TWI460234B - Pigment dispersion composition and production method thereof, colored polymerizable composition, and color filter and production method thereof - Google Patents

Description

Method for preparing pigment dispersion composition, pigment dispersion composition, coloring polymerizable composition, color filter, and color filter

The present invention relates to a pigment dispersion composition, a method for producing the pigment dispersion composition, a colored polymerizable composition containing the pigment dispersion composition, a color filter comprising the colored polymerizable composition, and the color filter. The method of film production.

The color filter is a colored polymerizable composition containing a pigment dispersion composition obtained by dispersing an organic pigment or an inorganic pigment, a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin, and other components, and is light-receiving. A photolithographic method or the like is formed to form a colored pattern.

In recent years, color filters have been used for liquid crystal display devices (LCDs), and they are not only used as monitors but also in terms of televisions (TVs), and the tendency to expand with this use has evolved into High color characteristics are required for chromaticity, contrast, and the like. In addition, in the use of image sensors (solid-state imaging devices), the same has been developed to require high color characteristics.

For the above-mentioned requirements, it is effective to use a pigment obtained by refining the primary particle diameter. The method of miniaturizing the primary particle diameter of the pigment is, for example, a water-soluble inorganic salt such as a synthetic resin or a salt of a salt which is solid and water-insoluble at room temperature, and at least a part of the synthetic resin as described above. The water-soluble organic solvent is mechanically kneaded together by a kneader or the like (hereinafter, the operation of kneading a mixture containing a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is referred to as "salt-salt" (salt- A method of removing a water-soluble inorganic salt and a water-soluble organic solvent by washing with water (see, for example, Japanese Laid-Open Patent Publication No. 7-13016). In this method, since the pulverization of the primary particles of the pigment and the crystallization growth are simultaneously performed, finally, a pigment having a narrow particle size distribution, a small average particle diameter, and a small surface area can be obtained, and thus, for example, a color filter is obtained. It is a suitable method to disperse a pigment having a fine particle size into a pigment for a high concentration.

However, with the pigment prepared as described above, since the drying process after desalination causes intense agglomeration, the dispersibility and dispersion stability are often not good, and therefore, when such a pigment is used, It is difficult to obtain a pigment dispersion having superior dispersibility and dispersion stability. If the dispersibility of the pigment is not sufficient, for example, a fringe (zigzag indent) or surface irregularity may be caused in the colored pattern formed of the polymerizable composition containing the pigment dispersion. The surface irregularity), the chromaticity or dimensional accuracy of the resulting color filter is lowered, or the contrast is significantly degraded.

In addition, when the dispersion stability of the pigment is not sufficient, the constituents of the colored polymerizable composition may agglomerate over time, so that the viscosity is increased, and the pot life becomes extremely short. . Further, when a color filter is produced by using the colored polymerizable composition, the uniformity of the film thickness in the coating step is lowered, and the sensitivity in the exposure step is easily caused, and the alkali in the developing step is easily caused. Problems such as fluctuations in solubility and unevenness. In particular, in the case of forming a colored film using a colored polymerizable composition on a glass substrate for producing a large-area color filter, a slit coating (or also referred to as die coating) is applied. In the case of the above, there is a problem in that defects such as streaks are easily caused on the coated surface, the state of the coated surface is lowered, and the pixel defects of the color filter are further formed.

Therefore, a method for improving the dispersibility and dispersion stability of a pigment has been proposed as a method of adding rosin or a rosin derivative or a synthetic polymer compound during salt milling (see, for example, Japanese invention). Patent Laid-Open No. 8-179111.).

In addition, regarding the diketopyrrolopyrrole-based pigment, there has been a proposal to promote micronization and improve contrast by adding a pigment-derivative during salt milling (see For example, Japanese Laid-Open Patent Publication No. 2001-220520 and Japanese Laid-Open Patent Publication No. 2007-31539.

However, according to the prior art as described above, when focusing only on the refinement of pigment particles and the comparison of the portraits, although a certain degree of improvement effect can be obtained, the micronized diketopyrrolopyrrole is obtained. The pigment is a step of producing a color filter, especially when the development is repeated, post-baking, or UV cleaning, which causes a problem of roughening of the surface.

Therefore, the present invention has been made in view of the above problems, and has achieved the following objects.

That is, the first object of the present invention is to provide a pigment dispersion composition having superior high pigment dispersibility and stability thereof and capable of forming a color film having superior contrast and a process for producing the same.

Further, a second object of the present invention is to provide a colored polymerizable composition which can form a film having superior contrast and further form a color filter having a smooth surface.

A third object of the present invention is to provide a color filter having a high contrast and a smooth surface, and a method of manufacturing the color filter.

The method for solving the above problems is as follows.

That is, the pigment dispersion composition of the present invention is characterized in that it contains a diketopyrrolopyrrole pigment in an amount of 0.1 to 30 parts by mass relative to 100 parts by mass of the diketopyrrolopyrrole pigment. A phthalimidoalkylated diketopyrrolopyrrole having 0.1 to 20 parts by mass of phthalic acid imidoalkylated quinolin relative to 100 parts by mass of the diketopyrrolopyrrole pigment Phthalimidoalkylated quinacridone, and at least one organic solvent.

The average primary particle diameter of the diketopyrrolopyrrole pigment as described above is preferably from 10 nm to 30 nm.

The diketopyrrolopyrrole pigment used in the pigment dispersion of the present invention is preferably obtained by using the following steps: a diketopyrrolopyrrole pigment, a water-soluble inorganic salt, and substantially insoluble of the water-soluble inorganic substance a step of mechanically kneading a water-soluble organic solvent of a salt; a step of removing the water-soluble inorganic salt and the water-soluble organic solvent; a step of drying the diketopyrrolopyrrole pigment; and drying the same Before the step, the method of the step of contacting the diketopyrrolopyrrole pigment with a resin is obtained.

Here, the resin which can be used for the addition is preferably a polymer compound having an acid value of 50 to 300 mgKOH/g.

The method for producing a pigment dispersion composition of the present invention comprises the steps of: adding a diketopyrrolopyrrole pigment having an average primary particle diameter of 10 nm to 30 nm to 0.1 part by mass to 100 parts by mass of the diketopyrrolopyrrole pigment 30 parts by mass of phthalic acid imidoalkylated diketopyrrolopyrrole, and 0.1 to 20 parts by mass of phthalimide with respect to 100 parts by mass of the diketopyrrolopyrrole pigment a step of alkylating at least a portion of the quinophthalone; and a diketopyrrolopyrrole pigment having 0.1 to 30 parts by mass relative to 100 parts by mass of the diketopyrrolopyrrole pigment An aminoalkylated diketopyrrolopyrrole, and 0.1 to 20 parts by mass of the phthalic acid imidoalkylated quinophthalone with respect to 100 parts by mass of the diketopyrrolopyrrole pigment and an organic solvent The steps of dispersing together.

The colored polymerizable composition of the present invention comprises the pigment dispersion composition, the photopolymerizable compound, and the photopolymerization initiator of the present invention as described above, and preferably further contains an alkali-soluble resin.

The color filter of the present invention is preferably formed using the colored polymerizable composition of the present invention as described above, and in particular, a preferred mode is a colored region formed by the colored polymerizable composition of the present invention.

Further, the color filter is characterized in that it uses the colored polymerizable composition of the present invention as described above, preferably a film is formed on the substrate by a coating method, and the formed film is exposed, and then Develop and remove the unhardened film.

The pigment dispersion composition of the present invention is a diketopyrrolopyrrole pigment, a specific amount of phthalimide alkylated diketopyrrolopyrrole, and phthalic acid imidoalkylated quinolin A ketone obtained by dispersing in an organic solvent.

In the present invention, by alkylating the diketopyrrolopyrrole and the phthalic acid imidoalkylation quinophthalone with a diketopyrrolopyrrole pigment and a phthalimidoalkylene group. Obtaining a colored polymerizable composition capable of forming a pigment dispersion composition having superior dispersion stability and contrast, a color filter having superior viscosity stability, high contrast, and further superior surface smoothness, and A color filter with high contrast and excellent surface smoothness.

By using phthalic acid imidoalkylated diketopyrrolopyrrole and phthalimidoalkylamine to quench the quinophthalone, thereby improving the stability of the diketopyrrolopyrrole pigment Since the large complementary phase is effective, the composition containing the pigment can form a color film having superior contrast and high surface smoothness. Although the mechanism of action is not clear, it can be considered as the surface of each of the phthalate imine alkylated pigment derivatives and the diketopyrrolopyrrole pigment having two different cores. Strong interactions occur in different parts, so that the unstable diketopyrrolopyrrole surface is protected, compared to the case where each is used alone, and the superior stability is obtained due to the success of these complementary phases. On the other hand, by the coloring polymerizable composition containing the pigment, it is possible to form a color film in which the pigment has been uniformly and stably dispersed, and the contrast is high and the surface smoothness is excellent.

According to the present invention, it is possible to provide a pigment dispersion composition which can form a color film having superior high pigment dispersibility and stability, and superior contrast, and a process for producing the same.

Further, according to the present invention, it is possible to provide a colored polymerizable composition which can form a film having superior viscosity stability, superior contrast, and excellent surface smoothness. The coloring polymerizable composition is suitable for producing a color filter.

Further, according to the present invention, it is possible to provide a color filter having high contrast and smooth surface, and a method of manufacturing the color filter.

[Best Embodiment of the Invention]

Hereinafter, the pigment dispersion composition, the method for producing a pigment dispersion composition, the coloring polymerizable composition, the color filter, and the method for producing the same according to the present invention will be described in detail.

<Pigment Dispersion Composition>

The pigment dispersion composition of the present invention is characterized in that it contains (A) a diketopyrrolopyrrole pigment in an amount of 0.1 to 30 parts by mass per 100 parts by mass of the diketopyrrolopyrrole pigment (B). The phthalic acid imidoalkylated diketopyrrolopyrrole is 0.1 to 20 parts by mass based on 100 parts by mass of the diketopyrrolopyrrole pigment (C) phthalimidoalkylene group The quinacridone, and (D) at least one organic solvent, and other components may be included as needed.

[(A) Diketopyrrolopyrrole pigment]

The diketopyrrolopyrrole type pigment (hereinafter, sometimes referred to as DPP type pigment) in the present invention is a red to orange pigment having a structure represented by the following general formula (A), and has excellent light resistance. Sexuality, heat resistance.

In the above formula (A), X and Y each independently represent a hydrogen atom, an alkyl group, a cyano group, an aryl group or a halogen group. Here, the alkyl group is a saturated or unsaturated alkyl group. The alkyl group or the aryl group may also be a group further having a substituent. The substituent which may be introduced into the alkyl group includes, for example, a halogen atom, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group and the like; and the substituent which may be introduced into the aryl group includes, for example, a halogen atom, an alkyl group, an alkoxy group. Base.

When a specific example of the DPP-based pigment represented by the above formula (A) is represented by a color index number, CI Pigment Red 254, 255, 264, and CI Pigment Orange are exemplified. 71. Among these, C.I. Pigment Red 254 is particularly suitably used in the present invention.

In order to obtain a high-contrast color filter, the particle size of the DPP-based pigment used in the present invention is preferably such that the particle size is small and the distribution is narrow, and the average primary particle diameter is preferably from 10 nm to 30 nm. By using particles in this range, a dispersion having superior dispersion stability can be obtained, and by using the dispersion, a high contrast colored cured film can be formed.

Here, the particle size of the DPP-based pigment can be measured, for example, by photographing a pigment at a magnification of 100,000 times using a transmission electron microscope. Further, regarding the average particle diameter, for example, the long diameter and the minor axis average value of the particles are measured for 500 particles, and the average value thereof is regarded as the average particle diameter. The average primary particle diameter in the present invention is determined by the method.

The diketopyrrolopyrrole pigment having such an average primary particle diameter can be obtained by a conventional method such as a dry pulverization method, a wet pulverization method, a recrystallization method, an acid paste method, or the like, but Fine particles having a narrow particle size distribution are obtained, and in the present invention, it is preferable to refine by a salt mill. Hereinafter, the case of producing a diketopyrrolopyrrole pigment which is refined by a salt mill will be described in detail.

In the present invention, the finely divided diketopyrrolopyrrole pigment is preferably obtained by a method comprising the steps of: a diketopyrrolopyrrole pigment, a water-soluble inorganic salt, and substantially insoluble a step of mechanically kneading (salting) the water-soluble organic solvent of the water-soluble inorganic salt, removing the water-soluble inorganic salt and the water-soluble organic solvent, and further drying; and before drying, The step of contacting the diketopyrrolopyrrole pigment with the resin.

Further, the resin added after the salt milling and before the drying step is preferably a polymer compound having an acid value of 50 to 300 mgKOH/g.

In the case of performing the salt milling treatment, an additive such as a pigment dispersing aid, a plasticizer, a surfactant, or the like may be used in combination in addition to the resin as described above, as long as the effect of the present invention is not impaired.

Each of them will be explained in detail as follows.

(DPP pigment)

The type of the diketopyrrolopyrrole pigment used in the salt mill is as described above. In order to obtain a preferred particle diameter as described above after salt milling, the particle diameter of the diketopyrrolopyrrole pigment before salt milling is preferably an average primary particle diameter of 20 nm to 300 nm, more preferably 25 nm to 200 nm, most preferably 30 nm to 150 nm.

In the present invention, the DPP pigment used in the salt milling can be synthesized by a known method or a commercially available product. Specific product names include: IRGAPHOR RED BT-CF, IRGAPHOR RED B-CF, IRGAZIN RED 2030, IRGAZIN DPP RED 80, IRGAZIN DPP RED BTR, IRGAZIN DPP RED BL, CROMOPHTAL RED 2030, CROMOPHTAL DPP RED BP, etc. Ciba Specialty Chemicals Co., Ltd.).

In the present invention, although the DPP-based pigment is preferably subjected to salt milling alone, the DPP-based pigment may be salt-milled in combination with other organic pigments.

Organic pigments which can be used in combination with DPP pigments include, for example, those listed below.

That is, 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, 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, 1 75,176,177,179,180,181,182,185,187,188,193,194,199,213,214; 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; CI Pigment Green 7, 10, 36, 37; CI Pigment Blue 1, 2, 15, 15: 1 , 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, change the C1 substituent of CI Pigment Blue 79 to OH (hydroxyl), CI Pigment Blue 80 CI Pigment Violet 1, 19, 23, 27, 32, 37, 42; CI Pigment Brown 25, 28; CI Pigment Black 1, 7, etc.

Further, in the present invention, the organic pigment which can be used in combination with the DPP pigment is preferably a pigment as described below.

That is, CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185; CI Pigment Orange 36; CI Pigment Red 122, 150, 171, 175, 177, 209, 224, 242.

In the present invention, when a DPP-based pigment is used in combination with other organic pigments as needed, the ratio of the DPP-based pigment can be arbitrarily changed according to the desired hue, but it is usually 0.1 mass with respect to all the organic pigments. More than %, less than 100% by mass.

(water soluble inorganic salt)

The water-soluble inorganic salt used in the salt mill is not particularly limited as long as it is soluble in water, and sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. may be used, but from the viewpoint of price For the sake of consideration, it is preferred to use sodium chloride or sodium sulfate.

The particle size of the water-soluble inorganic salt is smaller to obtain higher micronization efficiency, but since the small-sized inorganic salt is high in price, it is preferably from 0.1 μm to 100 μm, more preferably from 1 μm to 50 μm.

From the viewpoints of both the treatment efficiency and the production efficiency, the amount of the water-soluble inorganic salt used in the salt milling step is preferably from 1 to 30 times by mass of all the organic pigments including the DPP-based pigment, particularly preferably 5 to 25 times the mass. The larger the ratio of the inorganic salt to the organic pigment, the higher the refining efficiency. However, since the amount of the pigment to be treated once is relatively reduced, it is preferably set in the above range.

(water soluble organic solvent)

The water-soluble organic solvent is used to provide a function of wetting an organic pigment or an inorganic salt, and there is no particular one as long as it is soluble in water (mixed) and is substantially insoluble in the water-soluble inorganic salt used. limits.

However, since the temperature rises when the salt milling is performed, the solvent is easily evaporated, and from the viewpoint of safety, a high boiling point solvent having a boiling point of 120 ° C or higher is preferably used.

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

Further, the water-soluble organic solvent may be used singly or in combination of two or more.

The amount of the water-soluble organic solvent added is preferably from 5% by mass to 80% by mass based on the water-soluble inorganic salt as described above, more preferably from 10% by mass to 60% by mass based on the water-soluble inorganic salt. It is 15% by mass to 50% by mass based on the water-soluble inorganic salt.

When the addition amount is in the range as described above, uniform kneading can be achieved, the particle diameter is likely to be uniform, and since the softness of the kneaded composition is maintained in an appropriate range in the treatment, a moderate shear can be easily imparted at the time of kneading. Shearing force, so I can get the refinement effect I want.

The addition timing of the water-soluble organic solvent in the salt milling step may be added at the beginning of the step, or may be added separately.

(resin)

In the production of the micronized diketopyrrolopyrrole pigment in the present invention, in order to prevent the finely divided diketopyrrolopyrrole pigment from being strongly aggregated during drying, it is preferably easily dispersed. After kneading the pigment with a water-soluble inorganic salt or the like, and removing the water-soluble inorganic salt and the water-soluble organic solvent, the diketopyrrolopyrrole-based pigment is brought into contact with the resin before being supplied to the drying step.

Here, the contact of the DPP pigment with the resin means that the resin is adhered to at least a part of the surface of the DPP pigment.

The treatment for contacting the DPP pigment with the resin can be carried out in any step before drying, for example, at the beginning or on the way of the salt milling step (kneading), after the salt milling step, during the dispersion step after the salt milling, and washing with water. The step is carried out by adding a solid resin or a resin solution after the step.

The resin to be used in contact with the DPP pigment is preferably a polymer compound having an acid value of 50 to 300 mgKOH/g. When the DPP pigment is brought into contact with a polymer compound having an acid value of 50 to 300 mgKOH/g, a soft powder pigment can be obtained to obtain a fine DPP pigment having high dispersibility and dispersion stability.

The polymer compound having an acid value of 50 to 300 mgKOH/g used in the present invention is preferably water-insoluble, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. .

The natural resin is rosin as a representative; the modified natural resin can be a rosin derivative, a cellulose derivative, a rubber derivative, a protein derivative, and the like.

Further, the synthetic resin includes an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, a polyurethane resin, a polyamide resin, and the like. .

The acid group present in the molecule of the polymer compound having an acid value of 50 to 300 mgKOH/g is not particularly limited, and examples thereof include a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, a phenol group, a sulfonylamino group, and the like. A particularly preferred acid group carboxylic acid group.

The acid value is preferably from 50 to 300 mgKOH/g, more preferably from 50 to 250 mgKOH/g, most preferably from 70 to 250 mgKOH/g.

When the acid value is adjusted to be in this range, excellent alkali solubility in the fine DPP pigment, aggregation prevention effect during drying, storage stability, and dispersibility can be achieved.

The molecular weight of the polymer compound having an acid value of 50 to 300 mgKOH/g is preferably 1,000 or more and 50,000 or less, more preferably 3,000 or more and 30,000 or less, and most preferably 4,000 or more and 25,000 or less. When the molecular weight is adjusted within this range, excellent alkali solubility in the fine DPP pigment, aggregation prevention effect at the time of drying, and dispersibility can be achieved.

(polymer compound containing a pigment absorbing group)

Further, a polymer compound having an acid value of 50 to 300 mgKOH/g is also preferably a polymer compound having a pigment absorbing group.

Specifically, the polymer compound having a pigment absorbing group preferably contains a monomer derived from a monomer represented by the following formula (1), maleimide, and norbutene. A polymer of a polymerized unit of a monomer of a group consisting of a diterpene imine derivative (hereinafter, referred to as a "Specific Polymer"). Among them, a specific polymer is particularly preferably a polymer containing a polymerized unit derived from a monomer represented by the following general formula (1).

In the above formula (1), R ¹ represents a hydrogen atom or an alkyl group. R ² represents a single bond or a divalent linking group. The Y series represents -CO-, -C(=O)O-, -CONH-, -OC(=O)-, or a phenyl group. The Z series represents a group having a nitrogen-containing heterocyclic group.

The alkyl group represented by R ¹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms.

When the alkyl group represented by R ¹ has a substituent, the substituent includes, for example, a hydroxyl group or an alkoxy group such as a methoxy group, an ethoxy group or a cyclohexyloxy group. The alkoxy group is preferably one having a carbon number of from 1 to 5, more preferably from 1 to 3.

Specifically, preferred alkyl groups represented by R ¹ include, for example, methyl, ethyl, propyl, n-butyl, iso-butyl, tert-butyl, n-hexyl, and ring. Hexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxyethyl.

Among them, R ¹ is most preferably a hydrogen atom or a methyl group.

In the formula (1), the divalent linking group represented by R ² is preferably an alkylene group or a divalent group having an alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, still more preferably an alkylene group having 1 to 4 carbon atoms.

Further, when the alkylene group has a substituent, the substituent includes, for example, a hydroxyl group or the like.

Specifically, a preferred alkylene group represented by R ² includes, for example, a methylene group, an ethylidene group, a propyl group, a trimethylene group, and a tetramethylene group.

The divalent group containing an alkylene group represented by R ² may be one or more of which is bonded to the alkylene group via a hetero atom (for example, an oxygen atom, a nitrogen atom or a sulfur atom).

Further, the divalent group containing an alkylene group represented by R ² may be a terminal bonded to one side of Z in the alkylene group, and the bond is selected from -O-, -S-, -C (=O)O-, -CONH-, -C(=O)S-, -NHCONH-, -NHC(=O)O-, -NHC(=O)S-, -OC(=O)-, a hetero atom of -OCONH-, and -NHCO- or a partial structure containing a hetero atom.

Specifically, the nitrogen-containing heterocyclic structure for constituting the nitrogen-containing heterocyclic group represented by Z in the general formula (1) includes, for example, a pyridine ring and a pyridyl group. Ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, anthracene ring, quinoline ring, acridine ring, morphine Ring, brown Ring, acridone ring, anthracene ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic guanamine structure, cyclic urea structure, and cyclic quinone imine structure.

These nitrogen-containing heterocyclic structures may have a substituent, and the substituents include, for example, an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, an alkoxycarbonyl group and the like.

In particular, the nitrogen-containing heterocyclic group represented by Z is more preferably a group having a nitrogen-containing heterocyclic ring structure having a carbon number of 6 or more, and particularly preferably having a nitrogen-containing heterocyclic ring structure having a carbon number of 6 or more and 12 or less. The basis.

Specifically, the nitrogen-containing heterocyclic structure having a carbon number of 6 or more includes: preferably thiophene Ring, brown Ring, acridone ring, anthracene ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic guanamine structure, cyclic urea structure, and cyclic quinone imine structure; The structure represented by the following general formula (2), (3), or (4).

In the formula (2), X is selected from a single bond, an alkyl group (for example, methylene, ethyl, propyl, trimethylene, tetramethylene, etc.), -O-, -S Any of the groups consisting of -, -NR ^A -, and -C(=O)-. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include, for example, methyl group. , ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-octadecyl and the like.

Among the above, the X system in the formula (2) is preferably a single bond, a methylene group, -O-, or -C(=O)-, and particularly preferably -C(=O). )-.

In the general formula (4), the Y and Z series each independently represent -N=, -NH-, -N(R ^B )-, -S-, or -O-. When R ^B represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include, for example, methyl group. , ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-octadecyl and the like.

Among the above, the Y and Z systems in the formula (4) are particularly preferably -N=, -NH-, and -N(R ^B )-. Examples of the combination of Y and Z include: a combination of Y and Z is -N=, and the other is a combination of -NH- (imidazolyl group).

Among the general formulae (2), (3), or (4), the ring A, the ring B, the ring C, and the ring D each independently represent an aromatic ring. Examples of the "aromatic ring" include, for example, a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, an anthracene ring, a pyridine ring, and a pyridyl group. Ring, pyrimidine ring, pyrrole ring, imidazole ring, anthracene ring, quinoline ring, acridine ring, morphine Ring, brown a ring, an acridone ring, an anthracene ring, etc.; among them, a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, and a morphine are preferred. Ring, acridine ring, thiophene Ring, brown Ring, acridone ring, anthracene ring, and particularly preferably a benzene ring, a naphthalene ring, a pyridine ring.

Specifically, examples of the ring A and the ring B in the formula (2) include, for example, a benzene ring, a naphthalene ring, a pyridine ring, and a pyrene. Ring and so on.

Examples of the ring C in the formula (3) include, for example, a benzene ring, a naphthalene ring, a pyridine ring, and a pyrene. Ring and so on.

Examples of the ring D in the formula (4) include, for example, a benzene ring, a naphthalene ring, a pyridine ring, and a pyrene. Ring and so on.

In the structure represented by the general formula (2), (3), or (4), from the viewpoints of dispersibility and stability over time of the dispersion, the ring A, the ring B, the ring C, and the ring are considered. More preferably, D is a benzene ring or a naphthalene ring, and further preferably a benzene ring in the formula (2) or (4), and further preferably a naphthalene ring in the formula (3).

Further, the so-called maleimide derivative of the present invention means a maleimide substituted with a substituent such as an alkyl group or an aryl group at the N-position.

Hereinafter, preferred specific examples of the monomer represented by the formula (1), maleimide, and maleimide derivative (monomers M-1 to M-) are listed. 30), but the invention is not limited thereto.

The specific polymer in the present invention may contain only one kind or two or more kinds derived from a monomer selected from the group consisting of the formula (1), maleimide, and maleimide. a polymerized unit of one of the groups of derivatives.

Among the monomers represented by the formula (1), maleimide, and maleimide derivatives, especially due to the monomer represented by the formula (1) for the pigment It is preferred because it has high sorption.

In the specific polymer of the present invention, it is derived from a single group selected from the group consisting of a monomer represented by the general formula (1), a maleimide, and a maleimide derivative. The content of the polymerization unit of the bulk is preferably 5% by mass or more, and more preferably 10 to 50% by mass, based on 100% by mass of all the structural units contained in the polymer.

That is, in order to effectively suppress the formation of the secondary aggregate of the primary aggregate of the pigment or to effectively weaken the cohesive force of the secondary aggregate, it is derived from the monomer selected from the formula (1), The content of the polymerization unit of one of the groups consisting of butene diimine and the maleimide derivative is preferably 5% by mass or more. In addition, from the viewpoint of developability when a color filter is produced from a photopolymerizable composition containing a pigment-dispersed composition, it is derived from a monomer selected from the formula (1), maleic acid. The content of the polymerization unit of one of the groups consisting of the imine and the maleimide derivative is preferably 50% by mass or less.

The specific polymer in the present invention is preferably a polymerized unit derived from a monomer having an acid group. Since the specific polymer contains a polymer unit derived from a monomer having an acid group, when the pigment dispersion composition is applied to a photopolymerizable composition, it has superior development removability of the unexposed portion.

The single system having an acid group includes: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc.; maleic acid, maleic anhydride, fumaric acid , an unsaturated dicarboxylic acid such as itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like; an unsaturated polycarboxylic acid having three or more or an anhydride thereof; Acid mono(2-propenyloxyethyl) ester, mono(2-methylpropenyloxyethyl) succinate, mono(2-propenyloxyethyl) phthalate, ortho-benzene One of two or more polycarboxylic acids such as di(2-methylpropenyloxyethyl) dicarboxylate [(meth) propylene decyloxyalkyl] ester; ω-carboxy-polycaprolactone One of the two terminal carboxyl groups (meth) acrylate such as acrylate or ω-carboxy-polycaprolactone monomethacrylate.

The specific polymer in the present invention may contain only one kind or two or more kinds of polymerized units derived from a monomer having an acid group.

In the specific polymer, the content of the polymerized unit derived from the monomer having an acid group is preferably such that the acid value of the specific polymer is 50 mgKOH/g or more, particularly preferably 50 to 300 mgKOH/g. That is, from the viewpoint of suppressing the formation of precipitates in the developer, the content of the polymerized unit derived from the monomer having an acid group is preferably such that the acid value of the specific polymer is 50 mgKOH/g or more. The amount. In order to effectively suppress the formation of the secondary aggregate of the primary aggregate of the pigment or to effectively weaken the cohesive force of the secondary aggregate, the content of the polymerized unit derived from the monomer having an acid group is preferably The acid value of the specific polymer is made in an amount of 50 to 300 mgKOH/g.

Further, if the specific polymer in the present invention has an acid value of 50 to 300 mgKOH/g, the specific polymer can be used as a polymer compound having an acid value of 50 to 300 mgKOH/g as described above.

Further, the specific polymer in the present invention may further contain a polymerized unit derived from a vinyl monomer within a range that does not impair its efficacy.

Here, the vinyl single system which can be used is not particularly limited, but is preferably, for example, (meth) acrylates, crotonates, vinyl esters, maleic acid diesters. And fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth)acrylonitrile, and the like. Specific examples of such vinyl monomers are, for example, compounds including those described below. In addition, in the present specification, when either or both of "acrylic acid and methacrylic acid" are shown, it is sometimes called "(meth)acrylic acid".

Examples of (meth) acrylates include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (methyl) ) n-butyl acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (methyl) Tertiary-butylcyclohexyl acrylate, 2-ethylhexyl (meth)acrylate, tert-octyl (meth)acrylate, dodecyl (meth)acrylate, 18 (meth)acrylate Alkyl ester, ethoxylated ethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (methyl) ) 2-ethoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, (methyl) Benzyl acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, (A) Base) triethylene glycol monoethyl ether acetate, polyethylene glycol monomethyl ether glycol (meth)acrylate, Ethylene glycol monoethyl ether (meth)acrylate, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxyethylene glycol (meth)acrylate, (methyl) Dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctyl (meth)acrylate Ethyl ester, dicyclopentanyl (meth)acrylate, tribromophenyl (meth)acrylate, tribromophenoxyethyl (meth)acrylate, and the like.

Examples of the crotonate include: butyl crotonate, hexyl crotonate, and the like.

Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, methoxyvinyl acetate, and vinyl benzoate.

Examples of the maleic acid diesters include: dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of the fumaric acid diesters include: dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of the ikonic acid diesters include: dimethyl ikonate, diethyl itaconate, and dibutyl itaconate.

(Meth) acrylamides include: (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (methyl Acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-tertiary-butyl (meth) acrylamide, N-ring Hexyl (meth) acrylamide, N-(2-methoxyethyl) (meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl (Methyl) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryl hydrazino, diacetone acrylamide, and the like.

Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether and the like.

Examples of styrenes include: styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, methoxy Styrene, butoxy styrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, bases deprotected by acidic materials (eg, tertiary Hydroxystyrene, methyl benzoate, and α-methylstyrene protected by -butoxycarbonyl (t-Boc: t-butoxycarbonyl).

The preferred molecular weight of the specific polymer in the present invention is preferably such that the weight average molecular weight (Mw) is in the range of 1,000 to 50,000, and the number average molecular weight (Mn) is in the range of 400 to 30,000, more preferably The weight average molecular weight (Mw) is in the range of 3,000 to 30,000, and the number average molecular weight (Mn) is in the range of 1,000 to 20,000.

Particularly preferably, the weight average molecular weight (Mw) is in the range of 4,000 to 20,000, and the number average molecular weight (Mn) is in the range of 1,500 to 15,000.

That is, from the viewpoint of effectively suppressing the formation of the secondary aggregate of the primary aggregate of the pigment or effectively weakening the cohesive force of the secondary aggregate, the weight average molecular weight (Mw) of the specific polymer is compared. Good for more than 1,000. In addition, from the viewpoint of developability when a color filter is produced from a photopolymerizable composition containing a processed pigment, the weight average molecular weight (Mw) of the specific polymer is preferably 50,000 or less.

The specific polymer is produced, for example, by using a monomer represented by the formula (1) and another radical polymerizable compound as a copolymerization component, and is produced by a general radical polymerization method. In general, a suspension polymerization method, a solution polymerization method, or the like is used.

The "solvent" used in the synthesis of such specific polymers includes, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-di Methylformamide, N,N-dimethylacetamide, dimethyl hydrazine, toluene, ethyl acetate, methyl lactate, ethyl lactate, and the like. These solvents may be used singly or in combination of two or more.

Further, in the case of radical polymerization, a radical polymerization initiator may be used, and a chain transfer agent (for example, 2-hydrothioethanol and dodecylmercaptan) may be further used.

In the production step of the fine DPP pigment, the total amount of the resin used in contact with the DPP pigment in the step before drying is preferably from 1% by mass to 80% based on the total amount of the organic pigment containing the DPP pigment. quality%. A more preferable amount is 5% by mass to 60% by mass based on the total amount of the organic pigment containing the DPP pigment, and most preferably 7% by mass to 35% by mass based on the total amount of the organic pigment containing the DPP pigment. .

When the amount of addition is in the range of 1% by mass to 80% by mass, sufficient aggregation preventing effect at the time of drying can be obtained, and a color filter of a preferable hue can be obtained.

(pigment derivative)

In the present invention, in order to promote the miniaturization of the diketopyrrolopyrrole pigment, a pigment derivative can be added during salt milling.

Preferred skeletons of the pigment derivative include: quinacridone pigment, anthraquinone pigment, azo pigment, quinophthalone pigment, isoporphyrin pigment, isoindolinone pigment a skeleton such as a diketopyrrolopyrrole pigment or a benzimidazolone pigment. In addition, naphthalene, lanthanide, trinitrogen Light yellow aromatic polycyclic compounds such as phthalocyanines and the like are also included in the preferred skeleton. Among these skeletons, quinacone-based pigments, diketopyrrolopyrrole-based pigments, and azo-based pigments are particularly preferable from the viewpoint of the hue and the refinement-promoting effect.

In addition, examples of the pigment derivative which can be used for the addition include: Japanese Laid-Open Patent Publication No. 11-49974, Japanese Patent Laid-Open No. Hei 11-189732, Japanese Patent Application Laid-Open No. Hei 10-245501 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 2003-240938, Japanese Patent Application Laid-Open No. 2001-356210, Japanese Patent Laid-Open No. 2001-220520, Japanese Patent Laid-Open No. 2007-186681, and the like Revealed.

In the case of adding a pigment derivative at the time of salt milling, the pigment derivative is preferably used in a ratio of 0.1 to 20 parts by mass, more preferably 0.5%, per 100 parts by mass of the DPP pigment. Use in a range of up to 10 parts by mass. When the content is in the range of 0.1 to 20 parts by mass based on 100 parts by mass of the DPP-based pigment, superior micronization efficiency can be obtained.

In the present invention, in the case where a pigment derivative is added during salt milling, the DPP pigment and the pigment derivative are usually mixed in a powder before kneading, but a pigment derivative may be added in the middle of kneading. Further, the pigment derivative may be added in a single amount or divided into several times.

In the present invention, in the case where a pigment derivative is added at the time of salt milling, examples of the compound which can be used are shown below.

(salt grinding step and subsequent steps)

The salt milling step in the present invention is a diketopyrrolopyrrole pigment, a water-soluble inorganic salt, and a water-soluble organic solvent which does not substantially dissolve the water-soluble inorganic salt, and a resin further preferably an acid (preferably an acid) The polymer compound having a valence of 50 to 300 mgKOH/g is subjected to a mechanical kneading step.

This step can be carried out by any means such as a kneader or a planetary mixer, a continuous micronizing device, etc., but the temperature at the time of micronization is preferably from 10 ° C to 150 ° C, more preferably 20 ° C. Up to 120 ° C, most preferably 30 ° C to 90 ° C. When the atomization is carried out at a temperature higher than 150 ° C, the growth rate of the particles may exceed the rate of microparticulation, so that the atomization is not easily performed. In addition, when the atomization is carried out at 10 ° C or lower, the control of the particle size may be difficult due to the heat generation during the atomization, and the manufacturing stability may fluctuate, which is not preferable. The salt milling treatment can be carried out at any time to obtain the desired particle diameter, but it is usually from 2 hours to 24 hours, and from the viewpoint of productivity, it is preferably from 2 hours to 15 hours.

After the salt milling step as described above, the water-soluble inorganic salt in the kneaded material and the water-soluble organic solvent are removed, whereby a finely processed pigment can be obtained.

First, after the salt milling step, desalting treatment is usually applied to the obtained kneaded material.

The desalination treatment can be carried out by using any conventional apparatus, but it is usually a method in which a kneaded material and hot water are fed into a dispersion tank and stirred by a high-speed mixer or the like.

The dispersed pigment is usually filtered and washed. Filtration and washing can be carried out using any conventional means, but usually a filter press is used, and in the present invention, a filter press is also preferably used.

The desalted and filtered pigment is usually dried. Most of the drying uses a general oven, but a spray drying method or a vacuum drying method can also be used. In particular, the spray drying method is well known for obtaining a pigment powder which is weakly dried and agglomerated and which is easily dispersed.

The temperature at which the oven is dried is usually from 30 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, most preferably from 40 ° C to 90 ° C. If drying is carried out at a temperature higher than 150 ° C, there is a possibility of causing intense dry aggregation, which makes the dispersion difficult. Further, drying at a temperature lower than 30 ° C is not preferable from the viewpoint of productivity because it takes a long time.

The amount of moisture in the dried treated pigment is usually from 0.01% by mass to 10% by mass, preferably from 0.05% by mass to 5% by mass, most preferably from 0.05% by mass to 3% by mass.

Although the pigment dispersion composition of the present invention contains a DPP pigment, it is preferably composed of at least one micronized DPP pigment as described above.

The pigment dispersion composition of the present invention can also be used in combination with other pigments or dyes as needed. Specific examples of the combination are as follows.

For example, the red pigment may be at least one of a diketopyrrolopyrrole pigment (containing a micronized DPP pigment as described above), a disazo yellow pigment, an isoporphyrin yellow pigment, and a quinophthalone. A mixture of yellow pigments or lanthanide red pigments. Further, in order to obtain a preferable hue, a diketopyrrolopyrrole pigment may be used in combination with an anthraquinone pigment. Preferred pigments for the diketopyrrolopyrrole pigment include CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, etc., but from the viewpoint of hue and spectral characteristics, CI Pigment Red is preferred. 254. Preferred examples of the fluorene-based pigment include C.I. Pigment Red 89, C.I. Pigment Red 177, etc., but C.I. Pigment Red 177 is preferably used from the viewpoint of hue and spectral characteristics.

The content of the lanthanide pigment is preferably from 0 to 200 parts by mass, and most preferably from 0 to 120 parts by mass, per 100 parts by mass of the diketopyrrolopyrrole pigment.

Further, from the viewpoints of hue, spectroscopic characteristics, and contrast, a yellow pigment such as C.I. Pigment Red 254 and C.I. Pigment Red 177, and C.I. Pigment Yellow 150 or C.I. Pigment Yellow 139, C.I. Pigment Yellow 138 or the like is also preferable. Among them, from the viewpoint of comparison, it is particularly preferable to use C.I. Pigment Red 254 and C.I. Pigment Red 177 in combination with C.I. Pigment Yellow 150.

The pigment which can be used in combination with the pigment dispersion composition of the present invention is not particularly limited, and a conventionally known one of the diketopyrrolopyrrole pigments as described above may be used, but it is preferred. The combination is as described above. From the viewpoint of comparison, it is preferable that the pigment which can be used in combination is finely refined to the same extent as the fine DPP pigment.

The dye system which can be used in combination with the pigment dispersion composition of the present invention is not particularly limited, and a conventional dye which has been conventionally used as a color filter can be used. For example, Japanese Laid-Open Patent Publication No. SHO-64-90403, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 2,592,207, U.S. Patent No. 4,808,501, U.S. Patent No. 5,667,920, U.S. Patent No. 5,059,500, Japanese Patent Application Laid-Open No. 5-333207, Japanese Invention Japanese Laid-Open Patent Publication No. 6-35183, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei. No. 8-15522, Japanese Patent Application Laid-Open No. Hei 8-15771, Japanese Patent No. 8-29771, Japanese Invention Patent Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 2002-14222, Japanese Patent Application Laid-Open No. 2002-14222, Japanese Patent Laid-Open Publication No. 2002-14223, Japanese Patent Application Laid-Open No. Hei No. 8-302224 A pigment described in Japanese Laid-Open Patent Publication No. Hei 8- No. No. Hei.

As the chemical structure, a pyrazole azo system, an anilino azo system, a triphenylmethane system, a guanidine system, an anthrapyridone system, a benzylidene group, an oxyphthalocyanine (Oxonol) system, or a pyrazole triazole can be used. Azo system, pyridone azo system, Sainen series, thiophene Department, pyrrolopyrazole, methine azo, A dye such as a cord, an anthracycline, a benzopyran, or an indigo.

In the pigment dispersion composition of the present invention, the DPP pigments may be used alone or in combination of two or more.

The total content of the pigment including the DPP-based pigment and other pigments to be used in combination in the pigment dispersion composition is preferably a pigment ratio based on the total solid content (mass) of the pigment dispersion composition. 40 to 90% by mass, more preferably 50 to 80% by mass. When the content of the pigment is within this range, it is effective in ensuring sufficient color density and superior color characteristics.

In addition, the DPP-based pigment is preferably contained in an amount of 50% by mass or more, and more preferably 70% by mass or more, based on all the pigments in the pigment dispersion composition of the present invention. All of the pigments may be one or two or more DPP-based pigments.

[(B) o-phthalimidoalkylated diketopyrrolopyrrole and (C) phthalic acid imidoalkylated quinophthalone]

The pigment dispersion composition of the present invention comprises: (B) phthalic acid imidoalkyl group in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the (A) diketopyrrolopyrrole pigment as described above. a diketopyrrolopyrrole, and 0.1 to 20 parts by mass of (C) phthalic acid imidoalkylated quinolin relative to 100 parts by mass of the (A) diketopyrrolopyrrole pigment as described above Anthrone.

(B) Phthaloin imine alkylated diketopyrrolopyrrole is a diketopyrrolopyrrole obtained by bonding at least one phthalimidoalkylene group to a diketopyrrolopyrrole. Further, a typical phthalimidoimidomethyl group which is a phthalimidoalkylene group has the structure shown below.

The phthalic acid iminomethylated diketopyrrolopyrrole is a diketopyrrolopyrrole pigment derivative having the structure represented by the following general formula (B).

In the general formula (B) as shown above, the X and Y groups each independently represent a hydrogen atom, an alkyl group, a cyano group, an aryl group or a halogen group. The n series represents the substitution number of the o-phthalimidomethyl group and represents an integer of 1 to 3. The X and Y groups in the above formula (B) are synonymous with X and Y in the formula (A) as shown before, and the preferred mode is also the same.

(B) o-xylylenediamine-alkylated diketopyrrolopyrrole is prepared by a known method, for example, a diketopyrrolopyrrole red pigment in sulfuric acid with paraform, orthophthalic acid The quinone imine or hydroxymethylphthalimide is reacted, etc., whereby it can be easily produced. This synthesis method has been described in detail in Japanese Laid-Open Patent Publication No. 62-149759, and the like. The diketopyrrolopyrrole red pigment which can be used in the synthesis includes, for example, CI Pigment Red 254, 255, 264, and CI Pigment Orange 71, 73, etc., from the viewpoint of easiness of synthesis and hue, particularly It is preferred to use CI Pigment Red 255.

(B) o-xylylenediamine-alkylated diketopyrrolopyrrole can also be used as a phthalic acid imine group having a substitution number of 1 to 3 of phthalic acid iminomethyl group A mixture of a diketopyrrolopyrrole and a diketopyrrolopyrrole red pigment which is imidized without phthalic acid. The diketopyrrolopyrrole red pigment at this time includes, for example, C.I. Pigment Red 254, 255, 264, and, for example, C.I. Pigment Orange 71, 73, a diketopyrrolopyrrole pigment, and the like.

(C) phthalic acid iminoalkylated quinophthalone is a quinacridone in which at least one phthalimidoalkylene group is a hydrogen atom bonded to a quinacridone ring. Further, a typical phthalimidoimidomethyl group which is a phthalimidoalkylene group has the structure shown below.

The phthalic acid imidomethylated quinophthalone is a quinophthalone pigment derivative having a structure represented by the following general formula (C).

In the general formula (C) as shown above, X and Y each independently represent a hydrogen atom, a methyl group or a chlorine atom. The n series represents the substitution number of the o-phthalimidomethyl group and represents an integer of 1 to 3.

The (C) phthalic acid imidoalkylated quinophthalone group of the present invention which can be used for the structure represented by the above-mentioned structure includes, for example, phthalic acid imine methylation unsubstituted Quinone, phthalimide methylated dimethylquinacone, phthalimidomethylated dichloroquinanone, and the like.

The (C) phthalic acid imidoalkylated quinophthalone contained in the pigment dispersion composition of the present invention may be used alone or in a mixture of two or more.

(C) o-xylylenediamine-based alkylation of quinophthalones, for example, quinophthalone red pigment in sulfuric acid with paraformaldehyde, phthalimide or hydroxymethylphthalic acid The carbenamide is reacted or the like, whereby it can be easily produced. This method has been described in detail in Japanese Laid-Open Patent Publication No. 55-108466, and the like.

(C) o-phthalimidoalkylamine alkylquinacone can be used as the phthalic acid methylated quinone having a substitution number of 1 to 3 of phthalic acid iminomethyl group A mixture of anthrone and quinacone red pigment which is not imidized with phthalic acid. The quinacridone red pigment at this time includes, for example, an unsubstituted quinophthalone pigment of CI Pigment Violet 19, a dimethylquinoxanes pigment of CI Pigment Red 122, CI Pigment Red 202, and CI Pigment Red 209. Dichloroquinoxanes pigments, etc.

The pigment dispersion composition of the present invention must contain: (B) phthalic imidazolidine in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the (A) diketopyrrolopyrrole pigment as described above. a (1) phthalic acid imidoalkyl quinacone of (C) phthalic acid imidazolidinone according to 100 parts by mass of (A) diketopyrrolopyrrole pigment; The content of (B) phthalic acid imidoalkylated diketopyrrolopyrrole is preferably from 0.1 part by mass to 25 parts by mass based on 100 parts by mass of the diketopyrrolopyrrole pigment, most preferably 0.5 parts by mass to 20 parts by mass. Further, a particularly preferable content of "(C) phthalic acid imidoalkylated quinophthalone) is 0.1 parts by mass to 15 parts by mass based on 100 parts by mass of the diketopyrrolopyrrole pigment. The optimum is from 0.5 part by mass to 15 parts by mass.

The addition ratio of the two is preferably within the range of the respective contents as described above, and (B) the addition amount of the o-phthalimidoalkylamine diketopyrrolopyrrole is relative to (C) The xylylene iminoalkylation quinophthalone is equal or more. High pigment dispersibility, high contrast, by phthalate iodide alkylated diketopyrrolopyrrole and phthalimide alkylation quinophthalone Superior surface smoothness of color filters.

In the present invention, (B) phthalic acid imidoalkylated diketopyrrolopyrrole and (C) phthalic acid imidoalkylated quinacone may be used one or two each. The above is used together.

With regard to the preparation of the pigment dispersion composition of the present invention, (B) phthalic acid imidoalkylated diketopyrrolopyrrole and (C) phthalic acid imidoalkylation quinophthalone can be It is added to the (A) diketopyrrolopyrrole pigment at any timing, but it is preferred that at least a part is added after the miniaturization of the diketopyrrolopyrrole (preferably, the average primary particle diameter reaches 10 nm to 30 nm). Specifically, for example, the addition of the kneaded material after the completion of the salt milling, the addition of the desalting dispersion, the addition of the pigment powder after the dry pulverization, the addition of the pigment dispersion composition before the dispersion, the addition of the pigment dispersion, and the like. By adding at least a portion of the phthalic acid imidoalkylated diketopyrrolopyrrole and the phthalic acid imidoalkylation quinophthalone after the miniaturization of the diketopyrrolopyrrole, Excellent surface smoothness with high pigment dispersion, high contrast, and color filters.

In order to improve dispersion stability and obtain high contrast, the pigment dispersion composition of the present invention may be used in combination with (B) phthalic acid imidoalkylated diketopyrrolopyrrole and (C) adjacent Pigment derivatives other than xylylene iminoalkylated quinophthalone are also preferred.

A preferred "pigment derivative" which can be used in combination includes a portion having an affinity with a dispersing agent and which can be adsorbed on the surface of the DPP pigment. By using a pigment derivative having a absorbing point which can serve as a dispersing agent and absorbing the pigment derivative on the surface of the DPP pigment, the dispersing agent can be easily adsorbed on the surface of the DPP pigment, and the DPP pigment can be made into fine particles. It is dispersed in the pigment dispersion composition and, in addition, it can be prevented from reaggregating.

Specifically, a preferred "pigment derivative" which can be used in combination is an organic pigment as a matrix skeleton, and a compound obtained by introducing an acidic group or a basic group or an aromatic group as a substituent in a side chain. Specifically, the "organic pigment of the matrix skeleton" includes: anthraquinone pigment, azo pigment, quinophthalone pigment, isoporphyrin pigment, isoindolinone pigment, benzimidazole Ketone pigments, etc. Further, a pigment derivative having a skeleton of a diketopyrrolopyrrole pigment and not containing the component (B) as described above, or a skeleton having a quinophthalone pigment, and not contained in the component (C) as described above Derivatives and the like can also be used in combination as a pigment derivative.

In addition, the matrix skeleton also includes naphthalene, anthraquinone, and trinitrogen, which are not usually called pigments. A pale yellow aromatic polycyclic compound such as a quinolin or the like.

Among them, a preferred matrix skeleton is an azo pigment, and a matrix skeleton having a quinophthalone pigment or a diketopyrrolopyrrole pigment is also included, and has a structure different from the essential components of the present invention as described above. Pigment derivatives.

The pigment derivative which is suitable for use in the present invention includes, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 10-245501, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Publication No. 2005-234478, Japanese Patent Application Laid-Open No. 2003-240938, Japanese Patent Application Laid-Open No. 2001-356210, and Japanese Patent Laid-Open Publication No. 2007-186681 Narrator.

In the present invention, a pigment derivative other than (B) phthalic acid imidoalkylated diketopyrrolopyrrole and (C) phthalic acid imidoalkylated quinophthalone is used in combination. In other words, the amount of the other pigment derivative to be used in combination is preferably 0.1 part by mass in terms of mass, based on 100 parts of the pigment (including the diketopyrrolopyrrole pigment) contained in the pigment dispersion composition. Up to 30 parts, more preferably 0.5 parts to 30 parts, most preferably 1 part to 25 parts. If it is in this range, good dispersibility and high contrast can be obtained. When a pigment derivative other than the component (B) or the component (C) is used, the total amount of the other pigment derivative is preferably set so that the total amount of the component (B) and the component (C) is 10 times or less.

[(D) Organic Solvent]

The pigment dispersion composition of the present invention contains at least one organic solvent.

The (D) organic solvent which can be used to prepare the pigment dispersion composition of the present invention includes 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, Diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, positive -butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene (oxime), and the like.

The organic solvent is selected depending on the use of the pigment dispersion composition, and only one type or two or more types may be used in combination in the composition.

In addition, the amount of the organic solvent to be added is appropriately selected depending on the use of the pigment dispersion composition, etc., but when it is used to prepare the colored polymerizable composition described later, it is considered from the viewpoint of handling characteristics. Then, the solid content concentration including the pigment or the like can be added in an amount of 5 to 50% by mass.

[Other ingredients] -Dispersant-

From the viewpoint of improving the dispersibility of the pigment contained, the pigment dispersion composition of the present invention is preferably a dispersant.

The "dispersant" which can be used in the present invention includes: a polymeric dispersant [for example, polyamidoamine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, and a modified polycondensation. Carbamate, modified polyester, modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid-formaldehyde condensate, polyoxyethylene alkyl phosphate Ester, polyoxyethylene alkylamine, alkanolamine, and the like.

The polymer dispersant can be further classified into a linear polymer compound, a terminal modified polymer compound, a graft polymer compound, and a block polymer compound.

The polymeric dispersant provides the effect of sorbing on the surface of the pigment to prevent reaggregation. Therefore, a preferred structure is a terminal modified polymer compound having a fixed portion on the surface of the pigment, a graft polymer compound, and a block polymer compound.

Hereinafter, a block type polymer compound, a graft type polymer compound, and a terminal modified type polymer compound each suitable for the polymer dispersant of the present invention will be described.

(block type polymer compound)

The block type polymer compound which can be used as a polymer dispersant is not particularly limited, and a pigment adsorbing block and a non-pigment adsorbing block can be used. ) "Block type polymer compound".

The "monomer constituting the pigment absorbing block" is preferably a monomer having a pigment absorbing functional group, although not particularly limited. Specifically, it includes a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, a monomer having a basic nitrogen atom, and the like.

Hereinafter, a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, and a monomer having a basic nitrogen atom, which are suitable as a monomer constituting the pigment sorption block, will be described.

A single system having an organic dye structure or a heterocyclic structure includes, for example, an anthracycline system, an insoluble azo system, an azo lake system, an anthraquinone system, a quinacridone system, and a dioxins. a dye structure such as a diketopyrrolopyrrole, an indole pyridine, an anthrone ketone, an indanthrone, a ketone, an anthrone, an anthraquinone or a thioindigo; or, for example, a thiophene, Furan, , pyrrole, pyrroline, pyrrolidine, dioxane, pyrazole, pyrazoline, pyrazole, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, piperidine, pyridine, piperidine , dioxane, morpholine, hydrazine Pyrimidine, piperazine Trinitrogen , trithiane, isoporphyrin, isoindolinone, benzimidazolone, benzothiazole, amber imine, phthalimide, naphthyl imine, hydantoin, hydrazine A monomer having a heterocyclic structure such as quinoline, carbazole, acridine, acridone or hydrazine.

More specifically, although not particularly limited, a monomer having the structure shown below can be cited.

Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group, or a vinyl monomer having a sulfonic acid group, and a vinyl monomer having a phosphoric acid group.

The vinyl single system having a carboxyl group includes: (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, Cinnamic acid, acrylic acid dimer, and the like.

Further, an addition reaction of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate with a cyclic anhydride such as maleic anhydride or phthalic anhydride or cyclohexanedicarboxylic anhydride may also be used. , poly(meth)acrylic acid ω-carboxy-caprolactone and the like.

In addition to this, as the carboxyl group precursor, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride may be used.

Further, among these, (meth)acrylic acid is particularly preferable from the viewpoint of copolymerizability, cost, solubility, and the like.

Further, the vinyl single system having a sulfonic acid group includes 2-propenylamine-2-methylpropanesulfonic acid and the like. Further, the vinyl single system having a phosphoric acid group includes: mono(2-propenyloxyethyl ester) phosphate, mono(1-methyl-2-propenyloxyethyl phosphate), and the like.

A single system having a basic nitrogen atom includes: wherein the single system having a heterocyclic ring includes: vinyl pyridine, vinyl imidazole, vinyl triazole, etc.; (meth) acrylate type includes: (methyl) N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl (meth)acrylate, 1-(N,N-dimethylamino)-1 (meth)acrylate , 1-dimethylmethyl ester, N,N-dimethylaminohexyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N (meth)acrylate N-diisopropylaminoethyl ester, N,N-di-n-butylaminoethyl (meth)acrylate, N,N-di-iso-butylaminoethyl (meth)acrylate , morpholinoethyl (meth)acrylate, piperidinyl (meth)acrylate, 1-pyrrolidylethyl (meth)acrylate, N,N-dimethyl-2(meth)acrylate - pyrrolidinylaminoethyl ester, and N,N-dimethylphenylaminoethyl (meth)acrylate, etc.; (meth) acrylamide series include: N-(N', N'- Dimethylaminoethyl) acrylamide, N-(N',N'-dimethylaminoethyl)methacrylamide, N-(N',N'-diethylamino B Base) acrylamide, N-(N', N'- Diethylaminoethyl)methacrylamide, N-(N',N'-dimethylaminopropyl)propenylamine, N-(N',N'-dimethylaminopropyl Methyl acrylamide, N-(N',N'-diethylaminopropyl) acrylamide, N-(N',N'-diethylaminopropyl)methacryl oxime Amine, 2-(N,N-dimethylamino)ethyl(meth)acrylamide, 2-(N,N-diethylamino)ethyl(meth)acrylamide, 3- (N,N-Diethylamino)propyl (meth) acrylamide, 3-(N,N-dimethylamino)propyl (meth) acrylamide, 1-(N, N -dimethylamino)-1,1-dimethylmethyl(meth)acrylamide, and 6-(N,N-diethylamino)hexyl(methyl)propenamide, morpholine Base (meth) acrylamide, piperidinyl (meth) acrylamide, N-methyl-2-pyrrolidinyl (meth) acrylamide, etc.; styrenics include: N, N- Methylaminostyrene, N,N-dimethylaminomethylstyrene, and the like.

Further, a monomer having a urea group, a urethane group, a hydrocarbon group having a coordinating oxygen atom of 4 or more, an alkoxyalkyl group, an epoxy group, an isocyanate group, or a hydroxyl group can also be used.

Specifically, it includes a monomer having the following structure.

In addition to this, a monomer having an ionic functional group can be utilized.

Examples of the ionic vinyl monomer (anionic vinyl monomer, cationic vinyl monomer) include: wherein the anionic vinyl single system comprises: a vinyl monomer having an acidic group as described above An alkali metal salt or a salt with an organic amine (for example, a tertiary amine such as triethylamine or dimethylaminoethanol). The cationic vinyl single system comprises: a halogenated alkyl group (alkyl: C1 to 18; a halogen atom: a chlorine atom, a bromine atom or an iodine atom), which is a nitrogen-containing vinyl monomer as described above. a halogenated benzyl group such as a benzyl group or a benzyl bromide, an alkylsulfonate such as methanesulfonic acid (alkyl: C1 to 18), an arylsulfonate such as benzenesulfonic acid or toluenesulfonic acid A base ester (alkyl group: C1 to 18), a dialkyl sulfate (alkyl group: C1 to 4), etc., obtained by quaternization, a dialkyldiarylammonium salt or the like.

The "monomer having a pigment absorbing functional group" as described above can be appropriately selected depending on the kind of the pigment to be dispersed, and these may be used singly or in combination of two or more.

The "monomer constituting the non-pigment absorbing block" is not particularly limited, but includes, for example, (meth) acrylates, crotonates, vinyl esters, maleic acid. Diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleic acid A monomer having a non-pigment absorbing group such as a quinone imine or (meth)acrylonitrile.

These single systems constituting the non-pigment absorbing block may be used singly or in combination of two or more.

Further, in the case of being applied to a pigment dispersion composition requiring alkali development treatment, a monomer constituting the non-pigment absorbing block and a vinyl monomer having an acidic group as described above may be used in combination.

Examples of (meth) acrylates include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (methyl) ) n-butyl acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, n-hexyl (meth)acrylate, (meth)acrylic acid Cyclohexyl ester, tert-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tertiary-octyl (meth)acrylate, dodecyl (meth)acrylate , octadecyl (meth) acrylate, ethoxylated ethyl (meth) acrylate, phenyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methyl (meth) acrylate Oxyethyl ester, 2-ethoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, ( Vinyl vinyl methacrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, allyl (meth) acrylate, 2-allyloxy (meth) acrylate Ester, propargyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Glycol monomethyl ether ester, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, Poly(methyl) methacrylate monomethyl ether ester, poly(methyl) methacrylate monoethyl ether ester, (meth)acrylic acid β-phenoxyethoxyethyl ester, poly(methyl) ) nonylphenoxyethylene acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, (methyl) ) octafluoropentyl acrylate, perfluorooctyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenoxy (meth) acrylate Ethyl ester, γ-butyrolactone (meth)acrylate, and the like.

Examples of the crotonate include: butyl crotonate, hexyl crotonate, and the like.

Examples of the vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, methoxyvinyl acetate, and vinyl benzoate.

Examples of the maleic acid diesters include: dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of the fumaric acid diesters include: dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of the ikonic acid diesters include: dimethyl ikonate, diethyl itaconate, and dibutyl itaconate.

(Meth) acrylamides include: (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (methyl ) acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl propylene (methyl) decylamine, N-tertiary-butyl (meth) acrylamide, N- Cyclohexyl (meth) acrylamide, N-(2-methoxyethyl)(meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl Base (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl ( Methyl) acrylamide, (meth) propylene decyl morpholine, diacetone acrylamide, N-methylol acrylamide, N-hydroxyethyl acrylamide, vinyl (meth) acrylamide N,N-diallyl (meth) acrylamide, N-allyl (meth) acrylamide, and the like.

Examples of styrenes include: styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, methoxy Styrene, butoxy styrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, bases deprotected by acidic materials (eg, tertiary Hydroxystyrene, methyl benzoate, and α-methylstyrene protected by -butoxycarbonyl (t-Boc: t-butoxycarbonyl).

Examples of vinyl ethers include: methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl Vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.

Examples of the vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, and the like.

Examples of the olefins include ethylene, propylene, isobutylene, butadiene, isoprene, and the like.

Examples of the maleimide group include: maleimide, butyl maleimide, cyclohexylmethyleneimine, phenyl maleimide, and the like.

Examples of the (meth)acrylonitrile include methacrylonitrile, acrylonitrile, and the like.

Examples of the vinyl monomer having an acidic group as described above include a vinyl monomer having a carboxyl group, or a vinyl monomer having a sulfonic acid group, and a vinyl monomer having a phosphoric acid group.

The vinyl single system having a carboxyl group includes: (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, Cinnamic acid, acrylic acid dimer, and the like.

Further, an addition reaction of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate with a cyclic anhydride such as maleic anhydride or phthalic anhydride or cyclohexanedicarboxylic anhydride may also be used. , poly(meth)acrylic acid ω-carboxy-caprolactone and the like.

In addition to this, a monomer containing an anhydride such as maleic anhydride, itaconic anhydride, or citraconic anhydride may be used as the carboxyl precursor.

Further, among these, (meth)acrylic acid is particularly preferable from the viewpoint of copolymerizability, cost, solubility, and the like.

Further, the vinyl single system having a sulfonic acid group includes 2-propenylamine-2-methylpropanesulfonic acid and the like. The vinyl single system having a phosphoric acid group includes: - (2-propenyloxyethyl ester) phosphate, - (1-methyl-2-propenyloxyethyl ester), and the like.

In addition to this, a vinyl monomer having an acidic group may also use a vinyl monomer having a phenolic hydroxyl group or a vinyl monomer containing a sulfonamide group.

The method for obtaining the block type polymer compound of the present invention can be produced by a conventional method.

For example, a living polymerization method, an iniferter polymerization method, and the like are known. In addition to this, there is another method: when radically polymerizing a monomer having a pigment absorbing group or a monomer having a non-pigment absorbing group, the thiocarbamic acid or 2- a polymer obtained by polymerizing a compound containing a thioester and a thiol group in the presence of a compound containing a thioester and a thiol group, such as ethionyl thioethyl ether or 10-ethyl sulfonyl thiol thiol, is sodium hydroxide or ammonia. A method in which a base is treated as a polymer having a thiol group at a single terminal, and a monomer component of another block is subjected to radical polymerization in the presence of a polymer having a thiol group at a single terminal. Well known to everyone. Among these, a living polymerization method is preferred.

The weight average molecular weight of the block type polymer compound is not particularly limited, but is preferably in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. When the weight average molecular weight is 3,000 or more, the stabilizing effect can be more effectively obtained, and when the weight average molecular weight is 100,000 or less, it can be more effectively absorbed and exhibits good dispersibility.

Commercially available products can also be used as the block type polymer compound. Specific examples include "Disperbyk-2000, 2001" manufactured by BYK Chemie Corp., "EFKA 4330, 4340" manufactured by EFKA Additives B.V. (EFKA Additives B.V.), and the like.

(graft type polymer compound)

There is no particular limitation on the "graft-type polymer compound" which can be used as a polymer dispersing agent, and it is suitable for use in Japanese Patent Laid-Open No. 54-37082, and Japanese Patent Laid-Open No. 61-174939 A compound obtained by reacting a polyalkyleneimine with a polyester compound as disclosed in Japanese Laid-Open Patent Publication No. Hei No. 9-169821, which is disclosed in Japanese Laid-Open Patent Publication No. Hei 9-169821 a compound obtained by modifying an amine group of a side chain with a polyester, a polyester polyol addition urethane as disclosed in Japanese Laid-Open Patent Publication No. 60-166318, and the like; In addition, it is also suitable for use in the Japanese Patent Laid-Open Publication No. 9-171253, or the Chemistry and Technology of Macromonomers (IPC Publication, 1989). A graft type polymer compound in which a polymerizable oligomer (hereinafter referred to as a macromonomer) is used as a copolymerization component is described.

The branch part of the graft type polymer compound is preferably polystyrene, polyethylene oxide, polypropylene oxide, poly(meth)acrylate, polycaprolactone or the like. Among them, a graft type polymer compound having a structural unit represented by the following formula (5) in the branch portion is more preferable.

In the formula (5), R ⁷⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; Q represents a cyano group, an aryl group having 6 to 30 carbon atoms, or -COOR ⁷⁵ (herein) R ⁷⁵ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

In the formula (5), the alkyl group represented by R ⁷⁴ may have a substituent, and is preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group. The substituent which can be introduced into the alkyl group includes a halogen atom, a carboxyl group, an alkoxycarbonyl group, an alkoxy group and the like.

Specific examples of such alkyl groups include methyl, ethyl, hexyl, octyl, trifluoromethyl, carboxymethyl, methoxycarbonylmethyl and the like.

R ⁷⁴ is particularly preferably a hydrogen atom or a methyl group.

In the formula (5), the aryl group represented by Q may have a substituent, and is preferably an aryl group having 6 to 20 carbon atoms, particularly preferably a carbon number of 6 to 12. Aryl. The substituent which may be introduced into the aryl group includes a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group and the like.

Specific examples of such aryl groups include: phenyl, naphthyl, tolyl, fluorenyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, Ethoxyphenyl, butoxyphenyl, nonyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylbenzene Base.

Among these aryl groups, preferred are unsubstituted aryl groups, or aryl groups substituted with a halogen atom, an alkyl group or an alkoxy group, particularly preferably an unsubstituted aryl group, or an alkyl group. Substituted aryl.

When Q of the formula (5) is -COOR ⁷⁵ , the alkyl group represented by R ⁷⁵ may have a substituent, and is preferably an alkyl group having 1 to 12 carbon atoms, particularly preferably An alkyl group having 1 to 8 carbon atoms. The substituent which may be introduced into the alkyl group includes a halogen atom, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amine group, a mercaptoamine group, an amine mercapto group or the like.

Specific examples of such alkyl groups include: methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, thirteen, tetradecyl, hexadecanyl , octadecyl, 2-chloroethyl, 2-bromoethyl, 2-methoxycarbonylethyl, 2-methoxyethyl, 2-bromopropyl, 2-butenyl, 2-pentene , 3-methyl-2-pentenyl, 2-hexenyl, 4-methyl-2-hexenyl, benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2 -naphthylethyl, chlorobenzyl, bromobenzyl, methylbenzyl, ethylbenzyl, methoxybenzyl, dimethylbenzyl, dimethoxybenzyl, Cyclohexyl, 2-cyclohexylethyl, 2-cyclopentylethyl, bicyclo[3.2.1]oct-2-yl, 1-adamantyl, dimethylaminopropyl, ethionylamino Base, N, N-dibutylaminoamine, mercaptomethyl and the like.

Among these alkyl groups, an unsubstituted alkyl group or an alkyl group substituted with a halogen atom, an aryl group or a hydroxyl group is preferred, and an alkyl group which is preferably unsubstituted is particularly preferred.

When Q of the formula (5) is -COOR ⁷⁵ , the aryl group represented by R ⁷⁵ may have a substituent, and is preferably an aryl group having 6 to 20 carbon atoms, particularly preferably An aryl group having 6 to 12 carbon atoms.

The substituent which may be introduced into the aryl group includes a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a mercaptoamine group and the like.

Specific examples of such aryl groups include: phenyl, naphthyl, tolyl, fluorenyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, Ethoxyphenyl, butoxyphenyl, nonyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylbenzene Base, acetaminophen phenyl, acrylamidophenyl, decyl decyl phenyl, and the like.

Among these aryl groups, an unsubstituted aryl group or an aryl group substituted by a halogen atom, an alkyl group or an alkoxy group is preferable, and an alkyl group-substituted aryl group is particularly preferable.

Among these R ⁷⁵ , a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and particularly preferably a hydrogen atom and an alkyl group having 1 to 12 carbon atoms are preferable.

Specific examples of the branching portion of the graft type polymer compound having the structural unit represented by the formula (5) in the branching portion include: poly(methyl) methacrylate, poly(methyl) Acrylic-n-butyl ester, poly(meth)acrylic acid-iso-butyl ester, poly(methyl (meth) acrylate-co-(methyl) methacrylate), poly(methyl (meth) acrylate) -co-styrene), poly(methyl (meth)acrylate-co-(meth)acrylic acid), poly(methyl (meth)acrylate-co-acrylonitrile), and the like.

Any of conventionally known methods for synthesizing a graft type polymer compound having a structural unit represented by the formula (5) in the branching portion can be used.

Specifically, a copolymerization of a macromonomer having a structural unit represented by the general formula (5) with an ethylenically unsaturated monomer copolymerizable with the macromonomer can be exemplified.

Among the macromonomers having a structural unit represented by the general formula (5), those represented by the following general formula (6) are preferred.

In the formula (6), R ⁷⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and W represents a single bond, or a linking group as shown below, or a divalent group as shown below. A linking group composed of any combination, and A represents a group having a structural unit represented by the above formula (5).

In the above-mentioned linking group, Z ₁ and Z ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group or a hydroxyl group, and Z ₃ represents a hydrogen atom, An alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 20 carbon atoms.

Specific examples of such macromonomers represented by the general formula (6) include those shown below.

The A system in the specific structure of the macromonomer as described above is synonymous with A in the general formula (6) as shown before.

These macro-systems available from commercial products include: single-end methacryl-methylated polymethyl methacrylate oligomers (Mn = 6,000, trade name: AA-6, East Asia Synthetic Chemical Industry Limited) (manufactured by Toagosei Co., Ltd.); and single-end methacryl oxime-based poly-n-butyl acrylate oligomer (Mn=6,000, trade name: AB-6, manufactured by East Asia Synthetic Chemical Co., Ltd. A single-end methacryl oxime-based polystyrene oligomer (Mn = 6,000, trade name: AS-6, manufactured by Toagosei Chemical Co., Ltd.).

The molecular weight of the macromonomer as described above is preferably a number average molecular weight (Mn) in terms of polystyrene of 1,000 to 20,000, more preferably 2,000 to 15,000. If the number average molecular weight is within this range, the steric repulsion effect which the dispersant should have can be more effectively obtained.

The ethylenically unsaturated mono-system which can be copolymerized with the macromonomer as described above is preferably a "monomer constituting the pigment absorbing block" as described above to improve the dispersibility and dispersion stability of the pigment. Sex. Further, the "monomer constituting the non-pigment absorbing block" as described above may be copolymerized as another copolymerization component.

The weight average molecular weight of the graft type polymer compound as described above is not particularly limited, and is preferably in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. When the weight average molecular weight is 3,000 or more, the stabilizing effect can be more effectively obtained, and when the weight average molecular weight is 100,000 or less, it can be more effectively absorbed and exhibits good dispersibility.

Commercial products of the graft type polymer compound as described above include: "SOLSPERSE 24000, 28000, 32000, 38500, 39000, 55000" manufactured by The Lubrizol Corporation, manufactured by BYK Chemie Co., Ltd. "Disperbyk-161, 171, 174" and so on.

(terminal modified polymer compound)

The term "terminal-modified polymer compound" as a polymer dispersing agent is disclosed in, for example, Japanese Laid-Open Patent Publication No. Hei 9-77994, or Japanese Patent Laid-Open No. 2002-273191. A polymer compound having a functional group at the end of a polymer.

The method for synthesizing the polymer compound having a functional group at the terminal of the polymer is not particularly limited, and examples thereof include the following methods, or a combination thereof:

1. A method of synthesizing (for example, radical polymerization, anionic polymerization, cationic polymerization, or the like) using a polymerization initiator containing a functional group;

2. A method of synthesizing a radical polymerization using a chain transfer agent containing a functional group.

Here, the functional group for introduction includes: an organic dye structure selected from a heterocyclic structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, and a coordinating oxygen atom. A hydrocarbon group having 4 or more carbon atoms, an alkoxyalkyl group, an epoxy group, an isocyanate group, a hydroxyl group, and a site of an ionic functional group. Further, a functional group which can be derived from such a sorption site can also be used.

A polymerization initiator (polymerization initiator containing a functional group) which can introduce a functional group to a polymer terminal, which is used in the synthesis method as described above, includes, for example, 2,2'-azobis (2) -Cyanpropanol), 2,2'-azobis(2-cyanopentanol), 4,4'-azobis(4-cyanovaleric acid), 4,4'-azobis(4-cyanide) Valeric acid chloride), 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane], 2,2'-azobis[2-(2-imidazole) Benz-2-yl)propane], 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane], 2,2'-azobis{2 -[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propanoid Amines, etc., and derivatives thereof.

A chain transfer agent (a chain transfer agent containing a functional group) which can introduce a functional group to a polymer terminal, which is used in the synthesis method as described above, includes, for example, a thiol compound (for example, thioglycolic acid). , thiomalic acid, thiosusic acid, 2-hydrothiopropionic acid, 3-hydrothiopropionic acid, 3-hydrothiobutyric acid, N-(2-hydrothiopropyl) glycine, 2-Hexylthionicotinic acid, 3-[N-(2-hydrothioethyl)amine-methylmethyl]propionic acid, 3-[N-(2-hydrothioethyl)amino]propionic acid , N-(3-Hexylthiopropionyl)alanine, 2-hydrothioethanesulfonic acid, 3-hydrothiopropanesulfonic acid, 4-hydrothiobutanesulfonic acid, 2-hydrogenthio Ethanol, 3-hydrothio-1,2-propanediol, 1-hydrothio-2-propanol, 3-hydrothio-2-butanol, hydrothiophenol, 2-hydrothioethylamine, 2-hydrothioimidazole, 2-hydrothio-3-pyridinol, phenylthiol, toluenethiol, thiothioacetophenone, naphthylthiol, naphthylmethylmercaptan, etc.; such hydrosulfide compounds The disulfide compound of the oxide and the halogen compound (for example, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.).

A monomer which can be used for polymerizing a polymer compound having a functional group at the terminal of the polymer, for example, a monomer which constitutes a non-pigment absorbing block as described above can be used as the radical polymerizable single system.

The molecular weight of the terminal modified polymer compound is preferably a weight average molecular weight of 1,000 to 50,000. When the weight average molecular weight is 1,000 or more, the steric repulsion effect which should be obtained as a dispersing agent can be more effectively obtained, and if it is 50,000 or less, the steric effect can be more effectively suppressed, thereby further shortening the absorption of the pigment. Time.

Commercially available products of the terminal modified polymer compound include: SOLSPERSE 3000, 17000, 27000, etc. manufactured by The Lubrizol Co., Ltd.

In the present invention, the dispersant is preferably a graft type polymer compound or a terminal modified type polymer compound. Among them, a graft type polymer compound containing a copolymerized unit derived from a monomer having an organic dye structure or a heterocyclic structure; an organic dye structure, a heterocyclic structure, an acidic group, and a group having a basic nitrogen atom; A terminal modified polymer compound having a urea group or a urethane group as a terminal group.

Further, in the present invention, a dispersion resin may be used as needed. By using a dispersion resin, the dispersion stability and preservability of the treated pigment can be improved.

A specific example of the dispersion resin which can be used in the present invention is preferably a resin having a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amine group or the like.

A polymer having a carboxylic acid in a side chain is disclosed, for example, in Japanese Laid-Open Patent Publication No. 59-44615, Japanese Patent Application Laid-Open No. Hei No. 54-34327, and Japanese Patent Laid-Open No. 58-12577. A methacrylic acid copolymer, acrylic acid as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 59-538 Copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., in addition, also includes carboxylic acid in the side chain Acidic cellulose derivative.

The polymer having a carboxylic acid in a side chain includes, for example, a monomer having a carboxyl group such as (meth)acrylic acid, maleic acid (anhydride), crotonic acid, itaconic acid, or fumaric acid; Styrene, α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate , isobutyl (meth)acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth)acrylate, allyl glycidyl ether, glycidyl ethacrylate, croton Acid glycidyl ether ester, (meth) acrylonitrile chloride, benzyl (meth) acrylate, phenyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylol acrylamide, N,N-Dimethyl acrylamide, N-methylpropenyl morpholine, N,N-dimethylaminoethyl (meth) acrylate, N,N-dimethylaminoethyl propylene A polymer obtained by copolymerizing one or more copolymerization components such as decylamine, maleimide, and N-phenylmethyleneimine. Among them, it is particularly preferable that the (meth)acrylic resin containing at least (meth)acrylic acid or alkyl (meth)acrylate as a structural single system contains (meth)acrylic acid and styrene (methyl) ) Acrylic resin. These acrylic acid copolymerization components are not limited to those described above.

Further, these dispersed resins may also have an ethylenic double bond added to the side chain. By imparting a double bond to the side chain, the photocurability can be improved, and the resolution and adhesion can be further improved.

The method of synthesizing the olefinic double bond is, for example, the method disclosed in Japanese Laid-Open Patent Publication No. 50-34443, Japanese Patent Application Laid-Open No. Hei No. 50-34444, and the like. Specifically, it is a method of reacting a compound having a glycidyl group, an epoxycyclohexyl group, and a (meth)acryl fluorenyl group with a carboxyl group or a hydroxyl group. For example, glycidyl (meth)acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, glycidyl ether (iso)crotonate, (A) a compound such as (3,4-epoxycyclohexyl)methyl acrylate, (meth)acrylic acid chloride, or (meth)acryloyl chloride Further, it is reacted with a resin having a carboxyl group or a hydroxyl group, whereby a resin having a polymer group in a side chain can be obtained.

In particular, a resin obtained by reacting (3,4-epoxycyclohexyl)methyl (meth)acrylate is preferred. Specific compounds of the present invention include, for example, DIANAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (polyurethane acrylate oligomer containing COOH, Diamond Shamrock Co. Ltd.); BISCOAT R-264, KS RESIST (KS resist) 106 (all manufactured by Osaka Organic Chemical Industry Ltd.); CYCLOMER P series, PLACCEL CF200 series ( Both are manufactured by Daicel Chemical Industries, Ltd.; Ebecryl 3800 (manufactured by DAICEL-UCB Co., Ltd. (DAICEL-UCB Company Ltd.)) and the like.

Further, a polymer obtained by a copolymerization reaction of a monomer represented by the following general formula (7) and a monomer having at least an acidic group (which may be mentioned as a copolymerization component as described above) may also be used.

General formula (7)

H ₂ C=CRC(=O)OCR ⁴ R ⁵ C(=R ³ )=CR ² R ¹

In the above formula (7), R represents a hydrogen atom or a methyl group, and R ¹ to R ⁵ each independently represent a group selected from a hydrogen atom, a halogen atom, a cyano group, an alkyl group, and an aryl group. .

Specific examples of the halogen atom include: Cl, Br, I, and the like.

The alkyl group may be linear, branched, or cyclic, and examples thereof include a methyl group, a n-propyl group, an iso-propyl group, a tertiary-butyl group, and the like, and preferably have a carbon number of 1 to 7. By.

The aryl group includes, for example, a phenyl group, a furyl group, a naphthyl group and the like.

In the above, the dispersion resin may be selected from various monomers, and since the solubility and the acid value are controllable, a copolymer of (meth)acrylic acid and (meth)acrylate is preferred. The preferred range of the weight average molecular weight of the dispersion resins as measured by gel permeation chromatography (GPC) is from 1,000 to 80,000, more preferably from 3,000 to 50,000, and most preferably from 3,000 to 20,000. By setting the weight average molecular weight to 80,000 or less, good dispersibility and liquid fluidity can be obtained, and good developability can be obtained.

These dispersion resins are not only used for dispersing the pigment when the pigment dispersion composition is prepared, but also for use in preparing a colored polymerizable composition as described later.

The amount of the dispersant added is preferably from 0.5 to 100% by mass, more preferably from 3 to 100% by mass, particularly preferably from 5 to 80% by mass, based on the pigment.

When the amount of the dispersant added is within this range, sufficient pigment dispersion efficiency can be obtained, but the optimum amount of the dispersant to be added is appropriately adjusted depending on the combination of the pigment, solvent, and the like to be used.

Further, more specifically, in the case of using a polymer dispersant, the amount thereof is preferably from 5% by mass to 100% by mass, more preferably from 10% by mass to 80% by mass based on the pigment. The range of mass %.

Further, in the pigment dispersion composition of the present invention, in addition to the dispersant as described above, a surfactant or the like may be used for the purpose of improving dispersibility.

By using the pigment dispersion composition of the present invention to prepare a colored polymerizable composition and applying it to the production of a color filter, a color filter having high contrast and excellent surface smoothness can be obtained.

[Modulation of pigment dispersion composition]

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

Further, the mixing and dispersing step is preferably composed of a kneading dispersion and a subsequent microdispersion treatment, but kneading dispersion may be omitted.

The method for producing a pigment dispersion composition of the present invention is preferably: first, (A) a diketopyrrolopyrrole pigment is micronized, and when the average primary particle diameter thereof is in the range of 10 nm to 30 nm, the addition is carried out ( B) at least a part of the specific addition amount of the phthalic acid imidoalkylated diketopyrrolopyrrole and (C) the phthalic acid imidoalkylated quinophthalone, preferably the total amount a step of then performing alkylation of (A) diketopyrrolopyrrole pigment, (B) phthalic acid alkylated diketopyrrolopyrrole and (C) phthalic acid imino group The step of dispersing the quinophthalone with an organic solvent. Although (B) phthalic acid imidoalkylated diketopyrrolopyrrole and (C) may be added before the average primary particle diameter of the (A) diketopyrrolopyrrole pigment reaches 10 nm to 30 nm. a part of the phthalic acid imidoalkylation quinophthalone, but more preferably added after the fine primary particle diameter of the (A) diketopyrrolopyrrole pigment reaches 10 nm to 30 nm. The way to add the full amount of a specific amount.

Further, it is preferred to add (B) phthalic acid imidoalkylated diketopyrrolopyrrole and (C) phthalic acid imidoalkylated quinacridone at the beginning of dispersion. The total amount of the specific addition amount, but it is also possible to add a part of the specific addition amount at the beginning of the dispersion. In this case, for example, a residual amount can be added in the middle of the dispersion.

The method of the present invention will be specifically described as follows. For example, premixing (A) diketopyrrolopyrrole pigment with (B) phthalimidoalkylated diketopyrrolopyrrole and (C) phthalic acid imidoalkylation quinoline At least a portion of the specific addition amount of the ketone, and a dispersant which is further used herein as needed. In addition, the mixture previously dispersed by a homogenizer or the like is finely dispersed together with an organic solvent using a medium agitating type dispersing machine such as zirconia beads (for example, DISPERMAT manufactured by GETZMANN GmbH). The pigment dispersion composition of the present invention can then be prepared.

In the present invention, when the microdispersion treatment is carried out using a medium agitation type disperser, it is preferred to use an average particle diameter of 0.01 mm or more and 0.2 for the purpose of dispersing it gently for a short period of time without causing damage to the dispersion. Medium below mm. Here, the "average particle diameter" in the present invention means the circle-equivalent diameter of the medium, and is calculated from the average of the longest diameter and the shortest diameter of 100 media. Specifically, the medium can be photographed and magnified by a stereo microscope, and the particle size is determined from the image thereof.

In the present invention, it is preferred to carry out pre-dispersion to pre-crush the coarse particles before dispersing in a medium of 0.01 mm or more and 0.2 mm or less. Since the pre-dispersion is aimed at pulverizing coarse particles, it is preferred to use a medium having a larger size, that is, a medium having an average particle diameter of 0.3 mm or more and 1.0 mm or less, more preferably 0.4 mm or more. , medium below 1.0mm.

The dispersion time may be set according to the apparatus to be used, the amount of the pigment dispersion composition, and the like, but is usually about 1 to 24 hours.

In addition, detailed details on kneading and dispersion have been disclosed in "Paint Flow and Pigment Dispersion" by TC Patton (published by John Wiley and Sons in 1964), Japanese Patent Laid-Open No. 2007-16206, etc. .

Since the obtained pigment dispersion composition has superior dispersibility and dispersion stability of the diketopyrrolopyrrole pigment, it is suitably used for various uses containing a diketopyrrolopyrrole pigment as a colorant, for example, as described below. Coloring a polymerizable composition or the like.

<Coloring Polymerizable Composition>

The colored polymerizable composition of the present invention comprises the pigment dispersion composition, the photopolymerizable compound, and the photopolymerization initiator of the present invention as described above, and preferably further contains an alkali-soluble resin, and may optionally contain other ingredient.

Hereinafter, each component contained in the colored polymerizable composition of the present invention will be described in detail.

[Pigment Dispersion Composition]

The colored polymerizable composition of the present invention is composed of at least one of the pigment dispersion compositions of the present invention as described above. Detailed details regarding the pigment dispersion composition of the present invention for constituting the colored polymerizable composition are as described above.

The content of the pigment dispersion composition in the colored polymerizable composition of the present invention is preferably from 5 to 70% by mass based on the total solid content (by weight) of the colored polymerizable composition. The quantity is more preferably in the range of 15 to 60% by mass. When the content of the pigment dispersion composition is within this range, it is effective in securing a sufficient color density and having superior color characteristics.

[Photopolymerizable compound]

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

The photopolymerizable compound to be used in the invention may be an addition polymerizable compound having at least one ethylenically unsaturated double bond, and may be selected from at least one, preferably two or more terminal ethylenically unsaturated bonds. Compound. Such compound populations are well known to those skilled in the art and can be used without particular limitation in the present invention. The photopolymerizable compound has, for example, a monomer, a prepolymer, that is, a chemical form of a dimer, a trimer, and an oligomer, or a mixture thereof, and a copolymer of the above.

Examples of the monomer and the copolymer thereof include: an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), or an ester thereof And guanamines, and preferably an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound. Further, it is also suitable to use an unsaturated carboxylic acid ester or decyl amine having a nucleating substituent such as a hydroxyl group, an amine group or a thiol group, and an addition reaction product with a monofunctional or polyfunctional isocyanate or epoxy group. And a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid. Further, an addition reaction product of an unsaturated carboxylic acid ester or a guanamine having an isocyanate group or an electrophilic substituent such as an epoxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol; In addition to this, an unsaturated carboxylic acid ester or decylamine having a detachable substituent such as a halogen group or a tosyloxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol are substituted. The reactants are also suitable. Further, other examples may be changed to a compound group obtained by using an unsaturated carboxylic acid as described above and changing to an unsaturated phosphonic acid, styrene, vinyl ether or the like.

Specific examples of the ester monomer of the aliphatic polyol compound and the unsaturated carboxylic acid include: wherein the acrylate type includes: ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butyl diacrylate. Glycol ester, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene methoxypropyl) Ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl triacrylate Tetraol ester, neopentyl glycol tetraacrylate, di pentaerythritol diacrylate, di pentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentoxide, hexaacrylic acid Sorbitol ester, tris(propylene decyloxyethyl) isocyanurate, polyester acrylate oligomer, triacrylate modified with EO of isocyanuric acid, and the like.

The methacrylates include: tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, Trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimethacrylate, neopentyl dimethacrylate Alcohol ester, neopentyl glycol trimethacrylate, neopentyl glycol tetramethacrylate, di pentaerythritol dimethacrylate, dineopentaerythritol hexamethacrylate, sorbitol trimethyl acrylate Alcohol ester, sorbitan tetramethacrylate, bis[p-(3-methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(methacryl oxime) Oxyethoxy)phenyl]dimethylmethane and the like.

Ikonic acid esters include: ethylene glycol di-conconate, propylene glycol di-conconate, 1,3-butylene glycol di-conconate, 1,4-butanediol di-conconate, Di-methylene glycol ester of ikonic acid, neopentyl glycol di-iconate, tetraiconic acid Pear esters and the like.

The crotonate system includes: ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, neopentyl glycol dicrotonate, tetracrotonic acid Pear esters and the like. "Isocrotonate" includes: ethylene glycol diisocrotonate, neopentyl glycol diisocrotonate, tetraisocrotonate Pear esters and the like. "Maleate" includes: ethylene glycol maleate, triethylene glycol dimaleate, neopentyl glycol maleate, tetrabutylene Diacid Pear esters and the like.

Examples of the other esters are also suitable for use: for example, the aliphatic alcohol-based esters disclosed in Japanese Patent Application Laid-Open No. 51-47334, Japanese Laid-Open Patent Publication No. SHO 57-196231; Japanese Patent Application Laid-Open No. 59-5240, Japanese Patent Application Laid-Open No. 59-5241, Japanese Laid-Open Patent Publication No. 2-226149 The amine group-containing or the like as disclosed in No. 1-156613. In addition to this, the ester system as described above can also be used as a mixture.

Further, specific examples of the "aliphatic polyamine compound and the urethane monomer of an unsaturated carboxylic acid" include: methylene bis-acrylamide, methylene bis-methyl acrylamide, 1,6- Hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methyl acrylamide, di-ethyltriamine propylene amide, hydrazine bis acrylamide, hydrazine Acrylamide and the like. Other preferred examples of the "melamine-based monomer" include those having a cyclohexylene structure as disclosed in Japanese Laid-Open Patent Publication No. 54-21726.

Further, a urethane-based addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also suitably used, and specific examples thereof include, for example, by the Japanese Patent Publication No. 48-41708 The addition of a polyisocyanate compound having two or more isocyanate groups in one molecule to a vinyl group having a hydroxyl group represented by the following formula (a) as disclosed in the publication contains two or more molecules in one molecule. A polymerizable vinyl vinyl urethane compound or the like.

General formula (a)

CH ₂ =C(R)COOCH ₂ CH(R')OH

(However, R and R' represent H or CH ₃ respectively.)

Further, the urethane acrylates disclosed in, for example, Japanese Patent Laid-Open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, and Japanese Patent Application Laid-Open No. Hei No. 2-16765 Or the invention is disclosed in Japanese Patent No. 58-49860, Japanese Patent No. 56-17654, Japanese Patent No. 62-39417, and Japanese Patent Publication No. 62-39418. A urethane compound having an ethylene oxide skeleton is also suitable. In addition, the numerator disclosed in Japanese Laid-Open Patent Publication No. SHO-63-277653, Japanese Patent Application Laid-Open No. Hei No. No. Hei No. No. Hei No. Hei No. Hei No. Hei No. Hei No. When an addition polymerizable compound having an amine structure or a sulfide structure is contained, it is also possible to obtain a photopolymerizable composition having a very excellent photosensitive rate as the case may be.

Other examples include, for example, polyesters disclosed in Japanese Laid-Open Patent Publication No. 48-64183, Japanese Patent Application Laid-Open No. Sho 49-43191, and Japanese Patent Publication No. Sho. A polyfunctional acrylate or methacrylate such as an epoxy acrylate obtained by reacting an acrylate, an epoxy resin and (meth)acrylic acid. In addition, the specific unsaturated compound disclosed in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A vinylphosphonic acid-based compound or the like as disclosed in Japanese Laid-Open Patent Publication No. 2-25493. Further, in some cases, a structure containing a perfluoroalkyl group as disclosed in Japanese Laid-Open Patent Publication No. 61-22048 is also suitable. Further, it can also be used as a photocurable single in the Nippon Secchaku Kyokai Shi [Joufnal of the Adhesion Society of Japan], Vol. 20, No. 7, and pages 300 to 308 (1984). Body and oligomers.

The details of the structure of the addition polymerizable compound, the structure thereof, and the method of use alone or in combination, the amount of addition, and the like can be arbitrarily set with reference to the performance design of the final colored polymerizable composition.

For example, it can be selected according to the viewpoint described below. From the viewpoint of "sensitivity", it is preferred that the content of the unsaturated group per molecule is large, and in most cases, it is preferably a difunctional or higher. In addition, in order to improve the "strength of the cured film", it is preferably a trifunctional or higher functional group, and further has a different functional number and a different polymerizable group (for example, an acrylate, a methacrylate, or a styrene compound). The addition polymerization compound of the vinyl ether compound) is also effective in the method of adjusting both sensitivity and strength.

In addition, the compatibility and dispersibility with other components (for example, a binder polymer such as an alkali-soluble resin, a photopolymerization initiator, and a colorant (pigment)) in the colored polymerizable composition are additive polymerization properties. Selection of Compounds ‧ The method of use is an important factor. For example, by using a low-purity compound or a combination of two or more, it is also possible to obtain an increase in compatibility.

Further, it is also possible to select a specific structure for the purpose of improving adhesion to a substrate or the like. The addition polymerizable compound is preferably used in an amount of from 5 to 70% by mass, more preferably from 10 to 60% by mass, based on the nonvolatile component in the colored polymerizable composition. Further, these may be used alone or in combination of two or more. The method of using the addition polymerizable compound can arbitrarily select an appropriate structure, a blending amount, and the like from the viewpoints of the degree of polymerization resistance of oxygen, the degree of resolution, the degree of fogging, the change in refractive index, the surface tackiness, and the like. The amount added.

[Photopolymerization initiator]

The photopolymerization initiator constituting the colored polymerizable composition of the present invention includes, for example, a halomethyloxadiazole as disclosed in Japanese Laid-Open Patent Publication No. 60-3626; Halogenated methyl-s-trinitrogen as disclosed in Japanese Laid-Open Patent Publication No. 59-12881, Japanese Laid-Open Patent Publication No. SHO-53-133428 An aromatic halogen compound; an aromatic such as a ketal, an acetal, or a benzoin alkyl ether as disclosed in each of the specification of the U.S. Patent No. 4,318,791, the European Patent Application No. EP-88050 a carbonyl compound; an aromatic ketone compound of a benzophenone or the like as disclosed in the specification of U.S. Patent No. 4,199,420; (sulfur) as disclosed in the specification of French Patent No. Fr-2456741 a ketone or an acridine compound; a compound such as a coumarin or a horn phenodimer as disclosed in Japanese Laid-Open Patent Publication No. 10-62986; Japanese Patent Publication No. 8-015521 An organoboron complex or the like.

The photopolymerization initiator in the present invention is preferably an acetophenone-based, a ketal-based, a benzophenone-based, a benzoin-based, or a benzamidine-based system. Ketone system, active halogen compound (trinitrogen) A system, an oxadiazole system, a coumarin system, an acridine system, a biimidazole system, an oxime ester system, and the like.

The acetophenone-based photopolymerization initiator as described above includes, for example, preferably 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2- Methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl -Phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-tolyl-2-dimethylamine 1-(4-morpholinylphenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one Wait.

The ketal-based photopolymerization initiator as described above includes, for example, benzyldimethylketal, benzyl-β-methoxyethylacetal, and the like.

The benzophenone-based photopolymerization initiator as described above includes, for example, preferably benzophenone, 4,4'-(bisdimethylamino)benzophenone, 4,4'- (Diethylamino) benzophenone, 4,4'-dichlorobenzophenone.

The benzoin-based or benzamidine-based photopolymerization initiator as described above includes, for example, benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, Methyl o-benzhydrylbenzoate and the like.

As mentioned above The ketone photopolymerization initiator includes, for example, preferably diethyl oxysulfide Diisopropyl oxysulfide Isopropyl oxysulfide Chlorooxysulfide Wait.

Active halogen compound (trinitrogen) as described above System, oxadiazole system, coumarin system) includes, for example, preferably 2,4-bis(trichloromethyl)-6-p-methoxyphenyl-s-triazo 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazole , 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3-butadienyl-s-triazole 2,4-bis(trichloromethyl)-6-biphenyl-s-triazole , 2,4-bis(trichloromethyl)-6-(p-methylbiphenyl)-s-triazole , p-hydroxyethoxystyryl-2,6-di(trichloromethyl)-s-triazole Methoxystyryl-2,6-di(trichloromethyl)-s-triazole , 3,4-dimethoxystyryl-2,6-di(trichloromethyl)-s-triazole 4-benzooxetan-2,6-di(trichloromethyl)-s-triazole , 4-(o-bromo-p-N,N-bis(ethoxycarbonylamino)-phenyl)-2,6-di(chloromethyl)-s-triazole , 4-(p-N,N-bis(ethoxycarbonylamino)-phenyl)-2,6-di(chloromethyl)-s-triazole , 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(naphthoquinone-1-yl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-styryl)styryl-1 , 3,4-oxadiazole, 3-methyl-5-amino-((s-triazo) -2-yl)amino)-3-phenylcoumarin, 3-chloro-5-diethylamino-((s-trinitrogen) -2-yl)amino)-3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-trinitrogen) -2-yl)amino)-3-phenylcoumarin.

The acridine photopolymerization initiator as described above includes, for example, preferably 9-phenyl acridine, 1,7-bis(9-acridinyl)heptane or the like.

The bisimidazole-based photopolymerization initiator as described above includes, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2-(o-A- Oxyphenyl)-4,5-diphenylimidazolyl dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazolyl dimer, and the like.

In addition to the above, it also includes: 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, o-benzhydryl-4'-(benzohydrothiol) Benzylmercapto-hexyl-ketooxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphine oxide, hexafluorophosphonyl-trialkylphenyl phosphonium salt, and the like.

The present invention is not limited to the photopolymerization initiator as described above, and other conventional ones may be used. For example, a vicinal polyketolaldonyl compound as disclosed in the specification of U.S. Patent No. 2,367,660; the alpha-carbonyl compound disclosed in the specification of U.S. Patent Nos. 2,367,661 and 2,367,670; The affixed ethers disclosed in the specification of U.S. Patent No. 2,448,828; the α-hydrocarbon-substituted aromatic cryptic compound disclosed in the specification of U.S. Patent No. 2,722,512; U.S. Patent No. 3,046,127 And a combination of a triallyl imidazole dimer/p-aminophenyl ketone as disclosed in the specification of U.S. Patent No. 3,549,367; The benzothiazole compound/trihalomethyl-s-trinitrogen disclosed in Japanese Patent Publication No. 51-48516 Compounds; in JCS Perkin II (1979), pp. 1,653 to 1,660, JCS Perkin II (1979), pp. 156-162, "Journal of Photopolymer Science and Technology" (1995), pp. 202-232, Japanese Invention Patent An oxime ester compound or the like as disclosed in Japanese Laid-Open Patent Publication No. 2000-66385.

Further, these photopolymerization initiators may also be used in combination.

The content of the photopolymerization initiator in the coloring polymerizable composition is preferably from 0.1 to 10.0% by mass, more preferably from 0.5 to 5.0% by mass, based on the total solid content of the composition. When the content of the photopolymerization initiator is within this range, the polymerization reaction can be smoothly carried out to form a film having good strength.

[alkali soluble resin]

The colored polymerizable composition of the present invention preferably contains an alkali-soluble resin. When the alkali-soluble resin is contained in the colored polymerizable composition, when the colored polymerizable composition is applied to a pattern formed by photolithography, the pattern formation property can be further improved.

The alkali-soluble resin is a linear organic high molecular polymer, and may have at least one base which promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene-based copolymer as a main chain) (for example, An alkali-soluble resin of a carboxyl group, a phosphoric acid group, a sulfonic acid group or the like is appropriately selected. Among these, those which are soluble in an organic solvent and which can be developed by a weak alkali aqueous solution are more preferable.

The production of the alkali-soluble resin is, for example, a method according to a conventional radical polymerization method. The polymerization conditions in the case of producing an alkali-soluble resin by a radical polymerization method, such as the temperature, the pressure, the kind and amount of the radical initiator, the kind of the solvent, and the like, can be easily set by those skilled in the art, and can also be experimentally based on the experiment. To set the conditions.

The linear organic polymer is preferably a polymer having a carboxylic acid in a side chain. For example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent No. 54-34327, Japanese Invention Patent No. 58-12577, Japanese Invention Patent No. 54-25957, Japanese Invention The methacrylic acid copolymer, the acrylic acid copolymer, the itaconic acid copolymer, and the crotonic acid disclosed in the publications of Japanese Laid-Open Patent Publication No. 59-71048 a copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, or the like; and an acidic cellulose derivative having a carboxylic acid in a side chain and a polymer addition anhydride having a hydroxyl group; Further, a polymer having a (meth) acrylonitrile group in a side chain is also exemplified as a preferred example.

Among these, it is particularly preferably a benzyl (meth)acrylate/(meth)acrylic acid copolymer, or a benzyl (meth)acrylate/(meth)acrylic acid/other monomer. A multicomponent copolymer composed of.

Others, which are obtained by copolymerization with 2-hydroxyethyl methacrylate, and the like are also useful examples.

In addition to the above, other examples include: 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/methacrylic acid as disclosed in Japanese Laid-Open Patent Publication No. Hei. Benzene/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, methyl 2-hydroxyethyl acrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methacrylic acid benzoate Ester/methacrylic acid copolymer and the like.

The alkali-soluble resin which is particularly suitable for use in the present invention is a copolymer of (meth)acrylic acid and other monomers copolymerizable therewith. Here, the so-called (meth)acrylic acid is a generic term for combining acrylic acid and methacrylic acid, and is also the same as the general term of (meth)acrylate-based acrylate and methacrylate.

Other single systems copolymerizable with (meth)acrylic acid include: alkyl (meth)acrylate, aryl (meth)acrylate, vinyl compounds, and the like. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

Specific examples of the alkyl (meth)acrylate and the aryl (meth)acrylate as described above include: methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid Ester, butyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate Benzyl (meth)acrylate, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like.

Further, the "vinyl compound" as described above includes, for example, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrole. Pyridone, tetrahydrofuran methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH ₂ =CR ¹ R ² , CH ₂ =C(R ¹ )(COOR ³ ) [here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ³ represents an alkyl group having 1 to 8 carbon atoms or a carbon number of 6 to 12 aralkyl groups. ]Wait.

These other single systems which can be copolymerized may be used alone or in combination of two or more.

Preferred other copolymerizable systems are selected from the group consisting of CH ₂ =CR ¹ R ² , CH ₂ =C(R ¹ )(COOR ³ ), phenyl (meth)acrylate, benzyl (meth)acrylate And at least one of ethylene, and particularly preferably CH ₂ =CR ¹ R ² , and/or CH ₂ =C(R ¹ )(COOR ³ ).

The content of the alkali-soluble resin in the colored polymerizable composition is preferably from 1 to 30% by mass, more preferably from 1 to 20% by mass, particularly preferably from 2 to 15% by mass, based on the total solid content of the composition.

[solvent]

In general, the colored polymerizable composition of the present invention can be suitably prepared by using each component as described above together with a solvent.

Solvents which may be used include: esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, butyric acid Propyl ester, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate Ethyl methoxy decanoate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. - alkyl oxypropionates; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methyl Propyl oxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropanoate, 2-oxy-2-methyl Ethyl propionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, acetone Acid propyl ester, methyl acetoxyacetate, ethyl acetoxyacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.; ethers, for example, diethylene glycol dimethyl Ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl sarbutazone acetate, ethyl sarbutazone acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Ether, diethylene glycol monobutyl ether, ethyl hexyl acetate, butyl hexyl acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc.; ketones For example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone or the like; aromatic hydrocarbons such as toluene, xylene (oxime) and the like.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl sarbutazone acetate, ethyl lactate, diethylene glycol dimethyl ether, and acetic acid are preferred. - n-butyl ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl hexyl acetate, butyl hexyl acetate, propylene glycol methyl ether acetate, and the like.

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

[Other ingredients]

The colored polymerizable composition of the present invention may contain, in addition to a sensitizing dye, an epoxy resin, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, a filler, and the like as needed. Various additives such as a polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent other than the alkali-soluble resin.

[sensitized pigment]

The colored polymerizable composition of the present invention may be added with a sensitizing dye as needed. The sensitizing dye can accelerate the radical generating reaction of the photopolymerization initiator or the like by the exposure of the wavelength which the sensitizing dye can absorb, or the polymerization reaction of the photopolymerizable compound as described above.

Such sensitizing dyes include: conventional spectral sensitizing dyes or dyes, or dyes or pigments that absorb light and interact with photopolymerization initiators.

(Spectral sensitizing dye or dye)

Preferred spectroscopic sensitizing dyes or dyes which can be used as the sensitizing dye of the present invention include: polynuclear aromatics (for example, ruthenium, osmium, and terphenyl); Classes (eg, fluorescein, blush, red algae, rose red B, rose Bengal); cynins (eg, thiaquinoline blue, oxaquinoline blue); merocyanoids (eg, anthocyanins, carbonyl anthocyanins); thia Classes (eg, thiazide, methylene blue, toluidine blue); acridines (eg, acridine orange, chloroflavon, acridine flavin); anthracyclines (eg, anthracycline, metal phthalocyanin) Porphyrins (eg, tetraphenylporphyrins, porphyrins substituted with a central metal); chlorophylls (eg, chlorophyll, chlorophyllin, chlorophyll substituted by a central metal); metal complexes (eg, as follows) Compounds); terpenoids (for example, quinones); horned sharks (for example, horn sharks) and the like.

More preferred examples of the spectrally sensitizing dye or dye include those described below.

The cationic dye disclosed in Japanese Laid-Open Patent Publication No. 62-143044; the quinoxaline sulfonium salt disclosed in Japanese Laid-Open Patent Publication No. 59-24147; The novel methylene blue compound disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 64-56767; Benzoin The acridines disclosed in Japanese Laid-Open Patent Publication No. Hei No. 2-226148 and Japanese Patent Application Laid-Open No. Hei No. 2-226149; The sulfonium salt described in Japanese Laid-Open Patent Publication No. SHO-46-42363, the benzofuran dye disclosed in Japanese Laid-Open Patent Publication No. 2-63053; A conjugated ketone dye in the Japanese Patent Laid-Open Publication No. Hei No. 2- 216 154, and a pigment disclosed in Japanese Laid-Open Patent Publication No. Hei No. 57-10660 The azo- cinna-based derivative described in Japanese Laid-Open Patent Publication No. Hei. No. 2-30321, and the Sainen-based pigment disclosed in Japanese Laid-Open Patent Publication No. 1-287105; Japanese Laid-Open Patent Publication No. 62-31844, Japanese Laid-Open Patent Publication No. 62-31848, and Japanese Laid-Open Patent Publication No. 62-143043 Amino styrene ketone as disclosed in Japanese Laid-Open Patent Publication No. 59-28325; a pigment disclosed in Japanese Laid-Open Patent Publication No. 2-179643; Japanese Patent No. An anthocyanin pigment disclosed in Japanese Laid-Open Patent Publication No. 2-244050; an anthocyanin pigment disclosed in Japanese Laid-Open Patent Publication No. 59-28326; An anthocyanin pigment, which is disclosed in Japanese Laid-Open Patent Publication No. 8-129257, and a Japanese Patent Publication No. 8-334897. The benzopyran-based pigment disclosed in the publication.

(Colors with a maximum absorption wavelength from 350 nm to 450 nm)

Other preferred modes of sensitizing dyes include those which belong to the following group of compounds and which have a maximum absorption wavelength at 350 nm to 450 nm.

For example, polynuclear aromatics (eg, ruthenium, osmium, and extended triphenyl); Classes (eg, fluorescein, blush, red algae, rose red B, rose Bengal); cynins (eg, thiaquinoline blue, oxaquinoline blue); merocyanoids (eg, anthocyanins, carbonyl anthocyanins); thia Classes (eg, thiazide, methylene blue, toluidine blue); acridines (eg, acridine orange, chloroflavin, acridine flavin); terpenoids (eg, guanidine); horned sharks (eg, , horn shark 鎓).

More preferred examples of the sensitizing dye include compounds represented by the following general formulae (XIV) to (XVIII).

[In the general formula (XIV), A ¹ represents a sulfur atom or -NR ⁶⁰ -, R ⁶⁰ represents an alkyl group or an aryl group, and L ⁰¹ represents a basic nucleus which forms a pigment together with an adjacent A ¹ and a carbon atom. The non-metal atomic group of (basic nucleus), R ⁶¹ and R ⁶² each independently represent a hydrogen atom or a monovalent non-metal atomic group, and R ⁶¹ and R ⁶² may be bonded to each other to form an acid nucleus of the pigment. The W system represents an oxygen atom or a sulfur atom. ]

Preferred specific examples of the compound represented by the formula (XIV) are shown below as [(A-1) to (A-5)].

[In the general formula (XV), Ar ¹ and Ar ² each independently represent an aryl group, and they are linked together by a bond of -L ⁰² -. Here, -L ⁰² - represents -O- or -S-. Further, the W system is synonymous with those shown in the general formula (XIV). ]

Preferred examples of the compound represented by the formula (XV) include [(A-6) to (A-8)] shown below.

[In the general formula (XVI), A ² represents a sulfur atom or -NR ⁶⁹ -, and L ⁰³ represents a non-metal atomic group which forms a basic nucleus of a dye together with adjacent A ² and a carbon atom, R ⁶³ , R ⁶⁴ And R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and R ⁶⁸ each independently represent a group of a monovalent non-metal atomic group, and R ⁶⁹ represents an alkyl group or an aryl group. ]

Preferred examples of the compound represented by the formula (XVI) include: [(A-9) to (A-11)] shown below.

[In the general formula (XVII), A ³ and A ⁴ each independently represent -S-, or -NR ⁷³ -, R ⁷³ is a substituted or unsubstituted alkyl group, or substituted or unsubstituted The aryl group, L ⁰⁴ and L ⁰⁵ each independently represent a non-metal atomic group which forms a basic nucleus of a pigment together with adjacent A ³ , A ⁴ and a carbon atom, and R ⁷¹ and R ⁷² each independently represent a valence Metal radicals may also be bonded to each other to form an aliphatic or aromatic ring. ]

Preferred examples of the compound represented by the formula (XVII) include: [(A-12) to (A-15)] shown below.

Further, other preferred sensitizing dyes which can be used in the present invention include those represented by the following formula (XVIII).

[In the formula (XVIII), A ⁵ represents an optionally ring or heterocyclic ring which may have a substituent, and X represents an oxygen atom, a sulfur atom, or -N(R ⁷⁴ ) -, Y represents an oxygen atom, a sulfur atom, or =N(R ⁷⁴ ). R ⁷⁴ , R ⁷⁵ and R ⁷⁶ each independently represent a hydrogen atom or a monovalent non-metal atomic group, and A ⁵ and R ⁷⁴ , R ⁷⁵ and R ⁷⁶ may each bond to each other to form an aliphatic or aromatic group. Ring. ]

Here, when R ⁷⁴ , R ⁷⁵ and R ⁷⁶ represent a monovalent non-metal atomic group, it preferably represents a substituted or unsubstituted alkyl or aryl group.

Next, preferred examples of R ⁷⁴ , R ⁷⁵ , and R ⁷⁶ are specifically described below. Examples of preferred alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include methyl group, ethyl group, and propyl group. Butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, thirteen, hexadecanyl, octadecyl, icosyl, isopropyl, isobutyl Base, secondary-butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl 2, norbornene base. Among these, a linear chain having a carbon number of 1 to 12, a branched chain having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable.

The substituent of the substituted alkyl group is a group of a monovalent non-metal atomic group other than a hydrogen atom, and preferred examples thereof include a halogen atom (-F, -Br, -Cl, -I), Hydroxy, alkoxy, aryloxy, thiol, alkylthio, arylthio, alkyldithio, aryldithio, amine, N-alkylamine, N,N- Dialkylamino, N-arylamino, N,N-diarylamine, N-alkyl-N-arylamine, decyloxy, aminemethyloxy, N-alkylamine Methoxy, N-arylamine, methoxy, N,N-dialkylamine, methoxy, N,N-diarylamine, methoxy, N-alkyl-N-aryl Aminomethyloxy, alkylsulfonyloxy, arylsulfonyloxy, sulfonylthio, decylamino, N-alkyldecylamino, N-aryldecylamino, ureido, N- Alkyl urea group, N,N-dialkylureido group, N-arylureido group, N,N-diarylureido group, N-alkyl-N-arylureido group, N-alkyl-N -alkylureido, N,N-dialkyl-N-alkylureido, N,N-dialkyl-N-arylureido, N-aryl-N-alkylureido, N- Aryl-N-arylureido, N,N-diaryl-N-alkylureido, N,N-diaryl-N-arylureido, N-alkyl-N-aryl-N-alkylureido, N-alkyl-N-aryl-N-arylureido, alkoxycarbonylamino, aryloxycarbonylamino, N- Alkyl-N-alkoxycarbonylamino, N-alkyl-N-aryloxycarbonylamino, N-aryl-N-alkoxycarbonylamino, N-aryl-N-aryloxy Carbonylamino, carbenyl, decyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, N-alkylamine, fluorenyl, N,N-dialkylamine, fluorenyl, N -Arylamine, mercapto, N,N-diarylamine, N-alkyl-N-arylamine, alkyl sulfinyl, arylsulfinyl, alkyl a sulfonyl group, an arylsulfonyl group, a sulfonic acid group (-SO ₃ H) and a conjugated base thereof (hereinafter, referred to as a sulfonate group), an alkoxysulfonyl group, an aryloxysulfonate group Amino, sulfinyl, N-alkylamine sulfinyl, N,N-dialkylamine sulfinyl, N-arylamine sulfinyl, N,N-diarylamine Sulfonyl, N-alkyl-N-arylamine sulfinyl, amine sulfonyl, N-alkylamine sulfonyl, N,N-dialkylamine sulfonyl, N-arylamine Sulfonyl, N,N-diarylaminesulfonyl, N-alkyl-N-arylaminesulfonyl, phosphonic acid (- PO ₃ H ₂ ) and its conjugated base (hereinafter referred to as phosphonate group), dialkylphosphonic acid group (-PO ₃ (alkyl) ₂ ), diarylphosphonic acid group (-PO) ₃ (aryl) ₂ ), alkyl arylphosphonic acid group (-PO ₃ (alkyl) (aryl)), monoalkylphosphonic acid group (-PO ₃ H (alkyl)) and conjugate thereof a base (hereinafter, referred to as "alkylphosphonate"), an arylphosphonic acid group (-PO ₃ H(aryl)), and a conjugated base thereof (hereinafter, referred to as an aryl group) Phosphonate), phosphonic acidoxy (-OPO ₃ H ₂ ) and its conjugated base (hereinafter referred to as phosphonateoxy), dialkylphosphonic acidoxy (-OPO ₃₎ (alkyl) ₂ ), diarylphosphonic acid oxy (-OPO ₃ (aryl) ₂ ), alkyl arylphosphonic acid oxy (-OPO ₃ (alkyl) (aryl)), one An alkylphosphonic acid oxy group (-OPO ₃ H(alkyl)) and a conjugated base thereof (hereinafter, referred to as an alkylphosphonate oxy group), an arylphosphonic acid oxy group (- OPO ₃ H(aryl)) and its conjugated base (hereinafter, referred to as arylphosphonateoxy), cyano, nitro, aryl, heteroaryl, alkenyl, alkynyl,矽alkyl.

Among these substituents, specific examples of the alkyl group include an alkyl group as described above, and these systems may further have a substituent.

Further, specific examples of the aryl group in the substituent of the substituted alkyl group as described above include: a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a fluorenyl group, Base, cumyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, ethoxylated phenyl, Benzyloxyphenyl, methylthiophenyl, phenylthiophenyl, methylaminophenyl, dimethylaminophenyl, ethionylphenyl, carboxyphenyl, A Oxycarbonylcarbonylphenyl, ethoxyphenylcarbonyl, phenoxycarbonylphenyl, N-phenylamine-nonylphenyl, phenyl, cyanophenyl, sulfophenyl, sulfonate phenyl , phosphonic phenyl, phosphonate phenyl and the like.

The heteroaryl group in the substituent of the substituted alkyl group as described above is a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms, particularly preferably a hetero group. Examples of the heteroaryl ring in the aryl group include, for example, thiophene, thianthrene, furan, piper, isobenzofuran, Chromene, Brown , pyrrole, pyrazole, isothiazole, isoxazole, pyridyl Pyrimidine 吲哚 Heterogeneous , indole, carbazole, anthracene, quinine Isoquinoline , naphthyridine, quinazoline, Cinnoline, acridine, carbazole, porphyrin, phenanthrene, acridine, Pyridine (perimidine), phenanthroline, anthracene Arsenic (phenarsazine), furazan, etc.; and these may be further benzo ring-condensed or may have a substituent.

Further, examples of the "alkenyl group" in the "substituent of the substituted alkyl group" as described above include: vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group (cinnamyl group), 2- Examples of the "alkynyl group" in the "substituent of the substituted alkyl group" as described above include: an ethynyl group, a 1-propynyl group, a 1-butynyl group, Trimethyldecyl ethynyl and the like. The G ¹ system in the fluorenyl group (G ¹ CO-) includes a hydrogen atom, and an alkyl group or an aryl group as described above. Further, in the "substituted substituent of the substituted alkyl group", a halogen atom (-F, -Br, -Cl, -I), an alkoxy group, an aryloxy group, an alkylthio group, or an aromatic group is further more preferable. Thiothio group, N-alkylamino group, N,N-dialkylamino group, decyloxy group, N-alkylamine methyl methoxy group, N-arylamine methyl methoxy group, decylamino group, Mercapto, fluorenyl, carboxy, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, N-alkylamine, fluorenyl, N,N-dialkylamine, fluorenyl, N-arylamine Mercapto, N-alkyl-N-arylamine, mercapto, sulfonate, sulfonyl, N-alkylamine sulfonyl, N,N-dialkylamine sulfonate , N-arylamine sulfonyl, N-alkyl-N-arylamine sulfonyl, phosphonic acid, phosphonate, dialkylphosphonic acid, diarylphosphonic acid, monoalkyl Phosphonic acid group, alkylphosphonic acid group, monoarylphosphonic acid group, arylphosphonate group, phosphonic acidoxy group, phosphonic acid group oxy group, aryl group, alkenyl group.

Specific examples of the preferred substituted alkyl group as R ⁷⁴ , R ⁷⁵ or R ⁷⁶ obtained by combining the substituent and the alkylene group as described above include: chloromethyl, bromomethyl, 2- Chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, tolylmethyl, B Aminoethyl, diethylaminopropyl, morpholinylpropyl, ethoxymethyloxy, benzhydryloxymethyl, N-cyclohexylaminemethyloxyethyl, N-benzene Base amine methyl methoxyethyl, ethionylaminoethyl, N-methylbenzhydrylaminopropyl, 2-sided oxyethyl, 2-sided oxypropyl, carboxypropyl, Methoxycarbonylethyl, allyloxycarbonylbutyl, chlorophenoxycarbonylmethyl, aminemethylmethylmethyl, N-methylamine methyl decyl, N,N-dipropylamine Mercaptomethyl, N-(methoxyphenyl)amine, mercaptoethyl, N-methyl-N-(sulfonylphenyl)amine,carboxymethyl, sulfonylbutyl, sulfonic acid Root propyl, sulfonyl butyl, acesulfonyl butyl, N-ethylamine sulfonylmethyl, N,N-dipropylamine sulfonylpropyl , N-tolylamine sulfonylpropyl, N-methyl-N-(phosphonophenyl)amine sulfonyl octyl, phosphonic butyl, phosphonic hexyl, diethylphosphonic acid Butyl, diphenylphosphonylpropyl, methylphosphonic butyl, methylphosphonic butyl, tolylphosphonic hexyl, tolylphosphonate hexyl, phosphonicoxypropyl, Phosphonate oxybutyl, benzyl, phenethyl, α-methylbenzyl, 1-methyl-1-phenylethyl, p-methylbenzyl, cinnamyl (cinnamate) , allyl, 1-propenylmethyl, 2-butenyl, 2-methylallyl, 2-methylpropenylmethyl, 2-propynyl, 2-butynyl, 3-butene Alkynyl and the like.

Specific examples of the preferred aryl group as R ⁷⁴ , R ⁷⁵ or R ⁷⁶ include a condensed ring formed by one to three benzene rings, and a benzene ring and a 5-membered unsaturated ring. a condensed ring, and specific examples thereof include: a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, an ethane naphthyl group (an acenaphthenyl group), a fluorenyl group; among these, More preferred is phenyl or naphthyl.

Specific examples of the preferred substituted aryl group as R ⁷⁴ , R ⁷⁵ or R ⁷⁶ include: a substituent having a monovalent non-metal atom group (other than a hydrogen atom) as a substituent on a carbon atom forming a ring The aryl group as described above. Examples of preferred substituents include alkyl groups as described above, substituted alkyl groups, and those exemplified above with respect to substituted alkyl groups. Preferred specific examples of such substituted aryl groups include: biphenyl, tolyl, fluorenyl, Base, cumyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl , allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylphenylthio, ethylaminophenyl, diethylaminophenyl, morpholinylphenyl, acetamidine Oxyphenyl, benzyl methoxy phenyl, N-cyclohexylamine methoxy phenyl, N-phenylamine methyl phenyl phenyl, ethyl hydrazino phenyl, N-methyl benzene Mercaptophenyl phenyl, carboxyphenyl, methoxycarbonylphenyl, allyloxycarbonylphenyl, chlorophenoxycarbonylphenyl, aminemethantyl phenyl, N-methylamine fluorenyl Phenyl, N,N-dipropylamine,carbenylphenyl, N-(methoxyphenyl)amine,carbenylphenyl, N-methyl-N-(sulfophenyl)amine,formamidine Phenylphenyl, sulfonylphenyl, sulfonylphenyl, sulfonylphenyl, N-ethylaminesulfonylphenyl, N,N-dipropylaminesulfonylphenyl, N- Tolylamine sulfonylphenyl, N-methyl-N-(phosphonophenyl)amine sulfonylphenyl, phosphonic phenyl, phosphonate phenyl, diethylphosphonic acid , diphenylphosphonic phenyl, methylphosphonic phenyl, methylphosphonic phenyl, tolylphosphonic phenyl, tolylphosphonyl phenyl, allyl phenyl, 1 - allylphenylmethyl, 2-butenylphenyl, 2-methylallylphenyl, 2-methylpropenylphenyl, 2-propynylphenyl, 2-butynylphenyl , 3-butynylphenyl and the like.

Further, further more preferred examples of R ⁷⁵ and R ⁷⁶ are substituted or unsubstituted alkyl groups. Further, further preferred examples of R ⁷⁴ are substituted or unsubstituted aryl groups. Although the reason is not clear, it is presumed that due to such substituents, the interaction between the electron-excited state due to light absorption and the initiator compound is particularly enhanced, and the initiator compound is raised to generate free radicals, acids or The reason for the efficiency of the base.

Next, A ⁵ in the general formula (XVIII) will be described. A ⁵ represents an aromatic ring or a heterocyclic ring which may have a substituent, and specific examples of the aromatic ring or heterocyclic ring which may have a substituent include R ⁷⁴ and R ⁷⁵ which have been in the formula (XVIII), Or the ones exemplified in the foregoing description of R ⁷⁶ are the same.

Among them, a preferred A ⁵ group includes an aryl group having an alkoxy group, an alkylthio group, and an amine group, and a particularly preferred A ⁵ group includes an aryl group having an amine group.

Next, the Y in the general formula (XVIII) will be described. Y is a non-metal atom or a non-metal atom group directly bonded to the nitrogen-containing hetero ring in the formula (XVIII) via a double bond, and more specifically, represents an oxygen atom, a sulfur atom, or =N (R ⁷⁴ ). Here, R ⁷⁴ represents a hydrogen atom or a monovalent non-metal atomic group.

Further, X in the formula (XVIII) represents an oxygen atom, a sulfur atom, or -N(R ⁷⁴ )-. The R ⁷⁴ system is synonymous with the case of Y.

Next, a preferred mode of the compound represented by the formula (XVIII) used in the present invention will be described by a compound represented by the formula (XVIII-1).

In the above formula (XVIII-1), A ⁵ represents an aromatic ring or a heterocyclic ring which may have a substituent, and X represents an oxygen atom, a sulfur atom, or -N(R ⁷⁴ )-. R ⁷⁴ , R ⁷⁷ and R ⁷⁸ are each independently a hydrogen atom or a monovalent non-metal atomic group, and A ⁵ and R ⁷⁴ , R ⁷⁷ and R ⁷⁸ may each bond to each other to form an aliphatic or aromatic group. Ring. The Ar system represents "an aromatic ring or a heterocyclic ring having a substituent". However, the sum of the substituents on the Ar skeleton, Hammett's substituent constant, must be greater than zero. The sum of the so-called Harmant values herein is greater than 0 means that it may be one having a substituent and the Hammant value of the substituent is greater than 0, or having a plurality of substituents and having such substituents The sum of the Mante values is greater than zero.

In the formula (XVIII-1), A ⁵ and R ⁷⁴ are synonymous with the formula (XVIII), and R ⁷⁷ is the same as R ⁷⁵ and R ⁷⁸ in the formula (XVIII). R ^{76 is} synonymous in XVIII). Further, the Ar group represents an aromatic ring or a heterocyclic ring having a substituent, and is synonymous with A ⁵ in the formula (XVIII).

However, the substituent which can be introduced into Ar in the formula (XVIII-1) must have a total of the Harmant value of 0 or more, and examples of such substituents include a trifluoromethyl group, a carbonyl group, An ester group, a halogen atom, a nitro group, a cyano group, an anthranylene group, a decylamino group, a carboxyl group or the like. The Hammant values of these substituents are as follows: trifluoromethyl (-CF ₃ , m: 0.43, p: 0.54), carbonyl (for example, -COH, m: 0.36, p: 0.43), ester group ( -COOCH ₃ , m: 0.37, p: 0.45), halogen atoms (eg Cl, m: 0.37, p: 0.23), cyano (-CN, m: 0.56, p: 0.66), fluorenylene (eg -SOCH) ₃ , m: 0.52, p: 0.45), amidino group (for example, -NHCOCH ₃ , m: 0.21, p: 0.00), carboxyl group (-COOH, m: 0.37, p: 0.45), and the like. The parentheses represent the introduction position of the substituent in the aryl skeleton, and the Hammant value thereof, for example, (m: 0.50) indicates the Hammant value when the substituent is introduced into the meta position. It is 0.50. Among them, preferred examples of Ar include a phenyl group having a substituent, and preferred substituents on the Ar skeleton include an ester group and a cyano group. The position of substitution is particularly preferred as the ortho position on the Ar skeleton.

Hereinafter, preferred specific examples of the sensitizing dye represented by the general formula (XVIII) of the present invention [exemplified compound (F1) to exemplified compound (F56)] will be shown, but the present invention is not limited thereto. Wait.

[化41]

In the sensitizing dye as described above, it is preferably a compound represented by the formula (XVIII) as shown in the above, from the viewpoint of deep curing property.

With regard to the sensitizing dye as described above, various chemical modifications described below can be carried out for the purpose of improving the properties of the colored polymerizable composition of the present invention. For example, a sensitizing dye and an addition polymerizable compound structure (for example, an acrylonitrile group or a methacryl oxime group) are bonded by a covalent bond, an ionic bond, a hydrogen bond or the like, whereby cross-linking hardening can be obtained. The film is made to have high strength, or to enhance the unnecessary precipitation effect of the pigment from the crosslinked cured film.

The content of the sensitizing dye is preferably from 0.01 to 20% by mass, more preferably from 0.01 to 10% by mass, still more preferably from 0.1 to 5% by mass, based on the total solid content of the colored polymerizable composition.

If the content of the sensitizing dye is in this range, the exposure wavelength for the ultrahigh pressure mercury lamp can be obtained with high sensitivity, and the curability of lower layer portion can be obtained while developing margin ), pattern formation is also preferred.

(epoxy resin)

The colored polymerizable composition of the present invention can use an epoxy resin as a thermal polymerization component in order to increase the strength of the formed coating film.

The epoxy resin is a compound having two or more epoxy groups in a molecule such as a bisphenol A type, a cresol novolac type, a biphenyl type, or an alicyclic epoxy compound.

For example, bisphenol A type includes: EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. (The above is manufactured by Tohto Kasei Co., Ltd.); DENACOL EX-1101, EX-1102, EX-1103, etc. (The above is manufactured by Nagase ChemteX Corporation) ; PLACCEL GL-61, GL-62, G101, G102 (above is manufactured by DAICEL Chemical Industry Co., Ltd.); in addition, other includes: bisphenol F type and bisphenol S type similar to these. Further, an epoxy acrylate such as Ebecfyl 3700, 3701, 600 (the above is manufactured by DAICEL-UCB Co., Ltd.) can also be used.

The cresol novolak type includes: EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (The above is manufactured by Dongdu Chemical Co., Ltd.); DENACOL EM-125, etc. Made by Chemical Industry Co., Ltd.). The biphenyl type includes 3,5,3',5'-tetramethyl-4,4'-diglycidylbiphenyl and the like. The alicyclic epoxy compound includes: CELLOXIDE 2021, 2081, 2083, 2085, EPOLEAD GT-301, GT-302, GT-401, GT-403, EHPE-3150 (the above is manufactured by DAICEL Chemical Industry Co., Ltd.); SUNTOHTO ST-3000, ST-4000, ST-5080, ST-5100, etc. (above is manufactured by Dongdu Chemical Co., Ltd.); Epiclon 430, 673, 695, 850S, 4032 (above is Dainippon Ink Chemical Industry Co., Ltd. ( Dainippon Ink and Chemicals, Inc.)) and the like.

In addition, 1,1,2,2-indole (p-glycidoxyphenyl)ethane, ginseng (p-glycidoxyphenyl)methane, triglycidyl isocyanurate can also be used. Paraxyl (hydroxyethyl) ester, o-phthalic acid diglycidyl ester, diglycidyl terephthalate; amine epoxy resin EPOTOHTO YH-434, YH-434L; A glycidyl ester modified by introducing a dimer acid into the skeleton of the resin.

Among these, it is preferred that the "molecular weight/number of epoxy rings" is 100 or more, and more preferably 130 to 500. When the "molecular weight/number of epoxy groups" is small, the curability is high, and the shrinkage at the time of curing is large. When the amount is too large, there is a concern that the curability is insufficient, the reliability is poor, and the flatness is deteriorated.

Specific preferred compounds include: EPOTOHTO YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701; PLACCEL GL-61, GL-62; 3, 5, 3', 5'-four Base-4,4'-diglycidylbiphenyl; CELLOXIDE 2021, 2081, EPOLEAD GT-302, GT-403, EHPE-3150, and the like.

(fluorine-based organic compounds)

The colored polymerizable composition of the present invention contains a fluorine-based organic compound to improve liquid properties (particularly fluidity) when it is used as a coating liquid, to improve uniformity of coating thickness, and to save liquid.

In other words, the colored polymerizable composition containing a fluorine-based organic compound can reduce the surface tension between the surface to be coated and the coating liquid, thereby improving the wettability to the coated surface and improving the coated surface. The coating property can effectively form a film having a uniform thickness having a small thickness unevenness even when a film having a thickness of about several μm is formed with a small amount of liquid.

The fluorine content in the fluorine-based organic compound is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, particularly preferably from 7 to 25% by mass. When the fluorine content is in this range, it is effective from the viewpoint of coating thickness uniformity or liquid-saving property, and is also excellent in solubility in the composition.

The "fluorine-based organic compound" includes, for example, MEGAFAC F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (the above is manufactured by Dainippon Ink and Chemicals Co., Ltd.); FLUORAD FC430, FC431, FC171 (above is manufactured by Sumitomo 3M Limited); SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above is manufactured by Asahi Glass Co., Ltd.).

In particular, when a colored coating film of the present invention is used to form a thin coating film, the fluorine-based organic compound can effectively prevent coating unevenness or thickness unevenness. Further, it is also effective to apply the colored polymerizable composition of the present invention to the slit coating which is liable to cause liquid breakage.

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

(thermal polymerization initiator)

A measure containing a thermal polymerization initiator in the colored polymerizable composition of the present invention is also effective.

The "thermal polymerization initiator" includes, for example, various azo compounds and peroxide compounds.

The "azo compound" includes an azobis compound; the "peroxide compound" includes: a ketone peroxide, a peroxyketal, a hydrogen peroxide, a dialkyl peroxide, and a dioxane. A base peroxide, a peroxy ester, a peroxydicarbonate, and the like.

(surfactant)

In the colored polymerizable composition of the present invention, various surfactants may be added from the viewpoint of improving coatability. The surfactant may be a non-ionic, cationic or anionic surfactant other than the fluorine-based surfactant described above.

Among them, the fluorine-based surfactant is preferably a nonionic surfactant having a perfluoroalkyl group as described above or a nonionic surfactant.

Specific examples of the fluorine-based surfactant include the MEGAFACE (registered trademark) series manufactured by Dainippon Ink and Chemicals Co., Ltd., and the FLUORAD (registered trademark) series manufactured by Sumitomo 3M Co., Ltd., and the like.

Further, specific examples of the cationic surfactant include: an anthraquinone derivative (commercial product EFKA-745 (manufactured by EFKA Additives, Inc.)); an organic alkane polymer (Organo Siloxane) Polymer) KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic (co)polymer POLYFLOW No. 75, No. 90, No. 95 Co., Ltd. (manufactured by Kyoeisha Chemical Co., Ltd.); W001 (Yodo Co., Ltd. (Bodo) Chemie GmbH), etc.

Specific examples of the nonionic surfactant include: polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene decyl benzene Ether, polyethylene glycol dilaurate, polyethylene glycol distearate, dehydration Pear alcohol fatty acid ester; PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2, TETRONIC 304, 701, 704, 901, 904, 150R1, etc. manufactured by BASF Corporation.

In addition, specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yushang Co., Ltd.) and the like.

(other additives)

In addition to the above, the coloring polymerizable composition of the present invention may be added with various additives.

Specific examples of the additive include: fillers for glass, alumina, etc.; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer , an alkali-soluble resin such as an acid cellulose derivative, a polymer addition anhydride having a hydroxyl group, an alcohol-soluble nylon, a phenoxy resin formed of bisphenol A and epichlorohydrin; EFKA-46, EFKA- 47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (above is manufactured by Morishita Industrial Co., Ltd.) and other "polymer dispersants"; SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940 , 17000, 24000, 26000, 28000, etc. of various SOLSPERSE dispersants (The Lubrizol Co., Ltd.); Adekapluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101 , P103, F108, L121, P-123 (manufactured by Adeka Corporation); and IONET S-20 (manufactured by Sanyo Chemical Industries Co., Ltd.); -(3-tertiary-butyl-5-methyl A UV absorber such as -2-hydroxyphenyl)-5-chlorobenzotriazole or alkoxybenzophenone; and an anti-aggregation agent such as sodium polyacrylate.

Further, when it is desired to promote the alkali solubility of the uncured portion and to further improve the developability of the coloring polymerizable composition, it is preferred to add an organic carboxylic acid to the colored polymerizable composition of the present invention. It is a low molecular weight organic carboxylic acid having a molecular weight of 1,000 or less.

Specifically, for example, formic acid (formic acid), acetic acid (acetic acid), propionic acid, butyric acid (butyric acid), shikimic acid (valeric acid), trimethylacetic acid, caproic acid, diethyl acetic acid, heptanoic acid, octanoic acid, etc. Aliphatic monocarboxylic acid; oxalic acid (oxalic acid), malonic acid, succinic acid (succinic acid), glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, fatty acid ( Azelaic acid), Brazilian diacid (tridecanedioic acid), methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, citraconic acid, etc. Aliphatic dicarboxylic acid; "aliphatic tricarboxylic acid" such as 1,2,3-propanetricarboxylic acid, aconitic acid, and oxalic acid; benzoic acid (benzoic acid), o-toluic acid, and decanoic acid "Aromatic monocarboxylic acid" (p-isopropylbenzoic acid), 2,3-dimethylbenzoic acid, 3,5-dimethylbenzoic acid, etc.; phthalic acid, isophthalic acid, para-benzene Dicarboxylic acid, trimellitic acid (1,2,4-benzenetricarboxylic acid), trimesic acid (1,3,5-benzenetricarboxylic acid), pyromellitic acid (1,2,3,5-benzene IV "Aromatic polycarboxylic acid" such as formic acid), pyromic acid (1,2,4,5-benzenetetracarboxylic acid); phenylacetic acid, hydrogen Oleic acid, hydrogen cinnamic acid, bitter almond acid (phenylglycolic acid), phenyl succinic acid, atopic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnaminoacetic acid, coumaric acid, umbrella A carboxylic acid such as an acid.

In addition to this, a thermal polymerization inhibitor may be added to the colored polymerizable composition of the present invention.

Thermal polymerization inhibitors can be used, for example, hydroquinone, p-methoxyphenol, di-tertiary-butyl-p-cresol, gallic phenol, tert-butyl catechol, benzoquinone , 4,4'-thiobis(3-methyl-6-tertiary-butylphenol), 2,2'-methylenebis(4-methyl-6-tertiary-butylphenol), 2-Hydroxythiobenzimidazole and the like.

The colored polymerizable composition of the present invention is characterized in that a photopolymerizable compound, a photopolymerization initiator, a further alkali-soluble resin or a solvent, and a surfactant are added to the pigment dispersion composition of the present invention as described above. Etc.

The colored polymerizable composition of the present invention contains the pigment-dispersed composition of the present invention, and the pigment contained as a coloring agent has excellent dispersion stability. Further, by using the colored film obtained by using the colored polymerizable composition of the present invention, since the color material is uniformly and stably dispersed, the contrast is high and the surface smoothness is excellent.

Therefore, the colored polymerizable composition of the present invention is preferably a colored region for forming a color filter.

<Color filter, and its preparation method>

The color filter of the present invention is characterized in that it has a colored pattern formed on the substrate using the colored polymerizable composition of the present invention as described above. Hereinafter, the color filter of the present invention and the method of producing the same (the method of producing the color filter of the present invention) will be described in detail.

The color filter of the present invention is characterized in that it is coated on a substrate to form a film of the colored polymerizable composition of the present invention, and preferably prebaking, second exposure, and development are sequentially performed.

By such a method, it is possible to manufacture a color filter which can be used for a liquid crystal display element or a solid-state image pickup element with less difficulty in the process and with high quality and low cost.

Hereinafter, each step will be described in detail.

[Coating]

In the present invention, when a color filter is produced, a film of a colored polymerizable composition is formed by coating. The coating method is a conventional method such as a rotary type, a slit, a rotary type, or a slit type. However, from the viewpoint of productivity, slit coating is preferably used.

The substrate which can be used for the color filter of the present invention includes, for example, an alkali-free glass, a soda lime glass, a PYREX (registered trademark) glass, a quartz glass, and the like for use in a liquid crystal display element or the like. The transparent conductive film is attached to the obtained one or the like, or used in a photoelectric conversion element substrate such as a solid-state image sensor, for example, a germanium substrate or a plastic substrate.

On these substrates, a black matrix for isolating the respective pixels or a transparent resin layer provided to promote adhesion or the like may be formed.

Further, the plastic substrate preferably has a gas barrier layer and/or a solvent resistant layer on the surface thereof.

In addition, a substrate for driving a thin film transistor (TFT) in which a thin film transistor (TFT) type color liquid crystal display device is disposed (hereinafter, referred to as a "TFT substrate for liquid crystal driving") may be used. A color filter formed by using the colored polymerizable composition of the present invention is also formed on the driving substrate to produce a color filter.

The "substrate of the TFT-type liquid crystal driving substrate" includes, for example, glass, polyoxyethylene, polycarbonate, polyester, aromatic polyamide, polyamidolimine, polyimine, and the like. These substrates may be preliminarily subjected to an appropriate pretreatment such as chemical treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition. For example, a substrate obtained by forming a surface passivation film such as a tantalum nitride film on the surface of a TFT liquid crystal driving substrate can be used.

In the present invention, the method of applying the colored polymerizable composition of the present invention to a substrate is preferably a slit coating. The conditions of the slit coating differ depending on the size of the coated substrate. However, for example, when the fifth generation glass substrate (1,100 mm × 1,250 mm) is applied, the colored polymerizable composition from the slit nozzle is used. The discharge amount is usually 500 to 3,000 μl/sec, preferably 800 to 2000 μl/sec, and further, the coating speed is usually 50 to 300 mm/sec, preferably 100 to 250 mm/sec. .

Further, the solid content of the colored polymerizable composition which can be used in the slit coating step is usually 10 to 23%, preferably 13 to 20%.

When a coating film using the colored polymerizable composition of the present invention is formed on a substrate, the thickness of the coating film (after prebaking treatment) is usually 0.3 to 5.0 μm, preferably 0.5 to 4.0 μm, and most preferably 0.5 to 3.0 μm.

Further, in the case of a color filter for a solid-state image sensor, the thickness of the coating film (after the prebaking treatment) is preferably in the range of 0.5 μm to 5.0 μm.

[prebaking]

It is preferable to carry out prebaking after forming the film of the coloring polymerizable composition of the present invention on the substrate by a coating method as described above.

Further, a vacuum treatment may be applied before the prebaking as needed.

The vacuum drying conditions are usually from 0.1 to 1.0 torr (13 to 133 Pa), preferably from about 0.2 to 0.5 torr (27 to 67 Pa).

Further, when a prebaking treatment is applied as needed, a hot plate, an oven or the like may be used, in the temperature range of 50 ° C to 140 ° C, preferably at about 70 ° C to 110 ° C for 10 seconds to 300 seconds. Conditions are carried out. Further, the prebaking treatment may be combined with high frequency processing or the like. The high frequency processing system can also be used alone.

[exposure]

After the film formed as described above is dried or pre-baked as necessary, the coating film is exposed through a specific mask pattern.

The radiation system used for the exposure is particularly preferably an ultraviolet ray such as a g-line, an h-line, an i-line, or a j-line.

Further, when manufacturing a color filter for a liquid crystal display device, it is preferable to use a proximity light-exposure machine or a mirror projection light-exposure machine, and mainly use it. Exposure of h-line and i-line.

Further, in the case of manufacturing a color filter for a solid-state image sensor, a stepper light-exposure machine is preferably used, and an i-line is mainly used.

Further, when a color filter is manufactured using a TFT-type liquid crystal driving substrate, the photomask that can be used may be used to form a through-hole in addition to a pattern required for forming a pixel (colored pattern). Through hole or rectangular recess (rectangular- The pattern of the depression.

[development]

After the exposure as described above, development is carried out. By this development, the uncured portion of the coated film after exposure is dissolved in the developer to cause only the hardened portion to remain on the substrate.

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

The developing solution is a coating film which can be dissolved in the uncured portion of the colored polymerizable composition after the coloring polymerizable composition of the present invention is exposed and the exposed portion is polymerized and cured, but the hardened portion is not dissolved. Any one can be used.

Specifically, a developing solution obtained by combining various organic solvents or an aqueous alkaline solution can be used.

The organic solvent to be used in the developer may be a solvent as described above which can be used in the preparation of the colored polymerizable composition of the present invention.

Further, the "aqueous alkaline solution" includes, for example, by using sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine. , dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. The basic compound is dissolved in an alkaline aqueous solution obtained at a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass.

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

The development method may be any one of an immersion method, a shower method, a spray method, and the like, or may be used in combination with a shaking method, a rotation method, an ultrasonic method, or the like. The developed surface may be previously wetted with water or the like before contact with the developer to prevent uneven development. Alternatively, the substrate may be tilted for development.

Further, in the production of a color filter for a solid-state image sensor, paddle development can also be used.

After the development treatment, after the washing treatment for removing the remaining developer for washing and drying, the heat treatment (post-baking) is applied in order to complete the hardening.

Although the washing treatment is usually carried out in pure water, in order to save the liquid, pure water can be used in the final washing stage, and the used pure water is used in the initial stage of washing, and in addition, the substrate can be used at the inclination. The method of washing or supersonic irradiation is combined.

After the washing treatment, drainage, and drying, heat treatment at about 200 ° C to 250 ° C is usually carried out. The post-baking is heating after development which is made to complete the hardening, and heating (hard baking) is preferably carried out at 200 ° C to 250 ° C.

The heat treatment (post-baking) is a method of using a hot plate or a convection oven (hot air circulation dryer), a high frequency heater, or the like in a manner consistent with the above conditions, in a continuous manner. Or in batch mode.

After post-baking, it is preferred to apply UV wash prior to performing the application of another color. The UV cleaning system can be carried out by a glass substrate cleaning machine or the like (for example, LC4000, manufactured by Hitachi Electronics Engineering Co., Ltd.), and the UV irradiation amount is usually about 100 mJ/cm ² to 1,000 mJ. /cm ² . By applying UV cleaning, the development residue can be removed, or the pattern formation property of another color can be improved.

The steps as described above are carried out in order, whereby the color filter of the present invention can be produced.

Further, by repeating the above-described steps in accordance with the desired number of hue and repeating the respective colors (three colors or four colors) in order, a cured film (colored pattern) forming a colored complex color can be produced. Color filter.

"Embodiment"

In the following, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples without departing from the spirit and scope of the invention. In addition, "parts" means "parts by mass" unless otherwise stated.

First, the components used in the examples and comparative examples will be described.

<Synthesis of Resin B>

7.5 parts of the monomer M-11, 31.25 parts of methyl methacrylate, 11.25 parts of methacrylic acid, and 167 parts by mass of methoxypropanediol exemplified as described above were introduced into a three-necked flask substituted with nitrogen. The mixture was stirred with a stirrer (Shinto Scientific Co., Ltd.: Three-One Motor), and nitrogen gas was introduced into the flask while heating to a temperature of 78 °C. To this, 0.1 part of dimethyl-2,2'-azobis(2-methyl propionate) was added (trade name: V-601, Wako Pure Chemical Industries, Ltd.) Manufacture), heating and stirring at 78 ° C for 2 hours. After 2 hours, 0.1 part of V-601 was further added, and stirred under heating for 3 hours to obtain a 30% solution of Resin B. The obtained resin B is used as a resin used before the drying step of the pigment during salt milling.

<Synthesis of Resin A>

The resin A was synthesized in the same manner except that the monomer used in the synthesis of the resin B as described above and the feed amount thereof were changed to the monomer and the feed amount as shown in Table 1. The obtained resin A was used as a resin used before the drying step of the pigment during salt milling.

Table 1 below shows the monomers used in the synthesis of resins A and B and the amounts thereof fed, and the weight average molecular weight and acid value of the synthesized resin A and resin B. Here, the weight average molecular weight is a value obtained by measuring GPC (gel permeation chromatography) under the following conditions and measured in terms of polystyrene.

Pipe string used: TSKgel Multipore HXL-M (fine pore polydisperse linear column): manufactured by TOSCH Corporation;

Dissolved solution: THF;

Flow rate: 1.0 ml/min;

Temperature: 40 ° C;

Detection condition: RI;

System: Complete set of high-speed GPC devices (HLC-8220 manufactured by East Soda Co., Ltd.).

Further, the acid value is a value measured by the following method.

(Method for measuring acid value)

It was measured by titration with a 0.1 N ‧ ethanol solution. The acid value of the solution is based on the acid value determination method of JIS K 0070: 1992 "Test method for acid value, saponification price, ester price, iodine value, hydroxyl value and unsaponifiable matter of chemical products", and a certain amount The resin was dissolved in 1-methoxy-2-propyl acetate and measured by titration with a KOH/ethanol solution using phenolphthalein as an indicator.

In the above Table 1, the monomer M-11 is referred to as a monomer represented by the general formula (1), a maleimide, and a maleimide derivative as shown in the above. Preferred monomers are exemplified by preferred embodiments. Further, in Table 1, the details of the monomer for synthesizing the resin A are as follows:

St: Styrene

BzMA: benzyl methacrylate

MAA: Methacrylic acid

MMA: Methyl methacrylate

Next, various dispersants used in preparing the pigment dispersion composition in the examples and the comparative examples are explained below.

‧Resin (1):

*AA-6/monomer M-11/styrene/methacrylic acid=55/10/20/15 (% by mass) of copolymer (weight average molecular weight: 20,000) (*AA-6: single-end methyl group) Acryl thiolated polymethyl methacrylate oligomer (Mn=6000, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.)

‧Resin (2):

Copolymer of maleimide/styrene/methacrylic acid=20/65/15 (% by mass) (weight average molecular weight: 20,000)

In addition, the structure of the "pigment derivative" used in the salt milling and preparation of the pigment dispersion composition is as follows:

[Example 1] (Method of preparing treated pigment using salt mill)

50 g of IRGAPHOR RED BT-CF (manufactured by Ciba Specialty Chemicals Co., Ltd., Pigment Red 254) belonging to (A) diketopyrrolopyrrole pigment in the present invention, and 500 g of sodium chloride belonging to a water-soluble inorganic salt (Average particle diameter: 10 μm), and 150 g of a diethylene glycol (manufactured by Tokyo Chemical Co., Ltd.) belonging to a water-soluble organic solvent, fed into a 1-gallon kneader made of stainless steel ( It was manufactured by INOUE MFG., Inc. and kneaded at 50 ° C for 10 hours.

Next, 25 g of the resin A solution (solid content: 30% by mass) obtained by the above-described synthesis was added to the mixture, and mixed, and then the mixture was poured into about 3 liters of hot water and heated to one side. The mixture was stirred at about 70 ° C for about 1 hour in a high speed mixer to obtain a slurry. Thereafter, sodium chloride and a solvent were removed by filtration, washing with water, and then dried in a hot air oven at 60 ° C for about 24 hours to obtain a surface-treated (A) diketopyrrole attached to at least a part of the surface of the resin A. Pyrrole pigment.

The particle diameter of the obtained treated pigment was measured by a transmission electron microscope, and the average primary particle diameter was 30 nm. The measured value of the particles is an average value obtained by measuring the average of the major axis and the minor axis of 500 pigments at a magnification of 100,000 times.

[Example 1] <Preparation of pigment dispersion composition>

The components of the composition (1) were mixed as described below, and stirred and mixed for 1 hour at a number of revolutions of 3,000 r.p.m. using a homogenizer to prepare a mixed solution containing the pigment.

[Composition (1)]

Next, the mixed solution obtained as described above was applied for 20 minutes to pre-disperse in a bead disperser (DISPERMAT, manufactured by GETZMANN Co., Ltd.) using 0.8 mm Φ zirconia beads (manufactured by Nikkato Corporation). After that, it was subjected to formal dispersion for 2 hours by using a bead disperser ULTRA APEX MILL (manufactured by Kotobuki Industries Co., Ltd.) using 0.10 mm Φ zirconia beads (manufactured by Nikkato Co., Ltd.) to obtain The red pigment dispersion composition of Example 1.

[Evaluation of pigment dispersion composition]

The dispersibility and dispersion stability of the obtained pigment dispersion composition were evaluated.

For the prepared pigment dispersion composition, the viscosity η1 (25 ° C) immediately after the preparation and the viscosity η 2 (25 ° C) after one week after the preparation were measured using an E-type viscometer. Both the η1 and η2 systems were 9 cp, and thus it was confirmed that good dispersibility and dispersion stability were exhibited.

[Embodiment 2] <Preparation of Colored Polymerizable Composition>

The pigment-dispersed composition obtained in the above Example 1 was used to produce a colored polymerizable composition of the composition (2) as described below.

Further, the red pigment dispersion composition A and the yellow pigment dispersion composition A were prepared as described below.

(Red pigment dispersion composition A)

In the method of processing the pigment as described above, the same as in the first embodiment except that "IRGAPHOR RED BT-CF" is used instead of "Red Pigment (CROMOPHTAL Red A2B": PR177) manufactured by BASF Corporation). A salt mill is applied in such a manner that a treated pigment having an average particle diameter of 28 nm can be obtained. After that, the obtained pigment was obtained, and the red pigment dispersion composition was obtained in the same manner as in Example 1 except that the "pigment derivative (1)" was used instead of the "pigment derivative (1)". A.

Further, the yellow pigment dispersion composition A was prepared in the following manner.

(Yellow pigment dispersion composition A)

In the method of processing the pigment as described above, the same as in the first embodiment except that "Yellow pigment ("E4GN-GT: PY150" manufactured by Lanxess Corporation" is used instead of "IRGAPHOR RED BT-CF". The salt milling is applied in such a manner that a treated pigment having an average particle diameter of 30 nm can be obtained. After that, the obtained pigment was obtained, and the yellow pigment dispersion composition was obtained in the same manner as in Example 1 except that the "pigment derivative (1)" was used instead of the "pigment derivative (1)". A.

[Composition (2)]

Here, the pentaerythritol penta-hexaacrylate is represented by KAYARAD DPHA (Nippon Kayaku Co., Ltd.).

<Manufacture of Color Filter Using Colored Polymerizable Composition>

The obtained colored polymerizable composition (color resist liquid) was applied onto a 100 mm × 100 mm glass substrate (1737, manufactured by Corning Incorporated) so that x as an index of color concentration The value was 0.650 and it was dried in an oven at 90 ° C for 60 seconds (prebaking). After that, the entire coating film was exposed to 200 mJ/cm ² (illuminance: 20 mW/cm ² ), and then an alkali developer CDK-1 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was used. The 1% aqueous solution covered the exposed coating film and allowed to stand for 60 seconds. After standing, the pure water was sprayed in a spray form to wash off the developer. Then, the coating film subjected to the photohardening treatment and the development treatment as described above is heat-treated in an oven at 220 ° C for 30 minutes (post-baking) to form a colored film for constituting the color filter on the glass substrate. A color filter substrate (color filter) equipped with a monochrome colored area is prepared.

The substrate was further subjected to UV cleaning (at 20 mW/cm ² and 500 mJ/cm ² ) by a glass substrate cleaning machine (LC4000, manufactured by Hitachi Electronic Engineering Co., Ltd.), and then pre-baked again. Bake, develop, and post-bake. Thereafter, the UV cleaning, prebaking, developing, and post-baking are further carried out, whereby a color filter substrate (color filter) for evaluation can be obtained.

The colored polymerizable composition (color resist liquid) prepared by the above and the colored filter substrate (color filter) for evaluation prepared from the colored polymerizable composition are as follows The method described is evaluated. The results are shown in Table 2.

-1. Determination of viscosity -

With respect to the prepared colored polymerizable composition (color resist liquid), the viscosity η1 (25 ° C) immediately after the preparation and the viscosity η 2 (25 ° C) after one week after the preparation were measured using an E-type viscometer.

-2. Comparison of measurements ‧ Evaluation -

The comparison of the prepared colored filter substrates (color filters) was measured in the following manner.

In other words, the evaluation coloring filter substrate was placed between two polarizing plates, and then the BM-5 manufactured by TOPCON Corporation was used to measure the brightness when the polarizing axes were parallel and the brightness at the time of the orthogonal. The value obtained by dividing the luminance in parallel by the luminance at the time of orthogonality (= luminance in parallel/luminance in orthogonal) is used as an index for evaluating contrast. (The evaluation method is based on the "The Seventh Colorific Optics Conference" in 1990, the 512-color display, and the 10.4-inch "Color Filter for TFT-LCD (Thin Film Transistor-Liquid Crystal Display)" , Ueki, Ozeki, Fukunaga and (Yamanaka) et al.").

-3. Determination of surface roughness -

For the evaluation of the colored filter substrate (color filter) for evaluation, an Atomic Force Microscope (AFM: NanoScope IIIa, manufactured by Nano World) was used to measure the surface of the colored film. Surface roughness.

[Example 3]

In Example 1, except that 0.8 g of the pigment derivative (1) was further added at the time of salt milling, salt milling was carried out in the same manner as in Example 1, whereby a treated pigment was obtained. The treated primary pigment obtained had an average primary particle diameter of 26 nm. Thereafter, the obtained treated pigment was used, and a red pigment dispersion composition was obtained in the same manner as in Example 1. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, evaluation was carried out in the same manner as in Example 2. The results are shown in Table 2.

[Example 4]

In Example 1, a salt milling was carried out in the same manner as in Example 1 except that 0.9 g of the pigment derivative (2) was further added at the time of salt milling, whereby a treated pigment was obtained. The treated primary pigment obtained had an average primary particle diameter of 23 nm. Thereafter, the obtained treated pigment was used, and a red pigment dispersion composition was obtained in the same manner as in Example 1. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, evaluation was carried out in the same manner as in Example 2. The results are shown in Table 2.

[Example 5]

In Example 1, except that 0.9 g of the pigment derivative (2) was further added at the time of salt milling, the salt milling was carried out in the same manner as in Example 1, and further, the "Resin A solution was replaced except after kneading. (The solid content is 30% by mass), and the "Resin B solution (solid content: 30% by mass)" obtained in the synthesis example as described above was used, and the treated pigment was obtained in the same manner as in Example 1. . The treated primary pigment obtained had an average primary particle diameter of 23 nm. Thereafter, the obtained treated pigment was used, and a red pigment dispersion composition was obtained in the same manner as in Example 1. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, evaluation was carried out in the same manner as in Example 2. The results are shown in Table 2.

[Embodiment 6]

In Example 1, except that 0.9 g of the pigment derivative (2) was further added at the time of salt milling, the salt milling was carried out in the same manner as in Example 1, and further, the "Resin A solution was replaced except after kneading. The treated pigment was obtained in the same manner as in Example 1 except that the "resin B solution (solid content: 30% by mass)" was used. The treated primary pigment obtained had an average primary particle diameter of 23 nm. Thereafter, the obtained treated pigment was used, and the same procedure as in Example 2 was carried out except that "10 parts of the pigment derivative (1)" was used instead of "10 parts of the pigment derivative (2)". A red pigment dispersion composition was obtained. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 1, evaluation was carried out in the same manner as in Example 2. The results are shown in Table 2.

[Embodiment 7]

In Example 1, except that 0.9 g of the pigment derivative (2) was further added at the time of salt milling, the salt milling was carried out in the same manner as in Example 1, and further, the "Resin A solution was replaced except after kneading. The treated pigment was obtained in the same manner as in Example 1 except that the "resin B solution (solid content: 30% by mass)" was used. The treated primary pigment obtained had an average primary particle diameter of 23 nm. Thereafter, the obtained treated pigment is used, and "10 parts of the pigment derivative (1), 10 parts of the pigment derivative (3), and 5 parts of the pigment derivative (4)" are used instead of "11 parts". A red pigment dispersion composition was obtained in the same manner as in Example 1 except that the pigment derivative (2), the 7-part pigment derivative (3), and the 7-part pigment derivative (4). Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, evaluation was carried out in the same manner as in Example 2. The results are shown in Table 2.

[Comparative Example 1]

The salt milling was carried out in the same manner as in Example 1, whereby a treated pigment was obtained. The treated primary pigment obtained had an average primary particle diameter of 30 nm. Thereafter, the obtained treated pigment was used, and in place of "86 parts of the treated pigment obtained by the method described above", "103 parts of the treated pigment obtained by the method described above" was used, while A red pigment dispersion composition was obtained in the same manner as in Example 1 except that the "pigment derivative (3)" and the "pigment derivative (4)" were not used. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, evaluation was carried out in the same manner as in Example 2. The results are shown in Table 2.

[Comparative Example 2]

In Example 1, except that 0.8 g of the pigment derivative (1) was further added at the time of salt milling, salt milling was carried out in the same manner as in Example 1, whereby a treated pigment was obtained. The treated primary pigment obtained had an average primary particle diameter of 26 nm. Thereafter, the obtained treated pigment was used, and in place of "86 parts of the treated pigment obtained by the method described above", "103 parts of the treated pigment obtained by the method described above" was used, while A red pigment dispersion composition was obtained in the same manner as in Example 1 except that the "pigment derivative (3)" and the "pigment derivative (4)" were not used. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, evaluation was carried out in the same manner as in Example 2. The results are shown in Table 2.

[Comparative Example 3]

In Example 1, except that 0.8 g of the pigment derivative (1) was further added at the time of salt milling, salt milling was carried out in the same manner as in Example 1, whereby a treated pigment was obtained. The treated primary pigment obtained had an average primary particle diameter of 26 nm. After that, the obtained treated pigment is used, and in addition to "10 parts of the pigment derivative (3), 5 parts of the pigment derivative (4)", "15 parts of the pigment derivative (3)" is used. The remainder was obtained in the same manner as in Example 1 to obtain a red pigment dispersion composition. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, evaluation was carried out in the same manner as in Example 2. The results are shown in Table 2.

[Comparative Example 4]

In Example 1, except that 0.8 g of the pigment derivative (1) was further added at the time of salt milling, salt milling was carried out in the same manner as in Example 1, whereby a treated pigment was obtained. The treated primary pigment obtained had an average primary particle diameter of 26 nm. After that, the obtained treated pigment is used, and in addition to "10 parts of the pigment derivative (3), 5 parts of the pigment derivative (4)", "15 parts of the pigment derivative (4)" is used. The remainder was obtained in the same manner as in Example 1 to obtain a red pigment dispersion composition. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, evaluation was carried out in the same manner as in Example 2. The results are shown in Table 2.

[Comparative Example 5]

In Example 1, a salt milling was carried out in the same manner as in Example 1 except that 1 g of the pigment derivative (4) was further added at the time of salt milling, whereby a treated pigment was obtained. The treated primary pigment obtained had an average primary particle diameter of 24 nm. Thereafter, the obtained treated pigment was used, and in place of "86 parts of the treated pigment obtained by the method described above", "103 parts of the treated pigment obtained by the method described above" was used, while A red pigment dispersion composition was obtained in the same manner as in Example 1 except that the "pigment derivative (3)" and the "pigment derivative (4)" were not used. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, evaluation was carried out in the same manner as in Example 2. The results are shown in Table 2.

As is apparent from Table 2, the colored polymerizable compositions of Examples 2 to 7 prepared by using the pigment dispersion composition of the present invention of Example 1 were not observed to have an increased viscosity after storage. It is known that the organic pigments contained therein have superior dispersion stability. At the same time, it is also known that the color filter (color filter) formed by using the colored polymerizable composition has superior contrast and can form a color film having a small surface roughness.

From these results, it is presumed that the colored polymerizable composition according to the present invention can obtain a color filter which has high contrast and which has been reduced in pixel defects such as surface roughness.

Claims (10)

A pigment dispersion composition comprising: a diketopyrrolopyrrole pigment, which is 0.1 to 30 parts by mass of phthalic acid iminoalkylate relative to 100 parts by mass of the diketopyrrolopyrrole pigment. The diketopyrrolopyrrole is 0.1 to 20 parts by mass, based on 100 parts by mass of the diketopyrrolopyrrole pigment, of phthalic acid imidoalkylated quinophthalone, and at least one organic solvent. The pigment dispersion composition according to claim 1, wherein the diketopyrrolopyrrole pigment has an average primary particle diameter of 10 nm to 30 nm. The pigment dispersion composition according to claim 1, wherein the diketopyrrolopyrrole pigment is a diketopyrrolopyrrole pigment obtained by a method comprising the following steps: a diketopyrrolopyrrole a step of mechanically kneading a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent which does not substantially dissolve the water-soluble inorganic salt; and removing the water-soluble inorganic salt and the water-soluble organic solvent; a step of drying the diketopyrrolopyrrole pigment; and a step of contacting the diketopyrrolopyrrole pigment with the resin before the drying step. The pigment dispersion composition according to claim 3, wherein the resin is a polymer compound having an acid value of 50 to 300 mgKOH/g. The pigment dispersion composition according to any one of claims 1 to 4, wherein the phthalimidoalkylamine diketopyrrolopyrrole The content is equal to or greater than the content of the o-phthalimidoalkylamine quinacridone. A method for preparing a pigment dispersion composition, comprising the steps of: adding a diketopyrrolopyrrole pigment having an average primary particle diameter of 10 nm to 30 nm, and adding 0.1 to 30 parts by mass relative to 100 parts by mass of the diketopyrrolopyrrole pigment The phthalic acid alkylened diketopyrrolopyrrole in an amount of 0.1 to 20 parts by mass relative to 100 parts by mass of the diketopyrrolopyrrole pigment. And a diketopyrrolopyrrole pigment, wherein the diketopyrrolopyrrole pigment is 0.1 to 30 parts by mass relative to 100 parts by mass of the diketopyrrolopyrrole pigment The alkylated diketopyrrolopyrrole is dispersed in an amount of 0.1 to 20 parts by mass relative to 100 parts by mass of the diketopyrrolopyrrole pigment, and is dispersed together with an organic solvent. The steps. A colored polymerizable composition comprising the pigment dispersion composition according to item 1 of the patent application, a photopolymerizable compound, and a photopolymerization initiator. The colored polymerizable composition according to claim 7, which further comprises an alkali-soluble resin. A color filter comprising the colored polymerizable composition as described in claim 7 of the patent application. A method of producing a color filter by applying a colored polymerizable composition as described in claim 7 to a substrate to form a coating film, and exposing the formed film, followed by development.