromine atom and chlorine atom are also included. The sum of the number of atoms becomes one or more, and theoretically, 136 kinds of substituents can be manufactured in total.

As polyhalogenated zinc phthalocyanine in this invention, it is preferable that 8-16 of the 16 replaceable hydrogen atoms in a phthalocyanine ring are substituted, and it is more preferable that 12-16 are substituted. As a halogen atom substituted by a phthalocyanine ring, a bromine atom, a chlorine atom, a fluorine atom, and an iodine atom are mentioned, a bromine atom or a chlorine atom is more preferable, and a bromine atom is still more preferable. In addition, all substituted halogen atoms may be same or different, respectively.

When the number of substituents of the halogen atoms substituted for the phthalocyanine ring is constant, the color of the zinc phthalocyanine substituted with the bromine atom is darker than that of the zinc phthalocyanine substituted with the chlorine atom.

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

In 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 8 of X ¹ to X ¹⁶ are a chlorine atom or a bromine atom.

Here, the polyhalogenated zinc phthalocyanine contains 8 or more bromine atoms, which develops yellowish-bright green color and is optimal for use in the green pixel portion of the color filter. In the present invention, the polyhalogenated zinc phthalocyanine containing 8 or more bromine atoms is referred to as "polybrominated zinc phthalocyanine". This polybrominated zinc phthalocyanine is preferable as the polyhalogenated zinc phthalocyanine in the present invention.

More preferably, the polybrominated zinc phthalocyanine is one having 8 to 16 bromine atoms, still more preferably 12 to 16 bromine atoms.

The average composition of polyhalogenated zinc phthalocyanine is easily obtained from mass spectroscopy based on mass spectroscopy and halogen content analysis by flask-burning ion chromatography.

The polyhalogenated zinc phthalocyanine can be produced, for example, by a known production method such as chlorosulfonic acid method, halogenated phthalonitrile method or melting method. More specific manufacturing methods are described in detail in documents such as Japanese Patent Application Laid-Open No. 2008-19383, Japanese Patent Application Laid-Open No. 2007-320986, Japanese Patent Application Laid-Open No. 2004-70342, and the like. The manufacturing method described in these documents can also be applied to this 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, still more preferably 15 nm to 35 nm.

The pigment dispersion composition which is excellent in dispersibility, dispersion stability, and coloring power is obtained by the process pigment of this invention obtained using the polyhalogenated zinc phthalocyanine whose average primary particle diameter is in the said range, and the sight which comprises this pigment dispersion composition By using the chemical composition, a color filter having a pixel portion with high luminance and high contrast can be obtained.

In addition, the average primary particle diameter in this invention is a long diameter (with respect to 100 polyhalogenated zinc phthalocyanine primary particles which image | photograph particle | grains in a visual field with a transmission electron microscope, and comprise the aggregate on a two-dimensional image. The average value of the long diameter) and the short diameter (short diameter) are respectively calculated | required, and are the average values.

For obtaining polyhalogenated zinc phthalocyanine having an average primary particle diameter of 10 nm to 40 nm, it may be atomized by any of the methods, but it is possible to easily suppress crystal growth and obtain pigment particles having a relatively small average particle diameter. In view of the above, it is preferable to employ solvent salt milling.

This solvent salt milling means kneading and grinding of polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent. Polyhalogenated zinc phthalocyanine having a large particle diameter may be subjected to solvent salt milling after dry grinding in advance. More specifically, polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent which does not dissolve it are put into a kneading machine, and kneading grinding is performed therein. As a kneader at this time, kneader, mix mara, etc. can be used, for example.

As an inorganic salt used when solvent salt milling using polyhalogenated zinc phthalocyanine, a water-soluble inorganic salt is preferable, As said water-soluble inorganic salt, inorganic salts, such as sodium chloride, potassium chloride, sodium sulfate, are mentioned, for example. Moreover, it is more preferable to use the inorganic salt of an average particle diameter of 0.5 micrometer-50 micrometers. Such inorganic salts are easily obtained by pulverizing common inorganic salts.

For obtaining polyhalogenated zinc phthalocyanine having an average primary particle diameter of 10 nm to 40 nm, it is preferable 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 used is preferably 5 to 20 parts, more preferably 7 to 15 parts, based on 1 part of polyhalogenated zinc phthalocyanine in terms of mass.

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

These organic pigments can be used individually or in combination in order to raise color purity. The specific example of the combination of organic pigments is shown below.

For example, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them and a disazo yellow pigment, an isoindolin yellow pigment, a quinophthalone yellow pigment or peryl as a red pigment A mixture of a len red pigment, an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, and the like can be used. For example, CI Pigment Red 177 is listed as an anthraquinone pigment, CI Pigment Red 155 and CI Pigment Red 224 are listed as a perylene pigment, CI Pigment Red 254 is listed as a diketopyrrolopyrrole pigment, In view of reproducibility, mixtures with CI Pigment Yellow 83, CI Pigment Yellow 139 or CI Pigment Red 177 are preferred. Moreover, as for the mass ratio of a red pigment and another pigment, 100: 5-100: 80 are preferable. If it is 100: 4 or less, it may be difficult to suppress the light transmittance of 400 nm-500 nm, and color purity may not be improved. On the other hand, the coloring power may be lowered at 100: 81 or higher. Especially as said mass ratio, the range of 100: 10-100: 65 is optimal. In addition, in the case of the combination of red pigments, it can adjust to chromaticity.

As the green pigment, a halogenated phthalocyanine-based pigment may be used alone or in combination with a disazo-based yellow pigment, a quinophthalone-based yellow pigment, an azomethine-based yellow pigment or an isoindolin-based 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. As for the mass ratio of a green pigment and a yellow pigment, 100: 5-100: 200 are preferable. If the said mass ratio is less than 100: 5, it may be difficult to suppress the light transmittance of 400-450 nm, and color purity may not be raised. Moreover, when it exceeds 100: 200, a dominant wavelength may become long wavelength vicinity and the deviation from an NTSC target color may become large. As said mass ratio, the range of 100: 20-100: 150 is especially preferable.

When the halogenated phthalocyanine-based pigment to be used is the above-mentioned polyhalogenated zinc phthalocyanine, the color filter obtained by applying to the process pigment of this invention has a high brightness and high contrast pixel part. In addition, when using polyhalogenated zinc phthalocyanine, it is preferable to use it in combination with C. I. Pigment Yellow 150 from a viewpoint of obtaining the favorable color and high brightness as a color filter.

As a blue pigment, a phthalocyanine type pigment can be used individually by 1 type, or the mixture of this and a dioxadine type purple pigment can be used. As a particularly preferred example, a mixture of C. I. Pigment Blue 15: 6 and C. I. Pigment Violet 23 may be listed.

As for the mass ratio of a blue pigment and a purple pigment, 100: 0-100: 100 are preferable, More preferably, it is 100: 70 or less.

Moreover, as a pigment preferable for a black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide can be used individually or as a mixture, and the combination of carbon black and titanium black is preferable.

Moreover, the mass ratio of carbon black and titanium black has the preferable range of 100: 0-100: 60 from a viewpoint of dispersion stability.

[ii) water-soluble inorganic salts]

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.

It is preferable that the quantity of the water-soluble inorganic salt used at the time of salt milling is 1-30 mass times, especially 5-25 mass times of organic pigment from both processing efficiency and productive efficiency. This is because the higher the ratio of the amount of the water-soluble inorganic salt to the organic pigment is, the higher the miniaturization efficiency is, but the smaller the amount of single pigment treatment.

In addition, here, water solubility in a water-soluble inorganic salt means that 1 mass% or more melt | dissolves in 20 degreeC water.

[iii) a small amount of water-soluble organic solvent that 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, and dissolves (mixes) in water and does not substantially dissolve the inorganic salts used. However, at the time of salt milling, since a temperature rises and a solvent becomes easy to evaporate, the high boiling point solvent of boiling point 120 degreeC or more is preferable as a water-soluble organic solvent from a safety point.

As a water-soluble organic solvent, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monoethyl, for example Ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol And dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like.

As addition amount of water-soluble organic solvent, 5 mass%-50 mass% are preferable with respect to a water-soluble inorganic salt, More preferably, it is 10 mass%-40 mass% with respect to a water-soluble inorganic salt, 15 mass with respect to a water-soluble inorganic salt optimally It is% -35 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 the particle size becomes large, which is not preferable. When the amount of the water-soluble organic solvent added is 50% by mass or more, the kneading composition becomes so soft that it becomes difficult to share the kneading composition, so that a sufficient refinement effect cannot be obtained.

iii) A water-soluble organic solvent may be added all at the beginning of salt milling, and may be added separately. A water-soluble organic solvent may be used independently and may use 2 or more types together.

[iv) a polymer compound having a basic nitrogen atom]

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

Here, a basic nitrogen atom refers to the nitrogen atom which couple | bonds with a carbon atom only, is in an unoxidized state, and has one lone pair of electrons.

It is preferable that it is at least 1 sort (s) of high molecular compound chosen from following (1)-(4) as a specific high molecular compound.

(1) poly (alkyleneimines) having alkylene groups of 2 to 6 carbon atoms

(2) polyallylamine

(3) polyvinylamine

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

Specific polymer compounds can be further classified into two types of linear polymers and graft polymers from the structure.

Here, although the linear polymer in this invention means the linear polymer which has a basic nitrogen atom in a polymer chain, it is also the linear in this invention that the same kind of linear polymer was bridge | crosslinked with each other in a part of the structure. It is included in the chain polymer.

In addition, the graft type polymer in this invention means that the polymer chain which has a basic nitrogen atom, and the polymer chain different from it have the structure which graft-bonded.

It is preferable that a specific high molecular compound is a linear polymer from a viewpoint of maintaining a process pigment in the state of a primary particle, and effectively suppressing generation | occurrence | production of a secondary aggregate. Moreover, in the dispersion | distribution process in preparation of a pigment dispersion composition, it is preferable that a specific high molecular compound is a graft type polymer from a viewpoint of effectively weakening the cohesion force of a secondary aggregate.

<Straight polymer>

When a specific high molecular compound is a linear polymer, the high molecular compound is a basic nitrogen or a high molecular compound selected from poly (alkyleneimine), polyallylamine, and polyvinylamine having an alkylene group having 2 to 6 carbon atoms, or basic nitrogen. It is a high molecular compound containing the structural unit derived from the at least 1 sort (s) of monomer chosen from the (meth) acrylic acid ester which has an atom, vinylpyridine, and aminostyrene, and it is preferable to have a linear polymeric structure.

Poly (alkyleneimine) (hereinafter, appropriately referred to as “poly (lower alkyleneimine)”) having an alkylene group having 2 to 6 carbon atoms may be a chain or may have a mesh structure.

As poly (lower alkyleneimine), the high molecular compound containing the repeating unit represented with the following general formula (I-1) is mentioned suitably.

In General Formula (I-1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group. a represents the integer of 1-5. * Indicates a connection between repeating units. X represents a group containing a hydrogen atom, a monovalent organic group, or the functional group whose pKa is 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.

The high molecular compound which has a repeating unit represented by general formula (I-1) adds the repeating unit represented by the following general formula (I-2) as a copolymerization component in addition to the repeating unit represented by general formula (I-1). You may include it. By using such a repeating unit together, the dispersion performance of a process pigment can be improved further.

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 general formula (I-1) and general formula (I-2), it is especially preferable that R <^1> and R <^2> are hydrogen atoms. In addition, it is preferable that a is 2 from a viewpoint of raw material availability.

In general formula (I-1) and (I-1 '), it is especially preferable that R <^1> and R <^2> are hydrogen atoms, and it is preferable from a viewpoint of raw material availability that a is 2.

The high molecular compound containing the repeating unit represented by general formula (I-1) may further contain other repeating units as a copolymerization component in addition to the repeating unit represented by general formula (I-1) and general formula (I-2). As such a repeating unit, the unit etc. which repeat the lower alkyleneimine containing a primary or tertiary amino group are mentioned. You may bond with the nitrogen atom in the said lower alkylene imine repeating unit whose pKa represented by said X is 14 or less.

When X in general formula (I-1) shows the functional group whose pKa is 14 or less, if a physical property satisfy | fills this condition, the structure etc. will not be specifically limited, A well-known functional group will satisfy | fill pKa with the said range Are listed.

A pKa less than or equal to the functional group represented by X 14, specifically, for example, a carboxylic acid group (pKa: 3 ~ 5 degree), a sulfonic acid group (pKa: -3 ~ -2 degree), -COCH ₂ CO- (pKa : 8 to 10 or _{so), -COCH 2 CN (pKa:} 8 ~ 11 degree), -CONHCO-, a phenolic hydroxyl group, -R _F CH ₂ OH or _{- (R F) 2 CHOH (} R F is a perfluoroalkyl group PKa: about 9-11), sulfonamide group (pKa: about 9-11), and the like, carboxylic acid group (pKa: about 3-5), sulfonic acid group (pKa: about -3-2) ), -COCH ₂ CO- (pKa: about 8 to 10) is preferable, and a carboxylic acid group is particularly preferable for ease of introduction.

Specific examples of the poly (lower alkyleneimine) include polyethyleneimine, polypropyleneimine, and the like. Moreover, a commercial item can also be used as poly (lower alkyleneimine), For example, SP-003, SP-006, SP-012, SP-018, SP-200, SP-1000 (above, NIPPON SHOKUBAI CO. , LTD. Products).

As polyallylamine, the high molecular compound which has a repeating unit represented by the following general formula (II-1) is mentioned preferably.

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

The polymer compound having a repeating unit represented by General Formula (II-1) further includes a repeating unit represented by the following General Formula (II-2) as a copolymerization component in addition to the repeating unit represented by General Formula (II-1). You may also By using such a repeating unit together, the dispersion performance of a process pigment can be improved further.

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 'is synonymous with X' in general formula (I-2).

In general formula (II-1) and (II-2), it is preferable from a viewpoint of the availability of a raw material that R <^3> , R <^4> , R <^5> and R <^6> are hydrogen atoms.

The high molecular compound which has a repeating unit represented by general formula (II-1) may further contain other repeating units as a copolymerization component other than the repeating unit represented by general formula (II-1) and general formula (II-2). .

A commercial item can also be used as polyallylamine, For example, PAA-01, PAA-03, PAA-05, PAA-08, PAA-15, PAA-15C, PAA-25, PAA-H-10C, PAA- 1112, PAA-U5000 (above, manufactured by Nitto Boseki Co., Ltd.), and the like.

As polyvinylamine, the high molecular compound which has a repeating unit represented with the following general formula (III-1) is mentioned preferably.

In 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 said General formula (I-1).

The polymer compound having a repeating unit represented by General Formula (III-1) further includes a repeating unit represented by the following General Formula (III-2) as a copolymerization component in addition to the repeating unit represented by General Formula (III-1). You may also By using such a repeating unit together, the dispersion performance of a process pigment can be improved further.

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 'is synonymous with X' in general formula (I-2).

In general formula (III-1) and general formula (III-2), it is preferable from a viewpoint of the availability of raw material that R <^7> and R <^8> is a hydrogen atom.

The high molecular compound which has a repeating unit represented by general formula (III-1) may further contain other repeating units as a copolymerization component other than the repeating unit represented by general formula (III-1) and general formula (III-2).

Generally, polyvinylamine is a method of hydrolyzing all or part of a polymer or copolymer of N-vinylcarboxylic acid amide in the presence of an acid or an alkali, as described in Japanese Patent Laid-Open No. 2-222404. As described in JP-A 6-122712, a monomer aqueous solution can be synthesized by a method of polymerization using an azo initiator in an organic solvent or an aqueous solvent.

Said poly (lower alkyleneimine), polyallylamine, and polyvinylamine may further substitute an organic group from a viewpoint of improving the solubility to the solvent at the time of salt milling. As said organic group, a C1-C5 alkyl group, a C1-C5 alkylcarbonyl group, the carboxyl group which may be substituted, the hydroxyl group which may be substituted, etc. are mentioned specifically ,. These organic groups can be introduced by reacting low molecular weight compounds such as carboxylic acid chlorides, acid anhydrides, and lactones. One type of substituent may be sufficient and two or more types may be sufficient as it.

A high molecular compound comprising a structural unit derived from at least one monomer selected from (meth) acrylic acid ester, vinylpyridine and aminostyrene having a basic nitrogen atom in the ester portion may be a homopolymer containing only structural units derived from the monomer or A copolymer may be sufficient and the copolymer which has a structural unit derived from other monomers other than the said monomer may be sufficient.

As (meth) acrylic acid ester which has a basic nitrogen atom in an ester part, Specifically, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (Meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, di (dimethylaminoethyl) Ureidoethyl (meth) acrylate, di (dimethylaminopropyl) ureidoethyl (meth) acrylate, di (diethylaminopropyl) ureidoethyl (meth) acrylate, and the like.

Although it does not specifically limit as a monomer other than the above copolymerizable with the (meth) acrylic acid ester, vinylpyridine, and / or aminostyrene which has a basic nitrogen atom in an ester part, For example, methyl (meth) acrylate and ethyl (meth) acrylate Propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethyl acetate (meth) acrylate , Benzyl (meth) acrylic acid, styrene and the like.

Moreover, as a monomer of that excepting the above, the monomer which has an acidic radical may be sufficient. Specific examples of the monomer having an acid group include (meth) acrylic acid, succinic anhydride adduct of hydroxy (meth) acrylate, and 1,2-cyclohexylcarboxylic anhydride addition of hydroxy (meth) acrylate. Sieve, 1,2-cyclohexylcarboxylic anhydride adduct of hydroxy (meth) acrylate, 1,2-cyclohexenecarboxylic anhydride adduct of hydroxy (meth) acrylate, hydroxy (meth) acryl Phthalic anhydride adducts of the rate and the like.

By using the monomer which has such an acidic radical, when the pigment dispersion composition containing the process pigment of this invention is applied to the photocurable composition applied to color filter manufacture etc., it becomes excellent in the image development removal property of an unexposed part.

When the specific polymer compound is a polymer compound comprising a structural unit derived from a monomer of at least one monomer selected from (meth) acrylic acid ester having a basic nitrogen atom in the ester moiety, vinylpyridine and aminostyrene, the monomer is a specific polymer It is preferable to contain 30 mass%-100 mass% in a compound, and it is more preferable that it is 30 mass%-80 mass%.

Although the specific example of the specific high molecular compound classified into a linear polymer is listed below, this invention is not limited to these. In addition, the molecular weight of the polymeric compound illustrated below is the weight average molecular weight (Mw) of the range of 1,000-100,000, and number average molecular weight (Mn) is the range of 400-50,000.

What has one type of repeating unit in each said specific example is the specific high molecular compound which has 100 mass% of this repeating unit. In addition, when having content of the repeating unit which has a basic nitrogen atom is A, and having content of the repeating unit which is other than B as the thing which has a some repeating unit, the ratio (A / B) is A / B = 10 / It is a specific high molecular compound in the range of 90 mass%-90/10 mass%.

In each said specific example, when content of the repeating unit which has a basic nitrogen atom is A, and content of other repeating units is B, the ratio (A / B) is A / B = 10/90 mass% It is a specific high molecular compound in the range of -60/40 mass%.

<Grafted polymer>

In the case where the specific polymer compound is a graft polymer, the polymer compound preferably has an oligomer chain or a polymer chain having a number average molecular weight of 500 to 1,000,000 in the side chain. Moreover, as said oligomer chain or polymer chain, it is preferable that it is polycaprolactone from a viewpoint that a favorable dispersibility can be obtained.

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

Hereinafter, the specific polymer compound which is a graft type polymer is demonstrated in detail.

Particularly preferred forms of graft polymers are particularly preferred forms of polymer compounds in which poly (lower alkyleneimines), polyallylamines or polyvinylamines are combined with oligomer chains or polymer chains (hereinafter referred to as "graft polymer (1) Polymer compound formed by copolymerizing at least one monomer selected from (meth) acrylic acid ester having a basic nitrogen atom, vinylpyridine, and aminostyrene with at least a polymerizable oligomer (macro monomer) in the ester moiety (hereinafter referred to as &quot; , Also referred to as "grafted polymer 2").

Poly (lower alkyleneimine), polyallylamine and polyvinylamine constituting the graft polymer (1) are preferred examples of the linear polymer and include poly (lower alkyleneimine), polyallylamine and polyvinylamine. same.

In the graft polymer (1), the oligomer chain or polymer chain which can be combined with poly (lower alkyleneimine), polyallylamine or polyvinylamine is preferably polyester, and from the viewpoint of obtaining good dispersibility, It is more preferable that it is caprolactone.

As a synthesis | combining method of the graft-type polymer 1, the method of Unexamined-Japanese-Patent No. 2007-63472 and 9-176511 is applicable, for example.

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

In General 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 the integer of 1-5. * Represents a connection between repeating units. X represents a group containing a hydrogen atom, a monovalent organic group, or the functional group whose pKa is 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. Y represents an oligomer chain or a polymer chain having a number average molecular weight of 500 to 1,000,000.

Compounds containing a repeating unit represented by the general formulas (I-1) and (I-3) include the general formula (I-) in addition to the repeating units represented by the general formulas (I-1) and (I-3). You may further have a repeating unit represented by 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 the oligomer chain or polymer chain whose number average molecular weight which has an anion group is 500-1,000,000. The repeating unit represented by general formula (I-3) can be formed by adding and reacting oligomer or polymer which has group which reacts with an amine and forms a salt to resin which has a primary or secondary amino group in a principal chain part.

In general formula (I-1), general formula (I-3), and general formula (I-4), it is especially preferable that R <^1> and R <^2> are hydrogen atoms. In addition, it is preferable that a is 2 from a viewpoint of raw material availability.

The compound containing the repeating unit represented by general formula (I-1) and (I-3) is a repeat represented by general formula (I-1), general formula (I-2), and general formula (I-3). Other repeating units other than the unit may further be included as the copolymerization component, and such repeating units include units repeating lower alkyleneimines containing primary or tertiary amino groups. The group represented by said X, Y, or Y 'may further couple | bond with the nitrogen atom in the said lower alkylene imine repeating unit. The resin which includes both the repeating unit which the group represented by X couple | bonded with this main chain structure, and the repeating unit which Y couple | bonded is also contained in the specific resin of this invention.

As another preferable example of the graft-type polymer (1), the compound containing the repeating unit represented by the following general formula (II-1) and (II-3) is mentioned.

R <^3> , R <^4> , R <^5> and R <^6> respectively independently represent a hydrogen atom, a halogen atom, and an alkyl group in general formula (II-1) and (II-3). *, X, and Y are synonymous with *, X, and Y in General formula (I-1) and (I-3).

The compound containing the repeating unit represented by general formula (II-1) and (II-3) is added to the repeating unit represented by general formula (II-1) and the repeating unit represented by general formula (II-3) It is preferable to further include the repeating unit represented by the following general formula (II-4) as a copolymerization component. By using such a repeating unit together, dispersion performance improves further when this resin is used as particulate dispersing agents, such as a 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 General formula (I-4).

In general formula (II-1), (II-3) and (II-4), it is preferable from a viewpoint of the availability of a raw material that R <^3> , R <^4> , R <^5> and R <^6> are hydrogen atoms.

The polymer compound having a repeating unit represented by the general formulas (II-1) and (II-3) may have other repetitions in addition to the repeating units represented by the general formulas (II-1), (II-3) and (II-4). You may further include a unit as a copolymerization component.

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

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

The compound containing the repeating unit represented by general formula (III-1) and (III-3) is added to the repeating unit represented by general formula (III-1) and the repeating unit represented by general formula (III-3) The repeating unit represented by the following general formula (III-4) may further be included as a copolymerization component.

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 General formula (I-4).

In general formula (III-1), (III-3) and (III-4), it is preferable from a viewpoint of the availability of a raw material that R <^7> and R <^8> is a hydrogen atom.

The polymer compound having a repeating unit represented by the general formulas (III-1) and (III-3) has a repetition unit other than the repeating units represented by the general formulas (III-1), (III-3) and (III-4). You may further include a unit as a copolymerization component.

Moreover, a commercial item can also be used as the graft polymer 1, For example, Solsperse 24000GR, 28000, 32000, 38500 (brand name: The Lubrizol Corporation product), Ajisper-PB711, PN411, PA111, PB821, PB822 (brand name: Ajinomoto Fine-Techno Co., Inc.), EFKA 4047, 4050 (brand name: EFKA Additives Japan Inc. product), Disperbyk-161, 162, 167, 168 (brand name: BYK Japan KK product) can be mentioned.

The (meth) acrylic acid ester, vinylpyridine and aminostyrene having a basic nitrogen atom in the ester moiety which is a monomer capable of grafting the graft polymer (2) are described in the case where the polymer compound having a basic nitrogen atom is a linear polymer. It is the same as the monomer listed. In addition, as the monomer copolymerizable with these monomers, monomers other than those described above can be suitably used as any monomer capable of constituting the graft polymer 2.

Polymerizable oligomers (macro monomers), which are preferably used as the monomer capable of constituting the graft polymer 2, are oligomers having carbon-carbon double bonds at their ends, and specifically, polystyrene, polyethylene oxide, and polypropylene jade. Seed, poly (meth) acrylic acid ester, polycaprolactone, etc. are mentioned preferably. As a polymerizable oligomer (macro monomer), what has polycaprolactone is preferable from a viewpoint that a favorable dispersibility can be obtained.

As a synthesis | combining method of a polymerizable oligomer (macro monomer), the method described in each publication of Unexamined-Japanese-Patent No. 9-507255, Unexamined-Japanese-Patent No. 2001-518530, Unexamined-Japanese-Patent No. 2005-298401, and Unexamined-Japanese-Patent No. 2006-521442 is enumerated. do. Moreover, the method of connecting caprolactone to the hydroxy (meth) acrylate of Unexamined-Japanese-Patent No. 2007-63461, or the caprolactone is connected to the hydroxy (meth) acrylate of Unexamined-Japanese-Patent No. 2003-531001. And a method of reacting an acid chloride after the reaction is also listed.

The polymerizable oligomer (macro monomer) which can comprise the graft polymer 2 can be obtained also as a commercial item. As such a polymerizable oligomer (macro monomer), for example, a single-terminal methacryloylated polymethyl methacrylate oligomer having a radically polymerized oligomer (Mn = 6,000, trade name: AA-6, manufactured by TOAGOSEI CO., LTD.) , Single-ended methacryloylated poly-n-butylacrylate oligomer (Mn = 6,000, trade name: AB-6, manufactured by TOAGOSEI CO., LTD.), Single-ended methacryloylated polystyrene oligomer (Mn = 6,000, trade name: AS-6, manufactured by TOAGOSEI CO., LTD.). In addition, ε-caprolactone 2-mole adduct of hydroxymethyl methacrylate which has an oligomer which consists of polycaprolactone which has a hydroxyl group at the terminal (brand name: Placcel FM2D, DAICEL CHEMICAL INDUSTRIES, LTD. Product), hydroxymethyl methacryl Ε-caprolactone 3-mol adduct of product rate (brand name: Placcel FM3, product of DAICEL CHEMICAL INDUSTRIES, LTD.), Ε-caprolactone 5-mol adduct of hydroxymethyl methacrylate (brand name: Placcel FM5, DAICEL CHEMICAL INDUSTRIES, LTD.), Ε-caprolactone 2-mol adduct of hydroxymethyl acrylate (product name: Placcel FA2D, DAICEL CHEMICAL INDUSTRIES, LTD.), Ε-caprolactone 10-mol adduct of hydroxymethyl acrylate : Placcel FA10L, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.

The graft polymer 2 can be produced by a general radical polymerization method. Generally, suspension polymerization or solution polymerization is used.

Examples of the solvent used in synthesizing the graft polymer 2 include ethylene chloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl. Ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propylacetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, Ethyl acetate, methyl lactate, ethyl lactate, etc. are mentioned. These solvents may be used alone or in combination of two or more thereof.

In addition, a radical polymerization initiator can be used at the time of radical polymerization. In addition, chain transfer agents such as 2-mercaptoethanol and dodecyl mercaptan can be used.

Although the specific example of the specific high molecular compound classified into a graft polymer is listed below, this invention is not limited to these. In addition, the molecular weight of the polymeric compound illustrated below is the weight average molecular weight (Mw) of the range of 1,000-100,000, and number average molecular weight (Mn) is the range of 400-50,000.

In each said embodiment, when content of the repeating unit which has a basic nitrogen atom is A, and content of the other repeating unit which has a polymer chain in a side chain is B, the ratio (A / B) is A / B = 10 It is a specific high molecular compound in the range of / 90 mass%-70/30 mass%.

In each of the above specific examples, 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 the other repeating unit having a polymer chain in the side chain is C. When it does, the ratio (A / B / C) is a specific high molecular compound in the range of A / B / C = 10/10/80 mass%-60/10/30 mass%.

When a specific high molecular compound has a copolymer unit derived from the monomer which has an acidic radical, content of the copolymer unit derived from the monomer which has the said acidic radical becomes like this. Preferably it is 30 mgKOH / g-200 mgKOH / g, More preferably, it is 30 mgKOH / g- It is 100 mgKOH / g, More preferably, it is 50 mgKOH / g-80 mgKOH / g.

That is, when applying the pigment dispersion composition containing the process pigment of this invention to a photocurable composition, the content of the polymerized unit derived from the monomer which has an acidic radical is 50 mgKOH / g from the point of suppressing generation | occurrence | production of the precipitate in a developing solution. It is preferable that it is above. If the acid value is 200 mgKOH / g or more, the aggregation between the acid groups becomes strong, aggregation between processing pigments occurs, and dispersibility deteriorates, which is not preferable. In order to suppress generation | occurrence | production of the secondary aggregate which is an aggregate of the primary particle of a pigment effectively, or to weaken the cohesion force of a secondary aggregate effectively, the said range of content of the copolymerization unit derived from the monomer which has an acidic radical is preferable.

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

In addition, the specific high molecular compound can adjust the ease of coating to a pigment, and dispersion stability by adjusting the basicity, hydrophilicity, and molecular weight of the said high molecular compound suitably.

In view of the above, as the polymer compound having a basic nitrogen atom, a polymer compound containing a structural unit derived from poly (lower alkyleneimine) or a (meth) acrylic acid ester having a basic nitrogen atom is particularly preferable among the specific polymer compounds described above. .

As for the preferable molecular weight of a specific high molecular compound, it is preferable that the weight average molecular weights (Mw) are the range of 1,000-100,000, and the number average molecular weight (Mn) is the range of 400-50,000. It is more preferable that the weight average molecular weights (Mw) are 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. Most preferably, 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, it is preferable that the weight average molecular weight (Mw) of a specific high molecular compound is 1,000 or more from a viewpoint of effectively suppressing generation | occurrence | production of the secondary aggregate which is an aggregate of the primary particle of a pigment, or effectively weakening the cohesion force of a secondary aggregate. Moreover, it is preferable that the weight average molecular weight (Mw) of a specific high molecular compound is 100,000 or less from a developable viewpoint at the time of manufacturing a color filter by the photocurable composition containing the process pigment of this invention.

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

When manufacturing the process pigment of this invention, you may simultaneously use other high molecular compounds other than the specific high molecular compound mentioned above as needed. Preferably at least partially soluble in water-soluble organic solvents that are solid at room temperature, are insoluble in water, and are used as wetting agents in salt milling, and satisfy them, natural resins, modified natural resins, synthetic resins, Synthetic resins modified from natural resins are used.

When obtaining a dry process pigment, it is preferable that another high molecular compound is solid at room temperature.

Rosin is typical as a natural resin, and rosin derivative, a cellulose derivative, a rubber derivative, a protein derivative, and those oligomers are mentioned as a modified natural resin. Examples of the synthetic resins include epoxy resins, acrylic resins, maleic acid resins, butyral resins, polyester resins, melamine resins, phenol resins and polyurethane resins. Examples of the synthetic resin modified from natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.

Moreover, as synthetic resin, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic-type copolymer, naphthalene sulfonic acid formalin condensate This is listed.

The process pigment of the present invention is characterized in that i) pigment particles such as organic pigments are coated with iv) a specific polymer compound, and the polymer compound is firmly coated on part or all of the pigment particle surface to achieve the effect of the present invention. It is a thing different from what a general polymer dispersing agent adsorb | sucks to a pigment. This coating state can be confirmed by measuring the free amount (free ratio) of a high molecular compound in washing | cleaning with the organic solvent shown below. That is, most of the high molecular compound which is merely adsorbed to the pigment is freed or removed by washing with an organic solvent, specifically 65% or more. However, in the case of the surface-coated processed pigment as in the present invention, the glass ratio is extremely low. , 30% or less.

The free amount of the high molecular compound of the process pigment in this invention calculates by wash | cleaning a process pigment with 1-methoxy- 2-propanol. In the specific method, first, 10 g of the processed pigment is added to 100 ml of 1-methoxy-2-propanol, and shaken for 3 hours at room temperature in a shaker. Thereafter, the pigment is allowed to settle over 8 hours at 80,000 rpm in a centrifuge to obtain a solid content of the supernatant portion by a drying method. From the amount of this solid content, the mass of the polymer compound liberated by the pigment is obtained, and the ratio (%) is calculated from the ratio with the mass of the polymer compound used for the initial treatment.

In addition, the glass ratio of processed pigments, such as a commercial item, can be measured with the following method.

That is, after dissolving the whole processed pigment with a solvent for dissolving the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), it is separated from the organic solvent by using the difference in solubility between the polymer compound and the pigment, It calculates as "mass of the high molecular compound used for the initial process." Separately, the processed pigment is washed with 1-methoxy-2-propanol, and the above-mentioned free amount is divided by this "mass of the high molecular compound used for the initial treatment" to obtain the free ratio (%).

The smaller the glass ratio, the higher the coating ratio on the pigment, and the better the dispersibility and dispersion stability. The preferable range of free ratio is 30% or less, More preferably, it is 20% or less, Most preferably, it is 15% or less. Ideally 0%.

The processing pigments of the present invention are processing pigments excellent in dispersibility and dispersion stability in that the pigment surface is not liberated even when the pigment surface is firmly coated with a specific polymer compound and immersed in an organic solvent, and its application range is wide. It is especially useful for preparation of the pigment dispersion composition mentioned later.

Pigment Dispersion Composition

Next, the pigment dispersion composition of this invention using the process pigment of the said invention is demonstrated.

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

Moreover, when disperse | distributing the process pigment of this invention in the organic solvent, it is also a preferable aspect to use suitably a pigment derivative and a dispersing agent as needed.

[Organic Solvent]

There is no restriction | limiting in particular as an organic solvent in the pigment dispersion composition of this invention, If it is an organic solvent, it can select suitably from well-known things, For example, 1-methoxy- 2-propyl acetate, 1-methoxy- (Poly) alkylene glycol monoalkyl such as 2-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, 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; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, alkylene glycol monoalkyl ethers, its acetic acid esters, acetic acid esters, methyl ethyl ketone, etc. are preferable.

Content of the organic solvent in a pigment dispersion composition is suitably selected according to the use of a pigment dispersion composition, etc. When a pigment dispersion composition is used for preparation of the photocurable composition mentioned later, it can contain so that solid content concentration containing a process pigment etc. may be 5-50 mass% from a viewpoint of handleability.

Pigment Derivatives

The pigment derivative is added to the pigment dispersion composition of this invention as needed.

By adsorbing a portion having affinity with a dispersant or a pigment derivative having a polar group adsorbed onto the surface of the process pigment and using this as an adsorption point of the dispersant, the process pigment can be dispersed as fine particles in the pigment dispersion composition, and the ash Agglomeration can be prevented.

A pigment derivative is the compound which introduce | transduced an acidic group, a basic group, and an aromatic group into a side chain specifically, using an organic pigment as a mother skeleton. Specific examples of the organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindolin pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzimidazolones. Pigments and the like. Generally, pale yellow aromatic polycyclic compounds, such as naphthalene series, anthraquinone series, triazine series, and quinoline series, which are not called dyes, are also included. As a pigment derivative, Unexamined-Japanese-Patent No. 11-49974, Unexamined-Japanese-Patent No. 11-189732, Unexamined-Japanese-Patent No. 10-245501, Unexamined-Japanese-Patent No. 2006-265528, Unexamined-Japanese-Patent No. 8-295810 What is described in Unexamined-Japanese-Patent No. 11-199796, Unexamined-Japanese-Patent No. 2005-234478, Unexamined-Japanese-Patent No. 2003-240938, Unexamined-Japanese-Patent No. 2001-356210, etc. can be used.

As content in the pigment dispersion composition of a pigment derivative, 1-30 mass% is preferable with respect to the mass of a pigment, and 3-20 mass% is more preferable. When content of a pigment derivative is in the said range, dispersion can be performed favorable, suppressing a viscosity low, and the dispersion stability after dispersion can be improved.

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

[Dispersant]

The pigment dispersing composition of this invention can also add the conventionally well-known dispersing agent, such as a pigment dispersing agent and surfactant, for the purpose of further improving the dispersibility of a process pigment.

Known dispersants (pigment dispersants) include polymer dispersants [e.g., polyamideamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates. , (Meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates] and polyoxyethylene alkyl phosphate esters, polyoxyethylene alkylamines, alkanolamines, pigment derivatives, and the like.

Polymeric dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from the structure.

The polymeric dispersant adsorbs on the surface of the pigment and acts to prevent reagglomeration. Therefore, terminal modified polymers, graft polymers, and block polymers having anchor sites on the pigment surface can be listed as preferable structures. On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

In the dispersing process, the polymer dispersant is adsorbed on the surface of the pigment to act to prevent reagglomeration. Therefore, the block type polymer, the graft type polymer, and the terminal modified type polymer which have an anchor part to the pigment surface can be enumerated as a preferable structure. On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

(Grafted polymer)

Although it does not restrict | limit especially about a graft type polymer, The compound which made the polyalkylene imine and the polyester compound react as described in Unexamined-Japanese-Patent No. 54-37082, 61-174939, etc., Unexamined-Japanese-Patent No. 9 The compound which modified the amino group of the side chain of polyallylamine of Unexamined-Japanese-Patent No. 169821 with polyester, the polyester polyol addition polyurethane of Unexamined-Japanese-Patent No. 60-166318, etc. are mentioned preferably, and also the Japan patent publication As in 9-171253 and the chemistry of macromonomers and the industry (IPC Publishing, 1989) and the like, graft polymers containing a polymerizable oligomer (hereinafter referred to as a macromonomer) as a copolymerization component may also be preferably listed. Moreover, in the point which adsorb | sucks into a pigment and gives favorable dispersibility, the graft type polymer which has the organic pigment | dye part of Unexamined-Japanese-Patent No. 2003-238837 is preferable.

The branched portion of the graft polymer is preferably polystyrene, polyethylene oxide, polypropylene oxide, poly (meth) acrylic acid ester, polycaprolactone, or the like, but is preferably a graft polymer having a polycaprolactone chain.

Commercially available graft polymers include Solsperse 24000, Solsperse 28000, Solsperse 32000, Solsperse 38500, Solsperse 39000, Solsperse 55000 (above, The Lubrizol Corporation), Disperbyk-161, Disperbyk-171, Disperbyk-174 (above, BYK Japan KK) Products) and the like.

(Terminal modified polymer)

As the terminal-modified polymer, for example, the polymers described in Japanese Patent Laid-Open No. 9-77994, Japanese Patent Laid-Open No. 2002-273191, Japanese Patent Laid-Open No. 2007-277514, Japanese Patent Laid-Open No. 2007-140487, and the like. The polymer which has a functional group at the terminal of can be mentioned.

(Block type polymer)

Although it does not specifically limit as a block type polymer, The block type polymer which consists of a pigment adsorption block and the block which is not adsorb | sucked by a pigment is mentioned.

Although it does not specifically limit as a monomer which comprises a pigment adsorption block, For example, the monomer which has a functional group which can adsorb | suck to a pigment is mentioned. Specifically, the monomer which has an organic pigment | dye structure or heterocyclic structure, the monomer which has an acidic group, the monomer which has a basic nitrogen atom, etc. can be mentioned.

As a monomer which has an organic pigment | dye structure or a heterocyclic structure, the organic pigment | dye skeleton, maleimide derivative, etc. which were described in Unexamined-Japanese-Patent No. 2003-238837 are mentioned, for example.

It is also possible to use a commercial item as a block polymer. Specific examples include Disperbyk-2000, Disperbyk-2001 (above, manufactured by BYK Japan KK), EFKA 4330, EFKA 4340 (above, manufactured by EFKA Additives Japan Inc.), and the like.

Preparation of Pigment Dispersion Composition

The pigment dispersion composition of this invention can be prepared by going through the mixing-dispersion process which mix-disperses using various mixers and a disperser.

In addition, although the mixing-dispersion process preferably consists of kneading dispersion and subsequent non-dispersion treatment, it is also possible to omit the kneading dispersion.

Specifically, the pigment dispersion composition of the present invention contains, for example, the processed pigment of the present invention, an organic solvent, and optional components (pigment derivatives, dispersants, etc.) used as necessary in the vertical or horizontal sand grinder, pin mill, slit mill. It can be obtained by performing microdispersion treatment with beads made of glass, zirconium oxide, or the like having a particle diameter of 0.01 mm to 1 mm using an ultrasonic disperser or the like.

In addition, strong shear force is achieved by using two rolls, three rolls, a ball mill, a trom mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single screw, or a twin screw extruder before performing the dispersion by the beads. It is also possible to perform a kneading dispersion process while giving.

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

[Photocurable Composition]

It is preferable that the photocurable composition of this invention contains the pigment dispersion composition, polymeric compound, and photoinitiator of this invention mentioned above, and also contains alkali-soluble resin, and may contain another component as needed.

The photocurable composition of this invention is used suitably for the photocurable composition used for manufacture of a color filter. Hereinafter, each component contained in the photocurable composition of this invention is demonstrated in detail.

Pigment Dispersion Composition

The photocurable composition of this invention is comprised using at least 1 sort (s) of the pigment dispersion composition of this invention mentioned above. The detail of the pigment dispersion composition of this invention which comprises a photocurable composition is as above-mentioned.

As content of the pigment dispersion composition in the photocurable composition of this invention, content with the content of a processing pigment becomes the range of 5 mass%-70 mass% with respect to the total solid (mass) of a photocurable composition, 15 mass% is preferable. The amount which becomes the range of -60 mass% is more preferable. When content of a pigment dispersion composition exists in this range, color density is enough and it is effective also to ensure the outstanding color characteristic.

[Polymerizable Compound]

The photocurable composition of this invention contains at least 1 polymeric compound.

As a polymeric compound which can be used for this invention, the compound which has at least 1 addition-polymerizable ethylenically unsaturated group, and whose boiling point is 100 degreeC or more at normal pressure is preferable, and the tetrafunctional or more functional acrylate compound is especially preferable.

As a compound which has at least 1 addition-polymerizable ethylenically unsaturated group and whose boiling point is 100 degreeC or more at normal pressure, for example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) Monofunctional acrylates and methacrylates such as acrylates; Polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Multifunctional such as hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane (Meth) acrylated after addition of ethylene oxide or propylene oxide to alcohol, poly (meth) acrylated of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708, Japanese Patent Publication Urethane acrylates of 50-6034, Unexamined-Japanese-Patent No. 51-37193, Unexamined-Japanese-Patent No. 48-64183, Japanese patent Polyfunctional acrylates and methacrylates, such as the polyester acrylates of Unexamined-Japanese-Patent No. 49-43191, Japanese Unexamined-Japanese-Patent No. 52-30490, and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. Can be enumerated.

In addition, Japan Adhesion Society Vol. 20, No. 7, 300-308 can also use what was introduced as a photocurable monomer and an oligomer.

In addition, after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in Japanese Patent Application Laid-open No. Hei 10-62986 with the specific examples as General Formulas (1) and (2), (meth) acrylated Compounds can also be used.

Especially, the structure in which dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these acryloyl groups via ethylene glycol and a propylene glycol residue are preferable. These oligomer types can also be used.

A polymeric compound can be used in combination of 2 or more type other than using individually by 1 type.

As content in the photocurable composition of a polymeric compound, 3-55 mass parts is preferable with respect to 100 mass parts of total solids of the said composition, More preferably, it is 10-50 mass parts. If content of a polymeric compound is in the said range, hardening reaction can fully be performed.

[Photopolymerization Initiator]

As a photoinitiator, for example, the halomethyloxadiazole described in JP-A-57-6096, JP-A-59-1281, JP-A-53-133428 and the halomethyl-s- Active halogen compounds such as triazine, aromatic carbonyl compounds such as ketal, acetal, or benzoin alkyl ethers described in each specification such as US Patent USP-4318791, European Patent Publication EP-88050A, and US Patent USP-4199420 Aromatic ketone compounds such as benzophenones, (thio) xanthones or acridine compounds described in the Fr-2456741 specification, compounds such as coumarins or ropindimers described in JP-A-10-62986, and Japanese Patents Sulfonium organoboron complexes, such as Unexamined-Japanese-Patent No. 8-015521, etc. can be mentioned.

As said photoinitiator, acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, triazine series, halomethyl oxadiazole series, acridine series, coumarin series, ropindimer series, biimidazole series And oxime esters are preferable.

As said acetophenone type photoinitiator, 2, 2- diethoxy acetophenone, p-dimethylamino acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylamino, for example Acetophenone, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, etc. can be mentioned preferably.

As said ketal type photoinitiator, benzyl dimethyl ketal, benzyl- (beta)-methoxyethyl acetal, etc. can be mentioned preferably, for example.

As said benzophenone type photoinitiator, For example, benzophenone, 4,4'- (bisdimethylamino) benzophenone, 4,4'- (bisdiethylamino) benzophenone, 4,4'- dichloro benzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-tolyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, etc. can be mentioned preferably.

As said benzoin type or benzoyl type photoinitiator, benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl benzoate, etc. can be mentioned preferably, for example.

As said xanthone type photoinitiator, diethyl thioxanthone, diisopropyl thioxanthone, monoisopropyl thioxanthone, chloro thioxanthone, etc. can be mentioned preferably, for example.

As said triazine type photoinitiator, 2, 4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine and 2, 4-bis (trichloromethyl) -6-p-meth Oxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (Trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl -2,6-di (trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl) -s-triazine, 3,4-dimethoxystyryl-2,6 -Di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxy Carbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine and the like can be enumerated.

As said halomethyloxadiazole type photoinitiator, 2-trichloromethyl-5-styryl-1,3,4- oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1, 3,4-oxodiazole, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) sty Reel-1,3,4-oxodiazole etc. are mentioned preferably.

As said acridine type photoinitiator, 9-phenyl acridine, 1, 7-bis (9-acridinyl) heptane, etc. can be mentioned preferably, for example.

As said coumarin-type photoinitiator, 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s -Triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin and the like are preferably listed. Can be.

As said ropindimer type photoinitiator, 2- (o-chlorophenyl) -4,5-diphenyl imidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenyl are mentioned, for example. Midazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, etc. can be mentioned preferably.

As said biimidazole type photoinitiator, 2-mercapto benzimidazole, 2,2'- benzothiazolyl disulfide, etc. can be mentioned preferably, for example.

In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4'-benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6- Trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-trialkylphenylphosphonium salt and the like.

In this invention, it is not limited to the above photoinitiator, Another well-known thing can also be used. For example, the bisinalpolyketolaldonyl compounds described in US Pat. No. 2,367,660, the α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670, and the acyl inether described in US Pat. No. 2,448,828. , Aromatic acyloin compounds substituted with α-hydrocarbons as described in US Pat. No. 2,722,512, polynuclear quinone compounds as described in US Pat. Nos. 3,046,127 and 2,951,758, triallylimides as described in US Pat. No. 3,549,367 Combination of sol dimer / p-aminophenylketone, 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, the Journal of Photopolymer Science and Technology (1995) 202-232, the oxime ester compound of Unexamined-Japanese-Patent No. 2000-66385, etc. are mentioned.

Moreover, these photoinitiators can also be used together.

As content in the photocurable composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 0.5-5.0 mass%. When content of a photoinitiator exists in the said range, a polymerization reaction will advance favorably and film formation with favorable intensity | strength is possible.

[Alkali Soluble Resin]

As alkali-soluble resin, it is a linear organic high molecular polymer, group which promotes at least 1 alkali solubility in a molecule | numerator (preferably an acryl-type copolymer, the molecule which has a styrenic copolymer as main chain) (for example, a carboxyl group, a phosphate group, a sulfonic acid group) Etc. can be suitably selected from alkali-soluble resin which has. Among these, More preferably, it is soluble in an organic solvent and can develop with a weak alkali aqueous solution.

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

As said linear organic high polymer, the polymer which has a carboxylic acid in a side chain is preferable. For example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication 54-34327, Japanese Patent Publication 58-12577, Japanese Patent Publication 54-25957, Japanese 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 described in the respective publications of Japanese Patent Application Laid-Open No. 59-71048; And an acid cellulose derivative having a carboxylic acid in the side chain, an acid anhydride added to a polymer having a hydroxyl group, and the like, and polymer polymers having a (meth) acryloyl group in the side chain may also be listed as preferred.

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

In addition, those copolymerized with 2-hydroxyethyl methacrylate and the like are also listed as useful. The said polymer can be mixed and used in arbitrary quantity.

In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and 2-hydroxy-3-phenoxypropyl described in JP-A-7-140654 Acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macro monomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxy Ethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like.

About the specific structural unit of alkali-soluble resin, the copolymer of (meth) acrylic acid and another monomer copolymerizable with this is especially preferable. Here, (meth) acrylic acid is a general term containing acrylic acid and methacrylic acid, and (meth) acrylate is also a general term of acrylate and methacrylate similarly below.

As another monomer copolymerizable with the said (meth) acrylic acid, an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned. Here, the hydrogen atom of an alkyl group and an aryl group may be substituted by the 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, and isobutyl (meth). Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) Acrylate, cyclohexyl (meth) acrylate, etc. can be mentioned.

Moreover, as said vinyl compound, styrene, (alpha) -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene, for example Macromonomer, polymethylmethacrylate macromonomer, CH ₂ = CR ¹ R ² , CH ₂ = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R <^2> represents a C6-C10 aromatic hydrocarbon ring, R <^3> represents a C1-C8 alkyl group or a C6-C12 aralkyl group.] Etc. can be mentioned.

These copolymerizable other monomers can be used individually by 1 type or in combination of 2 or more types. Preferred copolymerizable other monomers are at least one selected from CH ₂ = CR ¹ R ² , CH ₂ = C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene, Especially preferred are CH ₂ = CR ¹ R ² and / or CH ₂ = C (R ¹ ) (COOR ³ ).

As content in the photocurable composition of alkali-soluble resin, 1-15 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 2-12 mass%, Especially preferably, it is 3-10 mass%.

[solvent]

Generally the photocurable composition of this invention can be preferably prepared by using each component and solvent mentioned above together.

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetic acid, oxyacetic acid butyl, methoxyacetic acid methyl, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid, methyl 3-oxypropionate, 3 3-oxypropionic acid alkyl esters such as ethyl oxypropionate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxy Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2-methylpropionic acid Ethyl, 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, methyl 2-oxobutanoate, 2- Ethyl oxobutanoic acid and the like; Ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene Glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene, xylene and the like.

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

You may use a solvent in combination of 2 or more type other than using independently.

[Other Ingredients]

In the photocurable composition of the present invention, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, a coloring agent, a photopolymerization initiator, other fillers, polymer compounds other than the alkali-soluble resins, surfactants, adhesion promoters, Various additives, such as antioxidant, a ultraviolet absorber, and an aggregation inhibitor, can be contained.

<Fluorinated Organic Compound>

By containing a fluorine-type organic compound, the liquid characteristic (particularly fluidity) at the time of using it as a coating liquid can be improved, and the uniformity of coating thickness and liquid saving property can be improved. That is, since the interfacial tension between the substrate and the coating liquid is lowered, the hygroscopicity on the substrate is improved, and the coating property on the substrate is improved. It is effective in that film formation is possible.

3-40 mass% is preferable, as for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Especially preferably, it is 7-25 mass%. If fluorine content is in the said range, it is effective at the point of application | coating thickness uniformity and liquid saving property, and the solubility in a composition is also favorable.

Examples of the fluorine-based organic compound include Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437 (above, manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431 , Fluorad FC171 (above, Sumitomo 3M Ltd.), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383 , Surflon S393, Surflon KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), And the like.

As a fluorine-type organic compound, the compound which has a fluoroalkyl or a fluoroalkylene group in at least one site | part of a terminal, a main chain, and a side chain can be used preferably. As a specific commercial item, for example, Megafac F142D, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F183, Megafac 780, Megafac 781, Megafac R30, Megafac R08, Megafac F-472SF, Megafac BL20, Megafac R-61, Megafac R-90 from DIC Corporation, Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431, Novec FC-4430 from Sumitomo 3M Ltd., Asahi Guard AG 7105, 7000, 950 , 7600, Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC -104, Surflon SC-105, Surflon SC-106 (manufactured by ASAHI GLASS CO., LTD.), Eftop EF351, Eftop 352, Eftop 801, Eftop 802 (manufactured by JEMCO Coopoerations Co., Ltd.).

The fluorine-based organic compound is particularly effective in preventing coating irregularities and thickness irregularities when the coating film is thinned. Moreover, it is effective also in the slit application | coating which is easy to produce liquid liquefaction.

As for the addition amount of a fluorine-type organic compound, 0.001-2.0 mass% is preferable with respect to the total mass of a photocurable composition, More preferably, it is 0.005-1.0 mass%.

<Thermal polymerization initiator>

It is also effective to contain a thermal polymerization initiator in the photocurable composition of this invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds, and azobis compounds may be cited as the azo compounds, and ketone peroxide, peroxy ketal, and hydro as the peroxide compounds. Peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxydicarbonate, etc. can be mentioned.

<Thermal polymerization component>

It is also effective to contain a thermal-polymerization component in the photocurable composition of this invention. As needed, in order to raise the intensity | strength of a coating film, an epoxy compound can be added. As an epoxy compound, it is a compound which has 2 or more epoxy rings in a molecule | numerator, such as bisphenol-A, cresol novolak-type, a biphenyl type, and an alicyclic epoxy compound. For example, as bisphenol A type, EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. Tohto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103 (above, NAGASE CHEMICAL CO., LTD.), Placcel GL-61, GL-62, G101, G102 ( As mentioned above, in addition to DAICEL CHEMICAL INDUSTRIES, LTD.), These similar bisphenol F type and bisphenol S type can also be enumerated. Moreover, epoxy acrylates, such as Ebecryl 3700, 3701, 600 (above, Daicel UBC Co., Ltd. product), can also be used. As the cresol novolac type, EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Tohto Kasei Co., Ltd.), Denacol EM-125, etc. (above, NAGASE CHEMICAL CO ., LTD.), 3,5,3 ', 5'-tetramethyl-4,4' diglycidyl biphenyl as biphenyl type, Seroxide 2021, 2081, 2083, 2085, Epolead as alicyclic epoxy compound GT-301, GT-302, GT-401, GT-403, EHPE-3150 (more than DAICEL CHEMICAL INDUSTRIES, LTD.), SUNTOHTO ST-3000, ST-4000, ST-5080, ST-5100 (more, Tohto Kasei Co., Ltd. product) etc. can be mentioned. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o -Phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and other amine epoxy resins EPOTOHTO YH-434, YH-434L, and glycidyl esters in which dimer acid is modified in the skeleton of a bisphenol A epoxy resin are also used. Can be.

<Surfactant>

It is preferable to comprise in the photocurable composition of this invention using various surfactant from a viewpoint of improving applicability | paintability, and various nonionic, cationic, and anionic surfactant can be used other than the above-mentioned fluorine-type surfactant. Can be. Especially, the said nonionic surfactant is preferable the fluorine-type surfactant and nonionic surfactant which have a perfluoroalkyl group.

Examples of nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and the like. Particular preference is given to nonionic surfactants. Specifically, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene polythiylated ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polytyryl ether, polyoxyethylene nonylphenyl ether; Ratios such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters and ethylenediamine polyoxyethylene-polyoxypropylene condensates Ionic surfactants, which are Kao Corporation, NOF CORPORATION, TAKEMOTO OIL & FAT Co., Ltd., ADEKA CORPORATION, SANYO KASEI CO., LTD. What is marketed from etc. can be used suitably. In addition to the above, the above-described dispersant may be used.

In addition to the above, various additives may be added to the photocurable composition. Specific examples of the additive include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, anti-agglomerating agents such as sodium polyacrylate, glass and alumina. Fillers such as; Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, acid anhydride added to a polymer having a hydroxyl group, alcohol soluble nylon, bisphenol A and epichlorohydrin Alkali-soluble resins such as phenoxy resins formed from

In addition, when promoting 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, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sublinic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethylsuccinic acid Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid and canforonic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, meropanic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamonic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamilidene acetic acid, coumalic acid and unbaric acid.

<Heat polymerization inhibitor>

It is preferable to further add a thermal polymerization inhibitor to the photocurable composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogarol, t -Butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2- Mercaptobenzoimidazole and the like are useful.

Since the photocurable composition of this invention contains the pigment dispersion composition (the pigment dispersion composition of this invention) containing the process pigment of this invention, it is excellent in the dispersibility of a process pigment, and also excellent in color characteristics.

Therefore, it is preferable to be used in order to form the colored area | region of the color filter for which the favorable color characteristic is calculated | required.

<Color filter>

The color filter of this invention has a coloring area formed on the board | substrate by the photocurable composition of this invention mentioned above.

Here, a coloring area | region includes both the coloring pattern (pixel part) of a 3 color or 4 color and a black matrix.

Hereinafter, the color filter of this invention is demonstrated in detail through the manufacturing method.

The manufacturing method of the color filter of this invention is demonstrated.

First, the photocurable composition of this invention is provided on a board | substrate directly or through another layer (preferably, it is apply | coated by application | coating methods, such as rotational coating, slit coating, casting | flow_spread coating, roll coating, etc.), and a photosensitive film (coating film) ) Is formed (coating step). Then, exposure is performed through the predetermined | prescribed mask pattern in the formed coating film (exposure process). After exposure, the uncured portion of the coating film is developed and removed with a developing solution (development step). By passing through these processes, the coloring pattern which consists of pixels of each color (three or four colors) is formed, and a color filter can be obtained.

By such a method, the color filter used for a liquid crystal display element or a solid-state image sensor can be produced in a high quality and low cost with little difficulty in a process.

Hereinafter, each process is explained in full detail.

[Application Process]

First, the board | substrate used at an application | coating process is demonstrated.

As a board | substrate used for the color filter of this invention, an alkali free glass, a soda glass, Pyrex (trademark) glass, quartz glass used for a liquid crystal display element etc., and the transparent conductive film adhered to these, a solid-state image sensor, etc. are used, for example. Photoelectric conversion element substrates used, for example, silicon substrates and plastic substrates are listed.

On these board | substrates, the black matrix which isolate | separates each pixel may be formed, or the transparent resin layer may be formed in order to promote close contact.

In addition, the plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, a driving substrate (hereinafter referred to as a "TFT system liquid crystal drive substrate") on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed is used. The coloring pattern which uses the photocurable composition of this invention is formed, and a color filter can be produced.

As a board | substrate in a TFT system liquid crystal drive board | substrate, glass, silicone, a polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. can be mentioned, for example. These substrates may be subjected to a suitable pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum evaporation as desired. For example, the board | substrate which provided the passivation film, such as a silicon nitride film, on the surface of a TFT system liquid crystal drive substrate can be used.

Although it does not specifically limit as a method of apply | coating the photocurable composition of this invention to a board | substrate in a coating process, The method of using slit nozzles, such as a slit and spin method and a spinless coating method (hereinafter, slit nozzle application | coating) Law).

In the slit nozzle coating method, the slit and spin coating method and the spinless coating method vary depending on the size of the coated substrate, but are, for example, the fifth generation glass substrate (1100 mm x 1250 mm) by the spinless coating method. In the case of coating, the discharge amount of the photocurable composition from the slit nozzle is usually 500 μl / sec to 2000 μl / sec, preferably 800 μl / sec to 1500 μl / sec, and the coating speed is usually 50 mm / sec to 300 mm. / Second, Preferably it is 100 mm / sec-200 mm / sec.

Moreover, as solid content of the photocurable composition used at a coating process, it is 10%-20% normally, Preferably they are 13%-18%.

When forming the coating film by the photocurable composition of this invention on a board | substrate, as thickness (after prebaking process) of the said coating film, it is generally 0.3 micrometer-5.0 micrometers, Preferably it is 0.5 micrometer-4.0 micrometers, Most preferably, 0.5 micrometer-3.0 micrometers.

Moreover, in the case of the color filter for solid-state image sensors, the thickness (after a prebaking process) of a coating film has the preferable range of 0.5 micrometer-5.0 micrometers.

In an application | coating process, a prebaking process is normally performed after application | coating. If necessary, vacuum treatment may be performed before prebaking.

The conditions for vacuum drying are usually about 0.1 tor to 1.0 tor, preferably about 0.2 tor to 0.5 tor.

In addition, a prebaking process is 50 degreeC-140 degreeC using a hotplate, oven, etc., Preferably it is about 70 degreeC-110 degreeC, and can be performed on the conditions of 10 second-300 second. In addition, you may use a high frequency process etc. together for a prebaking process. The high frequency treatment can be used alone.

Exposure process

In an exposure process, exposure is performed through the predetermined mask pattern with respect to the coating film which consists of a photocurable composition formed as mentioned above.

Especially as radiation used at the time of exposure, ultraviolet rays, such as g line | wire, h line | wire, i line | wire, j line | wire, are preferable.

In addition, when manufacturing the color filter for liquid crystal display devices, exposure using h line | wire and i line | wire is mainly used suitably by a proximity exposure machine and a mirror projection exposure machine.

Moreover, when manufacturing the color filter for solid-state image sensors, it is preferable to mainly use i line | wire in a stepper exposure machine.

In addition, the photomask used when manufacturing a color filter using a TFT type liquid crystal drive substrate is formed with a pattern for forming a through hole or a U-shape in addition to the pattern for forming a pixel (colored pattern). Which is used.

[Developing process]

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

As image development temperature, it is 20 degreeC-30 degreeC normally, and as image development time, it is 20 second-90 second.

As a developing solution, as long as it melt | dissolves the coating film of the photocurable composition in an uncured part, and a hardened part is not melt | dissolved, either can be used.

Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used.

As an organic solvent used for image development, the above-mentioned solvent which can be used when preparing the photocurable composition of this invention is mentioned.

As the aqueous alkaline solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, The concentration is 0.001% by mass to 10% by mass of alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, Preferably, the alkaline aqueous solution melt | dissolved so that it may become 0.01 mass%-1 mass% is mentioned.

A suitable amount of water-soluble organic solvents, such as methanol and ethanol, surfactant, etc. can also be added to alkaline aqueous solution.

The developing method may be any of a dipping method, a shower method, a spray method, and the like, and a swing method, a spin method, an ultrasonic method, or the like may be combined therewith. Before the contact with the developer, the surface to be developed may be wetted with water or the like beforehand to prevent development unevenness. Moreover, it can also develop by inclining a board | substrate.

In addition, when manufacturing the color filter for solid-state image sensors, a paddle phenomenon is also used.

After the development treatment, drying is carried out through a rinse treatment for washing out excess developer, and then heat treatment (post-baking) is performed to complete curing.

The rinse treatment is usually performed with pure water, but in order to save the liquid, pure water is used in the final cleaning, and in the initial stage of cleaning, the used pure water is used, or the substrate is cleaned by tilting the substrate, or ultrasonic irradiation is used in combination. Also good.

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

This heat treatment (post-baking) can be carried out continuously or collectively using heating means such as a hot plate, a convection oven (hot air circulation dryer), a high frequency heater, or the like so that the coating film after development becomes the above conditions.

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 a plurality of colored cured films (coloring patterns) are formed.

Since the color filter of this invention has high contrast, little color density nonuniformity, and favorable color characteristic, it can be used suitably for a solid-state image sensor or a liquid crystal display element.

Although the use of the photocurable composition of this invention was demonstrated mainly centering on the use to the coloring pattern of a color filter, it is applicable also to formation of the black matrix which isolate | separates the coloring pattern (pixel) which comprises a color filter.

The black matrix on the substrate can be formed by using a photocurable composition containing a work pigment of a black pigment such as carbon black, titanium black, and the like after coating, exposure and development, and post-baking as necessary. have.

<Liquid crystal display element, solid-state image sensor>

The color filter of this invention can be applied as a color filter with a liquid crystal display element or a solid-state image sensor. More specifically, for example, a panel which is a liquid crystal display element is obtained by forming an alignment film on the inner surface side of the color filter, facing the electrode substrate, and sealing the liquid crystal in the gap portion. For example, a solid-state image sensor is obtained by forming a color filter on a light receiving element.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples without departing from the spirit thereof. In addition, "part" is a mass reference | standard unless there is particular notice.

(Synthesis of Specific Polymer Compounds and Comparative Polymer Compounds)

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-substituted three-necked flask, followed by a stirrer (SHINTO Scientific Co., Ltd .: Three One). Motor), and heated to 90 ° C while flowing nitrogen into the flask. 6.0g of 2, 2- azobis (2, 4- dimethylvaleronitrile) (V-65 by Wako Pure Chemical Industries, Ltd.) was added to this, and it heated and stirred at 90 degreeC 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 the polymer compound 1 that is a specific polymer compound.

It was 2.00,000 when the weight average molecular weight of the obtained high molecular compound 1 was measured by the gel permeation chromatography method (GPC) which made polystyrene the reference material.

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 three-necked flask with nitrogen substitution, stirred with a stirrer (SHINTO Scientific Co., Ltd .: Three-One Motor), and It heated, heating up to 90 degreeC, flowing into the flask. 3.9g of 2, 2- azobis (2, 4- dimethylvaleronitrile) (V-65 by Wako Pure Chemical Industries, Ltd.) was added to this, and it heated and stirred at 90 degreeC 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% by mass solution of polymer compound 2 that is a specific polymer compound.

It was 2.50,000 when the weight average molecular weight of the obtained high molecular compound was measured by the gel permeation chromatography method (GPC) which made polystyrene the reference material.

Synthesis Examples 3 to 7 Synthesis of Polymer Compounds 3 to 7 and Polymer Compound C1

Polymer compounds 3 to 7, which are specific polymer compounds, and polymer compound C1, which is a comparative polymer compound, are prepared by changing the monomers used in the synthesis of polymer compound 1 to the composition (wt%) shown in Table 1 below. Synthesis was carried out in the same manner as synthesis.

Table 1 shows the monomers constituting the polymer compounds 1 to 7 and the polymer compound C1, their composition (wt%), and the weight average molecular weight (Mw) of each of the obtained polymer compounds.

 Polymer compound number Composition of Polymer Compound (wt%)  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, and AAEM is acetoacetate ethyl methacrylate. Acrylate, St is styrene, VyPy is vinylpyridine, ASt is p-aminostyrene, AA-6 is a single-terminal methacryloylated polymethylmethacrylate oligomer (Mn = 6,000, manufactured by TOAGOSEI CO., LTD.).

Synthesis Example 8: Synthesis of Polymer Compound 8

100 g of polyethyleneimine (SP-018, number average molecular weight 1,800, product of NIPPON SHOKUBAI CO., LTD.) And 40 g of acetic anhydride were added to 326 g of 1-methoxy-2-propanol, and stirred at 120 ° C. for 2 hours to give a high molecular compound 8 A 30 mass% solution of was obtained.

Synthesis Example 9: Synthesis of Polymer Compound 9

According to the method of Example 1 of Unexamined-Japanese-Patent No. 2003-531001, the high molecular compound 10 which is a condensate of 10 mole adduct of caprolactone of 2-butyloctanoic acid and polyethyleneimine was obtained. The solvent was performed with a 30 mass% solution of 1-methoxy-2-propanol.

Synthesis Example 10 Synthesis of Polymer Compound 10

According to the method of Example 1 of Unexamined-Japanese-Patent No. 2003-531001, 10 mol addition of caprolactone of 2-butyloctanoic acid and polyallylamine (PAA-03, number average molecular weight 3,000, Nitto Boseki Co., Ltd. Polymer compound 10 that is a condensate of the product) was obtained. The solvent was performed with a 30 mass% solution of 1-methoxy-2-propanol.

In addition, the polymer compounds 1 to 6 and 8 are specific polymer compounds corresponding to the polymer composed of the repeating unit 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]

<Production of Processed Pigments>

50 g of the pigment shown in Table 2, 500 g of sodium chloride, 25 g of a 30% solution of a specific polymer compound or a comparative polymer compound, and 100 g of diethylene glycol were added to a stainless gallon kneader (manufactured by 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, filtered, washed with water to remove sodium chloride and solvent (diethylene glycol), dried, and coated with a polymeric compound. And each process pigment of the comparative example was obtained.

(Measurement of Primary Particle Diameter of Pigment)

The primary particle diameter of a process pigment was calculated | required by observing the obtained process 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 the mixture was shaken at room temperature for 3 hours with a shaker. Thereafter, the pigment was allowed to settle over 80,000 rpm and 8 hours by a centrifuge. Solid content of the supernatant part was calculated | required from the drying method. The quantity of the polymeric compound liberated from the pigment was calculated | required, and the ratio (%) was computed from the ratio with the polymeric compound used for the process. The smaller the glass ratio, the higher the coating degree of the high molecular compound on the pigment.

 Process pigment number  Polymer compound number  Pigment Average Primary Particle Diameter of Processed Pigments  Ratio (%) Example 1-1 R-1 One PR 254 25 nm 3 Example 1-2 R-2 2 PR 254 25 nm 5 Example 1-3 R-3 3 PR 254 25 nm 7 Example 1-4 R-4 4 PR 254 25 nm 4 Example 1-5 R-5 5 PR 254 25 nm 3 Example 1-6 R-6 6 PR 254 25 nm 4 Example 1-7 R-7 7 PR 254 25 nm 12 Example 1-8 R-8 8 PR 254 25 nm 5 Example 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 -

Example 1-12 L-1 One PR 177 20 nm 8 Example 1-13 L-2 2 PR 177 20 nm 5 Example 1-14 L-3 6 PR 177 20 nm 9 Example 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 -

Example 1-16 G-1 One PG 36 25 nm 8 Example 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 - -

Example 1-20 Y-1 2 PY 150 20 nm 5 Example 1-21 Y-2 3 PY 150 20 nm 8 Example 1-22 Y-3 7 PY 150 20 nm 17 Example 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 - -

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

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

 Example 1-32  G-7  One Polybrominated Zinc Pc  25 nm  5  Example 1-33  G-8  3 Polybrominated Zinc Pc  25 nm  4  Example 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

In addition, the detail of the compound shown in Table 2 is 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)

<Polymer compound>

Polymer compound 1-11, C1: The specific polymer compound and comparative polymer compound which were obtained by the said synthesis example

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

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

<Preparation of pigment dispersion composition>

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

[Composition (1)]

95 parts of processed pigments (each processed pigment of Table 3)

(However, Comparative Example 2-1 was 82.7 parts.)

ㆍ 5 parts of pigment derivative A of the following structure

Dispersant The amount described in Table 3

(30% 1-methoxy-2-propylacetate solution of the dispersant described in Table 3)

750 parts of 1-methoxy-2-propyl acetate

Subsequently, the mixed solution obtained above was further subjected to dispersion treatment for 6 hours using a bead disperser dispermat (manufactured by GETZMANN) using 0.3 mmφ zirconium oxide beads. Thereafter, the dispersion treatment was further performed 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.) With a decompression mechanism. This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

<Evaluation of Pigment Dispersion Composition>

The following evaluation was performed about each obtained pigment dispersion composition. The results are shown in Table 3.

(1) Measurement and evaluation of viscosity

About each obtained pigment dispersion composition, the viscosity (eta) 2 of the pigment dispersion composition after 1 week at room temperature after dispersion and the viscosity (eta) 1 of the pigment dispersion composition immediately after dispersion | distribution was measured using the E-type viscosity meter, and the grade of the thickening was evaluated. Here, the thing with a low viscosity shows that the raise of the viscosity resulting from a dispersing agent is suppressed, and the dispersibility and dispersion stability of a pigment are favorable.

(2) Measurement and evaluation of contrast

Each obtained pigment dispersion composition was apply | coated on the glass substrate, and the sample was produced so that the thickness of the coating film after drying might be set to 1 micrometer. The board | substrate apply | coated between two polarizing plates was arrange | positioned, and the brightness at the time of a polarizing plate and the parallelism was measured by (BM-5 TOPCON CORPORATION make), and it calculated | required by the brightness | luminance at the time of contrast = parallel. High contrast indicates high transmittance, that is, high coloring power, since the pigment is uniformly dispersed in a highly refined state.

 Process pigment  Dispersant Initial Viscosity (mPas) Viscosity over time (mPas)  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 Example 2-4 R-8 D-1 18 20 2600 Comparative Example 2-1 R-13 D-1 50 100 1500

The detail of the dispersing agent D-1 in Table 3 is as follows.

D-1: BzMA / A-1 / MAA = 20/65/15 (mass ratio), weight average molecular weight: 2.30,000, acid value: 100 mgKOH / g polymer

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

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

<Preparation of pigment dispersion composition>

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

[Composition (2)]

100 parts of processed pigments (each processed pigment shown in Table 4)

(However, Comparative Examples 2-2 and 2-3 were 82.7 parts.)

Dispersant The amount described in Table 4

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

750 parts of 1-methoxy-2-propyl acetate

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser dispermat (manufactured by GETZMANN) using 0.3 mmφ zirconium oxide beads, and thereafter, a high pressure disperser NANO-3000-10 with a decompression mechanism (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 10 times to obtain a pigment dispersion composition.

<Evaluation of Pigment Dispersion Composition>

The following evaluation was performed about the obtained pigment dispersion composition.

The evaluation method and evaluation criteria are the same as those performed 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

 Process pigment  Dispersant Initial Viscosity (mPas) Viscosity over time (mPas)  Contrast Example 2-5 G-2 D-1 32 34 7800 Example 2-6 G-3 D-1 33 35 7700 Example 2-7 G-4 D-1 30 32 7500 Example 2-8 G-7 D-1 34 36 10000 Example 2-9 G-8 D-1 34 36 10500 Example 2-10 G-9 D-1 32 35 10000 Example 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

Dispersant D-1 in Table 4 is the same dispersant as Dispersant D-1 described in Table 3 above.

As shown in Table 4, it can be seen that the pigment dispersion composition of the Example has a high contrast, a small initial viscosity, and a small thickening with 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]

<Preparation of pigment dispersion composition>

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

[Composition (3)]

110 parts of processed pigments (process pigments described in Table 5)

ㆍ 250 parts of dispersant

(30% 1-methoxy-2-propylacetate solution of the dispersant described in Table 5)

20 parts of pigment derivative B having the structure

750 parts of 1-methoxy-2-propyl acetate

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser dispermat (manufactured by GETZMANN) using 0.3 mmφ zirconium oxide beads, and thereafter, a high pressure disperser NANO-3000-10 with a decompression mechanism (NIPPON BEE CHEMICAL CO , LTD.) Was used to perform dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3. This dispersion treatment was repeated 10 times to obtain each pigment dispersion composition (DG-1 to DG-11, DY-1 to DY-6) shown in Table 5 below.

Pigment dispersion composition Pigment Process 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 -

Dispersant D-1 in Table 5 is the same dispersant as Dispersant D-1 described in Table 3 above. In addition, the detail of dispersing agent D-2 is as follows.

D-2: Solsperse 24000 from The Lubrizol Corporation

<Preparation of photocurable composition>

The following photocurable compositions were prepared using each pigment dispersion composition obtained above.

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

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

ㆍ 120 parts of KAYARAD DPHA (Photopolymerizable compound, product made by NIPPON KAYAKU Co., Ltd.)

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

Methacrylic acid benzyl / methacrylic acid (= 75/35 [mass ratio]) copolymer

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

ㆍ 390 parts of 1-methoxy-2-propyl acetate (solvent)

<Production of Color Filter Using Photocurable Composition>

The obtained photocurable composition (color resist liquid) was slit-coated so that it might become a film thickness of 1.75 micrometers on the glass substrate (1737, Corning Corporation) of 100 mm x 100 mm, and it dried for 60 second by 90 degreeC oven (prebaking). Thereafter, 200 mJ / cm 2 (roughness 20 mW / cm 2) was exposed to the entire surface of the coating film, and the exposed coating film was shower-developed for 60 seconds with a 1% aqueous solution of alkaline developer CDK-1 (manufactured by FUJIFILM Electronic Materials Co., Ltd.). . After stopping, pure water was sprayed onto the shower, and the developer was washed. And the coating film which exposed and developed as mentioned above was heat-processed (post-baking) in 220 degreeC oven for 1 hour, and the coloring pattern (colored resin film) for color filters is formed on a glass substrate, and a colored filter A substrate (color filter) was produced.

<Evaluation of Color Filters>

Contrast was evaluated about the obtained colored filter substrate (color filter) as follows. The results are shown in Table 6.

(1) contrast

A polarizing plate was provided on the colored resin film of the colored filter substrate obtained above, the colored resin film was sandwiched, and the brightness at the time of parallel and the brightness at the time of orthogonality of the polarizing plate were measured using BM-5 made from Topcon, The value obtained by dividing the luminance by the luminance at orthogonality (= luminance at parallel / luminance at orthogonal angle) was used as an index for evaluating contrast. Larger values indicate higher 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 Example 3-6 DG-7 DY-1 10000 Example 3-7 DG-8 DY-2 10500 Example 3-8 DG-9 DY-3 10000 Example 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 turns out that the color filter of an Example has high contrast with the color filter of a comparative example.

Hereinafter, the example which prepared the photocurable composition for color filter formation of a solid-state image sensor use is demonstrated.

Examples 4-1 to 4-4 and Comparative Example 4-1

<B1. Preparation of Resist Liquid>

The components of the following composition were mixed and dissolved to prepare a resist liquid.

[Composition of Resist Liquid]

ㆍ 19.20 parts of propylene glycol monomethyl ether acetate

(PGMEA: solvent)

Ethyl lactate 36.67 parts

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

30.51 parts (40% PGMEA solution of molar ratio 60/22/18, weight average molecular weight: 15,000, number average molecular weight: 8,000)

Ethylenically unsaturated double bond-containing compounds

(Dipentaerythritol hexaacrylate) 12.20 parts

ㆍ polymerization inhibitor (p-methoxyphenol) 0.0061 parts

ㆍ 0.83 parts of fluorine-based surfactant (F-475, manufactured by DIC Corporation)

0.586 parts of photoinitiator (trihalomethyl triazine photopolymerization initiator)

(TAZ-107, product of Midori Kagaku Co., Ltd.)

<B2. Fabrication of Silicon Substrate with Undercoat Layer>

The 6 inch silicon wafer was heat treated at 200 ° C. for 30 minutes in an oven. Subsequently, the resist liquid was applied onto the silicon wafer so as to have a dry film thickness of 1.5 µm, and further dried by heating in an oven at 220 ° C. for 1 hour to form an undercoat layer to obtain a silicon wafer substrate on which an undercoat layer was formed.

<B3. Preparation of Pigment Dispersion Composition>

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

<B4. Preparation of Photocurable Composition (Coating Liquid)>

It stirred and mixed so that it might become the following composition ratio using each pigment dispersion composition obtained above, and prepared the photocurable composition solution.

ㆍ 600 parts of colorant (the pigment dispersion)

Photo polymerization initiator (oxime photopolymerization initiator)

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

ㆍ 25 parts of TO-1382 (product of TOAGOSEI CO., LTD.)

ㆍ Defentaerythol hexaacrylate 30 parts

ㆍ 900 parts of solvent (PGMEA)

ㆍ 1 part of substrate adhesive (3-methacryloxypropyltrimethoxysilane)

<B5. Fabrication and Evaluation of Color Filters Using Photocurable Compositions>

(1) Evaluation of Pattern Formability

The photocurable composition prepared as mentioned above was apply | coated on the undercoat layer of the silicon wafer in which the undercoat layer obtained by said B2. Was formed, and the coloring layer (coating film) was formed. And heat processing (prebaking) was performed for 120 second using the 100 degreeC hotplate so that the dry film thickness of this coating film might be set to 0.5 micrometer.

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

Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotating table of a spin shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and mounted on CD-2000 (FUJIFILM Electronic Materials Co. Ltd.). , Ltd.) was paddle developed at 23 ° C. for 60 seconds to form a colored pattern on the silicon wafer substrate.

The silicon wafer on which the coloring pattern is formed is fixed to the horizontal rotating table by a vacuum chuck method, and pure water is supplied from the jet nozzle to the shower image while the silicon wafer substrate is rotated at a rotational speed of 50 rpm by a rotating device from above the rotation center. The rinse treatment was performed, and then spray dried.

Pattern formation property was evaluated by observing the cross-sectional shape of the coloring pattern formed as mentioned above. The pattern cross-sectional shape is preferably rectangular, and inverse taper is undesirable.

The results are shown in Table 7.

(3) Evaluation of storage stability of photocurable composition

After storing the photocurable composition (coating liquid) prepared in said B4. For 1 month at room temperature, the viscosity of the liquid was measured and evaluated according to the following criteria. The results are shown in Table 7.

-Evaluation standard-

(Circle): A viscosity increase was not confirmed.

(Triangle | delta): The viscosity increase of 5% or more and less than 10% was confirmed.

X: The viscosity rise of 10% or more was confirmed.

(4) evaluation of color unevenness

The color unevenness was evaluated by the following method, and the luminance distribution was analyzed based on the percentage of pixels occupying the total number of pixels with an error from the average within ± 5%. Evaluation criteria are as follows.

The measuring method of a luminance distribution is demonstrated. First, the photocurable composition was apply | coated on the undercoat layer of the glass plate with the undercoat layer obtained by the method similar to said B2., And the colored layer (coating film) was formed. Heat processing (prebaking) was performed for 120 second using the 100 degreeC hotplate so that the dry film thickness of this coating film might be set to 0.7 micrometer. The image which image | photographed the brightness distribution of this coated glass plate with the microscope MX-50 (made by OLYMPUS CORPORATION) was analyzed.

The results are shown in Table 7.

-Evaluation standard-

(Circle): The pixel from which the error from the average is within ± 5% is 99% or more of the total number of pixels

(Triangle | delta): The pixel from which the error from an average is within ± 5% is 95% or more and less than 99% of all the pixels.

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

Pigment dispersion composition Retention stability  Color blotches 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 result of Table 7, it turns out that the photocurable composition using the process pigment of the Example is excellent in storage stability also in the solution state, even when used as a color filter formation for a solid-state image sensor use. Moreover, when a coloring pattern is formed on a support body using this photocurable composition, in comparison with a comparative example, while being excellent in developability, the color filter which is excellent in both a pattern cross-sectional shape and color unevenness is obtained. It turns out.

From these results, the photocurable composition containing the process pigment of an Example realizes the outstanding pattern formation property similarly to the case of producing the color filter for liquid crystal display element uses also when manufacturing the color filter for solid-state image sensor uses. Could know.

Claims (11)

A processed pigment formed by coating a pigment with a high molecular compound having a basic nitrogen atom. The method of claim 1, A processing pigment, wherein the polymer compound having a basic nitrogen atom is at least one polymer compound selected from the following (1) to (4). (1) poly (alkyleneimines) having alkylene groups of 2 to 6 carbon atoms (2) polyallylamine (3) polyvinylamine (4) A polymer compound comprising a structural unit derived from one or more monomers selected from (meth) acrylic acid esters having a basic nitrogen atom in the ester moiety, vinylpyridine and aminostyrene The method of claim 1, A process pigment characterized by having an average primary particle diameter in the range of 5 nm to 25 nm. The method of claim 1, Processed pigments, characterized in that the pigment is a pigment containing polyhalogenated zinc phthalocyanine. The method of claim 1, The process pigment characterized by the high molecular compound which has the said basic nitrogen atom having the oligomer chain or polymer chain of number average molecular weights 500-1,000,000 in a side chain. The method of claim 5, wherein The processing pigment characterized in that the oligomer chain or polymer chain contained in the high molecular compound having a basic nitrogen atom is polycaprolactone. The pigment dispersion composition formed by disperse | distributing the process pigment in any one of Claims 1-6 in the organic solvent. The method of claim 7, wherein A pigment dispersing composition further comprising a pigment dispersant. The pigment-dispersion composition of Claim 7, a polymeric compound, and a photoinitiator are contained, The photocurable composition characterized by the above-mentioned. It has a colored region formed using the photocurable composition of Claim 9, The color filter characterized by the above-mentioned. A process of forming a photosensitive film by applying the photocurable composition of Claim 9 on a board | substrate directly or via another layer, The process of forming a colored area | region by performing pattern exposure and image development to the formed photosensitive film sequentially, The manufacturing method of the color filter characterized by the above-mentioned.