JP2014024906A - Method for producing pigment fine particle, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a triarylmethane-based pigment fine particle capable of allowing a color filter for liquid crystal display devices, in which filter the triarylmethane-based pigment fine particle is used, to have high luminance, a tone to be unchanged even by a long-term thermal history and light irradiation, and high contrast.SOLUTION: The triarylmethane-based pigment fine particle shown by general formula (1) is obtained by respectively circulating a dyestuff-dissolved solution and a heteropolyoxometalate anion-dissolved solution in separate micro-sized tubes in liquid-tight states and reacting a dyestuff in the dyestuff-dissolved solution with a heteropolyoxometalate anion in the heteropolyoxometalate anion-dissolved solution in a minute space under a high reaction temperature condition while remarkably enhancing mixability thereof.

Description

The present invention relates to a method for producing triarylmethane pigment fine particles, and a color filter using pigment fine particles obtained by the production method.

  A color filter such as a liquid crystal display device has a red pixel portion (R), a green pixel portion (G), and a blue pixel portion (B). Each of these pixel portions has a structure in which a thin film of a synthetic resin in which an organic pigment is dispersed is provided on a substrate, and organic pigments of red, green, and blue are used as the organic pigment.

Among these pixel portions, as a blue organic pigment for forming a blue pixel portion, an ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) is generally used, and the color is adjusted as necessary. Therefore, a small amount of purple organic pigment dioxazine violet pigment (CI Pigment Violet 23) is used in combination.
Organic pigments used in the production of color filters have characteristics that are completely different from conventional general-purpose applications. Specifically, there is a demand for making display screens of liquid crystal display devices brighter (higher brightness). . However, when the dioxazine violet pigment is used in combination with the ε-type copper phthalocyanine pigment, high brightness cannot be achieved. Therefore, particularly high brightness is particularly required for the organic pigment used in the blue pixel portion (B).

  In order to cope with such high luminance, C.I. is superior to the ε-type copper phthalocyanine pigment in terms of luminance. I. Recently, it has been studied to use a triarylmethane pigment such as CI Pigment Blue 1 for a blue pixel portion of a color filter (Patent Documents 1 to 3).

This C.I. I. As CI Pigment Blue 1, a final color of BASF (FANAL BLUE D6340, D6390) having the following chemical structure is prominent. I. Pigment Blue 1 is obtained by lake-forming Victoria Pure Blue BO, which is a basic triarylmethane dye, with a heteropoly acid such as phosphomolybdic acid or phosphotungsten molybdic acid. Thus obtained C.I. I. Pigment Blue 1, a pair of cation wherein X ^- is to be Keggin _{PMo x W 12-x O 40} .

(In the general formula (I), R ¹ , R ² and R ³ are all ethyl groups, R ⁴ is a hydrogen atom, and X ⁻ is a Keggin-type lintongue molybdate anion or phosphomolybdate anion.)
However, even when these triarylmethane pigments are used for the preparation of the blue pixel portion of a color filter, satisfactory brightness can still be maintained for a long time under high temperatures exceeding 200 ° C and under light irradiation. However, the reality is that it is insufficient in terms of heat resistance and light resistance.

  On the other hand, the problem when using pigments in the color filter is the size of the particles. Pigments are rarely obtained in a single crystal and often exist as aggregates. The color characteristics of the aggregate change depending on the aggregate size and crystal form, and when the particle size is large, it is difficult to improve the color characteristics such as the color gamut, luminance, and hue. On the other hand, there is known a method for enhancing color characteristics by nano-size pigment particles using a microreactor (Patent Document 4). However, these are azo-based, phthalocyanine-based, quinacridone-based pigments, and a method for producing nano-sized particles using a triarylmethane-based pigment is not known.

JP 2001-81348 A JP 2010-83912 A JP 2010-85444 A Japanese Patent No. 4587757

  That is, an object of the present invention is to provide a liquid crystal display device having high contrast and higher contrast than that of the conventional method without losing the conventional characteristics of high brightness and long-term thermal history and no light change due to light irradiation. It is to provide triarylmethane-based pigment fine particles that can provide a color filter for use.

  As a result of intensive studies, the present inventors have found that a dye solution represented by the following general formula (2) and a heteropolyoxometalate anion solution represented by the following general formula (3) are separated from each other. The tria represented by the following general formula (1) is distributed in a liquid-tight state in the pipe, and the mixing property of the fluid is significantly higher than that of a general batch reaction under a high reaction temperature condition, and the reaction is performed in a fine space. Reel methane pigment fine particles can be obtained, and the resulting triarylmethane pigment fine particles have high brightness and long-term heat history and light irradiation, without losing the conventional characteristics of the hue. It has been found that a color filter for a liquid crystal display device having a higher contrast than the method can be provided, and the present invention has been completed.

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, X ⁻ represents (P ₂ Mo _y W _18-y O ₆₂ ) ⁶⁻ / 6, where y is an integer from 0 to 3.

^{(Wherein, R 1, R 2, R} 3, R 4, R 5 good hydrogen atoms be the same or different, an alkyl group having 1 to 8 carbon atoms or a phenyl ^{group,, A n-is,} n-valent And n represents an arbitrary natural number.)

(Y is an integer from 0 to 3.)

  According to the present invention, a triaryl that can provide a color filter for a liquid crystal display device having a higher contrast than that of the conventional method without impairing the conventional characteristics of high brightness and long-term heat history and no change in hue due to light irradiation. Methane pigment fine particles can be provided.

Schematic of microreactor. The disassembled perspective view of the laminated body which a microreactor has. The perspective view of the mixing plate which is a structural member of a microreactor. The top view of the mixing plate which is a structural member of a microreactor. The perspective view of the temperature control plate which is a structural member of a microreactor. The perspective view of the laminated body which a micro heat exchanger has Schematic of a micro heat exchanger. The disassembled perspective view of the laminated body which a micro heat exchanger has. Schematic diagram schematically showing the manufacturing equipment used in the examples

The triarylmethane-based pigment fine particles of the present invention include a dye solution represented by the general formula (2),
The solution of the heteropolyoxometalate anion represented by the general formula (3) is circulated in a separate fine tube in a liquid-tight state, and the fluid mixing property is higher than that of a general batch reaction under high reaction temperature conditions. It can be obtained by reacting in a fine space that is remarkably enhanced.

The reaction temperature under the high reaction temperature condition is not particularly limited as long as the reaction proceeds, but the reaction temperature is preferably higher than 40 ° C, more preferably 80 ° C or higher. When the reaction temperature is 40 ° C. or lower, contrast and the like are lowered.

The dye solution represented by the general formula (2) and the heteropolyoxometalate anion solution represented by the general formula (3) are circulated in separate microtubules in a liquid-tight state. The volume of the fine space that is significantly higher than that of the batch reaction is not particularly limited, but is preferably 100 cm ³ or less, more preferably 50 cm ³ or less, and even more preferably 25 cm ³ or less. 100
If it exceeds cm ³ , it is difficult to precisely control the mixing property and temperature, and the contrast and the like are lowered.

In the present invention, a dye solution represented by the general formula (2) and a heteropolyoxometalate anion solution represented by the general formula (3) are circulated in separate microtubules in a liquid-tight state. However, various mechanical means can be used as long as the miscibility of the fluid is significantly higher than that of a general batch reaction under a high reaction temperature condition and the reaction can be performed in a fine space. Examples of the mechanical means include a static mixer, an ejector, and a microreactor having a fine channel through which a plurality of fluids circulate and a mixing portion of the fluids.

  As the microreactor, a known and commonly used type such as Y type or T type can be used, and a commercially available microreactor can be used. For example, a microreactor having an interdigital channel structure, an institute Single mixer and caterpillar mixer manufactured by Tuto-Fle Microtechnic Mainz (IMM); Microglass reactor manufactured by Microglass; Cytos manufactured by CPC Systems; YM-1 and YM-2 mixers manufactured by Yamatake Corporation; Shimadzu GLC Mixing tees and tees (T-shaped connectors); IMT chip reactors manufactured by Micro Chemical Engineering Co., Ltd .; Toray Engineering Development Micro-Mixer, etc., can be used, both of which can be used in the present invention.

As an apparatus used in the present invention, a solution of a dye represented by the general formula (2) and a solution of a heteropolyoxometalate anion represented by the general formula (3) are respectively contained in separate microtubules. The microreactor which is distributed in a dense state, is significantly higher than a general batch reaction, has the fine space and can be easily controlled with precise temperature, and further, precise temperature control of each solution before passing through the microreactor. It is more preferable that a micro heat exchanger capable of generating
Hereinafter, an example of the microreactor and the micro heat exchanger that can be used more preferably will be described.

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, X ⁻ represents (P ₂ Mo _y W _18-y O ₆₂ ) ⁶⁻ / 6, where y is an integer from 0 to 3.

^{(Wherein, R 1, R 2, R} 3, R 4, R 5 good hydrogen atoms be the same or different, an alkyl group having 1 to 8 carbon atoms or a phenyl ^{group,, A n-is,} n-valent And n represents an arbitrary natural number.)

(Y is an integer from 0 to 3.)

Compounds of general formula (1) of the present invention, X ^- an anion portion made of, X ^- is a portion excluding the, comprising basic triarylmethane dyes cation. Conventionally known triarylmethane pigments and X ^- where was phosphate tongue strike molybdate anion or phosphomolybdate anion, it _is the table in _{(P 2 Mo y W 18-} y O 62) 6- / 6 of the present invention And y is a heteropolyoxometalate anion which is an integer from 0 to 3.

R ¹ , R ² , R ³ , R ⁴ , and R ⁵ in the compound of the general formula (1) of the present invention may be the same or different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or phenyl It is a group.
As a preferable cation moiety structure, for example, when R ¹ , R ² and R ³ on the nitrogen atom are ethyl groups and R ⁴ and R ⁵ are hydrogen atoms (corresponding to Victoria Pure Blue BO (Basic Blue 7)) When R ¹ and R ² on the nitrogen atom are both methyl groups, R ³ is a phenyl group and R ⁴ and R ⁵ are hydrogen atoms (corresponding to Victoria Blue B (Basic Blue 26)), R ¹ and R ² are both a methyl group, R ³ is an ethyl group, and R ⁴ and R ⁵ are hydrogen atoms (corresponding to Victoria Blue R (Basic Blue 11)), R ¹ on the nitrogen atom, R ² and R ³ are both methyl groups, R ⁴ is a phenyl group, and R ⁵ is a hydrogen atom [equivalent to Victoria Blue 4R (Basic Blue 8)]. The parentheses indicate corresponding dyes having the same cation moiety structure. That is, if only these cation structures are seen, they are all known as described later.

The compound of the present invention is characterized in that the counter anion X ⁻ is a specific anion. X of the present invention ^- _is represented by _{(P 2 Mo y W 18-} y O 62) 6- / 6, y is a heteropolyoxometalate anion is any integer of 0 to 3.

  Such a heteropolyacid can be easily obtained, for example, according to the method described in Inorganic Chemistry, vol 47, p3679. Specifically, it can be obtained by dissolving an alkali metal tungstate and an alkali metal molybdate in water, adding phosphoric acid thereto, and heating to reflux for 5 to 10 hours with heating and stirring. The heteropolyacid thus obtained can be converted to a Dawson type heteropolyoxometalate alkali metal salt in the same manner as described above by reacting with an alkali metal chloride.

Alternatively, an alkali metal molybdate salt is dissolved in water, hydrochloric acid is added thereto, and then α2-type deficient Dawson-type lintongue molybdate such as K ₁₀ (α2-type P ₂ W ₁₇ O ₆₁ ). It can be obtained by adding an alkali metal salt and stirring at 10 to 30 ° C. for 30 minutes to 2 hours. The heteropolyacid thus obtained can be converted to a Dawson type heteropolyoxometalate alkali metal salt in the same manner as described above by reacting with an alkali metal chloride.

  In the above-described method for producing a Dawson-type heteropolyoxometalate alkali metal salt, when precipitation from a reaction solution is difficult to obtain, the solubility is lowered by cooling the reaction solution, for example, to obtain a Dawson-type heteropolyoxometalate salt. Metallate alkali metal salts can be obtained with higher yield.

  The compound of the present invention can be easily produced, for example, by reacting the corresponding dye described above with the corresponding heteropolyacid or heteropolyoxometalate alkali metal salt described above. When the anion is a chloride ion and a heteropoly acid is used, a dehydrochlorination reaction is performed. When the anion is a chloride ion and the heteropolyoxometalate metal salt is used, a dealkalization is performed. It can manufacture by carrying out salt substitution by metal chloride reaction.

  Compared to the above-mentioned dehydrochlorination reaction using a heteropolyacid, it is possible to carry out the dealkali metal chloride reaction once after converting the heteropolyacid to a heteropolyoxometalate alkali metal salt, and the salt substitution can be carried out more reliably. This is preferable because not only the triarylmethane pigment of the present invention can be obtained at a high level, but also the triarylmethane pigment of the present invention can be obtained with a high purity with fewer by-products. Of course, the heteropolyoxometalate alkali metal salt can be used after being purified by recrystallization or the like. Deficient Dawson-type phosphotungstomolybdate alkali metal salts can be easily obtained using Dawson-type phosphotungstomolybdate heteropolyoxometalate alkali metal salt as a raw material, for example, according to the method described in Inorganic Synthesis, vol 27, p104. . Specifically, it can be obtained by dissolving a Dawson-type phosphotungstomolybdate heteropolyoxometalate alkali metal salt in water, adding an alkali metal hydrogencarbonate to this, and stirring while heating if necessary. .

Examples of the heteropolyoxometalate alkali metal salt include K ₆ (P ₂ MoW ₁₇ O ₆₂ ), K ₆ (P ₂ Mo ₂ W ₁₆ O ₆₂ ), and K ₆ (P ₂ Mo ₃ W ₁₅ O ₆₂ ). These may be used alone or in combination of two or more.

  Since the cation derived from the dye is monovalent, the use amount of the heteropolyacid or heteropolyoxometalate alkali metal salt, which is an anion source, is charged so as to be an equimolar number according to the ionic value. It is preferable to perform the above reaction.

  Since the triarylmethane pigment of the present invention includes a step of lake formation (water insolubilization) with a heteropolyacid (or since it is laked with water (water insolubilization) with a heteropolyacid), the triarylmethane pigment may be used during the production process or in any step after production. In the case of using water, in order to perform a more reliable reaction or prevent the rake structure of the obtained compound from being destroyed, for example, metal ions or halogen ions such as purified water, ion-exchanged water, pure water, etc. It is preferable to use water with as little content as possible.

  Since the triarylmethane pigment of the present invention has a structure combining a cation structure known per se and a known anion structure, the cation structure and the anion structure of the product obtained according to the production method described above are used. Can be easily identified by confirming that both are included. By measuring the infrared absorption spectrum of the product, it can be confirmed that the structure of the raw material used in the above reaction remains. In addition, since the product does not contain the anion of the dye used in the reaction or the cation of the heteropolyoxometalate, the reduction in the peak intensity inherent to the raw material by the fluorescent X-ray analysis or the disappearance of the peak It can be confirmed that the rake reaction has been performed. If necessary, more reliable identification is possible by performing elemental analysis on the product.

  The triarylmethane pigment of the present invention is a pigment because it has a lake structure and is insoluble in water. The triarylmethane pigment of the present invention thus obtained can be used as it is as a colorant such as a synthetic resin, but if necessary, it can be adjusted by adjusting the particle diameter by known and common pulverization or particle size increase. The colorant can be optimal for various applications. In the dry powder, the colorant preferably has an average primary particle diameter of 100 nm or less because a clearer blue colored product can be easily obtained.

  The liquid used for preparing the pigment solution can be used without limitation as long as it is a liquid that dissolves the pigment, and water can be mentioned as a preferable liquid. Alternatively, a mixture of water and an organic solvent may be used as long as it can dissolve the pigment.

  First, as the microreactor that can be preferably used, for example, a first flow path forming portion in which a first flow path through which a first fluid flows is formed, and a second flow path in which a second flow path through which a second fluid flows is formed. A mixing plate having a flow path forming portion, and an outlet of the first flow path and an outlet of the second flow path are opposed to each other via a merged flow path where the first fluid and the second fluid merge. The opening position of the outlet of the first flow path in the central axis direction of the combined flow path is included in or the same as the opening position of the second flow path in the central axis direction of the combined flow path. Mention may be made of microreactors.

  Hereinafter, an embodiment embodying the present invention will be described with reference to FIGS. FIG. 1 is a schematic view showing an example of the microreactor. The microreactor has a hollow case C, and a laminated body 11 in which various fine channels are formed is fixed in the case C. The laminated body 11 includes a first fluid F1 and a second fluid F2 that are mixed objects or reaction objects, and a first heat medium H1 (first medium) that performs heat exchange with each of the fluids F1 and F2. And the flow path through which the second heat medium H2 (second medium) flows is formed.

  A first fluid supply unit 4A that supplies the first fluid F1 into the case C is provided at the left end C1 of the case C, and a second fluid F2 that supplies the second fluid F2 into the case C is provided at the right end C2 of the case C. A fluid supply unit 4B is provided. Hereinafter, when the fluid supply units 4A and 4B are described without being distinguished from each other, the fluid supply unit 4 is simply described.

  The fluid supply unit 4 has an opening 2 formed at the end of the case C and a connector 3 connected to the opening 2. The connector 3 is connected to a tank for storing each of the fluids F1 and F2, a pressure pump, a pressure feeding mechanism including a pipe line connected to the pump, and the fluids F1 and F2 are pressurized by the mechanism. In the state, it is pumped to the connector 3 side. A space is provided between the opening 2 and each side surface 11a, 11b of the laminated body 11 fixed in the case C. The space temporarily stores the fluids F1, F2 sent from the pressure feeding mechanism. It functions as part S1, S2.

  In addition, at the upper end C3 of the case C, heating medium supply portions 7A and 7B for supplying the heating media H1 and H2 into the case C are formed, respectively. Similarly to the fluid supply unit 4, the heat medium supply units 7A and 7B have openings 5A and 5B and connectors 6A and 6B, respectively. The heat mediums H1 and H2 supplied to the heat medium supply units 7A and 7B pass through the flow path formed in the laminated body 11, and from the heat medium delivery units 7C and 7D formed at the lower end C4 of the case C. Each case C is sent to the outside. Each of the heat medium delivery sections 7C and 7D has openings 5C and 5D and connectors 6C and 6D, respectively, similarly to the fluid supply section 4.

In addition, the lower end C4 of the case C is provided with a delivery unit 10 that sends out the mixed liquid F3 (or reaction liquid) of the fluids F1 and F2 mixed or reacted in the stacked body 11 to the outside of the case C. The delivery unit 10 includes an opening 8 and a connector 9 connected to the opening 8.
That is, the fluids F1 and F2 are supplied from the fluid supply portions 4A and 4B to the inside of the case C, and are mixed or reacted in the fine flow path formed in the stacked body 11. Here, the fluids F1 and F2 are mixed in the fine flow path, whereby the diffusion distance is shortened and the mixing speed is increased, and only a desired processing amount is efficiently mixed. The mixed liquid F3 (or reaction liquid) is sent out from the sending section 10 to the outside of the case C. The position of the case C of the microreactor, the fluid supply units 4A and 4B, the delivery unit 10 and the like are not limited to the above configuration, and can be changed as appropriate.

Next, the laminate 11 will be described. As shown in FIG. 2, the laminated body 11 is provided with the plate group 12 in which the flow path was formed between each rectangular-shaped cover plates P1 and P2.
The plate group 12 is configured by laminating three temperature control plates 13 and two mixing plates 14. In the present embodiment, the temperature control plate 13 is the uppermost layer and the lowermost layer, and the mixing plate 14 is stacked in a state of being sandwiched between any of the temperature control plates 13.

  Each cover plate P1, P2, each temperature control plate 13, and each mixing plate 14 are formed in the same rectangular shape. Moreover, the material of each cover plate P1, P2, temperature control plate 13, and mixing plate is not specifically limited, For example, the process for forming a flow path, such as a metal material, resin, glass, ceramics, is easy, and each plate 13 , 14, P1, P2 may be any material that can be fixed to each other in a close contact state in which liquid leakage is unlikely to occur. Moreover, each plate 13, 14, P1, P2 may be formed from the same material, and may be formed from a different material. For example, each plate 13, 14, P2, P2 may be formed from stainless steel and fixed in a tight contact state by diffusion bonding. The processing method of each of the plates 13, 14, P2, P2 is in accordance with the material among various known methods such as injection molding, solvent casting method, melt replica method, cutting, etching, photolithography, laser application, and the like. A suitable method can be selected.

Next, the mixing plate 14 will be described in detail with reference to FIGS. As shown in FIG. 3, the mixing plate 14 of the present embodiment is composed of a pair of plates and has a rectangular and plate-shaped first flow path forming portion 14A and a second flow path forming portion 14B.
14 A of 1st flow-path formation parts have the three 1st flow paths 15 in the center part of the transversal direction (Y direction in a figure) in the upper surface 14a. The first flow paths 15 are arranged at equal intervals and are formed in a groove shape from the left end 14b to the right end 14c of the first flow path forming portion 14A, and the left end 14b, the right end 14c, and the upper surface 14a. Is open. Each opening of the left end 14 b is an inlet 15 a of the first flow path 15, and the opening of the right end 14 c is an outlet 15 b of the first flow path 15. The inlet 15a communicates with the first fluid supply unit 4A to which the first fluid F1 is supplied.

Further, the first flow path 15 is provided with a large diameter section 16 having a large flow path diameter, a small diameter section 17 having a small flow path diameter, and a tapered section 18 for gradual change in diameter from the large diameter section 16 to the small diameter section 17. It has been.
The large-diameter portion 16 is a flow path having a rectangular cross section in a direction orthogonal to the flow direction, and extends from the left end 14b to the right end 14c. The width and depth of the large-diameter portion 16 are preferably in the range of, for example, a width of 0.1 mm or more and 100 mm or less and a depth of 5 mm or less in order to ensure uniformity of the temperature distribution of the fluid and device strength. A range of 1 mm to 20 mm and a depth of 2 mm is more preferable. In other words, the shape of the large-diameter portion 16 is such that the pressure loss does not increase excessively, the flow path is not easily blocked, the flow path can be quickly controlled for heating and cooling, and the productivity can be improved. Any road shape may be used.

  The small-diameter portion 17 is also a flow channel formed in a rectangular cross section, and extends from the front of the right end 14c toward the right end 14c. The small-diameter portion 17 only needs to have a cross-sectional area that is at least smaller than the cross-sectional area of the large-diameter portion 16, for example, a range of width 0.1 mm to 20 mm, depth 5 mm or less, width 0.1 mm to 5 mm, depth The range of 2 mm or less is more preferable. That is, as the shape of the small-diameter portion 17, the pressure loss does not become excessively large, the flow path is not easily blocked, the flow path can be quickly controlled for heating and cooling, and the productivity can be improved. Any shape is acceptable.

  Further, a joint channel 19 having a space of a predetermined width is provided between the first channel forming portion 14A and the second channel forming portion 14B. In FIG. 3, the bottom surface and the top surface are opened, and the mixing plate 14 has an opening on the front surface 14g side and an opening on the back surface 14h side. The opening part 19c on the front surface 14g side is an outlet of the combined flow path 19 and communicates with the above-described delivery part 10. The opening 19b on the back surface 14h side is closed by the case C or other members. The joint channel 19 is a long channel having a rectangular shape in a plan view, each side surface of which is constituted by the first channel forming unit 14A and the second channel forming unit 14B, and its longitudinal direction. Is parallel to the short direction of the mixing plate 14.

  The second flow path forming portion 14B has a second flow path 20 through which the second fluid F2 flows, and is formed symmetrically (line symmetric) with respect to the first flow path forming portion 14A with respect to the combined flow path 19. Yes. That is, three second flow paths 20 are formed in a groove shape at the center in the short direction on the upper surface 14d of the second flow path forming portion 14B, and are arranged at equal intervals. Each second flow path 20 is open at the left end 14e, the right end 14f, the upper surface 14d, and the bottom surface. Each opening of the left end 14 e is an outlet 20 b of the second flow path 20, and the opening of the right end 14 f constitutes an inlet 20 a of the second flow path 20. These inlets 20a communicate with the second fluid supply unit 4B to which the second fluid F2 is supplied.

  Moreover, the 2nd flow path 20 has the large diameter part 21 and the small diameter part 22, and the taper part 23 provided among them. The large diameter portion 21 has the same shape and the same flow path diameter as the large diameter portion 16 of the first flow path forming portion 14A, and extends from the right end 14f of the second flow path forming portion 14B to the front of the left end 14e. The small diameter portion 22 also has the same shape and the same flow path diameter as the small diameter portion 17 of the first flow path forming portion 14A, and extends from the front of the left end 14e toward the left end 14e.

  As shown in FIG. 4, the first and second flow path forming portions 14 </ b> A and 14 </ b> B formed in this way are configured such that the outlet 15 b of the first flow path 15 and the outlet 20 b of the second flow path 20 are combined channels 19. It arrange | positions so that it may become the position which faced one-on-one via. Further, the outlet 15b of the first flow path 15 is arranged so that the opening position in the direction of the central axis X1 of the combined flow path 19 is the same as the opening position of the outlet 20b of the second flow path 20 in the central axis X1. The Furthermore, the opening surfaces of the outlets 15b and 20b are parallel. Moreover, the central axis in the cross section of exit 15b, 20b of the 1st flow path 15 and the 2nd flow path 20 is the same central axis X2. The first flow path 15 does not need to be provided on the left side in plan view, and may be on the right side, and the second flow path 20 does not have to be provided on the right side in plan view and may be on the left side. Further, the outlets 15b of the three first flow paths 15 are arranged along the longitudinal direction of the combined flow path 19 on one side face among the opposing side faces of the combined flow path 19, and three second flow streams are arranged on the other side face. The outlet 20 b of the channel 20 is arranged along the longitudinal direction of the combined channel 19.

  For this reason, when each fluid F1, F2 is supplied in a pressurized state from the inlets 15a, 20a of the first channel 15 and the second channel 20, respectively, the fluids F1, F2 flow through the large diameter portions 16, 21, It flows into each small diameter part 17 and 22 via each taper part 18 and 23. The fluids F1 and F2 that have flowed into the small diameter portions 17 and 22 flow into the combined flow path 19 from the outlets 15b and 20b at a flow velocity that is greater than the flow velocity when flowing into the inlets 15a and 20a. At this time, as described above, the outlets 15b and 20b are at the same opening position in the direction of the central axis X1 and are opposed one-to-one, so that the flows of the fluids F1 and F2 sent from the outlets 15b and 20b are merged. The road 19 collides from the front. For this reason, compared with the case where each fluid F1, F2 is made to merge in a laminar flow state, the contact area of each fluid F1, F2 can be increased and it can mix efficiently. Further, by causing the flows of the fluids F1 and F2 facing each other from the front to collide, the fluid element in each of the fluids F1 and F2 is a second fluid that is in the direction opposite to the direction of the flow of the first fluid F1. Since the shear force is received from the direction of the flow of F2, the mixing speed can be increased. In particular, when at least one of the fluids F1 and F2 is a fluid that has low fluidity and is difficult to mix, that is, when it is a high-viscosity fluid, or when the viscosities are greatly different from each other, it is particularly effective.

Since the rear surface side opening 19b of the combined channel 19 is closed, the fluids F1 and F2 that have collided flow toward the opening 19c due to the pressure of the main liquid pressure feeding mechanism.
Considering the pressure loss generated in the combined flow path 19, stable flow of high-viscosity fluid and heteroviscous fluid, mixing force, and device strength, the width of the combined flow path 19, that is, the distance between the outlets 15 b and 20 b is The depth is preferably 0.1 mm or more and 30 mm or less, and the depth is preferably 0.3 mm or more. This width can be changed according to the viscosity (ease of flow) of the fluids F1 and F2 and the target degree of mixing. If the width is shortened, the pressure loss becomes relatively large, but the collision force between the fluids can be increased and the shear force in the fluid can be increased. If the width is increased, the impact force becomes relatively weak, but the pressure loss can be reduced.

  Next, the temperature control plate 13 will be described with reference to FIG. The temperature control plate 13 is formed in a rectangular shape and a plate shape, and has almost the same size as the mixing plate 14. The temperature control plate 13 has a heat insulating portion 30 at a position in the center in the longitudinal direction and overlapping with the merge channel 19 when the mixing plate 14 is laminated. The heat insulating portion 30 is formed by cutting out in a long shape from the front surface 13c of the temperature control plate 13 in the depth direction (Y direction in the drawing), and penetrates in the thickness direction (Z direction in the drawing), and the front surface 13c. An opening 30a is provided on the side. The width of the heat insulating portion 30 is substantially the same as the width of the joint channel 19 of the mixing plate 14.

  A substantially rectangular recess 24 is formed on the left and right sides of the heat insulating portion 30. An inflow path 26 and an outflow path 27 formed in a groove shape on the upper surface 13 a of the temperature control plate 13 communicate with the recess 24.

  Further, on the front side and the back side of the recess 24, long wall portions 24 a and 24 b are formed so as to protrude from the bottom surface of the recess 24. The wall portions 24a and 24b are provided so as to extend in the longitudinal direction (X direction in the drawing) of the temperature control plate 13, and a part of the flow path is formed between the tip and the inner wall surface of the recess 24. A space is provided. Further, on the bottom surface of the recess 24, four long wall portions 25 are formed so as to protrude between the wall portions 24a and 24b. The wall portion 25 is shorter than the width of the recess 24 (the length in the X direction in the figure), and a space for forming a part of the flow path is provided between both ends of the wall portion 25 and the inner wall surface of the recess 24. Yes. These walls 24 a, 24 b, 25 divide the space in the recess 24 to form a flow path through which the heat medium H 1, H 2 flows, and the heat medium H 1, H 2 including the inflow path 26 and the outflow path 27 A heat medium flow path 31 is configured as a flowing medium flow path. The heat medium flow path 31 has the inflow path 26 on the back side as an inlet, extends from the center side of the temperature control plate 13 toward the left side 24c of the recess 24, bends in front of the left side 24c, and toward the right side 24d. Extend. Furthermore, it bends in front of the right side surface 24d and extends toward the left side surface 24c again. As described above, the heat medium flow path 31 has a bent shape that is bent a plurality of times in the recess 24, and uses the outflow path 27 provided on the front side as an outlet.

  The heat medium H1 is supplied to the heat medium flow path 31A formed in the left recess 24 of the temperature control plate 13, and the heat medium H2 is supplied to the heat medium flow path 31B formed in the right recess 24. When the mixing plate 14 is stacked above or below the temperature control plate 13, as shown in FIG. 12, the first heat flows through the heat medium H1 above or below the first flow path 15 through which the first fluid F1 flows. The medium flow path 31A overlaps, and the second heat medium flow path 31B through which the heat medium H2 flows is overlapped above or below the second flow path 20 through which the second fluid F2 flows. For this reason, heat exchange is performed between the first heat medium H1 and the first fluid, and heat exchange is performed between the second heat medium H2 and the second fluid.

  Since these heat medium flow paths 31A and 31B suppress heat transfer between the peripheral portions of the heat medium flow paths 31A and 31B due to the interposition of the heat insulating portion 30, the heat medium H1 and H2 having a large temperature difference are suppressed. Even if it supplies to each heat-medium flow path 31A, 31B, the temperature of heat-medium H1, H2 does not fall or raise remarkably from desired temperature. Therefore, even in the microreactor in which the temperatures of the fluids F1 and F2 in the flow path are likely to change, precise temperature adjustment of the first fluid and the second fluids F1 and F2 can be performed. Accordingly, since the fluids F1 and F2 can be prevented from falling below the desired temperature, the flow paths 15 and 20 and the combined flow path 19 are not clogged with precipitates, and in the production of fine particles by crystallization or the like. A reduction in productivity can be prevented.

  As shown in FIG. 5, when the three layers of the temperature control plates 13 and the two layers of the mixing plates 14 are alternately stacked, the heat insulating portion 30 of the temperature control plate 13 and the combined flow path 19 of the mixing plate 14 overlap to form the stacked body 11. The combined flow path 32 having the same depth as the length in the stacking direction is configured. On the left side of the combined flow path 32, six outlets 15 b of the first flow path 15 are opened, and on the right side, six second flow paths 20 are located at positions corresponding to the outlets 15 b of the first flow path 15. The outlet 20b is opened. When each temperature control plate 13 and each mixing plate 14 are bonded together, the first flow path 15 and the second flow path 20 of the mixing plate 14 are opened on the upper surface side by the bottom surface of the temperature control plate 13. Will be occluded. Further, the heating medium flow paths 31A and 31B of the temperature control plate 13 are closed at the upper surface side by the bottom surface of the mixing plate 14 or the bottom surface of the cover plate P1.

  In the laminated body 11 configured as described above, the first fluid F1 supplied in a pressurized state from the first fluid supply part 4A into the case C is temporarily stored in the storage part S1, and then stored in the laminated body 11. Divided into six first flow paths 15 provided. The second fluid F2 supplied in a pressurized state from the second fluid supply unit 4B into the case C is temporarily stored in the storage unit S2, and then the six second flow paths 20 provided in the stacked body 11. It is divided into.

  The first fluid F1 that has flowed into each first flow path 15 of the mixing plate 14 is sent from the large diameter part 16 to the small diameter part 17 while increasing the flow velocity, and is sent from the outlet 15b to the combined flow path 19. The second fluid F2 that has flowed into each second flow path 20 is sent from the large diameter part 21 to the small diameter part 22 while increasing the flow velocity, and is sent from the outlet 20b to the combined flow path 19.

  The minute flow of the first fluid F1 sent from the outlet 15b of each first flow path 15 has a one-to-one correspondence with the minute flow of the second fluid F2 sent from the outlet 20b of each second flow path 20 respectively. Collide from the front. For this reason, since the minute flows of the fluids F1 and F2 are mixed in the vicinity of the collision position, the mixing speed as a whole can be further increased.

  The fluids F1 and F2 sent from the six pairs of outlets 15b and 20b are mixed while generating turbulent flow in the combined flow path 19 and flow toward the outlet 32a of the combined flow path 32. The mixed solution F3 sent from the outlet 32a is sent to the sending unit 10 and is sent out of the case C from the sending unit 10.

  In this microreactor, when increasing the throughput of the fluids F1 and F2 to be mixed, the length of the combined flow path 32 is extended without changing the width of the combined flow path 32, that is, the distance between the outlets 15b and 20b. do it. Alternatively, without changing the width of the combined flow path 32, the number of the flow paths 15 and 20 that open to the side surface of the combined flow path 19 may be increased, or the number of layers of the mixing plate 14 may be increased. Therefore, the processing amount can be increased without reducing the mixing efficiency in the combined flow path 32. Further, in a microreactor having a small flow path width and a high pressure loss, the microreactor has a relatively large volume of the combined flow path 32 and can prevent the flow path from being blocked due to an increase in pressure loss. Furthermore, since the width of the combined flow path 32 can be appropriately changed according to the viscosity of the fluid to be mixed, the degree of freedom of the apparatus can be improved.

FIG. 6 shows a perspective view of a laminate that the micro heat exchanger has. FIG. 6 shows a structure in which a plate provided with a microtubular flow channel for flowing the mixed solution (A) and a plate provided with a flow channel for flowing a fluid for heat exchange between the mixed solution are alternately laminated. In the reactor, the laminate of the micro heat exchanger having the microtubular channel having a void size with a fluid cross-sectional area of 0.1 to 4.0 mm ² flowing in a liquid-tight manner in the microtubular channel It is a perspective view.

The micro heat exchanger is configured by alternately laminating a plurality of first plates (2 in 6) and second plates (3 in FIG. 6) having the same rectangular plate shape in 6, for example. Yes. Each one first plate is provided with a flow path having a cross-sectional area of 0.1 to 4.0 (mm ² ) (hereinafter, the plate provided with the flow path is referred to as a process plate). The second plate is provided with a flow channel for temperature control fluid (hereinafter referred to as a temperature control channel) (hereinafter, the plate provided with the temperature control channel is referred to as a temperature control plate). Then, as shown in FIG. 7, these supply ports and discharge ports are distributed and arranged in each region of the end surface 1b, 1c, side surface 1d, 1e of the chemical reaction device 1, and the mixed solution (A) is placed in these regions. And the joint part 32 which consists of the connector 30 and the joint part 31 for flowing a temperature control fluid is each connected.

  The fluid α (mixed solution) containing the mixed solution (A) is supplied from the end face 1b through these joint portions, and the fluid β containing the mixed solution (A) cooled by heat exchange is supplied to the end face 1c. The temperature control fluid γ is supplied from the side surface 1e and discharged to the side surface 1d.

  The shape of the micro heat exchanger in plan view is not limited to the rectangular shape shown in the figure, and may be a square shape or a rectangular shape with the side surfaces 1d and 1e longer than between the end surfaces 1b and 1c. Therefore, in accordance with the illustrated shape, the direction from the end surface 1b to the end surface 1c is referred to as the longitudinal direction of the process plate and the temperature control plate, and the direction from the side surface 1d to the side surface 1e is the short direction of the process plate and the temperature control plate. I will call it.

As shown in FIG. 8, the process plate has a channel 4 having a groove shape in cross section extending on one surface 2 a extending in the longitudinal direction of the process plate, and a plurality of process plates are arranged at a predetermined interval p ₀ in the short direction. Is. Let L be the length of the flow path 4. The cross-sectional shape is a width w ₀ and a depth d ₀ .

The cross-sectional shape of the flow path 4 can be appropriately set according to the type, flow rate, and flow path length L of the fluid α containing the mixed solution (A), but ensures the uniformity of the temperature distribution in the cross section. Therefore, the width w ₀ and the depth d ₀ are set in the range of 0.1 to 16 [mm] and 0.1 to 2 [mm], respectively. In addition, description of a width | variety and a depth is a case where a drawing is referred, Comprising: This value can be interpreted suitably so that it may become a wide value with respect to a heat transfer surface. Although it does not specifically limit, For example, 1-1000 pieces per plate, Preferably it is 10-100 pieces.

  The fluid α flows in each flow path 4, and is supplied from one end face 2b side and discharged to the other end face 2c side as shown by arrows in FIGS.

As shown in FIG. 6, the temperature control plate is provided with a temperature control flow path 6 having a concave groove shape on one surface 3 a at a predetermined interval. The cross-sectional area of the temperature control channel 6 is not particularly limited as long as heat can be transferred to the reaction channel, but is approximately in the range of 0.1 to 4.0 (mm ² ). More preferably, it is 0.3-1.0 (mm < ² >). The number of the temperature control flow paths 6 can adopt an appropriate number in consideration of heat exchange efficiency, and is not particularly limited, but is, for example, 1 to 1000, preferably 10 to 100 per plate. It is.

  As shown in FIGS. 6 and 8, the temperature control channel 6 flows in a plurality of main channels 6a arranged in the longitudinal direction of the temperature control plate and upstream and downstream ends of the main channel 6a. You may provide the supply side flow path 6b and the discharge side flow path 6c which are arrange | positioned substantially orthogonally to the path | route 4, and are connected to each main flow path 6a. 6 and 8, the supply-side flow path 6b and the discharge-side flow path 6c are bent at right angles twice and open to the outside from the side surfaces 3d and 3e of the temperature control plate, respectively. As for the number of each temperature control channel 6, only the main channel 6 a portion of the temperature control channel 6 is arranged, and the supply side channel 6 b and the discharge side channel 6 c are each composed of one. .

  In addition, each main flow path 6a of the temperature control flow path 6 is provided in a range in which the range in which the flow paths 4 are distributed overlaps the stack direction in the short direction of the temperature control plate.

Preferably, the main flow paths 6a are arranged in the stacking direction so as to be positioned between two adjacent flow paths 4, 4. More preferably, each main flow path 6a overlaps each flow path 4 in the stacking direction. Arrange as follows.
The plurality of process plates and temperature control plates are stacked by alternately stacking process plates and temperature control plates in the same direction, and are fixed to each other and stacked.
Therefore, in the form of the micro heat exchanger, each flow path 4 and the temperature control flow path 6 are covered with a lower surface of a plate on which a groove is opened, and a tunnel shape having a rectangular cross section with both ends open. It is said.
An appropriate metal material can be used for each process plate and temperature control plate.

The embodiment of the present invention will be described more specifically.
For example, when a lake pigment is produced by a batch method, a solution of a heteropolyoxometalate anion represented by the general formula (3) is dropped into a dye solution to cause a lake reaction to form a pigment. In the process, it is necessary to first rake at 40 ° C., and then raise the temperature to 80 ° C. In this case, if the rake temperature is increased, the particle size becomes large, and if the aging step is omitted, the particles have insufficient heat resistance. In other words, two processes of rake and aging are indispensable. It is expected that what is mainly happening in this process is particle formation and particle growth by rake formation and strengthening of the bond between the dye and pigment particles by aging. A low temperature that suppresses particle growth is desirable for obtaining fine particles, but a high temperature is required for strengthening bonding. Although the process is separated in the batch reaction, it is a reaction under contradictory conditions, and there is a limit to the refinement of the pigment.

  On the other hand, since the microreactor is a reaction fine space reaction, it is possible to solve these problems because the mixing property is high and the reaction time can be shortened. That is, by reacting at a high temperature using a microreactor, rake formation and ripening can be performed in a short time, and finer pigment particles can be produced for batch reaction.

  In the present invention, the average particle diameter of primary particles is measured as follows. First, the particle | grains in a visual field are image | photographed with a transmission electron microscope or a scanning electron microscope. And the longest length (maximum length) of the internal diameter of each particle | grain is calculated | required about 50 of the primary particles which comprise the aggregate on a two-dimensional image. The average value of the maximum length of each particle is defined as the average particle size of the primary particles.

  The triarylmethane pigment of the present invention has a small hue change and excellent heat resistance even after a thermal history at a high temperature in various known and commonly used applications. In such a case, it is possible to obtain a color filter of a liquid crystal display device that has high luminance, excellent heat resistance of the luminance, and capable of displaying a bright image for a long time.

  In the color filter of the present invention, as a backlight light source, a conventional cold cathode tube (CCFL light source), a white LED (LED; Light Emitting Diode) light source, a three-color independent LED light source, a white organic EL (EL; Electro Luminescence) Any light source or the like can be used.

  If necessary, the triarylmethane pigment of the present invention may be an ε-type copper phthalocyanine pigment or a dioxazine pigment (CI Pigment Violet 23, CI Pigment Violet 37, CI Pigment Blue 80, or the like). Of metal-free or metal phthalocyanine sulfonic acid derivatives, metal-free or metal phthalocyanine N- (dialkylamino) methyl derivatives, metal-free or metal phthalocyanine N- (dialkylaminoalkyl) sulfonic acid amide derivatives, dioxazine violet Organic pigment derivatives such as sulfonic acid derivatives, indanthrene blue sulfonic acid derivatives, phthalocyanine sulfonic acids, etc., and Dispavic 130, Dispersic 161, Dispersic 162, Dispersic 163, Disperse from Big Chemie 170, Dispersic 171, Dispersic 174, Dispersic 180, Dispersic 182, Dispersic 183, Dispersic 184, Dispersic 185, Dispersic 2000, Dispersic 2001, Dispersic 2020, Dispersic 2050, Dispersic 2070, Dispersic 2096, Dispersic 2150, Dispersic LPN21116, Disparvic LPN6919 Fuka 46, Fuka 47, Fuka 452, Fuka LP4008, Fuka 4009, Fuka LP4010, Fuka LP4050, LP4055, Fuka 401, Fuka 401, Fuka 401, Fuka 401, Fuka 401 402, Fuka 403, Fuka 450, Fuka 451, Fuka 453, F F 4540, Efka 4550, Efka LP 4560, Efka 120, Efka 150, Efka 1501, Evka 1502, Evka 1503, Lubrizol Solsperse 3000, Solsperse 9000, Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 17000, 18000, Solsperse 20000 Solsparse 21000, Solsparse 20000, Solsparse 24000, Solsparse 26000, Solsparse 27000, Solsparse 28000, Solsparse 32000, Solsparse 36000, Solsparse 37000, Solsparse 38000, Solsparse 41000, Solsparse 42000, Solsparse 43000, Solsparse 46000, Solsparse 4000, Solsperse 71000, Ajinomoto Co., Inc. Ajisper PB711, Ajisper PB821, Ajisper PB822, Ajisper PB814, Ajisper PN411, Ajisper PA111, dispersants, acrylic resins, urethane resins, alkyd resins, wood rosin, gum rosin, tall oil Natural rosin such as rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, modified rosin such as rosin oxide, maleated rosin, rosin amine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin modified phenolic rosin A synthetic resin that is liquid and water-insoluble at room temperature, such as a derivative, can be contained. Addition of these dispersants and resins also contributes to reduction of flocculation, improvement of pigment dispersion stability, and improvement of viscosity characteristics of the dispersion.

  The triarylmethane pigment of the present invention can be used for forming a color filter pixel portion by a conventionally known method. A typical method for dispersing the triarylmethane pigment of the present invention is a photolithography method, which is a photocurable composition described later on the side provided with the black matrix of a transparent substrate for a color filter. After applying to the surface, heating and drying (pre-baking), pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure the photocurable compound at the location corresponding to the pixel portion, and then the unexposed portion This is a method of developing with a developing solution, removing a non-pixel portion, and fixing the pixel portion to a transparent substrate. In this method, a pixel portion made of a cured colored film of a photocurable composition is formed on a transparent substrate.

  For each of the red, green, and blue colors, a photocurable composition to be described later is prepared, and a color filter having red, green, and blue colored pixel portions at predetermined positions is manufactured by repeating the above-described operation. I can do it. A blue pixel portion can be formed from the triarylmethane pigment of the present invention. In addition, in order to prepare the photocurable composition for forming a red pixel part and a green pixel part, a well-known and usual red pigment and green pigment can be used.

  Examples of the pigment for forming the red pixel portion include C.I. I. Pigment Red 177, 209, 242 and 254 are pigments for forming the green pixel portion, for example, C.I. I. Pigment Green 7, 10, 36, 47, 58 and the like. A yellow pigment can be used in combination for forming the red pixel portion and the green pixel portion. Thereafter, if necessary, the entire color filter can be heat-treated (post-baked) in order to thermally cure the unreacted photocurable compound.

Examples of a method for applying a photocurable composition described later on a transparent substrate such as glass include a spin coat method, a roll coat method, and an ink jet method.
Although the drying conditions of the coating film of the photocurable composition apply | coated to the transparent substrate differ also with the kind of each component, a compounding ratio, etc., they are 50-150 degreeC and are about 1 to 15 minutes normally. Moreover, as light used for photocuring of a photocurable composition, it is preferable to use the ultraviolet-ray of a wavelength range of 200-500 nm, or visible light. Various light sources that emit light in this wavelength range can be used.

  Examples of the developing method include a liquid piling method, a dipping method, and a spray method. After exposure and development of the photocurable composition, the transparent substrate on which the necessary color pixel portion is formed is washed with water and dried. The color filter thus obtained is subjected to a heat treatment (post-baking) at 90 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven to remove volatile components in the colored coating film, and at the same time, light The unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.

  The photocurable composition for forming the blue pixel portion of the color filter includes the triarylmethane pigment of the present invention, a dispersant, a photocurable compound, and an organic solvent as essential components, and if necessary, heat It can prepare by mixing these using a plastic resin. When the colored resin film that forms the blue pixel portion requires toughness that can withstand baking, etc. performed in the actual production of a color filter, a photocurable compound is used in preparing the photocurable composition. In addition, it is essential to use this thermoplastic resin in combination. When a thermoplastic resin is used in combination, it is preferable to use an organic solvent that dissolves it.

  As a method for producing the photocurable composition, the triarylmethane pigment of the present invention, an organic solvent and a dispersant are used as essential components, and these are mixed and stirred and dispersed so as to be uniform. After preparing a pigment dispersion for forming the pixel portion of the color filter, the photocurable composition is prepared by adding a photocurable compound and, if necessary, a thermoplastic resin or a photopolymerization initiator. Is generally used.

Here, as the dispersant and the organic solvent, those described above can be used.
Examples of the thermoplastic resin used for the preparation of the photocurable composition include urethane resins, acrylic resins, polyamide resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and the like. .

  Examples of the photocurable compound include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol di Bifunctional monomers such as acrylate, trimethylol propaton triacrylate, pentaerythritol triacrylate, tris [2- (meth) acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. Relatively high molecular weight such as low molecular weight polyfunctional monomer, polyester acrylate, polyurethane acrylate, polyether acrylate, etc. Functional monomer.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4 ′). -Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid and the like. Examples of commercially available photopolymerization initiators include “Irgacure (trade name) -184”, “Irgacure (trade name) -369”, “Darocur (trade name) -1173” manufactured by Ciba Specialty Chemicals, and BASF Corporation. “Lucirin-TPO”, Nippon Kayaku Co., Ltd. “Kayacure (trade name) DETX”, “Kayacure (trade name) OA”, Stofer “Bicure 10”, “Bicure 55”, Akzo Corporation “Trigonal PI” “Sandray 1000” manufactured by Sand, “Deep” manufactured by Upjohn, and “Biimidazole” manufactured by Kurokin Kasei.

  Moreover, a well-known and usual photosensitizer can also be used together with the said photoinitiator. Examples of the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom, nitriles or other compounds having a nitrogen atom. These can be used alone or in combination of two or more.

  The blending ratio of the photopolymerization initiator is not particularly limited, but is preferably in the range of 0.1 to 30% with respect to the compound having a photopolymerizable or photocurable functional group on a mass basis. If it is less than 0.1%, the photosensitivity at the time of photocuring tends to decrease, and if it exceeds 30%, crystals of the photopolymerization initiator are precipitated when the pigment-dispersed resist coating film is dried. May cause deterioration of film properties.

  Using each material as described above, on a mass basis, 300 to 1000 parts of organic solvent and 1 to 100 parts of dispersant are made uniform per 100 parts of the triarylmethane pigment of the present invention. The pigment dispersion can be obtained by stirring and dispersing. The pigment dispersion is then subjected to photopolymerization of 3 to 20 parts of the total thermoplastic resin and photocurable compound and 0.05 to 3 parts per part of photocurable compound per part of the triarylmethane pigment of the present invention. A photocurable composition for forming a color filter pixel portion can be obtained by adding an initiator and, if necessary, further an organic solvent and stirring and dispersing so as to be uniform.

  As the developer, a publicly known and commonly used organic solvent or alkaline aqueous solution can be used. In particular, when the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value and exhibits alkali solubility, the color filter can be washed with an alkaline aqueous solution. It is effective for forming the pixel portion.

  Among the pigment dispersion methods, the method for producing the color filter pixel portion by the photolithography method has been described in detail, but the color filter pixel portion prepared using the pigment composition for a color filter of the present invention has other electrodeposition methods, A color filter may be manufactured by forming a blue pixel portion by a transfer method, a micelle electrolysis method, a PVED (Photovoltaic Electrodeposition) method, an ink jet method, a reverse printing method, a thermosetting method, or the like.

  The color filter uses a photocurable composition of each color obtained by using a red pigment, a green pigment, and the triarylmethane pigment of the present invention as an organic pigment, and encapsulates a liquid crystal material between a pair of parallel transparent electrodes. The transparent electrode is divided into discontinuous fine sections, and a color selected from any one of red, green, and blue is provided for each of the fine sections divided into a grid by the black matrix on the transparent electrode. It can be obtained by providing filter colored pixel portions alternately in a pattern, or by providing a transparent electrode after forming color filter colored pixel portions on a substrate.

  The triarylmethane pigment of the present invention can provide a color pigment dispersion excellent in sharpness and lightness, and in addition to color filter applications, paints, plastics (resin molded products), printing inks, rubber, leather, textile printing, electrostatic images It can also be applied to coloring developing toner, ink jet recording ink, thermal transfer ink and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the range of these Examples from the first. Unless otherwise specified, “part”, “%”, and “ppm” are based on mass.

(Devices used in this example)
C. I. As shown in FIG. 9, a tank for storing a basic blue 7 solution and a K6 (P ₂ MoW ₁₇ O ₆₂ ) solution, a micro heat exchanger, a microreactor, and a tank for collecting a dispersion containing the obtained pigment fine particles are connected as shown in FIG. A manufacturing apparatus was used. The microreactor 72 in FIG. 9 is the microreactor shown in FIG. 2, and this microreactor has one mixing plate 14 and two temperature control plates 13 stacked on the upper limit of the mixing plate. Is sandwiched between two cover plates P1 and P2. The plate thickness is 2 mm for the mixing plate 14 and 1.0 mm for the temperature control plate 13. Two each of the first and second flow paths 15 and 20 formed in the mixing plate 14 are formed, and the wide flow path sections 16 and 21 are 8 mm wide × 1 mm deep × 36 mm long, with a narrow width. The parts 17 and 22 were made into width 2.0mm x depth 1.0mm x length 3mm. Further, the combined flow path 19 was 1.0 mm wide × 2.0 depth × 30 mm long. The heat medium flow paths 31A and 31B formed in the temperature control plate 13 were set to width 1.2 mm × depth 0.5 mm × length 40 mm. Further, the combined flow path 19 was 2.5 mm wide × 1.0 mm deep × 30 mm long.

  The micro heat exchangers 70 and 71 in FIG. 9 used the micro heat exchanger shown in FIG. In the micro heat exchanger, two process sheets having five flow paths 4 and three temperature control plates having five temperature control paths 6 are alternately stacked. The cross-sectional dimensions of the flow path 4 and the temperature control flow path 6 are both width 1.2 mm × depth 0.5 mm.

(Synthesis Example 1)
<Synthesis of Dawson type ^{_{(P 2 MoW 17 O 62)}} 6- hetero polyoxometalate>
(1) Adjustment _{6 of} K ₆ (P ₂ MoW ₁₇ O ₆₂ )
NaWO ₄ · 2H ₂ O (reagent manufactured by Wako Pure Chemical Industries, Ltd.) 44.0 g and Na ₂ MoO ₄ · 2H ₂ O (reagent manufactured by Kanto Chemical Co., Inc.) 1.90 g were dissolved in 230 g of purified water. While stirring, 64.9 g of 85% phosphoric acid was added using a dropping funnel. The resulting solution was heated to reflux for 8 hours. The reaction solution was cooled to room temperature, 1 drop of bromine water was added, and 45 g of potassium chloride was added with stirring. A heteropolyacid was thus obtained.

After further stirring for 1 hour, the resulting yellow precipitate K ₆ (P ₂ MoW ₁₇ O ₆₂ ) was filtered off and dried at 90 ° C. The yield was 29.4 g.
Analysis with a Fourier transform infrared spectrophotometer (FT-IR) (KBr / cm ⁻¹ ):
1091,960,915,783,530
From the analysis result of FT-IR, it was confirmed that this dried product is K ₆ (P ₂ MoW ₁₇ O ₆₂ ).

Example 1
(1) Production of Dawson type (P ₂ MoW ₁₇ O ₆₂ ) triarylmethane pigment by microreactor I. Basic Blue 7 (Tokyo Kasei Co., Ltd. reagent) 5.30g was put into purified water 350mL, and it stirred at 40 degreeC and melt | dissolved. Next, 8.3 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) obtained in Preparation 1 was dissolved in 50 mL of purified water. C. I. Dispersion containing basic blue solution and tanks 61 and 63 for containing K ₆ (P ₂ MoW ₁₇ O ₆₂ ) solution, pumps 65 and 66 for feeding, heat exchangers 71 and 70, microreactor 72, and pigment fine particles obtained. A container 67 for storing the body was connected as shown in FIG.

Using the diaphragm pumps 65 and 66, the C.I. I. The basic blue solution and the K6 (P ₂ MoW ₁₇ O ₆₂ ) solution in the tank 63 were heated to 80 ° C. in each of the heat exchangers 71 and 70, and then a flow rate of 63 g / wt at a weight ratio of 5.3: 1. The mixed solution (A) was obtained in the microreactor 72. The liquid temperature (T1) of the mixed solution (A) at this time was 80 ° C. Next, the mixed solution (A) was transferred to a storage container 67 heated to 80 ° C. to obtain a dispersion 1 of pigment fine particles having a liquid temperature (T 1) of 80 ° C. After storing a predetermined amount, the heating source was removed and the mixture was cooled to 50 ° C. From the start of storage to the end of cooling, the inside of the storage container was stirred at 300 rpm with a stirring bar. After cooling, Dispersion 1 was filtered and washed 3 times with 300 mL of purified water. After the obtained solid was dried at 90 ° C., 10.4 g of a black-blue solid was obtained. The average particle diameter of the primary particles of the product consisting of the solid was 30 nm. The solid was pulverized with a commercially available juicer. In general formula (1), R ¹ , R ² and R ³ are ethyl groups and R ⁴ is a hydrogen atom, and X ⁻ is (P ₂ MoW ₁₇ O ₆₂ ) ^{6. A} triarylmethane-based lake pigment which is an anion composed of a heteropolyoxometalate represented by ⁻ / 6 was obtained.
Analysis with a Fourier transform infrared spectrophotometer (FT-IR) (KBr / cm ⁻¹ ):
2970, 1579, 1413, 1342, 1273, 1185, 1155, 1073, 954, 911, 786

C. I. From the results of FT-IR analysis of Basic Blue 7 itself, the results of FT-IR analysis of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) itself, and the results of FT-IR analysis of the above product, this product was obtained from C.I. I. It was confirmed that the cation structure of Basic Blue 7 and the anion structure of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) were maintained. In addition, as a result of fluorescent X-ray analysis, the peak intensity of this product based on the potassium ion of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) used for rake formation is significantly lower than when the raw materials are charged for rake formation. And C.I. I. It was inferred that the cation structure of Basic Blue 7 and the anion structure of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) were ionically bonded.

From these facts, the product thus obtained was obtained from the general formula (1) in which R ¹ , R ² and R ³ are ethyl groups and R ⁴ is a hydrogen atom, and X ⁻ is (P ₂ MoW ₁₇ O ₆₂₎ 6 ^/ it was possible to identify a triarylmethane pigment consisting of an anion consisting of Dawson-type polyoxometalate represented by ^6.

(Comparative Example 1)
Production of Dawson type (P ₂ MoW ₁₇ O ₆₂ ) triarylmethane pigment by batch method C.I. I. Basic Blue 7 (Tokyo Kasei Co., Ltd. reagent) 5.30g was put into purified water 350mL, and it stirred at 40 degreeC and melt | dissolved. Next, 10.0 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) obtained in the above adjustment 1 was dissolved in 40 mL of purified water. C. I. A K ₆ (P ₂ MoW ₁₇ O ₆₂ ) solution was added to the Basic Blue 7 solution, and the solution was stirred at 40 ° C. for 1 hour. Next, the internal temperature was raised to 80 ° C., and the mixture was further stirred at the temperature for 1 hour. After cooling, it was filtered and washed with 300 mL of purified water three times. After the obtained solid was dried at 90 ° C., 10.4 g of a black-blue solid was obtained. The average particle diameter of the primary particles of the product consisting of the solid was 30 nm. The solid was pulverized with a commercially available juicer. In general formula (I), R ¹ , R ² and R ³ are ethyl groups and R ⁴ is a hydrogen atom, and X ⁻ is (P ₂ MoW ₁₇ O ₆₂ ) ^{6. A} triarylmethane-based lake pigment which is an anion composed of a heteropolyoxometalate represented by ⁻ / 6 was obtained.
Analysis with a Fourier transform infrared spectrophotometer (FT-IR) (KBr / cm ⁻¹ ):
2970, 1579, 1413, 1342, 1273, 1185, 1155, 1073, 954, 911, 786

C. I. From the results of FT-IR analysis of Basic Blue 7 itself, the results of FT-IR analysis of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) itself, and the results of FT-IR analysis of the above product, this product was obtained from C.I. I. It was confirmed that the cation structure of Basic Blue 7 and the anion structure of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) were maintained. In addition, as a result of fluorescent X-ray analysis, the peak intensity of this product based on the potassium ion of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) used for rake formation is significantly lower than when the raw materials are charged for rake formation. And C.I. I. It was inferred that the cation structure of Basic Blue 7 and the anion structure of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) were ionically bonded.

From these facts, the product thus obtained was obtained from the general formula (1) in which R ¹ , R ² and R ³ are ethyl groups and R ⁴ is a hydrogen atom, and X ⁻ is (P ₂ MoW ₁₇ O ₆₂₎ 6 ^/ it was possible to identify a triarylmethane pigment consisting of an anion consisting of Dawson-type polyoxometalate represented by ^6.

(Comparative Example 2)
Production of Dawson type (P ₂ MoW ₁₇ O ₆₂ ) triarylmethane pigment by microreactor Each heat exchanger 71, 70 heating temperature and storage container 67 heating temperature in Example 1 were changed from 80 ° C. to 40 ° C. The same treatment as in Example 1 was performed, and 10.4 g of a black-blue solid was obtained. The average particle diameter of the primary particles of the solid product was 20 nm. The solid was pulverized with a commercially available juicer. In general formula (I), R ¹ , R ² and R ³ are ethyl groups and R ⁴ is a hydrogen atom, and X ⁻ is (P ₂ MoW ₁₇ O ₆₂ ) ^{6. A} triarylmethane-based lake pigment which is an anion composed of a heteropolyoxometalate represented by ⁻ / 6 was obtained.
Analysis with a Fourier transform infrared spectrophotometer (FT-IR) (KBr / cm ⁻¹ ):
2970, 1579, 1413, 1342, 1273, 1185, 1155, 1073, 954, 911, 786

C. I. From the results of FT-IR analysis of Basic Blue 7 itself, the results of FT-IR analysis of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) itself, and the results of FT-IR analysis of the above product, this product was obtained from C.I. I. It was confirmed that the cation structure of Basic Blue 7 and the anion structure of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) were maintained. In addition, as a result of fluorescent X-ray analysis, the peak intensity of this product based on the potassium ion of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) used for rake formation is significantly lower than when the raw materials are charged for rake formation. And C.I. I. It was inferred that the cation structure of Basic Blue 7 and the anion structure of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) were ionically bonded.

From these facts, the product thus obtained was obtained in the general formula (I) in which R ¹ , R ² and R ³ are ethyl groups and R ⁴ is a hydrogen atom, and X ⁻ is (P ₂ MoW ₁₇ O ₆₂₎ 6 ^/ it was possible to identify a triarylmethane pigment consisting of an anion consisting of Dawson-type polyoxometalate represented by ^6.

(Color filter)
1.80 parts of the triarylmethane pigment obtained in Example 1, 2.10 parts of BYK-2164 (Big Chemie), 11.10 parts of propylene glycol monomethyl ether acetate, and 0.3-0.4 mmφ sepul beads are placed in a polybin. The mixture was dispersed for 4 hours with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) to obtain a pigment dispersion. 75.00 parts of this pigment dispersion, 5.50 parts of polyester acrylate resin (Aronix (trade name) M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerythritol hexaacrylate (KAYARAD (trade name) DPHA, Nippon Kayaku) 5.00 parts manufactured by KK, 1.00 parts benzophenone (KAYACURE (trade name) BP-100, manufactured by Nippon Kayaku Co., Ltd.), 13.5 parts euker ester EEP (manufactured by Union Carbide) with a dispersion stirrer. The mixture was stirred and filtered through a filter having a pore size of 1.0 μm to obtain a color resist (photocurable composition).

This color resist was applied to a 50 mm × 50 mm, 1 mm thick glass using a spin coater so that the dry film thickness was 2 μm, and then pre-dried at 90 ° C. for 20 minutes to form a coating film. Including color filter.
In place of the triarylmethane pigment obtained in Example 1, the same operation as in the above color filter was performed except that the same amount of the triarylmethane pigment obtained in Comparative Examples 1 and 2 was used. A color filter containing was obtained.
For each of the color filters of Example 1 and Comparative Examples 1 and 2, the degree of change in hue and luminance immediately after preparation (before light irradiation) and after light irradiation was determined as follows.

<Light resistance test>
Each blue color filter created above was irradiated with light using a xenon light resistance tester (Suntest CPS + manufactured by ATLAS) under the conditions of 550 W / m ² , 63 ° C., 48 hours, and the chromaticity and brightness before and after irradiation were measured. The color difference ΔE * ab was compared with the luminance change as measured with a spectrophotometer CM-3500d manufactured by Konica Minolta. The results are shown in Table 1.

<Heat resistance test>
The blue color filters of Example 1 and Comparative Examples 1 and 2 were placed in an oven at 210 ° C. for 3 hours, and the chromaticity and luminance before and after heating were measured with a spectrophotometer CM-3500d manufactured by Konica Minolta, Inc. The luminance difference was compared with the color difference ΔE * ab. The results are shown in Table 2.

<Heat resistance test-contrast>
Each blue color filter was placed in an oven at 210 ° C. for 3 hours, and the contrast before and after heating was measured with a contrast meter CT-1 manufactured by Aisaka Electric Co., Ltd., and the contrast and the rate of change in heat resistance were compared.

  From the above Tables 1 to 3, when the triarylmethane pigment of the present invention is heated and reacted at 80 ° C. in a microreactor, it has light resistance equivalent to that of the triarylmethane pigment obtained in a batch type and high contrast is obtained. I understood it. When the reaction was carried out at 40 ° C. in a microreactor, the particle size was small and the contrast, light resistance and heat resistance were low.

  The fine particles of the triarylmethane pigment of the present invention can be used for a blue pixel portion of a color filter.

1: Microreactor 11: Laminate as fluid mixing structure,
13: Temperature control plate as temperature control plate,
14: Mixing plate,
14A: 1st flow-path formation part,
14B: 2nd flow-path formation part,
15: 1st flow path 16: 2nd flow path,
15b, 20b: exit,
19: Joint channel,
30: heat insulation part,
31A: a first heat medium flow path as a first medium flow path,
31B: a second heat medium flow path as a second medium flow path,
46: Heat medium flow path,
F1: first fluid,
F2: second fluid,
H1: a first heat medium as a first medium,
H2: second heat medium as the second medium,
X1, X2: central axes.
The following are the symbols related to the micro heat exchanger 1 .alpha.... Fluid containing the mixed fluid (A) .beta.... Fluid containing the mixed fluid (A) .gamma. ··· Micro heat exchanger 1b ··· End surface 1c of the laminate included in the micro heat exchanger · · · End surface 1d of the laminate included in the micro heat exchanger 1d ··· Layer included in the micro heat exchanger Side surface of body 1e... Side surface of laminated body of micro heat exchanger 2... First plate (process plate)
2a ... the first plate surface 2b ... the first plate end surface 2c ... the first plate end surface 2d ... the first plate side surface 2e ... the first plate side surface 3 ... 2nd plate (temperature control plate)
3a ··· surface of the second plate 3b ··· end surface of the second plate 3c ··· end surface of the second plate 3d ··· side surface of the second plate 3e ··· side surface of the second plate 4... Cross-sectional groove-shaped channel 6... Cross-sectional groove-shaped temperature control channel 6 a... Cross-sectional groove-shaped main channel 6 b. Supply side flow path 6c ··· Discharge side flow path having a groove shape in cross section p ₀ · · · Predetermined interval w ₀ ··· width d ₀ ··· depth L ···· Flow path length 30 ... Connector 31 ... Joint part 32 ... Joint part 80 ... Manufacturing apparatus 61 ... Dye solution (C.I. Basic blue solution)
62... Tank 63... Solution of heteropolyoxometalate anion (K6: P ₂ MoW ₁₇ O ₆₂ solution)
64 ... Tank 65 ... Diaphragm pump 66 ... Diaphragm pump 67 ... Storage container 70 ... Micro heat exchanger 71 ... Micro heat exchange 72 ... Microreactor 73 ... Temperature control device 74 ... Temperature control device 75 ... Temperature control device 80 ... Production equipment used in the examples Schematic diagram schematically shown

Claims (4)

A method for producing fine particles of a triarylmethane pigment represented by the general formula (1),
Fine particles of triarylmethane pigment, characterized in that a solution of a dye represented by formula (2) and a solution of a heteropolyoxometalate anion represented by formula (3) are reacted in a fine space Manufacturing method.

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, X ⁻ represents (P ₂ Mo _y W _18-y O ₆₂ ) ⁶⁻ / 6, where y is an integer from 0 to 3.

^{(Wherein, R 1, R 2, R} 3, R 4, R 5 good hydrogen atoms be the same or different, an alkyl group having 1 to 8 carbon atoms or a phenyl ^{group,, A n-is,} n-valent And n represents an arbitrary natural number.)

(Y is an integer from 0 to 3.) After flowing the solution of the dye represented by the general formula (2) and the solution of the heteropolyoxometalate anion represented by the general formula (3) in a liquid-tight state in separate microtubules, respectively. The method for producing fine particles of a triarylmethane pigment according to claim 1, wherein the reaction is performed in a fine space. The method for producing fine particles of a triarylmethane pigment according to claim 1 or 2, wherein the fine space is 100 cm ³ or less. The color filter which used the triarylmethane pigment fine particle (1) obtained by the manufacturing method of Claims 1-3 for a blue pixel part.

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