JP5952228B2 - Pigment colorant - Google Patents

Description

The present invention relates to a Pigment colorants.

  In general, it is difficult to stably mix and disperse pigments (particles) in vehicles such as paints, gravure inks and offset inks. For example, fine pigment particles once dispersed in a vehicle tend to agglomerate in the vehicle. A vehicle in which pigment particles are aggregated has a problem that its viscosity increases. In addition, various problems such as a reduction in the coloring power of inks and paints using a vehicle in which pigment particles are dispersed and a reduction in the gloss of the coating film tend to occur.

  By the way, the color filter used for manufacturing a liquid crystal color display, an imaging device, etc. is manufactured by the following methods, for example using a pigment dispersion liquid. First, a pigment dispersion for a color filter (a pigment colorant for a color filter (CF)) in which three color pigments of red (R), green (G), and blue (B) are dispersed in a photosensitive resin solution, respectively. ). These CF pigment colorants are applied to a color filter substrate by spin coating to form a colored film. Next, after the colored film formed through the photomask is exposed, development is performed to pattern the colored film, and a desired pixel is formed on the substrate, whereby a color filter can be obtained.

  Examples of the pigment for producing the color filter include a green pigment, a red pigment, and a blue pigment. Examples of the green pigment include C.I. I. Commonly used are phthalocyanine greens such as CI Pigment Green (hereinafter referred to as “PG”) 36, PG7, and PG58. Examples of red pigments include C.I. I. Commonly used are diketopyrrolopyrrole reds such as Pigment Red (hereinafter referred to as “PR”) 254; anthraquinone reds such as PR177; azo reds such as PR242. Examples of the blue pigment include C.I. I. Phthalocyanine blue such as pigment blue (hereinafter referred to as “PB”) 15: 6 is common.

  Since there is a difference between the hue of these pigments and the color characteristics required for the liquid crystal display, pigments for complementary colors are used in combination. For example, for green and red pigments, C.I. I. Yellow pigments such as Pigment Yellow (hereinafter referred to as “PY”) 138, PY139, and PY150 are used in small amounts as complementary pigments. For blue pigments, C.I. I. A small amount of a violet pigment such as Pigment Violet (hereinafter referred to as “PV”) 23 is used as a complementary color pigment.

  It is difficult to disperse the above-mentioned pigment in a dispersion medium using an ordinary disperser, and only a pigment dispersion having a poor pigment dispersion state may be obtained. A color filter pixel formed using a CF pigment colorant in which the pigment is not well dispersed has insufficient light transmittance, and light transmittance as a color filter pixel is insufficient. That is, a CF pigment colorant obtained by dispersing a pigment using a normal disperser is insufficient as a colorant for forming a pixel of a color filter.

  On the other hand, an acrylic polymer having a high acid value is mainly used as a resin for a photoresist, which is a pigment dispersion medium, so that a colored film after exposure can be easily developed with an alkaline aqueous solution. However, the pigment colorant (photoresist) containing the above-mentioned pigment and an acrylic polymer having a high acid value has a problem that the pigment tends to aggregate and the viscosity tends to increase. Moreover, since the aggregation of the pigment proceeds with time and the viscosity increases, there is a problem that the storage stability is low. If a color filter is produced using a pigment colorant having high viscosity or agglomeration of pigments and exhibiting thixotropic viscosity, the central portion of the colored film before exposure is raised. For this reason, there arises a problem that unevenness of hue or density difference occurs between the pixel located in the central portion of the substrate and the pixel located in the peripheral portion. This problem becomes more prominent when trying to manufacture a color filter having a larger screen.

  Therefore, the CF pigment colorant is required to have a good pigment dispersion state and a low viscosity as compared with general ordinary dry paints and baked paints while containing a pigment at a high concentration. . In general, even when the pigment concentration is 5 to 20% by mass, the pigment is not aggregated, the viscosity is about 5 to 20 mPa · s, and the storage stability is required to be good.

  In order to satisfy the above requirements, conventionally, a method of adding a pigment derivative as a pigment dispersant, a method of treating a pigment with a pigment derivative, and the like have been proposed. Specifically, when an anthraquinone red such as PR177 is used as a pigment, it has been proposed to use a substituted derivative of anthraquinone as a pigment dispersant (for example, see Patent Documents 1 to 3).

Japanese Patent No. 3625143 JP 60-88185 A JP-A-9-272812

  In recent years, there is a desire to further improve the performance of color filters. Specifically, it is necessary to further improve the transparency of the colored pixel, increase the contrast of the transmitted light of the colored pixel, or increase the pigment concentration of the colored pixel. However, it has been difficult to obtain a pigment colorant that can produce a color filter that satisfies the above-described performance with the conventional techniques proposed in Patent Documents 1 to 3 and the like. Furthermore, since the pigment colorant obtained by the conventional technique may generate foreign substances in the coating film (colored film), improvement is desired.

The present invention has been made in view of such problems of the prior art, and the problem is that the fluidity of pigment-containing inks and paints can be remarkably improved, and it is possible to prevent particle agglomeration, and, while preventing the occurrence of foreign material, to provide a provided that pigment colorants obtained using a pigment dispersing agent capable of producing a colored article showing excellent gloss and vividness It is in.

That is, according to the present invention, the following pigment colorant is provided.
[1] A pigment colorant for a color filter comprising a pigment composition containing a pigment and a pigment dispersant, and a film-forming material, wherein the pigment dispersant is represented by the following general formula (1) pigment colorant comprising a first compound and a second compound represented by the following general formula (2), the that.

（前記一般式（１）中、Ｘは、水素原子又はアシルアミノ基を示し、Ｙは、５位に水素原子又はアシルアミノ基を有するアントラキノニルアミノ基、フェニルアミノ基、又はフェノキシ基を示し、Ｒ₁〜Ｒ₄は、それぞれ独立に置換若しくは未置換のアルキル基又はシクロアルキル基を示し、ｎ及びｍは、それぞれ独立に２〜３０の数を示す。ただし、Ｒ₁とＲ₂及びＲ₃とＲ₄は、それぞれ隣接する窒素原子とともに窒素原子、酸素原子、又は硫黄原子を含むことがある環を形成してもよい）

(In the general formula (1), X represents a hydrogen atom or an acylamino group, Y represents an anthraquinonylamino group, a phenylamino group, or a phenoxy group having a hydrogen atom or an acylamino group at the 5-position; _{1 to} R ₄ each independently represents a substituted or unsubstituted alkyl group or cycloalkyl group, and n and m each independently represent a number of 2 to 30, provided that R ₁ , R _2, R ₃ and R ₄ may form a ring that may contain a nitrogen atom, an oxygen atom, or a sulfur atom together with the adjacent nitrogen atom.

（前記一般式（２）中、Ｚは、それぞれ独立に炭素数１〜４の分岐状又は直鎖状のアルキレン基を示し、ＰＩＭは、置換又は未置換のフタルイミドメチル基を示し、ａは、１〜２の数を示し、ｂは、０〜３の数を示す）

(In the general formula (2), each Z independently represents a branched or straight chain alkylene group having 1 to 4 carbon atoms, PIM represents a substituted or unsubstituted phthalimidomethyl group, and a represents 1 represents a number of 1 to 2 and b represents a number of 0 to 3)

［３］前記顔料組成物中の前記顔料１００質量部に対する前記第１の化合物の配合量が、０．５〜３０質量部であり、前記顔料組成物中の前記顔料１００質量部に対する前記第２の化合物の配合量が、０．５〜３０質量部である前記［１］又は［２］に記載の顔料組成物。
［４］前記顔料組成物中の前記第１の化合物と前記第２の化合物の配合比（質量基準）が、第１の化合物：第２の化合物＝２５：７５〜７５：２５である前記［１］〜［３］のいずれかに記載の顔料着色剤。 [ 2] The first compound is a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-5). In [1], the second compound is at least one of a compound represented by the following formula (2-1) and a compound represented by the following formula (2-2). The pigment colorant described.

[3] the amount of the pigment composition wherein the SL front against the pigment 100 parts by weight first compound in is a 0.5 to 30 parts by weight, the pigment 100 parts by weight of the pigment composition amount of pre-Symbol second compound against the said 0.5 to 30 parts by weight [1] or pigment composition according to [2].
[4] The blend ratio (mass basis) of the first compound and the second compound in the pigment composition is 1st compound: 2nd compound = 25: 75 to 75:25 The pigment colorant according to any one of [1] to [3].

  The pigment dispersant of the present invention contains a specific derivative of an anthraquinonylaminotriazine-based yellow pigment and a bianthraquinone compound having a cyclohexylaminoalkyl group. The pigment dispersant of the present invention can remarkably improve the fluidity of pigment-containing inks and paints, can prevent pigment particles from agglomerating, and is excellent in preventing the generation of foreign matters. A colored article exhibiting gloss and sharpness can be produced. Therefore, the pigment dispersant of the present invention includes printing inks such as offset inks and gravure inks, various paints, plastics, pigment printing agents, electrophotographic dry or wet toners, ink jet recording inks, thermal transfer recording inks, and color filters. It can be used for vehicles used for resists for writing, ink for writing instruments, and the like. Further, by using the pigment dispersant of the present invention, it is possible to provide a pigment dispersant and a pigment colorant that remarkably improve the fluidity of various paints and the like, prevent pigment particle aggregation, and prevent the generation of foreign matters. Can do. Furthermore, the pigment colorant of the present invention is less susceptible to thickening and gelation during storage, and can produce a colored product having excellent gloss and sharpness. For this reason, the pigment colorant of the present invention is suitable as a pigment colorant for color filters.

<Pigment dispersant>
Hereinafter, the details of the present invention will be described with reference to preferred embodiments. One of the main features of the pigment dispersant of the present invention is that it contains a compound represented by the following general formula (1) and a compound represented by the following general formula (2). The pigment dispersant of the present invention having such characteristics has excellent affinity for various pigments, and is used as a pigment dispersant for dispersing various pigments regardless of organic or inorganic. can do. Moreover, since the pigment dispersant of this invention has the outstanding pigment dispersion effect, it can be used as a material for preparing the pigment colorant of various uses. Hereinafter, for convenience, the compound represented by the general formula (1) is also referred to as “first compound”. Further, the compound represented by the general formula (2) is also referred to as “second compound”.

In general formula (1), X represents a hydrogen atom or an acylamino group, and Y represents an anthraquinonylamino group, a phenylamino group, or a phenoxy group having a hydrogen atom or an acylamino group at the 5-position. R _{1 to} R ₄ each independently represent a substituted or unsubstituted alkyl group or cycloalkyl group, and n and m each independently represent a number of 2 to 30. However, R ₁ and R ₂ and R ₃ and R ₄ may each form a ring that may contain a nitrogen atom, an oxygen atom, or a sulfur atom together with the adjacent nitrogen atom.

  In general formula (2), Z represents a C1-C4 branched or linear alkylene group each independently, and PIM represents a substituted or unsubstituted phthalimidomethyl group. Moreover, a shows the number of 1-2, b shows the number of 0-3.

  The pigment dispersant of the present invention exhibits an excellent action as a pigment dispersant even in a small amount. In addition, the pigment composition and pigment colorant prepared using the pigment dispersant of the present invention are less prone to thickening and gelation during storage, and foreign matter is less likely to occur in the formed coating film.

  Specific examples of the compound (first compound) represented by the general formula (1) include compounds represented by the following formulas (1-1) to (1-8). Note that the first compound is not limited to the following examples.

  Specific examples of the compound (second compound) represented by the general formula (2) include compounds represented by the following formulas (2-1) to (2-4). Note that the second compound is not limited to the following examples.

  The compound represented by the general formula (1) can be synthesized, for example, as follows. 1-aminoanthraquinone or a derivative thereof (and aniline or phenol used as necessary) and cyanuric chloride are reacted at 130 ° C. to 160 ° C. for 2 to 6 hours in an inert solvent such as o-dichlorobenzene. . Subsequently, the compound represented by General formula (1) can be obtained by adding the polyamine represented by following General formula (3), and making it react at 150-170 degreeC for 3 to 4 hours.

In General Formula (3), R _{1 to} R ₄ each independently represent a substituted or unsubstituted alkyl group or cycloalkyl group, and n and m each independently represent a number of 2 to 30. However, R ₁ and R ₂ and R ₃ and R ₄ may each form a ring that may contain a nitrogen atom, an oxygen atom, or a sulfur atom together with the adjacent nitrogen atom.

  Specific examples of the polyamine represented by the general formula (3) include N, N, N ″, N ″ -tetramethyldiethylenetriamine, N, N, N ″, N ″ -tetraethyldiethylenetriamine, N, N, N ″, N ″ -tetra (n-propyl) diethylenetriamine, N, N, N ″, N ″ -tetra (i-propyl) diethylenetriamine, N, N, N ″, N ″ -tetra (n-butyl) diethylenetriamine, N, N , N ″, N ″ -tetra (i-butyl) diethylenetriamine, N, N, N ″, N ″ -tetra (t-butyl) diethylenetriamine, 3,3′-iminobis (N, N-dimethylpropylamine), 3 , 3′-iminobis (N, N-diethylpropylamine), 3,3′-iminobis (N, N-di (n-propyl) propylamine), 3,3′-imino (N, N-di (n-butyl) propylamine), 3,3′-iminobis (N, N-di (i-butyl) propylamine), 3,3′-iminobis (N, N-di ( t-butyl) propylamine), 3,3′-iminobis (N, N-dimethylpropylamine), 2,9-dimethyl-2,5,9-triazadecane, 2,10-dimethyl-2,10-triazadecane, 2,12-dimethyl-2,6,12-triazatridecane, 2,12-dimethyl-2,5,12-triazatridecane, 2,16-dimethyl-2,9,16-triazaheptadecane 3-ethyl-10-methyl-3,6,10-triazaundecane, 5,13-di (n-butyl) -5,9,13-triazaheptadecane, di- (2-picolyl) amine, Di- (3-picolyl) amine It can be mentioned.

  The compound represented by the general formula (2) can be synthesized, for example, as follows. First, a PR177 derivative obtained by introducing a substituted or unsubstituted phthalimidomethyl group into PR177 or PR177 by a conventional method and cyanuric chloride are reacted at 100 to 110 ° C. in an inert solvent such as dimethylacetamide. . Subsequently, the compound represented by General formula (2) can be obtained by adding N-aminoalkyl-N-cyclohexylamine and making it react at 130-140 degreeC.

  Specific examples of N-aminoalkyl-N-cyclohexylamine include N- (1-aminoethyl) -N-cyclohexylamine, N- (1-aminopropyl) -N-cyclohexylamine, N- (1-aminobutyl). ) -N-cyclohexylamine, N- (2-aminopropyl) -N-cyclohexylamine, N- (2-aminobutyl) -N-cyclohexylamine, N- (3-aminopropyl) cyclohexylamine, N- (3 -Aminobutyl) cyclohexylamine and the like. Among these N-aminoalkyl-N-cyclohexylamines, N- (3-aminopropyl) cyclohexylamine is preferable.

  Specific examples of the substituted or unsubstituted phthalimidomethyl group include phthalimidomethyl group, 3,4,5,6-tetrachlorophthalimidomethyl group, 3,4,5,6-tetrabromophthalimidomethyl group, 3,4, Examples include 5,6-tetrafluorophthalimidomethyl group.

  The compounding ratio (mass basis) of the compound represented by the general formula (1) and the compound represented by the general formula (2) contained in the pigment dispersant of the present invention is as follows: General formula (1): General formula (2) ) = 5: 95 to 95: 5, and it is more preferable that general formula (1): general formula (2) = 25: 75 to 75:25.

Although the usage method in particular of the pigment dispersant of this invention is not restrict | limited, The usage method as shown below is illustrated. Whichever method is used, the desired pigment dispersion effect can be obtained.
(1) A pigment and a pigment dispersant are mixed in advance by a known method, and the obtained pigment composition is added to a vehicle or the like to disperse the pigment in the vehicle.
(2) A pigment and a pigment dispersant are separately added at a predetermined ratio to a vehicle or the like, and the pigment is dispersed in the vehicle.
(3) The pigment and the pigment dispersant are separately dispersed in a vehicle or the like, and then the obtained dispersions are mixed at a predetermined ratio to disperse the pigment in the vehicle.
(4) A pigment dispersant is added at a predetermined ratio to a dispersion obtained by dispersing the pigment in a vehicle or the like, and the pigment is dispersed in the vehicle.

<Pigment composition>
The pigment composition of the present invention contains a pigment and the pigment dispersant described above. The pigment composition of the present invention can be obtained, for example, by dispersing a pigment with the above pigment dispersant. The compounding amount of the compound represented by the general formula (1) with respect to 100 parts by mass of the pigment is preferably 0.5 to 30 parts by mass, and more preferably 3 to 20 parts by mass. Moreover, it is preferable that the compounding quantity of the compound represented by General formula (2) with respect to 100 mass parts of pigments is 0.5-30 mass parts, and it is further more preferable that it is 3-20 mass parts. If the blending amount of the pigment dispersant is too small, the effect of the intended dispersant may be insufficient. On the other hand, if the amount of the pigment dispersant is too large, the dispersion effect reaches its peak, and it may be disadvantageous in terms of productivity. Furthermore, the physical properties of paint and ink vehicles using a pigment composition containing an excessive amount of pigment dispersant may decrease, or the hue of the pigment may change greatly depending on the color of the pigment dispersant itself.

  The compounding ratio (mass basis) of the compound represented by the general formula (1) and the compound represented by the general formula (2) contained in the pigment composition of the present invention is represented by the general formula (1): general It is preferable that it is Formula (2) = 5: 95-95: 5, and it is further more preferable that it is General formula (1): General formula (2) = 25: 75-75: 25. The compounding ratio of the compound represented by the general formula (1) and the compound represented by the general formula (2) takes into consideration the physical properties of the pigment, the viscosity characteristics of the resulting pigment composition (solution), storage stability, and the like. It is preferable to adjust. For example, when the compounding amount of the compound represented by the general formula (1) is reduced, the viscosity is lowered and the viscosity stability tends to be improved. For this reason, it is effective because it is possible to widen the range of the amount of the pigment to be used and improve the storage stability of the pigment composition. Moreover, when the compounding quantity of the compound represented by General formula (2) is reduced, it exists in the tendency for a viscosity to rise. This is effective in that the viscosity can be adjusted according to the type of pigment used. In summary, by adjusting the compounding ratio of the compound represented by the general formula (1) and the compound represented by the general formula (2), the viscosity and storage stability of the pigment composition according to the type of pigment used. It is possible to control the physical properties and characteristics of the.

  Specific examples of pigments that can obtain an effective dispersion effect by using the pigment dispersant of the present invention include soluble / insoluble azo pigments, high molecular weight azo pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, diketopyrrolopyrrole pigments. Quinophthalone pigment, methine / azomethine pigment, perylene pigment, perinone pigment, isoindolinone pigment, isoindoline pigment, metal complex pigment, and the like. Among them, it is preferable to use PR177 which is red and has an anthraquinone pigment.

The method for producing the pigment composition of the present invention is not particularly limited. For example, the pigment composition of the present invention can be obtained by mixing a pigment and a pigment dispersant by a conventionally known method. Specific examples of the method for producing the pigment composition of the present invention include the following methods (1) to (4).
(1) Method of mixing pigment powder and pigment dispersant powder without using a disperser (2) Mixing pigment and pigment dispersant with various dispersers such as kneaders, rolls, attritors and horizontal bead mills Method of mechanical mixing (3) Method of adding and mixing a liquid in which a pigment dispersant is dissolved or finely dispersed into an aqueous or organic solvent suspension of pigment, and uniformly depositing the pigment dispersant on the surface of the pigment (4) A method in which a pigment and a pigment dispersant are dissolved in a solvent having strong dissolving power such as sulfuric acid and then co-precipitated with a poor solvent such as water.

  The properties of the pigment dispersant used for preparing the pigment composition may be any of solution, slurry, paste, and powder. The desired effect can be obtained even when any kind of pigment dispersant is used.

<Pigment colorant>
The pigment colorant of the present invention contains the pigment composition described above and a film forming material. The pigment colorant of the present invention can be obtained, for example, by mixing the above-described refined pigment composition and a film forming material such as a resin ((co) polymer), oligomer, or monomer. The pigment colorant of the present invention can be used in a wide range of fields as a colorant for image display, image recording, printing ink, writing ink, plastic, pigment printing, paint and the like. In particular, it is suitable as an image display material in which the transparency of colored pixels is a problem, particularly as a pigment colorant for a color filter. Of course, the pigment colorant of the present invention is also useful as a material for an image recording agent such as an inkjet ink, an electrodeposition recording liquid, and an electrophotographic developer. These materials for image recording agents are used in image recording methods such as an ink jet recording method, an electrodeposition recording method, and an electrophotographic method. By using the pigment colorant of the present invention, a material for an image recording agent capable of providing a high-quality image can be prepared by any image recording method.

  Hereinafter, further details of the pigment colorant of the present invention will be described by taking as an example a color filter pigment dispersion (color filter (CF) pigment colorant) which is a pigment colorant for image display. In order to prepare a pigment dispersion for a color filter, first, the aforementioned pigment composition is added to a liquid containing a film-forming material and premixed. Next, if a dispersion treatment is performed, a pigment dispersion for a color filter can be obtained. More specifically, a pigment composition that has been uniformly ground using a dispersing machine such as a vertical medium disperser, a horizontal medium disperser, or a ball mill is added to and mixed with a liquid containing a film-forming material. Thus, a pigment dispersion for a color filter can be obtained. Further, a solution obtained by dissolving a pigment and a pigment dispersant in sulfuric acid or the like is mixed with water, and a pigment composition containing the pigment and the pigment dispersant is precipitated as a solid solution or a eutectoid and separated. The separated pigment composition is added to and mixed with a liquid containing a film-forming material or a cationic polymer dispersant, and then ground and dispersed using a horizontal wet medium disperser (bead mill) such as Dino Mill. However, a pigment dispersion for a color filter can be obtained.

  As a liquid containing a film forming material used for preparing a pigment dispersion for a color filter, a solution of a film forming polymer contained in a conventionally known pigment dispersion for a color filter can be used. Examples of the liquid medium used for the liquid containing the film forming material include an organic solvent, water, and a mixed liquid of an organic solvent and water. In addition, conventionally well-known additives, such as a dispersion | distribution adjuvant, a smoothing agent, an adhesive agent, can be added to the pigment dispersion liquid for color filters as needed.

  The amount of the pigment composition contained in the pigment colorant of the present invention is preferably 5 to 500 parts by mass, more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the film forming material. Further, as the liquid containing the film forming material, a liquid containing a photosensitive film forming material or a liquid containing a non-photosensitive film forming material can be used. Specific examples of the liquid containing the photosensitive film-forming material include liquid containing a photosensitive film-forming material used for ultraviolet curable ink, electron beam curable ink, and the like. Specific examples of liquids containing non-photosensitive film-forming materials include varnishes used for printing inks such as letterpress inks, lithographic inks, gravure inks and screen inks; varnishes used for room temperature drying or baking paints; Examples thereof include varnishes used for coating and varnishes used for thermal transfer ribbons.

  The pigment dispersion for a color filter is required to have a good pigment dispersion state and a low viscosity as compared with general ordinary dry paints and baking paints while containing a pigment at a high concentration. In general, even when the pigment concentration is 5 to 20% by mass, the pigment is not aggregated, the viscosity is about 5 to 20 mPa · s, and the storage stability is required to be good. More preferably, the viscosity is 5 to 15 mPa · s, and the viscosity increase rate after being allowed to stand at 25 ° C. for 1 month (after being left) is required to be within 10%. When the viscosity increases, it becomes difficult to form a film with a certain thickness.

  Specific examples of photosensitive film forming materials include photosensitive cyclized rubber resins, photosensitive phenol resins, photosensitive polyacrylate resins, photosensitive polyamide resins, photosensitive polyimide resins, and unsaturated polyester resins. And photosensitive resins such as polyester acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, and polyol acrylate resins. In addition, you may add various monomers as a reactive diluent to the liquid containing these photosensitive resins.

  If a photopolymerization initiator such as benzoin ether or benzophenone is added to a pigment colorant containing a photosensitive resin as a film-forming material and kneaded by a conventionally known method, a photocurable photosensitive pigment dispersion is obtained. be able to. Further, if a thermal polymerization initiator is used instead of the photopolymerization initiator, a thermosetting pigment dispersion can be obtained.

  On the other hand, specific examples of non-photosensitive film-forming materials include styrene- (meth) acrylic acid ester (co) polymers, soluble polyamide resins, soluble polyimide resins, soluble polyamideimide resins, and soluble polyesterimide resins. Resin, water-soluble salt of styrene-maleic acid ester copolymer, water-soluble salt of (meth) acrylic acid ester- (meth) acrylic acid copolymer, water-soluble aminopolyester resin, and water-soluble resin Mention may be made of salts.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. Hereinafter, “parts” and “%” are based on mass unless otherwise specified.

[Synthesis of first compound and second compound]
<Synthesis Example 1>
44 parts of PR177 and 37 parts of cyanuric chloride were added to 800 parts of dimethylacetamide and stirred at 100 to 110 ° C. for 5 hours. After cooling, 125 parts of N- (3-aminopropyl) cyclohexylamine was further added and reacted at 130-140 ° C. for 3 hours. After cooling, the mixture was filtered and washed with methanol and water. By drying, 110 parts of a yellowish brown second compound (A) represented by the following formula (2-1) was obtained.

<Synthesis Example 2>
It is represented by the following formula (2-2) in the same manner as in Synthesis Example 1 except that instead of 44 parts of PR177, 60 parts of a compound obtained by introducing about 1 phthalimidomethyl group into PR177 is used in the usual manner. 124 parts of a second compound (B) was obtained.

  It was confirmed by elemental analysis and mass spectrometry by MALDI that the synthesized second compounds (A) and (B) had the intended composition. The results of elemental analysis for the second compounds (A) and (B) are shown in Tables 1 and 2. As shown in Tables 1 and 2, for any of the elements C, H, and N, a value substantially close to the calculated value (theoretical value) was obtained. For the second compound (A), a peak at m / z = 1219 was detected by mass spectrometry. Furthermore, for the second compound (B), a peak at m / z = 1378 was detected by mass spectrometry. For this reason, it was confirmed that the compound of the target composition was obtained from the result of the used raw material, elemental analysis, and mass spectrometry.

[Preparation of pigment compositions (1) to (10)]
< Reference Example 1>
2000 parts of water was added to a press cake of PR177 (solid content concentration 23%) weighed so that the pigment content was 100 parts, and the slurry was sufficiently reslurried to obtain a slurry. In the obtained slurry, 50 parts of a 5% dilute acetic acid solution (2.5 parts solids) of the first compound (C) represented by the following formula (1-5) described in Patent Document 1, and the second 150 parts of a 5% dilute acetic acid solution of compound (A) (7.5 parts solids) was added and stirred for 1 hour. A 5% aqueous sodium carbonate solution was gradually added dropwise until the pH reached 9 to 10, and then filtered and washed thoroughly with water. Subsequently, it dried at 80 degreeC and obtained 110 parts of pigment compositions (1).

< Reference Example 2>
A pigment composition (2) was obtained in the same manner as in Reference Example 1 except that the second compound (B) was used in place of the second compound (A).

< Reference Example 3>
Replacing 50 parts of 5% dilute acetic acid solution of the first compound (C) (2.5 parts solids) with 100 parts (5 parts solids) and 5% dilute acetic acid of the first compound (A) A pigment composition (3) was obtained in the same manner as in Reference Example 1 except that 150 parts (7.5 parts solids) of the solution was replaced with 100 parts (5 parts solids).

< Reference Example 4>
A pigment composition (4) was obtained in the same manner as in Reference Example 3 except that the second compound (B) was used in place of the second compound (A).

< Reference Example 5>
The 50% 5% dilute acetic acid solution of the first compound (C) (2.5 parts solids) was replaced with 150 parts (7.5 parts solids), and 5% of the second compound (A) A pigment composition (5) was obtained in the same manner as in Reference Example 1 except that 150 parts (solid content: 7.5 parts) of dilute acetic acid solution was replaced with 50 parts (solid content: 2.5 parts).

< Reference Example 6>
A pigment composition (6) was obtained in the same manner as in Reference Example 5 except that the second compound (B) was used in place of the second compound (A).

< Reference Example 7>
It replaces with the 1st compound (C), and is the same as the above-mentioned reference example 3 except having used the 1st compound (D) denoted by the following formula (1-2) described in patent documents 1. Thus, a pigment composition (7) was obtained.

< Reference Example 8>
A pigment composition (8) was obtained in the same manner as in Reference Example 7 except that the second compound (B) was used in place of the second compound (A).

< Reference Example 9>
It is the same as that of the above-mentioned reference example 3 except having replaced with the 1st compound (C) and having used the 1st compound (E) represented by the following formula (1-1) described in patent document 1. Thus, a pigment composition (9) was obtained.

< Reference Example 10>
A pigment composition (10) was obtained in the same manner as in Reference Example 9 except that the second compound (B) was used in place of the second compound (A).

  Table 3 shows combinations of pigments and pigment dispersants (first compound and second compound) used in preparing the pigment compositions (1) to (10).

[Preparation of pigment dispersion (pigment colorant for color filter (CF))]
<Example 11>
Acrylic resin varnish having an average molecular weight of 12000 and a solid content concentration of 40% obtained by copolymerizing methacrylic acid / benzyl acrylate / styrene / hydroxyethyl acrylate in a molar ratio of 25/50/15/10 is used as follows: A pigment dispersion was prepared according to the method shown in (1). 50 parts of the above acrylic resin varnish, 20 parts of the pigment composition (1) and 20 parts of propylene glycol-1-monomethyl ether-2-acetate as a solvent are mixed and premixed, and then dispersed using a horizontal bead mill. Thus, a pigment colorant for CF (Example 11) was obtained.

<Examples 12 to 20>
A pigment colorant for CF (Examples 12 to 20) was obtained in the same manner as in Example 11 except that the pigment compositions (2) to (10) were used in place of the pigment composition (1). .

<Comparative Example 1>
A pigment colorant for CF (Comparative Example 1) was obtained in the same manner as in Example 11 except that PR177 not treated with a pigment dispersant was used in place of the pigment composition (1).

<Comparative example 2>
Other than replacing 50 parts of 5% dilute acetic acid solution (2.5 parts solids) of the first compound (C) with 200 parts (10 parts solids) and not using the second compound (A) Obtained a pigment composition (11) in the same manner as in Reference Example 1 described above. A CF pigment colorant (Comparative Example 2) was obtained in the same manner as in Example 11 except that the pigment composition (11) was used instead of the pigment composition (1).

<Comparative Example 3>
A CF pigment colorant (Comparative Example 3) was obtained in the same manner as in Comparative Example 2 except that the first compound (C) was replaced with the first compound (D).

<Comparative example 4>
A CF pigment colorant (Comparative Example 4) was obtained in the same manner as in Comparative Example 2 except that the first compound (C) was replaced with the first compound (E).

<Comparative Example 5>
A CF pigment as in Comparative Example 2 except that the first compound (C) is replaced with another compound (X) represented by the following formula (X) described in Patent Document 3. A colorant (Comparative Example 5) was obtained.

  Combinations of pigments used in preparing the pigment colorants for CF of Examples 12 to 20 and Comparative Examples 1 to 5 and pigment dispersants (first compound, second compound, and other compounds) Table 4 shows.

[Evaluation]
For the pigment colorants for CF of Examples 11 to 20 and Comparative Examples 1 to 5, (1) fluidity (storage stability), (2) gloss on the color development surface, (3) presence or absence of foreign matter in the coating film And (4) Contrast was evaluated. Each evaluation method is shown below. The evaluation results are shown in Table 5.

(1) Fluidity (storage stability)
Using an E-type viscometer, the viscosity (mPa · s) of the CF pigment colorant immediately after preparation (initial stage) and after standing for 1 month at 25 ° C. (after standing) is measured to evaluate fluidity. Standard. The measurement conditions were temperature: room temperature (25 ° C.) and rotor rotation speed: 6 rpm. Further, “viscosity after standing / initial viscosity (%)” was calculated, and storage stability was evaluated according to the following criteria.
○: “Viscosity after standing / initial viscosity” is 110% or less ×: “Viscosity after standing / initial viscosity” exceeds 110%

(2) A color development surface was formed by developing a CF pigment colorant on a polypropylene film using a gloss bar coater (winding thickness: 0.45 mm). The gloss of the developed color surface was visually observed and observed using a gloss meter, and “gloss of the developed color surface” was evaluated according to the following criteria. It can be determined that the higher the gloss of the color development surface, the better.
◎: Very good ○: Good ×: Bad

(3) Presence / absence of foreign matter in coating film Using a spinner, a CF pigment colorant was applied to a glass substrate, dried at 90 ° C for 2 minutes, and then heated at 270 ° C for 30 minutes to form a coating film. Using a microscope, the surface (application surface) of the formed coating film was observed at 200 times to confirm the presence or absence of foreign matter, and “existence of foreign matter in the coating film” was evaluated according to the following criteria.
◎: No foreign matter ○: Slight foreign matter ×: Foreign matter

(4) Contrast A CF pigment colorant was applied to a glass substrate using a spinner, dried at 90 ° C. for 2 minutes, and then heated at 230 ° C. for 30 minutes to form a coating film. Further, three coating films were formed by changing the spinner speed. The contrast (bright / dark) was measured by measuring the brightness and dark brightness of the coating film formed using a contrast meter (manufactured by Eye System Co., Ltd.). Furthermore, the color of the coating film was measured using a spectrophotometer (trade name “U-2000A”, manufactured by Hitachi, Ltd.), and chromaticity x was measured. An approximate straight line was drawn on the graph created by plotting contrast against chromaticity x, and the contrast at chromaticity x = 0.650 was read. The contrast ratio (%) of each Example and Comparative Example was calculated with the contrast of Comparative Example 2 being “100%”. Further, “contrast” was evaluated according to the following criteria.
○: 110% or more Δ: 90% or more and less than 110% ×: less than 90%

As shown in Table 5, the pigment colorant for CF of the Examples has a low viscosity, good storage stability, and good gloss on the color development surface compared to the CF pigment colorant of Comparative Example. It is clear that no foreign matter is generated in the coating film and the contrast is high. From the above, it is clear that the pigment dispersant of the reference example has an excellent effect.

Further, the pigment composition of Reference Example was used for printing ink such as offset ink; various paints such as nitrocellulose lacquer and melamine alkyd paint; and colorant of synthetic resin such as vinyl chloride resin. As a result, in any case, the pigment did not aggregate and showed good dispersibility. In addition, the pigment dispersant of Reference Example was used for the preparation of electrophotographic dry or wet toners, ink jet recording inks, thermal transfer recording inks, writing instrument inks, etc., which have recently been particularly required to have high dispersibility. . As a result, excellent dispersibility was exhibited in all cases.

  The pigment dispersant of the present invention includes printing ink (offset ink, gravure ink, etc.), various paints, plastics, pigment printing agents, electrophotographic dry or wet toner, ink jet recording ink, thermal transfer recording ink, color filter resist. It is useful as a dispersant blended in ink for writing instruments.

Claims (4)

A pigment colorant for a color filter comprising a pigment composition containing a pigment and a pigment dispersant, and a film-forming material,
The pigment dispersing agent, a pigment colorant comprising a second compound, a represented by a first compound represented by the following general formula (1), the following general formula (2).

(In the general formula (1), X represents a hydrogen atom or an acylamino group, Y represents an anthraquinonylamino group, a phenylamino group, or a phenoxy group having a hydrogen atom or an acylamino group at the 5-position; _{1 to} R ₄ each independently represents a substituted or unsubstituted alkyl group or cycloalkyl group, and n and m each independently represent a number of 2 to 30, provided that R ₁ , R _2, R ₃ and R ₄ may form a ring that may contain a nitrogen atom, an oxygen atom, or a sulfur atom together with the adjacent nitrogen atom.

(In the general formula (2), each Z independently represents a branched or straight chain alkylene group having 1 to 4 carbon atoms, PIM represents a substituted or unsubstituted phthalimidomethyl group, and a represents 1 represents a number of 1 to 2 and b represents a number of 0 to 3) The first compound is at least one of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-5). And
The pigment colorant according to claim 1, wherein the second compound is at least one of a compound represented by the following formula (2-1) and a compound represented by the following formula (2-2).

Amount of the pigment 100 parts by weight against that before Symbol first compound of the pigment composition is a 0.5 to 30 parts by weight,
Pigment colorant of claim 1 or 2 the amount is 0.5 to 30 parts by weight of the pigment composition wherein the SL front against the pigment 100 parts by weight the second compound in the. The blending ratio (by mass) of the first compound and the second compound in the pigment composition is first compound: second compound = 25: 75 to 75:25. The pigment coloring agent as described in any one of these.