JP2006301307A - Resin composition for inkjet system color filter, color filter, and method for manufacturing color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for an inkjet system color filter, with which occurrence of phase separation is prevented by improving dispersion stability, and depolarizing property and uneven film thickness are dissolved by improving a film material property in film forming, the color filter using the resin composition, and a method for manufacturing the color filter with the inkjet system. <P>SOLUTION: The resin composition for the inkjet system color filter contains a micro-capsulated pigment provided with pigment particles, a polymer as a resin component to cover the pigment particles, and an ionic group mounted on the polymer surface, and water. The color filter has a pixel pattern formed with the inkjet system from the composition. The method for manufacturing the color filter includes a step to jet the resin composition from an inkjet head to respective transmissive regions of a substrate with partition walls formed thereon in advance and subsequently to form the pixel pattern with drying. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is an ink jet color filter resin composition for producing a color filter used in a color liquid crystal display device, a color image pickup tube element and the like by an ink jet method, and formed from the color filter resin composition by an ink jet method. The present invention relates to a color filter having a pixel pattern and a method for producing a color filter by an inkjet method using the resin composition for a color filter.

  A color filter used in a color liquid crystal display (LCD) or the like is configured integrally with a color liquid crystal display or the like, and has a role of improving the image quality and giving each pixel a color of each primary color. Yes. As a method for producing such a color filter, conventionally, a radiation-sensitive resin coating film is irradiated with radiation through a photomask to cure the radiation-emitting portion, followed by development treatment, and the coating film radiation is After removing the unirradiated portion to form a pattern, dyeing method (dyeing method), or using a composition in which a red, green or blue colorant is dispersed in a radiation sensitive resin, as above, In addition, there is known a photographic method in which coating film formation, radiation irradiation and development treatment are performed. However, these methods have problems such as a complicated pixel pattern forming process and high cost.

  On the other hand, Japanese Patent Application Laid-Open No. 63-235901 discloses an ink jet type color filter manufacturing method including a step of forming a colored layer of a color filter using an ink jet head. Control of the position where the droplets of the color filter resin composition are discharged is easy, and the waste of the resin composition is reduced, so that there is an advantage that the manufacturing cost can be reduced. However, in the conventional color filter manufacturing method using the inkjet method, the color density of the discharged color filter resin composition may be uneven. For this reason, as seen in JP-A-7-318723 and the like. Thus, a method has been proposed in which the discharge amount of the color filter composition is adjusted to suppress the color density unevenness of the pixel pattern. However, these publications do not fully consider the composition suitable for the ink jet system for the color filter resin composition, and do not fully disclose details of the manufacturing process of the color filter.

  In addition, regarding the behavior in the color filter manufacturing process of the resin composition for a color filter used for manufacturing a color filter by an inkjet method, each pixel pattern constituting the color filter has a very small area, so that the inkjet used It is necessary to discharge the droplets of the resin composition for the color filter with good straightness without clogging the head, and for that purpose, the droplet drying speed when discharging the resin composition for the color filter is reduced. Further, it is necessary to suppress an excessive increase in the viscosity of the droplets due to drying and to prevent precipitation of solid contents. For this reason, Japanese Patent Application Laid-Open No. 2000-310706 discloses a colorant, a binder resin, and a boiling point at room temperature as a resin composition optimized for the production of a color filter by a low-cost inkjet method with a simple pixel pattern formation process. Has been proposed an ink jet color filter resin composition containing a solvent having a temperature of 250 ° C. or higher.

However, the conventional color filter resin composition as described above has the following problems particularly when pigment particles are used as a colorant in an ink jet method.
(1) Since the dispersion is due to adsorption of the dispersant, the dispersion state is thermally unstable.
(2) Unbiasing property (property of reducing contrast) due to pigment particles.
(3) The transmittance of the pigment particles is reduced due to diffusion (decrease in brightness and contrast).
(4) Since the dispersion state is not uniform, the inkjet discharge stability is small.
(5) Film thickness non-uniformity occurs due to the coffee stain phenomenon during film formation and drying.
(6) Phase separation occurs due to dispersion instability during film formation and drying.
JP-A 63-235901 JP 7-318723 A JP 2000-310706 A

  Accordingly, the present invention provides an ink jet color filter resin that prevents phase separation by improving dispersion stability and eliminates unevenness and non-uniform film thickness by improving film properties during film formation. An object is to provide a composition.

  Another object of the present invention is to provide a color filter having a pixel pattern formed from the color filter resin composition by an inkjet method. Still another object of the present invention is to provide a method for producing a color filter by an inkjet method using the resin composition for a color filter.

The present invention relates to the following 1. -26. The object is achieved by providing the invention.
1. Inkjet color characterized by containing at least water, a microencapsulated pigment comprising pigment particles, a polymer as a resin component for coating the pigment particles, an ionic group provided on the surface of the polymer, and water Filter resin composition.

  2. Resin composition for ink jet type color filter comprising at least water containing a microencapsulated pigment comprising pigment particles, a polymer as a resin component for coating the pigment particles, an ionic group provided on the surface of the polymer, and water And a contact angle with a partition formed from the partition wall-forming resin composition is 45 degrees or more.

  3. The microencapsulated pigment is a polymer in which pigment particles having an anionic group on the surface have a repeating structural unit derived from a cationic polymerizable surfactant having a cationic group, a hydrophobic group, and a polymerizable group. 3. The resin composition for ink-jet color filters according to 1 or 2, which is coated.

  4). The microencapsulated pigment polymerizes a cationic polymerizable surfactant having a cationic group, a hydrophobic group, and a polymerizable group in an aqueous dispersion in which pigment particles having an anionic group on the surface are dispersed. The resin composition for inkjet color filters according to 1 or 2, wherein the pigment particles are coated with a polymer.

  5. The microencapsulated pigment has a repeating structural unit in which pigment particles having an anionic group on the surface are derived from a cationic polymerizable surfactant having a cationic group, a hydrophobic group, and a polymerizable group; An anionic polymerizable surfactant having a group, a hydrophobic group and a polymerizable group and / or a polymer having a repeating structural unit derived from a hydrophilic monomer having an anionic group, 3. The resin composition for inkjet color filters according to 1 or 2.

  6). The microencapsulated pigment includes a cationic polymerizable surfactant having a cationic group, a hydrophobic group, and a polymerizable group, an anion in an aqueous dispersion in which pigment particles having an anionic group on the surface are dispersed. The pigment particles are coated with a polymer by polymerizing an anionic polymerizable surfactant having an ionic group, a hydrophobic group and a polymerizable group and / or a hydrophilic monomer having an anionic group, 3. The resin composition for inkjet color filters according to 1 or 2.

  7). 7. The resin composition for an inkjet color filter according to any one of 3 to 6, wherein the polymer further has a repeating structural unit derived from a hydrophobic monomer.

  8). Any of 3 to 7 above, wherein the polymer further comprises a repeating structural unit derived from a crosslinkable monomer and / or a repeating structural unit derived from a monomer represented by the following general formula (1): The resin composition for inkjet color filters described in 1.

［ただし、Ｒ1は水素原子又はメチル基を表す。Ｒ2はｔ−ブチル基、脂環式炭化水素基、
芳香族炭化水素基、又はヘテロ環基を表す。ｍは０〜３、ｎは０又は１の整数を表す。］

[However, R1 represents a hydrogen atom or a methyl group. R2 is a t-butyl group, an alicyclic hydrocarbon group,
An aromatic hydrocarbon group or a heterocyclic group is represented. m represents an integer of 0 to 3, and n represents an integer of 0 or 1. ]

  9. 8. The ink composition color filter resin composition as described in any one of 1 to 7 above, wherein the pigment constituting the pigment particles is an organic pigment.

10. The anionic group of the pigment particles is a sulfonate anion group (—SO ³⁻ ) and / or a sulfinate anion group (—RSO ²⁻ : R is a C1 to C12 alkyl group or phenyl group or a modified product thereof). 10. The resin composition for an ink jet color filter according to any one of 3 to 9 above.

11. 10. The resin composition for an inkjet color filter according to any one of 3 to 9, wherein the anionic group of the pigment particle is a carboxylic acid anion group (—COO ⁻ ).

  12 The cationic group of the cationic polymerizable surfactant is selected from the group consisting of a primary amine cation, a secondary amine cation, a tertiary amine cation, and a quaternary ammonium cation. The resin composition for inkjet color filters according to any one of -6.

  13. The inkjet color filter according to any one of 3 to 6, wherein the hydrophobic group of the cationic polymerization surfactant is selected from the group consisting of an alkyl group, an aryl group, and a group in which these are combined. Resin composition.

  14 The polymerizable group of the cationic polymerization surfactant is an unsaturated hydrocarbon group capable of radical polymerization, and includes a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinylene group. The resin composition for inkjet color filters according to any one of 3 to 6 above, which is selected from:

  15. 2. The ink jet color filter as described in 1 above, comprising an aqueous dispersion containing a microencapsulated pigment comprising pigment particles, a polymer as a resin component for coating the pigment particles, and an ionic group provided on the surface of the polymer. Resin composition.

  16. Further comprising polymer fine particles, wherein the polymer fine particles have an anionic group on the surface thereof, have a glass transition temperature of 30 ° C. or less, and have a volume average particle diameter of 10 to 200 nm. 15. The resin composition for an inkjet color filter according to any one of 15 above.

  17. 17. The resin composition for an ink jet color filter as described in 16, wherein the anionic group on the surface of the polymer fine particle is the same kind as the anionic group on the surface of the microencapsulated pigment.

18. When the polymer fine particles are brought into contact with 3 volumes of an aqueous emulsion of 0.1% by weight thereof and 1 volume of a divalent metal salt aqueous solution having a concentration of 1 mol / l, the light transmittance at a wavelength of 700 nm is an initial value of 50. The resin composition for an ink jet color filter according to any one of 16 or 17 above, wherein the resin composition has reactivity with a divalent metal salt such that the time of% is 1 × 10 ⁴ seconds or less. object.

  19. 19. The resin composition for an inkjet color filter according to any one of 1 to 18 above, further comprising a water-soluble organic solvent.

  20. 20. The ink-jet color filter resin composition as described in 19 above, wherein the water-soluble organic solvent is a high-boiling water-soluble organic solvent having a boiling point of 180 ° C. or higher.

  21. 21. The resin composition for ink-jet color filters as described in 19 or 20, wherein the water-soluble organic solvent is glycerin.

  22. The water-soluble organic solvent is one or more compounds selected from the group consisting of alkyl ethers of polyhydric alcohols and / or 1,2-alkyl diols, according to any one of 19 or 20 above. Resin composition for inkjet color filter.

  23. 23. The resin composition for an ink jet color filter according to any one of 1 to 22, further comprising a solid wetting agent in an amount of 3 to 20% by weight based on the total weight of the resin composition.

  24. 24. The ink jet color according to item 23, wherein the solid wetting agent is one or more compounds selected from the group consisting of trimethylolpropane, 1,2,6-hexanetriol, sugars, and sugar alcohols. Filter resin composition.

  25. A color filter having a pixel pattern formed by an inkjet method using the resin composition for an inkjet color filter described in any one of 1 to 24 above.

  26. An ink-jet color filter manufacturing method using the ink-jet color filter resin composition described in any one of 1 to 24 above, wherein each light transmitting region that transmits light of a transparent substrate on which a partition wall has been previously formed is provided. A step of discharging the resin composition from the inkjet head and storing the resin composition in each light transmission region partitioned by the partition; and drying the resin composition stored in each light transmission region to form a pixel pattern A method for producing a color filter by an ink jet method, comprising: a forming step; and a step of forming a protective layer so as to cover the pixel pattern.

According to the present invention, an ink jet color filter resin that prevents occurrence of phase separation by improving dispersion stability and eliminates unevenness and non-uniform film thickness by improving film properties during film formation. A composition is provided.
The present invention also provides a color filter having a pixel pattern formed from the color filter resin composition by an ink jet method, and a method for producing a color filter by an ink jet method using the color filter resin composition. The

  According to the resin composition for a color filter of the present invention, pigment particles are encapsulated by using a so-called AMP (Admicelle Polymerization) method, and the dispersion stability of the pigment particles is dramatically improved. For this reason, it is possible to form a strong film by improving the pot life, ensuring the inkjet discharge stability, and increasing the cohesive force between the pigment particles during drying. As a result, the problems of conventional bias and non-uniformity of film thickness and phase separation are solved at once.

The effects of the present invention further include the following.
(1) Since the pigment particles are encapsulated, the redissolving (dispersing) property is high, and the nozzle clogging of the inkjet head can be prevented.
(2) Since the pigment particles are encapsulated, the nozzle plate of the ink jet head is prevented from being soiled and cleaning is facilitated.
(3) Since the dispersion stability of the pigment particles is high, it is possible to increase the color material content (conventionally about 10% by weight) in the resin composition to about 20% by weight without increasing the viscosity. Thereby, since the film thickness can be earned, productivity by the ink jet method is improved.
(4) Since the dispersion stability of the pigment particles is high, it can be easily applied to a color filter with a deep color scheme for TV.
(5) Since the viscosity does not increase, the resin composition has no thixotropy and becomes a Newtonian. Therefore, inkjet discharge is stable, and a dot size of 2 pl or less can be achieved. Due to the improvement in accuracy, the ink jet method can be applied to fine color filters of about 250 PPI or more.
(6) Since the resin composition that has landed on the bank can smoothly enter the recess, the pigment residue hardly remains on the bank. In addition, the wettability to the concave portion is improved, and a uniform film is easily formed.
(7) Since wettability can be obtained at 1 Pass, productivity by the ink jet method is also improved.
(8) Since a difference in liquid repellency occurs between the bank and the recess, the luminous efficiency by the coating can be improved.

Hereinafter, the present invention will be described in detail.
[Resin composition for inkjet color filter]
As described above, the microencapsulated pigment used in the resin composition for an inkjet color filter of the present invention includes pigment particles, a polymer as a resin component that coats the pigment particles, and ions provided on the surface of the polymer. It has a sex group. Such a microencapsulated pigment is not particularly limited in color tone, and is appropriately selected according to the use of the obtained color filter. Since the color filter is required to have high-definition color development and heat resistance, the pigment particles constituting the microencapsulated pigment in the present invention are high color development and high heat resistance pigments, particularly high heat decomposition resistance. A pigment is preferable, and any of an organic pigment and an inorganic pigment may be used, and an organic pigment is particularly preferably used. Moreover, the pigment particle which has a hydrophilic group on the surface can be suitably produced by processing the surface of the pigment particle with a hydrophilic group-imparting agent. Therefore, the pigment constituting the pigment particles having a hydrophilic group on the surface is not particularly limited as long as it is a pigment that does not dissolve in the hydrophilic group-imparting agent.

  Examples of the organic pigment include compounds classified as Pigment in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following Color Index (CI) numbers. Can be mentioned. CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment ..... DOO Yellow 155, C.I Pigment Yellow 156, C.I Pigment Yellow 166, C.I Pigment Yellow 168, C.I Pigment Yellow 175, C.I Pigment Yellow 180, C.I. Pigment Yellow 185;

  CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Buy Olet 32, C.I. pigment violet 36, C.I. pigment violet 38;

  CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 58: 2, CI Pigment Red 58: 4, CI Pigment Red 60 : 1, CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI Pigment Red 97, CI Pigment Red 1 1, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171 and CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 1 8, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 2 5;

  CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60; CI Pigment Green 7, CI Pigment Green 36; CI Pigment Brown 23, CI Pigment Brown 25 CI pigment black 1, CI pigment black 7. These organic pigments can be used alone or in admixture of two or more. The organic pigment can be used after being purified by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.

  Specific examples of inorganic pigments include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, Examples thereof include chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black. These inorganic pigments can be used alone or in admixture of two or more.

  In a preferred embodiment of the microencapsulated pigment according to the present invention, a pigment particle having an anionic group on its surface, a cationic polymerizable surfactant having a cationic group, a hydrophobic group and a polymerizable group, and an anionic property And an anionic polymerizable surfactant having a group, a hydrophobic group and a polymerizable group and / or a polymer having a repeating structural unit derived from a hydrophilic monomer having an anionic group.

  Such a microencapsulated pigment is a method for producing a microencapsulated pigment in which pigment particles having an anionic group on the surface thereof are coated with a polymer, and the aqueous dispersion of the pigment particles having an anionic group on the surface thereof. After adding and mixing a cationic polymerizable surfactant, emulsifying by adding the anionic polymerizable surfactant and / or the hydrophilic monomer having the anionic group, then adding a polymerization initiator and emulsion polymerization, It can manufacture suitably.

  According to such an emulsion polymerization method, first, the anionic group on the surface of the pigment particle having an anionic group on the surface and the cationic group of the cationic polymerizable surfactant are ionically bonded, and this cationic polymerization is performed. The hydrophobic group of the anionic surfactant and the hydrophobic group of the anionic polymerizable surfactant face each other to form a structure in which the anionic group of the anionic polymerizable surfactant is oriented toward the aqueous phase side. When the polymerization reaction is performed in this state, a polymer layer maintaining the above structure is formed on the surface of the pigment particles. That is, the arrangement of the cationic polymerizable surfactant and the anionic polymerizable surfactant existing around the pigment particles before the polymerization reaction is extremely highly controlled, and the outermost shell is anionic toward the aqueous phase. A state in which the groups are oriented is formed. Then, the cationic polymerizable surfactant and the anionic polymerizable surfactant are converted into a polymer by the emulsion polymerization reaction in the highly controlled form. Therefore, the structure of the microencapsulated pigment of the present invention is controlled with extremely high accuracy. Thereby, the microencapsulated pigment according to the embodiment of the present invention has excellent dispersion stability, excellent ejection stability from the inkjet head, and prevents the occurrence of phase separation by improving the dispersion stability. By improving the film properties at the time of film formation, it is possible to obtain the effect of eliminating the unevenness and the non-uniformity of the film thickness.

  In the case of a conventional microencapsulated pigment in which a polymer prepared in advance on a pigment is coated by using a phase inversion emulsification method, an acid precipitation method, or the like, pigment particles are obtained by preparing the polymer in advance. It is considered that the coating state with respect to the pigment particles of the polymer satisfying the above effect is not achieved because the coating state with respect to is limited.

  Here, the aspect ratio (long and short) of the microencapsulated pigment is 1.0 to 1.3, and the Zingg index is 1.0 to 1.3 (more preferably 1.0 to 1.2). It is preferable that Thereby, the effect of this invention can be satisfied more reliably.

When the short diameter of a particle is b, the long diameter is l, and the thickness is t (l ≧ b ≧ t> 0), the aspect ratio (long / shortness) is 1 / b (≧ 1), and the flatness is b / t ( ≧ 1) and Zingg index = long / short / flatness = (l · t) / b ² . That is, the true sphere has an aspect ratio of 1 and a Zingg index of 1. When the Zingg index is larger than 1.3, the microencapsulated pigment becomes flatter and the isotropic property is lowered, so that a sufficient effect tends not to be obtained. The method for setting the aspect ratio and Zingg index within the above ranges is not particularly limited, but microencapsulated pigments in which pigment particles having an anionic group on the surface are coated with a polymer by the above-described emulsion polymerization method can easily satisfy this condition. Can meet.

  In addition, in a microencapsulated pigment produced by a method other than an emulsion polymerization method such as an acid precipitation method or a phase inversion emulsification method, the aspect ratio and the Zingg index are unlikely to fall within the above ranges. When the microencapsulated pigment is in the range of the above aspect ratio and Zingg index, it becomes a true sphere, but this tends to make the flow characteristics of the resin composition Newtonian and excellent discharge stability. Further, since it is spherical, it is excellent in dispersibility and dispersion stability.

  Hereinafter, embodiments of the present invention will be described with reference to possible dispersion states of pigment particles in the above-described preferred production method. However, the dispersion state of the pigment particles listed below includes estimation.

   FIG. 1 shows that pigment particles 31 having an anionic group 54 on the surface as a hydrophilic group are dispersed in a solvent containing water as a main component (hereinafter also referred to as an aqueous solvent), and a cationic group 51 and a hydrophobic group 52. And a cationic polymerizable surfactant 32 having a polymerizable group 53, and an anionic polymerizable surfactant 33 having an anionic group 54 ′, a hydrophobic group 52 ′, and a polymerizable group 53 ′. It is a figure which shows the state which coexists. The cationic polymerizable surfactant 32 is disposed such that the cationic group 51 faces the anionic group 54 of the pigment particle 31 and adsorbs with a strong ionic bond. Then, the hydrophobic group 52 and the polymerizable group 53 of the cationic polymerizable surfactant 32 are bonded to the hydrophobic group 52 ′ and the polymerizable group of the anionic polymerizable surfactant 33 by hydrophobic interaction. 53 ′ is directed, and the anionic group 54 ′ of the other anionic polymerizable surfactant 33 is directed in the direction in which the aqueous solvent exists, that is, in the direction away from the pigment particles 31.

  By polymerizing the polymerizable group 53 of the cationic polymerizable surfactant 32 and the polymerizable group 53 ′ of the anionic polymerizable surfactant 33 by adding, for example, a polymerization initiator to such an aqueous dispersion. As shown in FIG. 2, a microencapsulated pigment 100 ′ in which pigment particles 31 are coated with a polymer layer 60 ′ is produced. Here, since the surface of the polymer layer 60 ′ has the anionic group 54 ′, the microencapsulated pigment 100 ′ can be dispersed in an aqueous solvent. In the case where a hydrophilic monomer having an anionic group as a hydrophilic group is used instead of the anionic polymerizable surfactant 33, a microencapsulated pigment can be prepared in the same manner. In the polymerization, the cationic polymerizable surfactant and an anionic polymerizable surfactant and / or a hydrophilic monomer having an anionic group can be copolymerized in an aqueous dispersion as required. A comonomer may be present, in which case the polymer layer is copolymerized from a cationic polymerizable surfactant, an anionic polymerizable surfactant and / or a hydrophilic monomer having an anionic group, and a comonomer. Copolymer layer.

  In addition to the above, the possible dispersion state of the pigment particles is increased in the above-described preferred production method. FIG. 3 shows that pigment particles 31 having an anionic group 54 on the surface as a hydrophilic group are dispersed in a solvent containing water as a main component (hereinafter also referred to as an aqueous solvent), and a cationic group 51 and a hydrophobic group 52. And a cationic polymerizable surfactant 32 having a polymerizable group 53, and an anionic polymerizable surfactant 33 having an anionic group 54 ′, a hydrophobic group 52 ′, and a polymerizable group 53 ′. It is a figure which shows the state which coexists. The cationic polymerizable surfactant 32 is disposed such that the cationic group 51 faces the anionic group 54 of the pigment particle 31 and adsorbs with a strong ionic bond. Then, the hydrophobic group 52 and the polymerizable group 53 of the cationic polymerizable surfactant 32 are bonded to the hydrophobic group 52 ′ and the polymerizable group of the anionic polymerizable surfactant 33 by hydrophobic interaction. 53 ′ is directed, and the anionic group 54 ′ of the other anionic polymerizable surfactant 33 is directed in the direction in which the aqueous solvent exists, that is, in the direction away from the pigment particles 31.

  The surface of the pigment particle 31 has an anionic group 54 chemically bonded at a specific density, and has a hydrophobic region 50 between the anionic groups 54. The hydrophobic region 50 includes, for example, a cation. The hydrophobic group 52 and the polymerizable group 53 of the polymerizable polymerizable surfactant 32 are suitable. The anionic polymerizable surfactant 33 is disposed on the cationic group 51 of the cationic polymerizable surfactant 32 so that the anionic group 54 'faces, and adsorbs with a strong ionic bond. The hydrophobic group 52 ′ and the polymerizable group 53 ′ of the anionic polymerizable surfactant 33 are separated from the hydrophobic group 52 ′ and the polymerizable group of another anionic polymerizable surfactant 33 by a hydrophobic interaction. 53 ′ is oriented, and the anionic group 54 ′ of the anionic polymerizable surfactant 33 is oriented in the direction in which the aqueous solvent exists, that is, in the direction away from the pigment particles 31.

  By polymerizing the polymerizable group 53 of the cationic polymerizable surfactant 32 and the polymerizable group 53 ′ of the anionic polymerizable surfactant 33 by adding, for example, a polymerization initiator to such an aqueous dispersion. As shown in FIG. 4, the microencapsulated pigment 100 in which the pigment particles 31 are coated with the polymer layer 60 is produced. Here, since the surface of the polymer layer 60 has the anionic group 54 ′, the microencapsulated pigment 100 can be dispersed in an aqueous solvent. In the case where a hydrophilic monomer having an anionic group as a hydrophilic group is used instead of the anionic polymerizable surfactant 33, a microencapsulated pigment can be prepared in the same manner. In the polymerization, the cationic polymerizable surfactant and an anionic polymerizable surfactant and / or a hydrophilic monomer having an anionic group can be copolymerized in an aqueous dispersion as required. A comonomer may be present, in which case the polymer layer is copolymerized from a cationic polymerizable surfactant, an anionic polymerizable surfactant and / or a hydrophilic monomer having an anionic group, and a comonomer. Copolymer layer.

  As mentioned above, although the dispersion state was mentioned using drawing, first, the pigment particle 31 is in the state disperse | distributed to the aqueous solvent by having an anionic group as a hydrophilic group on the surface. The dispersion of the pigment particles 31 in the aqueous solvent is highly dispersed as compared with the case where the pigment particles having no hydrophilic group (anionic group) on the surface are dispersed with a dispersant. According to the microencapsulated pigment in which the pigment particles having the anionic group on the surface are coated with the polymer, as shown in FIGS. 2 and 4, the anionic group on the surface of the microencapsulated pigment is an aqueous solvent. Since it is regularly and densely oriented in the existing direction, the dispersion stability of the microencapsulated pigment in an aqueous solvent can be improved. Therefore, when the microencapsulated pigment is used as the colorant of the resin composition for an ink jet color filter according to the present invention, and the solvent of the composition is an aqueous solvent, a larger amount of the microencapsulated pigment is contained in the composition. Even if it is added to the resin composition, the dispersion stability superior to that of a conventional resin composition for a color filter containing a microencapsulated pigment can be imparted while maintaining a low viscosity without causing an increase in viscosity. If the dispersion stability is excellent, the possibility of clogging the nozzles of the inkjet head by the microencapsulated pigment is reduced, so that the ejection stability is also improved. In other words, it has excellent dispersion stability and ejection stability, and at the same time contains a microencapsulated pigment with an improved colorant content (weight concentration) compared to conventional color filter resin compositions containing microencapsulated pigments. A resin composition for a color filter can be produced.

  The microencapsulated pigment used in the present invention has a small particle diameter, and hydrophilic groups (particularly anionic groups) on the particle surface are regularly and densely oriented toward the aqueous phase side. By using a resin composition for a color filter having a high content (weight concentration) of the microencapsulated pigment according to the present invention, ejection by an ink jet method can improve the film properties at the time of film formation, thereby reducing the bias and film thickness. Unevenness can be eliminated and an excellent pixel pattern can be obtained.

  More specifically, in the microencapsulated pigment used in the present invention, as described above, it is considered that the anionic groups are regularly and densely oriented toward the aqueous solvent side. It is considered that an effective electrostatic repulsive force is generated between the pigments. In addition to the electrostatic repulsive force, the effect of the steric hindrance caused by the polymer coating the pigment particles (polymer effect) is also due to the fact that the microencapsulated pigment according to the present invention is in an aqueous medium. This is considered to be one of the factors that have excellent dispersion stability.

  In addition, the resin composition for a color filter according to the present invention is excellent in fixability to a substrate as compared with a resin composition using conventional surface-treated pigment particles as a colorant because the pigment is coated with a polymer. As a result, it is possible to make the discharged material excellent in scratch resistance.

  The pigment particles having a hydrophilic group constituting the macroencapsulated pigment used in the embodiment of the present invention on the surface can be suitably produced by treating the surface of the pigment particle with a hydrophilic group-imparting agent. Therefore, the pigment constituting the pigment particles having a hydrophilic group on the surface is not particularly limited as long as it is a pigment that does not dissolve in the hydrophilic group-imparting agent.

As the hydrophilic group-imparting agent for treating the surface of the pigment particles, first, a treatment agent containing sulfur can be preferably cited. Examples of the treatment agent containing sulfur include sulfuric acid, fuming sulfuric acid, sulfur trioxide, chlorosulfuric acid, fluorosulfuric acid, amidosulfuric acid, sulfonated pyridine salt, and sulfamic acid. Among them, sulfur trioxide, sulfonated pyridine salt or sulfamine. Sulfonating agents such as acids are preferred. These can be used alone or in admixture of two or more. (Note that “sulfonating agent” refers to sulfonic acid (—SO ₃ H) and / or sulfinic acid (—RSO ₂ H: R is a C _{1 to} C ₁₂ alkyl group, or a phenyl group and a modified product thereof) Is a treatment agent for imparting

  In addition, a solvent capable of forming a complex with sulfur trioxide (a basic solvent such as N, N-dimethylformamide dioxane, pyridine, triethylamine, trimethylamine, nitromethane, acetonitrile, etc.) and a solvent described later. It is also useful to form a complex with a mixed solvent with one or more kinds. In particular, when sulfur trioxide itself is too reactive to decompose or alter the pigment itself, or when it is difficult to control the reaction with a strong acid, a complex of sulfur trioxide and a tertiary amine is used as described above. It is preferable to use the pigment particles for surface treatment (in this case, sulfonation).

  In addition, when sulfuric acid, fuming sulfuric acid, chlorosulfuric acid, fluorosulfuric acid, or the like is used alone, the pigment particles are easily dissolved, and it is necessary to suppress the reaction for strong acids that react per molecule. It is necessary to pay attention to the type of solvent and the amount used. The solvent used in the reaction is selected from those which do not react with the treatment agent containing sulfur and in which the above-mentioned pigment becomes insoluble or hardly soluble, and sulfolane, N-methyl-2-pyrrolidone, dimethylacetamide, Examples include quinoline, hexamethylphosphoric triamide, chloroform, dichloroethane, tetrachloroethane, tetrachloroethylene, dichloromethane, nitromethane, nitrobenzene, liquid sulfur dioxide, carbon disulfide, and trichlorofluoromethane.

  The treatment with the treatment agent containing sulfur is performed by dispersing pigment particles in a solvent, adding a treatment agent containing sulfur to this dispersion, heating to 60 to 200 ° C., and stirring for 3 to 10 hours. Specifically, a high-speed shearing dispersion using a high-speed mixer or the like, or impact-dispersing using a bead mill or a jet mill to form a slurry (dispersion liquid) is preferable. Then, after moving to gentle stirring, a treatment agent containing sulfur is added to introduce hydrophilic groups onto the surface of the pigment particles. At this time, the reaction conditions and the type of the treatment agent containing sulfur greatly depend on the determination of the introduction amount of the hydrophilic group. After this heat treatment, the treating agent containing solvent and residual sulfur is removed from the slurry of pigment particles. Removal is carried out by repeatedly washing with water, ultrafiltration, reverse osmosis, etc., centrifugation, filtration and the like.

Further, the sulfonic acid (—SO ₃ H) and / or sulfinic acid (—RSO ₂ H: R is a C _{1 to} C ₁₂ alkyl group, or a phenyl group and a modified product thereof) described above is treated with an alkali compound. As a hydrophilic group, a sulfonic acid anion group (—SO ₃ ⁻ ) and / or a sulfinate anion group (—RSO ₂ ⁻ : R is a C _{1 to} C ₁₂ alkyl group or phenyl group and a modified product thereof) are surfaced. The pigment particles can be obtained. In the present invention, it is preferably used in this state.

As the alkali compound, the cation may be an alkali metal ion or a chemical formula (R ₁ R ₂ R ₃ R ₄ N) ⁺ (R ₁ , R ₂ , R ₃ and R ₄ may be the same or different, and may be a hydrogen atom, an alkyl group, An alkali compound that is a monovalent ion represented by (showing a hydroxyalkyl group or an alkyl halide group) is selected. Preferably, an alkali compound in which the cation becomes an alkanolamine cation such as lithium ion (Li ⁺ ), potassium ion (K ⁺ ), sodium ion (Na ⁺ ), ammonium ion (NH ₄ ⁺ ), and triethanolamine cation. It is.

  Hydroxyl anion is preferably used as the anion of the alkali compound. Specific examples thereof include ammonia, alkanolamine (monoethanolamine, diethanolamine, N, N-butylethanolamine, triethanolamine, propanolamine, aminomethyl). Propanol, 2-aminoisopropanol, etc.) and monovalent alkali metal hydroxides (LiOH, NaOH, KOH).

  The amount of the alkali compound added is preferably at least the neutralization equivalent of the sulfonic acid group and / or sulfinic acid group of the pigment particles. Furthermore, for volatile additives such as ammonia and alkanolamine, addition of 1.5 times or more of the neutralization equivalent is generally preferred.

  The operation can be performed by placing pigment particles having the sulfonic acid group and / or sulfinic acid group chemically bonded to the surface in an alkali compound, and shaking with a paint shaker or the like.

  Moreover, a carboxylating agent can also be mentioned suitably as a hydrophilic group provision agent for processing the surface of a pigment particle. Here, the “carboxylating agent” is a treatment agent for imparting a carboxylic acid group (—COOH). As the carboxylating agent, an oxidizing agent such as hypohalite such as sodium hypochlorite or potassium hypochlorite is used to cut off the partial bond (C = C, C-C) on the pigment particle surface. And by oxidizing. In addition to the chemical treatment described above, a carboxylic acid group may be imparted by physical oxidation such as plasma treatment, but in the present invention, if the treatment method can ensure dispersion stability in an aqueous medium, Various methods can be selected. Further, in the exemplified carboxylic acid introduction treatment, a quinone group or the like may be introduced although the amount is small. Even in such a case, if the dispersion stability of the microencapsulated pigment in the aqueous medium can be ensured, it does not contradict the gist of the present invention.

  As an example of treatment with a carboxylating agent, pigment particles are preliminarily sheared and dispersed in an aqueous medium with a high-speed mixer or the like, or impact-dispersed with a bead mill or a jet mill to form a slurry (dispersion). Next, a hypohalite such as sodium hypochlorite having an effective halogen concentration of 10 to 30% is mixed in an appropriate amount of water and heated to 60 to 80 ° C. for about 5 to 10 hours, preferably 10 It is carried out by stirring for more than an hour. This operation involves a considerable amount of heat and requires safety attention. Thereafter, the solvent and the remaining carboxylating agent are removed from the surface-treated pigment particle slurry by heat treatment. Further, if necessary, it is possible to obtain a desired aqueous dispersion by repeatedly performing washing, ultrafiltration, reverse osmosis and the like, centrifugation, filtration and the like.

Again, by treating pigment particles having a carboxylic acid group (—COOH) with an alkali compound, pigment particles having a carboxylic acid anion group (—COO ⁻ ) on the surface as a hydrophilic group can be obtained. In the present invention, it is preferably used in this state. The kind of alkali compound and the treatment method with the alkali compound are the same as described above.

  Next, a preferable introduction amount of the hydrophilic group to the pigment surface and a method for examining the introduction state will be described. First, when hydrophilization is performed using a sulfonating agent, the amount of hydrophilic groups introduced into the pigment particle surface is preferably 0.01 mmol equivalent or more per gram of pigment particles. When the introduction amount of the hydrophilic group is less than 0.01 mmol / g, in the microencapsulation step of the pigment particles in the aqueous solvent, the aggregation of the pigment particles is likely to occur, and the average particle size of the microencapsulated pigment is increased. There is a tendency to increase. As the average particle size of the microencapsulated pigment increases, it becomes difficult to obtain a resin composition for a color filter having excellent dispersion stability and ejection stability.

  The upper limit of the introduction amount of the hydrophilic group with respect to the pigment particles is not particularly limited, but when it exceeds 0.15 mmol / g, the average particle diameter of the pigment particles may not be changed as the introduction amount of the hydrophilic group is increased. Therefore, it is preferably 0.15 mmol / g or less from the viewpoint of cost.

Next, the amount of hydrophilic groups introduced into the pigment surface by the carboxylating agent will be described. In the surface treatment method used in the present invention, it is considered that a carboxylic acid group (—COOH) and / or a carboxylic acid anion group (—COO ⁻ ) is introduced to the pigment surface. Since this is not possible, in the present invention, the amount introduced is measured by the surface active hydrogen content. A detailed measurement method will be described later. The active hydrogen content in the pigment obtained by such a method is preferably 1.0 mmol / g or more, and more preferably 1.5 mmol / g or more. When the concentration is 1.0 mmol / g or less, water dispersibility is deteriorated, and coalescence (particles naturally gather and increase in particle size) easily occurs in the microencapsulation process.

  Although the pigment particles having a hydrophilic group on the surface have been described in detail above, the average particle diameter of the pigment particles having the hydrophilic group on the surface can be easily reduced to 150 nm or less by the above method. In particular, it is more preferable to set the average particle size to 20 nm to 80 nm by selecting the kind of pigment or hydrophilic group imparting agent, the amount of hydrophilic group introduced, and the like, and thereby excellent dispersion stability and ejection stability. A microencapsulated pigment capable of more reliably producing a resin composition for a color filter can be obtained. (In this specification, the description of the average particle diameter is described by the measured value of the laser light scattering method.)

  The pigment particles having a hydrophilic group on the surface thereof are continuously composed of a repeating structural unit derived from a cationic polymerizable surfactant having a cationic group, a hydrophobic group and a polymerizable group, an anionic group and a hydrophobic group. And an anionic polymerizable surfactant having a polymerizable group and / or a polymer having a repeating structural unit derived from a hydrophilic monomer having an anionic group, according to an embodiment of the present invention The microencapsulated pigment is used in a color filter resin composition. As described above, such a microencapsulated pigment is prepared by adding a cationic polymerizable surfactant to an aqueous dispersion of pigment particles having an anionic group on the surface and mixing them, and then mixing the anionic polymerizable surfactant and / or Alternatively, it can be suitably prepared by adding a hydrophilic monomer having an anionic group and emulsifying, and then adding a polymerization initiator and emulsion polymerization.

The cationic group of the cationic polymerizable surfactant is preferably a cationic group selected from the group consisting of a primary amine cation, a secondary amine cation, a tertiary amine cation, and a quaternary ammonium cation. The primary amine cation is a monoalkyl ammonium cation (RNH ₃ ⁺ ), the secondary amine cation is a dialkyl ammonium cation (R ₂ NH ₂ ⁺ ), and the tertiary amine cation is a trialkyl ammonium cation (R ₃ NH ⁺ ) and the like, and examples of the quaternary ammonium cation include (R ₄ N ⁺ ) and the like. Here, R is a hydrophobic group and a polymerizable group, and examples thereof include those shown below.

Examples of the counter anion of the above-mentioned cationic group include Cl ⁻ , Br ⁻ and I ⁻ . The hydrophobic group is preferably selected from the group consisting of an alkyl group, an aryl group, and a group in which these are combined. The polymerizable group is preferably an unsaturated hydrocarbon group, and more specifically selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinylene group. preferable. Among these, an acryloyl group and a methacryloyl group can be exemplified as preferable examples.

  Specific examples of the cationic polymerizable surfactant include a cationic allylic acid derivative as described in JP-B-4-65824.

The cationic polymerizable surfactants used in the present invention, for example, the general formula _{R [4- (l + m +} n)] R 1 l R 2 m R 3 n N + · X - a compound represented by (R is a polymerizable group, R ¹ , R ² and R ³ are each an alkyl group or an aryl group, X is Cl, Br or I, and l, m and n are each 1; Or 0.) Here, as the polymerizable group, a hydrocarbon group having an unsaturated hydrocarbon group capable of radical polymerization can be preferably exemplified, and more specifically, an allyl group, an acroyl group, a methacryloyl group, a vinyl group, a propylene group, and a propylene group. Nyl group, vinylidene group, vinylene group and the like can be mentioned.

  Specific examples of the cationic polymerizable surfactant include dimethylaminoethyl methyl chloride methacrylate, dimethylaminoethyl benzyl methacrylate methacrylate, methacryloyloxyethyltrimethylammonium chloride, diallyldimethylammonium chloride, 2-hydroxy-3-methacryloxypropyl. Examples thereof include trimethylammonium chloride.

  A commercial item can also be used as said cationic polymerizable surfactant. Examples include Acryester DMC (Mitsubishi Rayon Co., Ltd.), Acryester DML60 (Mitsubishi Rayon Co., Ltd.), C-1615 (Daiichi Kogyo Seiyaku Co., Ltd.), and the like.

  The cationic polymerizable surfactants exemplified above can be used alone or as a mixture of two or more.

  The amount of the cationic polymerizable surfactant added is the total number of moles of anionic group relative to the amount of pigment having an anionic group on the surface (= weight of the pigment used (g) × anionic group on the pigment surface (mol). / G)) is preferably in the range of 0.5 to 2 moles, more preferably in the range of 0.8 to 1.2 moles. By setting the addition amount to 0.5 times mol or more, the pigment particles having an anionic group as a hydrophilic group are strongly ionically bound and can be easily encapsulated. By setting the addition amount to 2 times or less, it is possible to reduce the generation of a cationic polymerizable surfactant that is not adsorbed on the pigment particles, and polymer particles that do not have pigment particles as a core substance (particles made of polymer only). ) Can be prevented.

  Specific examples of the anionic polymerizable surfactant include anionic properties as described in JP-B-49-46291, JP-B-1-24142, or JP-A-62-104802. Allyl derivatives, anionic propenyl derivatives as described in JP-A-62-221431, anions as described in JP-A-62-34947 or JP-A-55-11525 And anionic itaconic acid derivatives as described in JP-B-46-34898 or JP-A-51-30284.

  Examples of the anionic polymerizable surfactant used in the present invention include a general formula (31):

[Wherein, R ²¹ and R ³¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Z ¹ represents a carbon-carbon single bond or a formula —CH ₂ —O—CH ₂ - a group represented by, m is an integer of 2 to 20, X is a group represented by the formula -SO ₃ M ^1, M ¹ is an alkali metal, an ammonium salt, or an alkanolamine]
Or a compound represented by formula (32):

[Wherein, R ²² and R ³² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and D represents a carbon-carbon single bond or a formula —CH ₂ —O—CH ₂ — Wherein n is an integer of 2 to 20, Y is a group represented by the formula —SO ₃ M ² , and M ² is an alkali metal, an ammonium salt, or an alkanolamine]
The compound represented by these is preferable.

The polymerizable surfactant represented by the formula (31) is described in JP-A-5-320276 or JP-A-10-316909. By appropriately adjusting the type of R ²¹ and the value of x in the formula (31), it is possible to correspond to the degree of hydrophilicity or hydrophobicity of the pigment particle surface. As a preferable polymerizable surfactant represented by the formula (31), a compound represented by the following formula (310) can be exemplified. Specifically, in the following formulas (31a) to (31d) Mention may be made of the compounds represented.

［式中、Ｒ³¹，ｍ，Ｍ¹は式（３１）で表される化合物と同様］

[Wherein R ³¹ , m and M ¹ are the same as the compound represented by formula (31)]

A commercial item can also be used as said anionic polymerizable surfactant. For example, Aqualon HS series (Aqualon HS-05, HS-10, HS-20, HS-1025) from Daiichi Kogyo Seiyaku Co., Ltd. or Adeka Soap SE-10N, SE-20N from Asahi Denka Kogyo Co., Ltd. Can be mentioned. Adeka Soap SE-10N manufactured by Asahi Denka Kogyo Co., Ltd. is a compound represented by formula (310) in which M ¹ is NH ₄ , R ³¹ is C ₉ H ₁₉ , and m = 10. Adeka Soap SE-20N manufactured by Asahi Denka Kogyo Co., Ltd. is a compound represented by the formula (310) in which M ¹ is NH ₄ , R ³¹ is C ₉ H ₁₉ , and m = 20.

  Examples of the anionic polymerizable surfactant used in the present invention include a general formula (33):

［式中、ｐは９又は１１であり、ｑは２〜２０の整数であり、Ａは−ＳＯ₃Ｍ³で表わされる基であり、Ｍ³はアルカリ金属、アンモニウム塩又はアルカノールアミンである]
で表される化合物が好ましい。式（３３）で表される好ましいアニオン性重合性界面活性剤としては、以下の化合物を挙げることができる。

[Wherein p is 9 or 11, q is an integer of 2 to 20, A is a group represented by —SO ₃ M ³ , and M ³ is an alkali metal, an ammonium salt or an alkanolamine]
The compound represented by these is preferable. Preferred examples of the anionic polymerizable surfactant represented by the formula (33) include the following compounds.

［式中、ｒは９又は１１、ｓは５又は１０］

[Wherein r is 9 or 11, s is 5 or 10]

  A commercial item can also be used as said anionic polymerizable surfactant. For example, Aqualon KH series (Aqualon KH-5, Aqualon KH-10) from Daiichi Kogyo Seiyaku Co., Ltd. can be mentioned. Aqualon KH-5 is a mixture of a compound represented by the above formula wherein r is 9 and s is 5 and a compound where r is 11 and s is 5. Aqualon KH-10 is a mixture of a compound represented by the above formula wherein r is 9 and s is 10, and a compound where r is 11 and s is 10.

  Moreover, as an anionic polymerizable surfactant, the compound represented by the following formula (A) is also preferable.

［上式中、Ｒ⁴は水素原子または炭素数1から12の炭化水素基を表し、ｌは2〜20の数を表し、Ｍ⁴はアルカリ金属、アンモニウム塩、またはアルカノールアミンを表す。］

[In the above formula, R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, 1 represents a number of 2 to 20, and M ⁴ represents an alkali metal, an ammonium salt, or an alkanolamine. ]

  The anionic polymerizable surfactants exemplified above can be used alone or as a mixture of two or more.

  The addition amount of the anionic polymerizable surfactant is preferably in the range of about 1 to 10 times mol, more preferably in the range of about 1.0 to 5 times mol with respect to the cationic polymerizable surfactant. It is. By setting the addition amount to 1 mol or more, the dispersibility and dispersion stability of the encapsulated particles are excellent, and the discharge stability is also excellent. The addition amount of 10 times mol or less can suppress the generation of an anionic polymerizable surfactant that does not contribute to encapsulation, and can prevent the generation of polymer particles having no core substance other than the capsule particles.

  The anionic group of the anionic polymerizable surfactant is considered to be present on the capsule surface after being microencapsulated and oriented on the aqueous phase side. Thereby, the dispersibility and dispersion stability of the encapsulated particles in the aqueous phase become excellent.

  The hydrophilic monomer having an anionic group that can be used in the present invention has at least an anionic group and a polymerizable group as a hydrophilic group in the structure, and the hydrophilic group is a sulfonic acid group or a sulfinic acid group. And those selected from the group of carboxyl groups, carbonyl groups and salts thereof. The polymerizable group is an unsaturated hydrocarbon group capable of radical polymerization, and is preferably selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinylene group. .

  Anionic groups such as sulfonic acid groups, sulfinic acid groups, carboxyl groups, carbonyl groups, and salts thereof are considered to be oriented on the water phase side on the capsule surface, and thus in the aqueous phase of the encapsulated particles. The dispersibility and the dispersion stability in this are excellent. Preferable specific examples of the hydrophilic monomer having an anionic group include, for example, methacrylic acid, acrylic acid, phosphoric acid group-containing (meth) acrylate, sodium vinyl sulfonate, 2-sulfoethyl methacrylate, 2-acrylamido-2-methyl. And propanesulfonic acid.

  The addition amount of the hydrophilic group monomer having an anionic group is preferably in the range of about 1 to 10 times mol, more preferably 1.0 to 5 times the molar amount of the cationic polymerizable surfactant. It is in the range of about a mole. By setting the addition amount to 1 mol or more, the dispersibility and dispersion stability of the encapsulated particles are excellent, and the discharge stability is also excellent. By setting the addition amount to 10 times mol or less, it is possible to suppress the generation of hydrophilic monomers that do not contribute to encapsulation, and to prevent the generation of polymer particles having no core substance other than the capsule particles.

  In the case where an anionic polymerizable surfactant and a hydrophilic group monomer having an anionic group are used in combination, the total amount of addition is about 1 to 10 times mol with respect to the cationic polymerizable surfactant. Is more preferable, and more preferably in the range of about 1.0 to 5 times mole. As described above, when the addition amount is 1 mol or more, the dispersibility and dispersion stability of the encapsulated particles are excellent. By setting the addition amount to 10 times mol or less, it is possible to suppress the generation of hydrophilic monomers that do not contribute to encapsulation, and to prevent the generation of polymer particles in which no core substance exists other than the encapsulated particles.

More specifically, the microencapsulated pigment according to the embodiment of the present invention is preferably produced by the following procedure.
(1) A cationic polymerizable surfactant is added to a dispersion in which a pigment having an anionic group on its surface is dispersed in water. Here, the cationic group of the cationic polymerizable surfactant is adsorbed and ionically bound to the anionic group of the pigment having an anionic group on the surface, and is immobilized.
(2) Comonomers copolymerizable with cationic polymerization surfactants, more specifically, anionic polymerizable surfactants having an anionic group, a hydrophobic group and a polymerizable group and / or anionic A hydrophilic monomer having a group and a polymerization initiator are added to carry out emulsion polymerization.
By such a procedure, a repeating structural unit derived from a cationic polymerizable surfactant and a repeating structural unit derived from an anionic polymerizable surfactant and / or a hydrophilic monomer having an anionic group are included. A microencapsulated pigment coated with a polymer can be suitably produced.

  Furthermore, in particular, for the purpose of controlling the fixing property to the substrate, the scratch resistance and the solvent resistance when the resin composition for the color filter is ejected by the ink jet method, or for controlling the storage stability of the resin composition, etc. The comonomer may be added. Examples of other comonomers include hydrophilic monomers (hydrophilic monomers other than the hydrophilic monomers having an anionic group) and / or hydrophobic monomers. In particular, the fixability and scratch resistance of the ejected material on the substrate are controlled by controlling the glass transition point (Tg) of the copolymer (copolymer) covering the pigment particles of the microencapsulated pigment used in the present invention. Is possible.

  When the glass transition point (Tg) of the copolymer (copolymer) covering the pigment particles of the microencapsulated pigment is below room temperature, the microencapsulation is caused by the capillary pressure generated in the gap between the microencapsulated pigment particles. Since the copolymer (copolymer) that coats the pigment particles of the pigment is fused to encapsulate the pigment inside (encapsulated), the film is fixed to the substrate and the abrasion resistance Can be made particularly good.

  Generally, in polymer solids, especially amorphous polymer solids, when the temperature is raised from a low temperature to a high temperature, a state where a large amount of deformation occurs with a small force from a state where a very large force is required for slight deformation (glass state). The temperature at which this phenomenon occurs is called the glass transition point (or glass transition temperature). In general, in the differential heat curve obtained by temperature rise measurement with a differential scanning calorimeter, the intersection of the base line when the tangent line is drawn from the bottom of the endothermic peak toward the end point of the endothermic peak. Let temperature be the glass transition point. In addition, it is known that other physical properties such as elastic modulus, specific heat, and refractive index also change abruptly at the glass transition point, and it is known that the glass transition point is also determined by measuring these physical properties. ing. In this invention, the glass transition point obtained by the temperature rising measurement with a thermal scanning calorimeter (DSC) was used.

  The glass transition point (Tg) of the copolymer (copolymer) covering the pigment particles of the microencapsulated pigment is preferably 30 ° C. or lower, more preferably 15 ° C. or lower, and further preferably 10 ° C. or lower. Therefore, the copolymer (copolymer) covering the pigment particles of the microencapsulated pigment is preferably designed so that the glass transition point is 30 ° C. or less, more preferably 15 ° C. or less, and still more preferably It is preferably designed to be 10 ° C. or lower. However, when the glass transition point is lower than −20 ° C., the solvent resistance tends to decrease.

  The glass transition point of such a copolymer (copolymer) can be within the above range by appropriately selecting the type and composition ratio of the hydrophobic monomer to be used. If it is possible to heat the ink jetted film at a temperature higher than the glass transition point (Tg) of the copolymer (copolymer) covering the pigment particles of the microencapsulated pigment, the glass transition Since the film can be formed if the point is equal to or lower than the heating temperature, the glass transition temperature may exceed 30 ° C. In this case, it is necessary to attach the heating mechanism to the ink jet device, etc. Since problems such as an increase in the cost of the apparatus occur, the glass transition point is preferably set to 30 ° C. or lower.

  Examples of the hydrophilic monomer other than the hydrophilic monomer having an anionic group include those having a hydroxyl group, an ethylene oxide group, an amide group, or an amino group as the hydrophilic group.

  Examples of hydrophilic monomers other than hydrophilic monomers having an anionic group include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, etc. having an OH group, ethyl diethylene glycol acrylate having an ethylene oxide group, polyethylene glycol Monomethacrylate, methoxypolyethylene glycol methacrylate, etc., acrylamide having an amide group, N, N-dimethylacrylamide, etc., N-methylaminoethyl methacrylate containing amino group, N-methylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate Acrylic acid or meta, such as diethylaminoethyl methacrylate, diethylaminoethyl methacrylate Alkylamino esters of silyl acid; unsaturated amides having alkylamino groups such as N- (2-dimethylaminoethyl) acrylamide, N- (2-dimethylaminoethyl) methacrylamide, N, N-dimethylaminopropylacrylamide, etc. And vinyl ethers having an alkylamino group such as dimethylaminoethyl vinyl ether; vinyl imidazole, N-vinyl-2-pyrrolidone, and the like.

  In order to satisfy the required characteristics such as fixability, scratch resistance, water resistance, and solvent resistance of the color filter formed by the inkjet method, a hydrophobic monomer can be preferably used. That is, the microencapsulated pigment includes a repeating structural unit in which pigment particles having an anionic group on the surface thereof are derived from a cationic polymerizable surfactant having a cationic group, a hydrophobic group, and a polymerizable group; In addition to repeating structural units derived from an anionic polymerizable surfactant having a hydrophobic group, a hydrophobic group and a polymerizable group and / or a hydrophilic monomer having an anionic group, a repeating structure derived from a hydrophobic monomer You may have a unit further.

  The hydrophobic monomer has at least a hydrophobic group and a polymerizable group in its structure, and the hydrophobic group is selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Can be illustrated. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, and a propyl group. Examples of the alicyclic hydrocarbon group include a cyclohexyl group, a dicyclopentenyl group, a dicyclopentanyl group, and an isobornyl group, and an aromatic hydrocarbon group. Examples thereof include a benzyl group, a phenyl group, and a naphthyl group. The polymerizable group is an unsaturated hydrocarbon group capable of radical polymerization, and is preferably selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinylene group. .

  Specific examples of the hydrophobic monomer include styrene and methylstyrene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, p-chloromethylstyrene, divinylbenzene, and other styrene derivatives; methyl acrylate, ethyl acrylate, acrylic acid n-butyl, butoxyethyl acrylate, benzyl acrylate, phenyl acrylate, phenoxyethyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tetrahydrofurfuryl acrylate, isobol Monofunctional acrylic esters such as nyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate Butoxymethyl methacrylate, benzyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, etc. Monofunctional methacrylate esters of allyl compounds such as allylbenzene, allyl-3-cyclohexanepropionate, 1-allyl-3,4-dimethoxybenzene, allylphenoxyacetate, allylphenylacetate, allylcyclohexane, allyl polycarboxylic acid allyl, etc. ; Ester cheeks of fumaric acid, maleic acid, itaconic acid; radically polymerizable groups such as N-substituted maleimides and cyclic olefins Monomer, and the like that.

  As the hydrophobic monomer, those satisfying the above-mentioned required characteristics are appropriately selected, and the addition amount thereof is arbitrarily determined.

  In addition, the polymer that coats the pigment particles preferably further has a repeating structural unit derived from a crosslinkable monomer. By having a repeating structural unit derived from a crosslinkable monomer, a crosslinked structure is formed in the polymer, and the solvent resistance (the solvent contained in the resin composition for ink jet color filter is contained in the polymer coating the pigment). It is possible to improve the properties that do not easily penetrate. When the solvent penetrates the inside of the polymer that coats the pigment particles, the polymer swells and deforms, and the orientation of the anionic group of the pigment particles facing the aqueous medium is disturbed. Stability etc. may be reduced. In such a case, by forming a crosslinked structure in the polymer that coats the pigment particles, the solvent resistance of the microencapsulated pigment is improved, and in the resin composition in which the water-soluble organic solvent coexists, the dispersion stability is further improved. It will be excellent.

  Examples of the crosslinkable monomer that can be used in the present invention include compounds having two or more unsaturated hydrocarbon groups selected from a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinylene group. For example, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, allyl acrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate, bis (acryloxy) Neopentyl glycol) adipate, 1,3-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, Bylene glycol diacrylate, polypropylene glycol diacrylate, 2-hydroxy-1,3-diacryloxypropane, 2,2-bis [4- (acryloxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) Phenyl] propane, 2,2-bis [4- (acryloxyethoxy diethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy polyethoxy) phenyl] propane, hydroxypentylglycol dipentyl glycoldi Acrylate, 1,4-butanediol diacrylate, dicyclopentanyl diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, penta Lithritol triacrylate, tetrabromopisphenol A diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene Glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol Dimethacrylate, 2-hydroxy-1,3-dimetac Liloxypropane, 2,2-bis [4 (methacryloxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxydiethoxy) ) Phenyl] propane, 2,2-bis [4- (methacryloxyethoxypolyethoxy) phenyl] propane, tetrabromobisphenol A dimethacrylate, dicyclopentanyl dimethacrylate, dipentaerythritol hexamethacrylate, glycerol dimethacrylate, hydroxybiba Neopentyl glycol dimethacrylate phosphate, dipentaerythritol monohydroxypentamethacrylate, ditrimethylolpropane tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol Tetramethacrylate, trimethylolpropane triglycidyl Se roll dimethacrylate, trimethylolpropane trimethacrylate, tris (methacryloxyethyl) isocyanurate, allyl methacrylate, divinylbenzene, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diethylene glycol bis allyl carbonate.

  Moreover, it is preferable that the polymer which coat | covers a pigment particle further has the repeating structural unit induced | guided | derived from the monomer represented by following General formula (1).

［ただし、Ｒ¹は水素原子又はメチル基を表す。Ｒ²はｔ−ブチル基、脂環式炭化水素基、芳香族炭化水素基、又はヘテロ環基を表す。ｍは０〜３、ｎは０又は１の整数を表す。］

[However, R ¹ represents a hydrogen atom or a methyl group. R ² represents a t-butyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group. m represents an integer of 0 to 3, and n represents an integer of 0 or 1. ]

The R ² group, which is a “bulky” group derived from the monomer represented by the general formula (1) in the polymer, reduces the flexibility of the polymer molecule, that is, restricts the mobility of the molecule. The color filter pixel of the color filter resin composition using the microencapsulated pigment of this embodiment coated with the polymer is improved in mechanical strength and heat resistance of the polymer and has excellent abrasion resistance and durability. Can be. In addition, since the R ² group, which is a “bulky” group, is present in the polymer, penetration of the organic solvent into the polymer can be suppressed, so that the microencapsulated pigment of this embodiment has excellent solvent resistance. In a resin composition in which a water-soluble organic solvent coexists, more stable ejection properties, dispersibility, and long-term storage can be obtained.

In the general formula (1), examples of the alicyclic hydrocarbon group represented by R ² include a cycloalkyl group, a cycloalkenyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantane group, a tetrahydrofuran group, and the like. Is mentioned.

  As described above, a polymer having a repeating structural unit derived from a crosslinkable monomer and a polymer having a repeating structural unit derived from the monomer represented by the general formula (1) have high Tg, mechanical strength, and heat resistance. There is an advantage that it has excellent properties and solvent resistance. However, microencapsulated pigments coated with such polymers tend to be in a state in which the polymer is not sufficiently plastic and hardly adheres to the substrate, and as a result, the microcapsule pigment can be fixed to the substrate and rub-resistant. May decrease.

  On the other hand, since the polymer having a repeating structural unit derived from a monomer having a long-chain alkyl group among the above-mentioned hydrophobic monomers has flexibility, the repeating structural unit derived from a crosslinkable monomer and / or a general formula By adjusting the ratio of the repeating structural unit derived from the monomer represented by (1) and the repeating structural unit derived from the monomer having a long-chain alkyl group, the mechanical strength and resistance to the extent that the plasticity is not impaired. It can be set as the polymer which has solvent property. The microencapsulated pigment coated with such a polymer is easy to adhere to the substrate, has excellent fixability, and has excellent solvent resistance. Therefore, the resin composition for a color filter using the microencapsulated pigment can obtain excellent ejection stability, dispersion stability, and long-term storage stability even in a resin composition in which a water-soluble organic solvent coexists. In addition, the color filter pixel obtained from the color filter resin composition using the microencapsulated pigment has good fixability, and can be excellent in abrasion resistance, durability, and solvent resistance. .

  Moreover, the following are mentioned as a specific example of the monomer represented by the said General formula (1).

  Copolymerization of a cationic polymerizable surfactant with an anionic polymerization surfactant and / or a hydrophilic monomer having an anionic group, in addition to these, a hydrophobic monomer, a crosslinkable monomer, or the above general formula (1) The copolymerization with the monomer represented by the formula (1) is preferably initiated by the addition of a polymerization initiator. As such a polymerization initiator, a water-soluble polymerization initiator is preferred, and potassium persulfate, ammonium persulfate, Examples thereof include sodium sulfate, 2,2-azobis- (2-methylpropionamidine) dihydrochloride, or 4,4-azobis- (4-cyanovaleric acid).

  The microencapsulated pigment according to the embodiment of the present invention is manufactured by adding the cationic polymerizable surfactant to an aqueous dispersion of pigment particles having an anionic group on the surface as a hydrophilic group, and if necessary. Then, water or water and an aqueous solvent are added and mixed, and after irradiation with ultrasonic waves for a predetermined time, an anionic polymerization surfactant and / or a hydrophilic monomer having an anionic group (in addition to the above hydrophobic monomers) And a monomer represented by the general formula (1) can be added.) And water is added if necessary, and ultrasonic waves are irradiated again for a predetermined time to disperse, and ultrasonic irradiation and stirring are performed. The temperature is raised to a predetermined temperature (the temperature at which the polymerization initiator is activated) while performing the polymerization, and the polymerization initiator is added to activate the polymerization initiator to carry out emulsion polymerization.

  When the hydrophobic monomer is used, more specifically, a cationic polymerizable surfactant having a cationic group, a hydrophobic group, and a polymerizable group in an aqueous dispersion of pigment particles having the anionic group on the surface. A step of adding and mixing an agent and irradiating with ultrasonic waves, a step of adding and mixing a hydrophobic monomer, an anionic polymerizable surfactant having an anionic group, a hydrophobic group and a polymerizable group, and It comprises a step of adding and mixing a hydrophilic monomer having the anionic group and mixing and irradiating with ultrasonic waves, and a step of emulsion polymerization by adding a polymerization initiator, and is more preferable by carrying out in the order of the steps. Can be manufactured.

  When the crosslinkable monomer and / or the monomer represented by the general formula (1) are used, more specifically, a cationic group and a hydrophobic group are added to an aqueous dispersion of pigment particles having the anionic group on the surface. A step of adding a cationic polymerizable surfactant having a polymerizable group and a polymerizable group, mixing and irradiating with ultrasonic waves, and a crosslinkable monomer and / or a monomer represented by the general formula (1) In addition, a step of mixing, an anionic polymerizable surfactant having an anionic group, a hydrophobic group and a polymerizable group and / or a hydrophilic monomer having the anionic group are added and mixed and irradiated with ultrasonic waves. And a process of emulsion polymerization with the addition of a polymerization initiator, and can be more suitably manufactured by carrying out in the order of the steps.

  Further, when the crosslinkable monomer and / or the monomer represented by the general formula (1) is used, more specifically, a cationic group is added to the aqueous dispersion of pigment particles having the anionic group on the surface. And a step of adding and mixing a cationic polymerizable surfactant having a hydrophobic group and a polymerizable group and irradiating with ultrasonic waves, and a crosslinkable monomer and / or the general formula (1). A step of adding and mixing a monomer and a monomer having a long-chain alkyl group, an anionic polymerizable surfactant having an anionic group, a hydrophobic group and a polymerizable group and / or a hydrophilic monomer having the anionic group Are added to the mixture and processed by irradiating with ultrasonic waves, and a step of emulsion polymerization by adding a polymerization initiator, and can be more suitably produced by carrying out in the order of the steps.

  According to the emulsion polymerization method of the present invention, first, a cationic polymerizable surfactant is adsorbed to a hydrophilic group (particularly an anionic group) on the surface of pigment particles having an anionic group on the surface, and then a hydrophobic monomer. In addition, an anionic polymerizable surfactant and / or a hydrophilic monomer having an anionic group is added and treated by irradiating with ultrasonic waves, so that the polymerizable surfactant or monomer present around the pigment particles can be removed. The arrangement form is very highly controlled, and in the outermost shell, a state in which anionic groups are oriented toward the aqueous phase is formed. Then, the monomer is converted into a polymer by the emulsion polymerization while maintaining this highly controlled form, and the microencapsulated pigment according to the embodiment of the present invention is obtained. According to said method, the production | generation of the water-soluble oligomer and polymer which are a by-product can be reduced. Thereby, the viscosity of the obtained dispersion liquid of the microencapsulated pigment can be reduced, and a purification process such as ultrafiltration can be facilitated. A resin composition for a color filter using such a microencapsulated pigment is The dispersion stability is excellent, and the ejection stability from the inkjet head is excellent.

  The polymerization reaction preferably uses a reaction vessel equipped with an ultrasonic generator, a stirrer, a reflux condenser, a dropping funnel and a temperature controller. The polymerization reaction is performed by raising the temperature to the cleavage temperature of the water-soluble polymerization initiator added to the reaction system to cleave the polymerization initiator to generate an initiator radical. It starts by attacking unsaturated groups or unsaturated groups of monomers. The addition of the polymerization initiator into the reaction system can be suitably carried out by dropping an aqueous solution obtained by dissolving a water-soluble polymerization initiator in pure water into the reaction vessel. Activation of the polymerization initiator in the reaction system can be suitably carried out by raising the temperature of the aqueous dispersion to a predetermined polymerization temperature. The polymerization temperature is preferably in the range of 60 ° C. to 90 ° C., and the polymerization time is preferably 3 hours to 10 hours. After the polymerization is completed, it is preferable to perform filtration after adjusting the pH within the range of 7.0 to 9.0. Filtration is preferably ultrafiltration. In addition, when the pigment particles having an anionic group on the surface as a hydrophilic group are not in the state of an aqueous dispersion, as a pretreatment, a dispersion treatment is performed using a general disperser such as a ball mill, a roll mill, an Eiger mill, or a jet mill. It is preferable to carry out.

  In the microencapsulated pigment used in the embodiment of the present invention obtained as described above, the pigment particles having a small average particle diameter are completely covered with the polymer layer (no defect portion), and the hydrophilicity of the polymer layer Since it is considered that the group is regularly oriented toward the aqueous solvent (see FIGS. 2 and 4), it has high dispersion stability with respect to the aqueous solvent.

  Although the microencapsulated pigment according to the embodiment of the present invention has been described above, the particle size of these microencapsulated pigment is preferably 400 nm or less, more preferably 300 nm or less, and particularly preferably 20 to 200 nm.

  The resin composition for a color filter according to the embodiment of the present invention can contain an aqueous dispersion containing the above-described microencapsulated pigment. As such an aqueous dispersion, the liquid after emulsion polymerization in the embodiment of the present invention can be preferably exemplified. The resin composition for an ink jet color filter according to the embodiment of the present invention can be produced by adding other compounding components for making an ink jet color filter resin composition to this aqueous dispersion by a conventional method. .

  The resin composition for a color filter according to the embodiment of the present invention is preferably obtained by purifying an aqueous dispersion containing this microencapsulated pigment. This aqueous dispersion contains unreacted substances derived from the monomers used in addition to the microencapsulated pigment, that is, (a) a cationic polymerizable surfactant, (b) a hydrophobic monomer, and (c) an anionic polymerization. In some cases, an unreacted substance derived from a hydrophilic surfactant having an anionic surfactant and / or an anionic group or the like may be contained.

  By refining the aqueous dispersion in this manner to reduce the concentration of unreacted substances derived from the components constituting the coating polymer of the microencapsulated pigment, the resin composition for a color filter according to the embodiment of the present invention The product preferably has a glass transition point of the coating polymer of the microencapsulated pigment of 30 ° C. or less, more preferably 15 ° C. or less, and still more preferably 10 ° C. or less.

  The concentration of unreacted (c) anionic polymerizable surfactant and / or hydrophilic monomer having an anionic group in the aqueous dispersion after the purification treatment is preferably 50000 ppm or less with respect to the aqueous component. More preferably, it is 10,000 ppm or less. Here, the “aqueous component” refers to a component obtained by removing a water-insoluble component such as a microencapsulated pigment contained in an aqueous dispersion, for example, an aqueous medium, an unreacted polymerizable surfactant, an unreacted monomer. Etc. are included. In addition, “unreacted (c) anionic polymerizable surfactant and / or hydrophilic monomer” means microencapsulation of added (c) anionic polymerizable surfactant and / or hydrophilic monomer. This refers to those which did not contribute to the formation of the coating polymer of the pigment, and this includes not only the anionic polymerizable surfactant and / or the hydrophilic monomer as a monomer, but also the anionic polymerizable surfactant and / or the hydrophilic monomer. Also included are oligomers and polymers formed by polymerizing the polymerizable monomer.

  Among the components constituting the coating polymer of the microencapsulated pigment, in particular, (c) the anionic polymerizable surfactant and / or the hydrophilic monomer having an anionic group is encapsulated before the polymerization reaction as described above. In order to stabilize the particles, it is preferably added in excess. When (c) is added excessively in this way, the concentration of unreacted (c) in the aqueous dispersion after the polymerization reaction tends to increase. By controlling the concentration of unreacted (c), It is estimated that the above advantages become more prominent.

  Further, after the purification treatment of the aqueous dispersion containing the microencapsulated pigment, the total concentration of unreacted (a) and (c) is preferably 50000 ppm or less with respect to the aqueous component in the aqueous dispersion. More preferably, it is 10,000 ppm or less. In addition, in the case where the microencapsulated pigment is formed by adding (b) a hydrophobic monomer in addition to the polymerizable surfactant and performing a polymerization reaction, unreacted ( The total concentration of a), (b) and (c) is preferably 50000 ppm or less, more preferably 10000 ppm or less with respect to the aqueous component in the aqueous dispersion. The unreacted hydrophobic monomer is considered to be solubilized by the unreacted polymerizable surfactant. The concentration of unreacted material before the purification treatment is usually 5 to 40% by weight for (a), 5 to 40% by weight for (b), and 5 to 40% by weight for (c) with respect to the charged amount. It is preferable to be in the range.

  As a method for purifying the aqueous dispersion containing the microencapsulated pigment, a centrifugal separation method, an ultrafiltration method, or the like can be used. Moreover, in this invention, the density | concentrations of said (a), (b), (c), etc. in aqueous dispersion liquid can be measured with the following 1st method or 2nd method.

(First method)
That is, the spectrophotometer was used to measure the spectral characteristics of a cationic polymerizable surfactant, an anionic polymerizable surfactant, and a hydrophilic monomer having an anionic group dissolved in ion-exchanged water in advance. A calibration curve is obtained from the amount dissolved in the exchanged water and the absorbance at the characteristic absorption wavelength. Next, the obtained aqueous dispersion of microencapsulated pigment is centrifuged at 20000 revolutions for 30 minutes in a centrifuge, and the resulting supernatant is diluted to a predetermined magnification (for example, 100 times). The diluted solution is measured for absorbance at 200 to 400 nm with a spectrophotometer, and the amount of each substance in the supernatant is determined from the calibration curve.

  As for the hydrophobic monomer, the spectral characteristics of the hydrophobic monomer dissolved in an organic solvent such as n-hexane in advance is measured with a spectrophotometer, and the dissolved amount and the characteristic absorption wavelength in the organic solvent such as n-hexane are measured. Obtain a calibration curve from the absorbance. Next, the obtained aqueous dispersion of microencapsulated pigment is mixed with an organic solvent such as n-hexane, and the organic solvent phase is collected and diluted to a predetermined magnification. The absorbance of this diluted solution is measured at 200 to 400 nm with a spectrophotometer, and the amount of hydrophobic monomer extracted into an organic solvent such as n-hexane is determined from the above calibration curve.

(Second method)
Obtain a calibration curve of the cationic polymerizable surfactant, anionic polymerizable surfactant and hydrophilic monomer previously dissolved in ion-exchanged water from the dissolved amount and retention time of each substance in ion-exchanged water by liquid chromatography. deep. Next, the supernatant obtained by performing the centrifugation operation of the obtained microencapsulated pigment dispersion at 20000 rotation for 30 minutes in a centrifuge is separated by liquid chromatography, a cationic polymerizable surfactant, Retention amount of anionic polymerizable surfactant and hydrophilic monomer for each retention time and the amount of dissolution of cationic polymerizable surfactant, anionic polymerizable surfactant and hydrophilic monomer in the supernatant liquid from the above calibration curve Ask for.

  As for the hydrophobic monomer, a calibration curve is obtained in advance from the amount of the hydrophobic monomer dissolved in an organic solvent such as n-hexane and the retention time in an organic solvent such as n-hexane by liquid chromatography. Next, the obtained aqueous dispersion of the microencapsulated pigment is mixed with an organic solvent such as n-hexane, and the organic solvent phase is collected and separated by liquid chromatography. The amount of hydrophobic monomer extracted in an organic solvent such as n-hexane is determined from the above calibration curve.

  The resin composition for an ink jet color filter according to an embodiment of the present invention includes at least the above-described microencapsulated pigment and water. Moreover, it is preferable that the resin composition for inkjet type color filters which concerns on other embodiment of this invention contains an above described aqueous dispersion. The content of the microencapsulated pigment is preferably 1% by weight to 20% by weight, and more preferably 3% by weight to 15% by weight with respect to the total weight of the resin composition for a color filter. In particular, 5 to 15% by weight is preferable.

  In addition, the resin composition for an ink jet color filter according to an embodiment of the present invention preferably contains water as a basic solvent and contains a water-soluble organic solvent, and may contain any other component as necessary. .

  Examples of water-soluble organic solvents include alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monomethyl ether acetate. Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, Triethylene glycol mono-n-butyl ether, Tylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl Ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, propylene glycol mono-n- Glycol ethers such as butyl ether or dipropylene glycol mono-n-butyl ether; There may be mentioned formamide, acetamide, dimethylsulfoxide, sorbit, sorbitan, acetin, diacetin, triacetin, or sulfolane and the like.

  The resin composition for a color filter according to an embodiment of the present invention is a wetting agent comprising a high-boiling water-soluble organic solvent as a water-soluble organic solvent for the purpose of providing water retention and wettability of the color filter resin composition. It is preferable to contain. As such a high boiling water-soluble organic solvent, a high boiling water-soluble organic solvent having a boiling point of 180 ° C. or higher can be exemplified.

  Specific examples of the water-soluble organic solvent having a boiling point of 180 ° C. or higher include ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3- Hexanediol, 2-methyl-2,4-pentanediol, tripropylene glycol monomethyl ether, dipropylene glycol monoethyl glycol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, triethylene glycol monomethyl ether, Tetraethylene glycol, triethylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl Ether, tripropylene glycol, polyethylene glycol having a molecular weight of 2000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1, Examples include 6-hexanediol, glycerin, mesoerythritol, and pentaerythritol. An organic solvent having a boiling point of 200 ° C. or higher is preferable. These can be used alone or as a mixture of two or more. Accordingly, it is possible to provide a resin composition for a color filter that maintains fluidity and redispersibility for a long time even when left in an open state (a state where it is exposed to air at room temperature). In addition, nozzle clogging is less likely to occur during inkjet discharge or restarting after discharge interruption, and high discharge stability is obtained.

  The content of these water-soluble organic solvents is preferably about 10 to 50% by weight, more preferably 10 to 30% by weight, based on the total weight of the color filter resin composition.

  Further, as the water-soluble organic solvent, polar solvents such as 2-pyrrolidone, N-methylpyrrolidone, ε-caprolactam, dimethyl sulfoxide, sulfolane, morpholine, N-ethylmorpholine, 1,3-dimethyl-2-imidazolidinone are used. One or more of these may be selected and used. The addition of these polar solvents has an effect on dispersibility, and can improve the ejection stability of the resin composition. The content of these polar solvents is preferably 0.1% by weight to 20% by weight, more preferably 1% by weight to 10% by weight, based on the total weight of the resin composition for color filters.

  The resin composition for a color filter according to the embodiment of the present invention preferably contains a penetrant for the purpose of promoting the dispersion of the microencapsulated pigment. As such a penetrant, polyhydric alcohol alkyl ethers (also referred to as glycol ethers) and 1,2-alkyldiols are preferably used. Specifically, as the alkyl ether of polyhydric alcohol, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol mono- n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono- t-butyl ether, diethylene glycol mono-t-butyl Ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene Glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, etc. It is done. Specific examples of the 1,2-alkyldiol include 1,2-pentanediol and 1,2-hexanediol. In addition to these, linear carbonization such as 1,3-propanediol, 1,4-butanediol 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, etc. It may be appropriately selected from hydrogen diols.

  In particular, in the embodiment of the present invention, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, 1,2-pentanediol, and 1,2-hexanediol are preferable. The content of these penetrants is preferably 1 to 20% by weight, more preferably 1 to 10% by weight, based on the total weight of the resin composition for a color filter. When the content of the penetrant is less than 1% by weight, there is no dispersion effect, and when it exceeds 20% by weight, problems such as an increase in viscosity occur. In particular, the use of 1,2-alkyldiols such as 1,2-pentanediol and 1,2-hexanediol significantly improves the drying properties after ejection.

  In particular, in the embodiment of the present invention, by including glycerin, the clogging reliability and storage stability of the resin composition can be sufficiently ensured. Further, since the pigment dispersibility can be improved by including one or more compounds selected from the group consisting of alkyl ethers of polyhydric alcohols and 1,2-alkyldiols, the effects and effects of microencapsulated pigments can be enhanced. As a result, the quality of the color filter can be significantly improved.

  Moreover, when using the above-mentioned glycol ethers, it is particularly preferable to use glycol ethers in combination with an acetylene glycol compound as a surfactant described later.

  Moreover, it is preferable that the resin composition for color filters which concerns on embodiment of this invention contains surfactant, especially anionic surfactant and / or nonionic surfactant. Specific examples of anionic surfactants include alkane sulfonate, α-olefin sulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonic acid, acylmethyl tauric acid, dialkyl sulfosuccinic acid and other sulfonic acid types, alkyl sulfuric acid Ester salt, sulfated oil, sulfated olefin, polyoxyethylene alkyl ether sulfate ester salt; carboxylic acid type such as fatty acid salt, alkyl sarcosine salt; alkyl phosphate ester salt, polyoxyethylene alkyl ether phosphate ester salt, And phosphoric acid ester type such as monoglycerite phosphoric acid ester salt; Specific examples of nonionic surfactants include ethylene oxide addition types such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amide; glycerin alkyl ester, sorbitan alkyl ester Polyol ester type such as sugar alkyl ester; polyether type such as polyhydric alcohol alkyl ether; alkanolamide type such as alkanolamine fatty acid amide.

  More specifically, examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium laurate, ammonium salt of polyoxyethylene alkyl ether sulfate, and specific examples of the nonionic surfactant include polyoxyethylene. Nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, etc. Ether type, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sol Tanraureto, sorbitan monostearate, may be mentioned sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, the ester and the like, such as polyoxyethylene stearate.

  In particular, the resin composition for a color filter according to the embodiment of the present invention desirably contains an acetylene glycol surfactant and / or an acetylene alcohol surfactant as a surfactant. Preferable specific examples of the acetylene glycol compound used in the present invention include compounds represented by the following formula (6).

In the above formula (6), m and n are numbers satisfying 0 ≦ m + n ≦ 50, respectively. R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group (preferably an alkyl group having 6 or less carbon atoms). Among the compounds represented by the above formula (6), 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3, 6-diol, 3,5-dimethyl-1-hexyn-3-ol and the like. As the compound represented by the above formula (6), a commercially available product that is commercially available as an acetylene glycol surfactant can be used. Specific examples thereof include Surfynol 104, 82, 465, 485 or TG (all available from Air Products and Chemicals. Inc.), Orphine STG, Orphine E1010 (above, Nissin Chemical Co., Ltd. trade name).

  Examples of the acetylene alcohol surfactant include Surfynol 61 (available from Air Products and Chemicals. Inc.).

  The content of these surfactants is preferably in the range of 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, with respect to the total weight of the color filter resin composition.

Moreover, the resin composition for color filters which concerns on embodiment of this invention can further contain polymer microparticles | fine-particles. The polymer fine particles preferably have the following forms 1) to 3).
1) Polymer fine particles having an anionic group on the surface, a glass transition temperature of 30 ° C. or less, and a volume average particle diameter of 10 to 200 nm.
2) Polymer fine particles having an anionic group of the same type as the anionic group on the surface of the microencapsulated pigment, a glass transition temperature of 30 ° C. or less, and a volume average particle diameter of 10 to 200 nm.
3) An anionic group on the surface, a glass transition temperature of 30 ° C. or less, a volume average particle size of 10 to 200 nm, and 3 volume of 0.1 wt% aqueous emulsion and a concentration of 1 mol / L Reactivity with a divalent metal salt such that when it is brought into contact with one volume of the divalent metal salt aqueous solution, the time during which the light transmittance at a wavelength of 700 nm is 50% of the initial value is 1 × 10 ⁴ seconds or less. Polymer fine particles having In this case, the anionic group on the surface may be the same as or different from the anionic group on the surface of the microencapsulated pigment.

  As described above, a microencapsulated pigment coated with a polymer having a repeating structural unit derived from a crosslinkable monomer and / or a polymer having a repeating structural unit derived from a monomer represented by formula (1) is: Although it has high mechanical strength, heat resistance, and solvent resistance, the plasticity of the polymer becomes insufficient, and the fixability to the substrate and the abrasion resistance tend to be lowered. However, a resin composition for a color filter containing a microencapsulated pigment coated with a polymer having insufficient plasticity and the polymer fine particles has a polymer property when the polymer fine particles have film-forming properties. Fine particles can cover the microencapsulated pigment on the substrate. Therefore, particularly in the case where the polymer that coats the pigment has a crosslinked structure and / or a “bulky” group, the advantages due to the aforementioned crosslinked structure and / or “bulky” group as well as fixability and abrasion resistance are obtained. A compatible resin composition for a color filter can be obtained.

  Here, the film formability means that when polymer fine particles are dispersed in water to form an aqueous emulsion, a polymer film is formed when the water component of the aqueous emulsion is evaporated. The color filter resin composition of the present invention containing the polymer fine particles has a property of forming a polymer film in the same manner as the solvent component is evaporated. With this polymer film, the microencapsulated pigment in the color filter resin composition can be more firmly fixed to the substrate surface. Thereby, a pixel of a color filter having better scratch resistance and water resistance can be realized.

  In order for the polymer fine particles to have film-forming properties, the polymer glass transition point of the polymer fine particles is preferably 30 ° C. or lower, more preferably 15 ° C. or lower, and even more preferably 10 ° C. or lower. When the resin composition for a color filter using the microencapsulated pigment containing the polymer fine particles is ejected to the substrate by the ink jet method, the microencapsulated pigment particles and the polymer fine particles are close to each other, and the polymer fine particles and / or Since the coating polymers of the microencapsulated pigment particles and / or the polymer fine particles and the coating polymer of the microencapsulated pigment particles are fused to form a film in a state where the pigment particles are encapsulated (encapsulated), the color filter Fixability of the resin composition for a substrate to a substrate and abrasion resistance can be particularly improved.

  The polymer fine particles are preferably designed so that the glass transition point of the polymer is 30 ° C. or less, more preferably 15 ° C. or less, and still more preferably 10 ° C. or less. The glass transition point of the polymer can be within the above range by appropriately selecting the type and composition ratio of the monomer used.

  When the resin composition can be heated at a temperature equal to or higher than the glass transition point of the polymer constituting the polymer fine particles, film formation is possible if the glass transition point is equal to or lower than the heating temperature. However, in this case, it is necessary to attach a heating mechanism to the ink jet device, which causes a problem such as an increase in the cost of the device. Therefore, the glass transition temperature is set to 30 ° C. or lower. It is preferable. The glass transition point of the polymer of the polymer fine particles may be obtained from the elastic modulus, specific heat, refractive index, etc., but in the present invention, the glass transition point obtained by measuring the temperature rise with a thermal scanning calorimeter (DSC) is used. Using. That is, the temperature at the intersection with the baseline when a tangent line is drawn from the bottom of the endothermic peak toward the end point of the endotherm in the differential heat curve obtained by temperature rise measurement with a differential scanning calorimeter. Was the glass transition temperature.

  According to a preferred embodiment of the present invention, the polymer fine particles preferably have a minimum film-forming temperature of room temperature or lower, more preferably 30 ° C. or lower, most preferably 10 ° C. or lower. It is preferable. This is because the polymer fine particles are preferably deposited at room temperature or lower. Here, the minimum film-forming temperature refers to the formation of a transparent continuous film when the polymer emulsion obtained by dispersing polymer particles in water is cast thinly on a metal plate such as aluminum and the temperature is raised. Refers to the lowest temperature to be played. A white powder is formed in the temperature range below the minimum film formation temperature. Furthermore, according to the preferable aspect of this invention, it is preferable that the glass transition point of a polymer microparticle is 30 degrees C or less.

Moreover, since the polymer fine particles have an anionic group on the surface, they can be stably dispersed without coagulation even if they coexist in the resin composition with the microencapsulated pigment used in the present invention. . Further, the polymer fine particles described in the following were obtained: “When a 0.1% by weight aqueous emulsion (3 volumes) and a 1 mol / L divalent metal salt aqueous solution (1 volume) were contacted, the light transmittance at a wavelength of 700 nm had an initial value. Since the time of 50% is 1 × 10 ⁴ seconds or less, the amount of anionic groups on the surface of the polymer fine particles is large, and good dispersion stability is obtained even when the microencapsulated pigment and the resin composition coexist. Here, when the time exceeds 1 × 10 ⁴ seconds, the amount of anionic groups on the surface of the polymer fine particles is small, and dispersion occurs when the microencapsulated pigment of the present invention coexists in the resin composition. It tends to be inferior in stability.

The time when the transmittance of light having a wavelength of 700 nm when contacting with 1 volume of the divalent metal salt aqueous solution is 50% of the initial value is preferably 1 × 10 ³ seconds or less, more preferably 1 × 10 6. ² seconds or less. The polymer fine particles used in the embodiment of the present invention react with a divalent metal ion to react with each other to generate a suspended matter and reduce the transparency of the solution. The amount of the suspended matter produced is measured by the light transmittance. Here, the divalent metal ions include Ca ²⁺ , Cu ²⁺ , Ni ²⁺ , Mg ²⁺ , Zn ²⁺ , and Ba ²⁺ , and anions that form salts with them include Cl ⁻ , NO ³⁻ , I ⁻ , Br ⁻ , ClO ³⁻ and CH ₃ COO ⁻ can be mentioned.

  Such high reactivity is considered to be caused by the polymer fine particles having a relatively large number of anionic groups on the surface thereof. The resin composition comprising polymer fine particles having a large amount of anionic groups on the surface thereof exhibiting a high reactivity as described above has no affinity for the nozzle plate of the water-repellent inkjet head. . Therefore, the resin composition does not wet the nozzle plate, and as a result, there is a great advantage that the flight bending of the resin composition droplets and the occurrence of ejection failure are effectively prevented. Examples of the anionic group include a sulfonic acid group, a sulfinic acid group, a carboxyl group, and a carbonyl group. In particular, when the anionic group is the same as the anionic group on the surface of the microencapsulated pigment, the dispersion stability is excellent when the polymer fine particles and the microencapsulated pigment coexist in the resin composition. Moreover, it is preferable that the particle diameter of the said polymer fine particle is the range of 50-200 nm by a volume average particle diameter. When the volume particle diameter exceeds 200 nm, the discharge of the resin composition tends to be unstable.

According to a preferred embodiment of the present invention, the contact angle on the Teflon (registered trademark) plate of an aqueous emulsion in which polymer fine particles are dispersed in an aqueous medium at a concentration of 10% by weight is preferably 70 ° or more. Furthermore, the surface tension of an aqueous emulsion in which polymer fine particles are dispersed in an aqueous medium at a concentration of 35% by weight is preferably 40 × 10 ⁻³ N / m (40 dyne / cm, 20 ° C.) ”or more. By using the polymer fine particles as described above, it is possible to prevent the flight bending and to perform good discharge.

  Furthermore, due to the high hydrophilicity of the surface of the polymer fine particles, the resin composition for a color filter of the present invention using such polymer fine particles can obtain excellent storage stability without reducing the performance of the microencapsulated pigment. There are also advantages.

  According to a preferred embodiment of the present invention, the polymer fine particles comprise 1 to 10% by weight of a structure derived from an unsaturated vinyl monomer having an anionic group and have two or more polymerizable double bonds. It preferably has a structure crosslinked with a crosslinkable monomer and contains 0.2 to 4% by weight of a structure derived from the crosslinkable monomer. By using a crosslinkable polymer obtained by copolymerizing three or more crosslinkable monomers having two or more polymerizable double bonds, more preferably three or more during polymerization, the nozzle plate surface has a resin composition. Further, it becomes difficult to get wet by the object, flight bending can be further prevented, and discharge stability can be further improved.

  In the present invention, a polymer fine particle having a single particle structure can be used. On the other hand, in the present invention, it is also possible to use polymer fine particles having a core-shell structure comprising a core portion and a shell portion surrounding the core portion. In the present invention, the “core-shell structure” means “a form in which two or more kinds of polymers having different compositions are present in phase separation in particles”. Therefore, the shell portion may not only cover the core portion completely, but may cover a portion of the core portion. Further, a part of the shell polymer may form a domain or the like in the core particle. Furthermore, it may have a multilayer structure of three or more layers including layers having different compositions in the middle between the core part and the shell part.

  The polymer fine particles used in the present invention can be obtained by known emulsion polymerization. That is, it can be obtained by emulsion polymerization of an unsaturated vinyl monomer (unsaturated vinyl monomer) in water containing a polymerization initiator and an emulsifier.

  As unsaturated vinyl monomers, acrylic acid ester monomers, methacrylic acid ester monomers, aromatic vinyl monomers, vinyl ester monomers, vinyl, which are generally used in emulsion polymerization Examples include cyanide monomers, halogenated monomers, olefin monomers, and diene monomers. Furthermore, specific examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate. Acrylates such as octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n- Hexyl methacrylate, 2-e Methacrylic esters such as ruhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, and vinyl esters such as vinyl acetate; acrylonitrile, methacrylonitrile, etc. Vinyl cyanide compounds; halogenated monomers such as vinylidene chloride and vinyl chloride; aromatic vinyl units such as styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole and vinylnaphthalene Olefins such as ethylene, propylene and isopropylene; dienes such as butadiene and chloroprene; vinyl ether and vinyl Ketones, vinyl monomers such as vinyl pyrrolidone. For monomers having no carboxyl group, it is essential to use unsaturated vinyl monomers having a carboxyl group. Preferred examples thereof include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid. And the use of methacrylic acid is preferred. Examples of emulsifiers that can be used include anionic surfactants, nonionic surfactants, and mixtures thereof.

  Moreover, as described above, in the present invention, it is preferable that the monomer-derived molecule has a structure crosslinked by a crosslinkable monomer having two or more polymerizable double bonds. Examples of the crosslinkable monomer having two or more polymerizable double bonds include polyethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,6-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4-acryloxypropyloxyphenyl) propane, 2,2 ′ -Diacrylate compounds such as bis (4-acryloxydiethoxyphenyl) propane, triacrylate compounds such as trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolmethane triacrylate , Tetraacrylate compounds such as ditrimethylol tetraacrylate, tetramethylol methane tetraacrylate, pentaerythritol tetraacrylate, hexaacrylate compounds such as dipentaerythritol hexaacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol Dimethacrylate, 2 , 2′-bis (4-methacryloxydiethoxyphenyl) propane, and the like, trimethacrylate compounds such as trimethylolpropane trimethacrylate and trimethylolethane trimethacrylate, methylenebisacrylamide, and divinylbenzene.

  Furthermore, in addition to the above monomers, the discharge stability can be further improved by adding acrylamides or hydroxyl group-containing monomers. Examples of acrylamides include acrylamide and N, N′-dimethylacrylamide. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate. These may be used alone or in combination of two or more. can do.

  Further, the polymer fine particles having a core-shell structure are produced by a known method, generally by multi-stage emulsion polymerization. For example, it can be produced by the method disclosed in JP-A-4-76004. Examples of the unsaturated vinyl monomer used for the polymerization include those described above.

  In addition, a polymerization initiator, a surfactant, a molecular weight adjusting agent, a neutralizing agent and the like used in the emulsion polymerization may be used according to a conventional method.

  In the present invention, the polymer fine particles may be mixed with the other components of the resin composition for a color filter as fine particle powder. It is preferably mixed with other components of the resin composition. The content of the polymer fine particles in the color filter resin composition is preferably about 0.01 to 10% by weight, more preferably about 0.01 to 5% by weight.

  Moreover, according to another aspect of the present invention, according to the present invention, there are provided polymer fine particles and a polymer emulsion in which the polymer fine particles are dispersed in water, which are used in a resin composition for a color filter. By using the polymer fine particles and the polymer emulsion, a resin composition preferably used in an ink jet method having good performance can be obtained.

  Moreover, the resin composition for inkjet color filters which concerns on embodiment of this invention can also contain a pH adjuster, Preferably, pH is the range of 7-9, More preferably, it is 7.5-8. A range of 5 is set. Specific examples of the pH adjuster include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, lithium carbonate, sodium phosphate, potassium phosphate, lithium phosphate, diphosphate. Potassium metal such as potassium hydrogen, dipotassium hydrogen phosphate, sodium oxalate, potassium oxalate, lithium oxalate, sodium borate, sodium tetraborate, potassium hydrogen phthalate, potassium hydrogen tartrate, ammonia, methylamine, ethylamine , Diethylamine, trimethylamine, triethylamine, tris (hydroxymethyl) aminomethane hydrochloride, triethanolamine, diethanolamine, diethylethanolamine, triisopropenolamine, butyldiethanolamine, morpholine, And amines such as Ropanoruamin are preferred. Among these, when an alkali hydroxide compound or an amine alcohol is added, the dispersion stability of the pigment particles can be improved even in the resin composition.

  The addition amount of the alkali hydroxide compound is preferably 0.01 wt% to 5 wt%, more preferably 0.05 to 3 wt%, based on the total amount of the color filter resin composition. The amount of amine alcohol added is preferably 0.1 wt% to 10 wt%, more preferably 0.5 to 5 wt%, based on the total amount of the color filter resin composition.

Moreover, the resin composition for color filters which concerns on embodiment of this invention is benzoic acid, a dichlorophen, hexachlorophene, sorbic acid, p-hydroxybenzoic acid ester, ethylenediamine quaternary for the purpose of a fungicide, antiseptic | preservation, and rust prevention. Contains acetic acid (EDTA), sodium dehydroacetate, 1,2-benchazolin-3-one [product name: Proxel XL (manufactured by Avicia)], 3,4-isothiazoline-3-one, 4,4-dimethyloxazolidine be able to.
Moreover, the resin composition for color filters which concerns on embodiment of this invention can contain urea, thiourea, and / or ethylene urea etc. in order to prevent the nozzle of an inkjet head from drying.

Particularly preferred resin composition for color filter according to the embodiment of the present invention,
(1) microencapsulated pigment,
(2) one or more compounds (penetrant) selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and / or 1,2-alkyldiol having 4 to 10 carbon atoms,
(4) glycerin,
(5) water,
At least.
Such a resin composition for a color filter is particularly excellent in dispersion stability and discharge stability, and can stably discharge over a long period of time without clogging of the nozzles.

Another aspect of the resin composition for a color filter according to a particularly preferred embodiment of the present invention is:
(1) microencapsulated pigment,
(2) one or more compounds (penetrant) selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and / or 1,2-alkyldiol having 4 to 10 carbon atoms,
(3) Acetylene glycol surfactant and / or acetylene alcohol surfactant,
(4) glycerin,
(5) water,
At least.
Such a resin composition for a color filter is particularly excellent in dispersion stability and discharge stability, and can stably discharge over a long period of time without clogging of the nozzles.

  Generally, when dispersing a pigment, a dispersant such as a surfactant or a polymer dispersant is used. However, since these dispersants are merely adsorbed on the surface of the pigment particles, The dispersant tends to be easily detached from the pigment particle surface due to environmental factors. On the other hand, in the embodiment of the present invention, as described above, the surface of the pigment particle having the hydrophilic group on the surface is completely encapsulated with the polymer film or the crosslinked polymer film, and the surface of the pigment particle is surrounded. It is considered that the polymer film or the cross-linked polymer film is very firmly fixed to the surface of the pigment particle and thus is difficult to be detached from the surface of the pigment particle.

  More specifically, the above acetylene glycol surfactant and / or acetylene alcohol surfactant and diethylene glycol using a pigment dispersion obtained by dispersing a pigment using a dispersant such as a surfactant or a polymer dispersant. In resin compositions using penetrants such as monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, or 1,2-alkyl diol, added when discharged through a thin nozzle Due to the strong shearing force, the dispersant is easily detached from the pigment surface, resulting in deterioration of dispersibility, and discharge tends to be unstable.

  On the other hand, in the resin composition for color filters using the microencapsulated pigment according to the embodiment of the present invention, such a phenomenon is not recognized at all and is stably ejected. In addition, since the polymer film includes the pigment particles, good solvent resistance can be obtained, so that the penetration of the penetrant from the pigment particles and the swelling of the polymer are less likely to occur. Excellent dispersion stability can be maintained.

  In addition, resin compositions using pigment dispersions in which pigments are dispersed using a dispersant such as a surfactant or a polymer dispersant are generally not adsorbed on the pigment surface from the beginning of dispersion, but dissolved in the liquid. The viscosity of the resin composition is increased by the dispersing agent, or the dispersing agent is detached from the pigment as time passes after dispersion, and the viscosity of the resin composition tends to be increased by the detached dispersing agent. . For this reason, the pigment content is often limited. In contrast, in the color filter resin composition using the microencapsulated pigment according to the embodiment of the present invention, as described above, the polymer coating includes the pigment particles, so that the polymer is detached from the pigment particles. It is difficult to increase the viscosity of the resin composition. Therefore, it is easy to lower the viscosity of the resin composition, and there is an advantage that more pigment particles can be contained.

  In the above-described particularly preferred embodiment of the present invention, the addition amount of diethylene glycol monobutyl ether and triethylene glycol monobutyl ether as the penetrating agent of (2) is preferably 10% with respect to the total weight of the color filter resin composition. % Or less, more preferably 0.5 to 5% by weight. Addition of diethylene glycol monobutyl ether or triethylene glycol monobutyl ether helps to improve dispersion stability. Further, diethylene glycol monobutyl ether and / or triethylene glycol monobutyl ether improves the solubility of the acetylene glycol surfactant.

  In the particularly preferred embodiment of the present invention described above, the amount of the 1,2-alkyldiol having 4 to 10 carbon atoms as the penetrant of (2) is preferably based on the total weight of the color filter resin composition. Is 15% by weight or less. A 1,2-alkyldiol having 3 or less carbon atoms is not preferable because sufficient dispersibility cannot be obtained. If the carbon number exceeds 15, it is difficult to dissolve in water. If the added amount exceeds 15% by weight, a tendency to increase the viscosity appears, which is not suitable. Specifically, 1,2-pentanediol or 1,2-hexanediol is preferably used as the 1,2-alkyldiol, and these can be used alone or in combination. 1,2-pentanediol is preferably added in the range of 3 to 15% by weight. If it is less than 3% by weight, good dispersibility cannot be obtained. 1,2-hexanediol is preferably added in the range of 0.5 to 10% by weight. If it is less than 0.5% by weight, good dispersibility cannot be obtained.

  In particular, the resin composition for a color filter according to the embodiment of the present invention is provided with a solid wetting agent based on the total weight of the resin composition in order to improve the characteristic that clogging is less likely to occur (clogging reliability). The content is preferably 3 to 20% by weight.

In this specification, the solid wetting agent refers to a water-soluble substance that is solid at room temperature (25 ° C.) and has a water retention function. Preferred solid wetting agents are sugars, sugar alcohols, hyaluronate, trimethylolpropane, 1,2,6-hexanetriol. Examples of sugars include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol. (Sorbit), maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like. Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature, such as alginic acid, α-cyclodextrin, and cellulose. The derivatives of these saccharides are represented by the reducing sugars of the saccharides described above (for example, sugar alcohol (general formula HOCH ₂ (CHOH) _n CH ₂ OH (where n represents an integer of 2 to 5)). ), Oxidized sugars (eg, aldonic acid, uronic acid, etc.), amino acids, thiosaccharides, etc.). Sugar alcohol is particularly preferable, and specific examples include maltitol, sorbitol, xylitol and the like. As the hyaluronate, a commercially available sodium hyaluronate 1% aqueous solution (molecular weight 350,000) can be used. These solid wetting agents are used alone or in combination of two or more. Particularly preferred solid wetting agents are trimethylolpropane, 1,2,6-hexatriol, sugars and sugar alcohols.

  By using a solid wetting agent, water evaporation can be suppressed by its water retention function, so the resin composition does not increase in viscosity around the flow path and nozzle, and clogging occurs because it is difficult to form a film. It becomes difficult. Moreover, since the above-mentioned solid wetting agent is chemically stable, the performance can be maintained over a long period without being decomposed in the resin composition. Further, even when the above-described solid wetting agent is added, the resin composition does not wet the nozzle plate, and stable ejection can be obtained. In particular, it is excellent when trimethylolpropane, 1,2,6-hexanetriol, saccharides or sugar alcohols are used.

  In the present invention, the content of the solid wetting agent is preferably 3 to 20% by weight, more preferably 3 to 10% by weight based on the total weight of the color filter resin composition when used alone. When two or more types are used in combination, the total amount of the two or more types is preferably 3 to 20% by weight, more preferably 3%, based on the total weight of the color filter resin composition. -10% by weight. A preferable combination in the case of using a mixture of two or more kinds is a combination of a group of saccharides, sugar alcohols and hyaluronate with a group of trimethylolpropane and 1,2,6-hexanetriol. This combination is preferable because it is possible to suppress an increase in the viscosity of the resin composition due to the addition. If the content of the solid wetting agent is less than 3% by weight, a sufficient effect for improving the clogging property cannot be obtained, and if it exceeds 20% by weight, the viscosity increases and it is difficult to obtain a stable discharge. .

  In the above-described particularly preferred embodiment of the present invention, the amount of the acetylene glycol surfactant and / or acetylene alcohol surfactant of (3) is preferably based on the total weight of the resin composition for color filters. 0.01 to 10% by weight, more preferably 0.1 to 5% by weight.

  As described above, the ink composition color filter resin composition according to the embodiment of the present invention has been described. However, as described above, the microencapsulated pigment contained as a colorant has a true spherical shape and a resin composition. It is thought that the fluidity of the water is likely to be Newtonian, and the anionic groups on the surface are regularly and densely oriented toward the aqueous solvent side, and it is considered that an effective electrostatic repulsive force is generated. . Therefore, compared with conventional microencapsulated pigments, it has superior ejection stability, more dispersibility (high dispersibility) and dispersion stability, and further improved colorant content concentration. A composition can be made.

  The ejection by the ink jet method is preferably performed by mounting the resin composition for an ink jet color filter according to the embodiment of the present invention on a known ink jet printer device and ejecting the resin composition to a filter substrate. The discharge stability of the resin composition from the head can be made excellent.

  In the ink composition color filter resin composition of the present invention, a binder resin that functions as a binder for the aforementioned microencapsulated pigment is usually used. Any suitable resin can be used as the binder resin as long as it acts as a binder for the microencapsulated pigment. A preferred binder resin in the present invention is a polymer containing a carboxyl group, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter simply referred to as “carboxyl group-containing unsaturated monomer”). ) And other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as “other unsaturated monomers (b1)”) (hereinafter referred to as “carboxyl group-containing copolymer (B1)”). ) ").

  Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, Unsaturated dicarboxylic acids (anhydrides) such as itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; trivalent or higher unsaturated polycarboxylic acids (anhydrides); succinic acid mono (2- A polyvalent carboxylic acid having two or more valences such as acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), etc. Mono [(meth) acryloyloxyalkyl] esters of acids; ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycap It can be mentioned mono (meth) acrylates such as polymers having a carboxyl group and a hydroxyl group at both terminals such as lactone monomethacrylate. Succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are commercially available under the trade names M-5300 and M-5400 (manufactured by Toagosei Co., Ltd.), respectively. Has been. These carboxyl group-containing ethylenically unsaturated monomers can be used alone or in admixture of two or more.

  Other unsaturated monomers (b1) include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m -Methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether Aromatic vinyl compounds such as indene and indene such as 1-methylindene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate , I-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl Acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene Glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol Acrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, Unsaturated carboxylic esters such as glycerol monomethacrylate;

  2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl Unsaturated carboxylic acid aminoalkyl esters such as methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; glycidyl unsaturated carboxylic acid such as glycidyl acrylate and glycidyl methacrylate Esters: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and other carboxylic acid vinyl esters; vinyl Unsaturated ethers such as til ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylamide, α-chloro Unsaturated amides or unsaturated imides such as acrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide and maleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene , Polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, etc. There may be mentioned macromonomers or the like having a mono methacryloyl group. These other unsaturated monomers (b1) can be used alone or in admixture of two or more.

  As the carboxyl group-containing copolymer (B1), (1) acrylic acid and / or methacrylic acid and (2) styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl A copolymer with at least one selected from the group of methacrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer is preferred.

  Specific examples of preferred carboxyl group-containing copolymer (B1) include acrylic acid / benzyl acrylate copolymer, acrylic acid / styrene / methyl acrylate copolymer, acrylic acid / styrene / benzyl acrylate copolymer, acrylic acid / Methyl acrylate / polystyrene macromonomer copolymer, acrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer Polymer, acrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polystyrene macromonomer copolymer, acrylic acid / 2-hydroxyethyl acrylate / benzyl acetate Rate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl methacrylate copolymer, acrylic acid / styrene / methyl methacrylate copolymer, acrylic acid / styrene / benzyl methacrylate copolymer, acrylic acid / methyl methacrylate / polystyrene macro Monomer copolymer, acrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate DOO / benzyl methacrylate / polymethyl methacrylate macromonomer copolymers of acrylic acid copolymers such as;

  Methacrylic acid / benzyl acrylate copolymer, methacrylic acid / styrene / methyl acrylate copolymer, methacrylic acid / styrene / benzyl acrylate copolymer, methacrylic acid / methyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl acrylate / Polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polystyrene Macromonomer copolymer, methacrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polymethyl methacrylate Mer copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / styrene / methyl methacrylate copolymer, methacrylic acid / styrene / benzyl methacrylate copolymer, methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid Acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / Benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate DOO / polymethyl methacrylate macromonomer copolymers methacrylic acid copolymers such as and the like.

  Among these carboxyl group-containing copolymers (B1), in particular, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / styrene / methyl methacrylate copolymer, methacrylic acid / styrene / benzyl methacrylate copolymer, methacrylic acid / Methyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer Polymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / 2-hydroxy Chill methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymers. The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer (B1) is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this invention, a carboxyl group-containing copolymer (B1) can be used individually or in mixture of 2 or more types.

  Another preferable binder resin that can be used in the present invention is an N-substituted maleimide and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as “other unsaturated monomer (b2)”). And a copolymer (hereinafter referred to as “N-position-substituted maleimide copolymer (B2)”). Examples of the N-substituent in the N-substituted maleimide include a (Cyclo) alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and these groups. Among these N-substituents, aryl groups having 6 to 20 carbon atoms and substituted derivatives thereof are preferable.

  Specific examples of the N-substituted maleimide include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide, N -N- (cyclo) alkyl-substituted maleimides such as n-pentylmaleimide, Nn-hexylmaleimide, N-cyclohexylmaleimide, N-4-methylcyclohexylmaleimide, N-4-chlorocyclohexylmaleimide, and substitutions thereof Derivatives: N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide, N- p-methylphenylmaleimide, N N-aryl-substituted maleimides such as o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, Np-chlorophenylmaleimide, and substituted derivatives thereof; N-benzylmaleimide; N-phenethylmaleimide, N-o-hydroxybenzylmaleimide, Nm-hydroxybenzylmaleimide, Np-hydroxybenzylmaleimide, N-o-methylbenzylmaleimide, Nm-methylbenzylmaleimide, Np-methyl N-aralkyl-substituted maleimides such as benzylmaleimide, N-o-methoxybenzylmaleimide, Nm-methoxybenzylmaleimide, Np-methoxybenzylmaleimide, Np-chlorobenzylmaleimide, and substituted derivatives thereof etc It can be mentioned.

  Of these N-substituted maleimides, N-cyclohexylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenyl Maleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide are preferred. The N-substituted maleimides can be used alone or in admixture of two or more.

  The other unsaturated monomer (b2) is not limited as long as it can be copolymerized with the N-substituted maleimide, but one or more of the carboxyl group-containing unsaturated monomers and the other A monomer mixture containing at least one unsaturated monomer (b1) is preferred.

  As the N-substituted maleimide copolymer (B2), a copolymer of N-phenylmaleimide is preferable, and N-phenylmaleimide, a carboxyl group-containing unsaturated monomer, and other unsaturated monomers ( b1), in particular (1) N-phenylmaleimide, (2) acrylic acid and / or methacrylic acid, (3) styrene, (4) methyl acrylate, methyl methacrylate, 2 -Copolymerization with at least one selected from the group consisting of hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer Coalescence is preferable.

  Specific examples of preferable N-position-substituted maleimide copolymer (B2) include N-phenylmaleimide / methacrylic acid / styrene / allyl acrylate copolymer, N-phenylmaleimide / methacrylic acid / styrene / allyl methacrylate copolymer. N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate copolymer, N-phenylmaleimide / methacrylic acid / styrene / phenyl methacrylate copolymer, N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate / polystyrene macromonomer copolymer Polymer, N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / phenylmeta Relate / polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / phenyl methacrylate / polymethyl methacrylate macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / Polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / Phenyl methacrylate / polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / 2-hi It can be exemplified b methacrylate / phenyl methacrylate / polymethyl methacrylate macromonomer copolymers.

  The copolymerization ratio of the N-substituted maleimide in the N-substituted maleimide copolymer (B2) is usually 5 to 50% by weight, preferably 10 to 40% by weight. When the N-substituted maleimide copolymer is a copolymer of an N-substituted maleimide, a carboxyl group-containing unsaturated monomer, and another unsaturated monomer (b1), the carboxyl group-containing unsaturated The copolymerization ratio of the monomer is usually 5 to 50% by weight, preferably 10 to 40% by weight, and the copolymerization ratio of the other unsaturated monomer (b1) is usually 10 to 90% by weight. , Preferably 20 to 80% by weight. In the present invention, the N-position-substituted maleimide copolymer (B2) can be used alone or in admixture of two or more.

  In the present invention, when a binder resin is used, a polystyrene equivalent weight average molecular weight (hereinafter simply referred to as “weight average molecular weight”) measured by gel permeation chromatography (GPC; elution solvent tetrahydrofuran) of each resin component constituting the binder resin. Is preferably 3,000 to 300,000, particularly preferably 5,000 to 100,000. The use ratio of the binder resin in the present invention is usually 10 to 1,000 parts by weight, preferably 20 to 500 parts by weight, with respect to 100 parts by weight of the (A) microencapsulated pigment. In this case, if the use ratio of the binder resin is less than 10 parts by weight, for example, the discharge property of the resin composition for color filters and the hardness of the formed pixels tend to decrease, while if it exceeds 1,000 parts by weight, Since the colorant concentration is relatively lowered, it may be difficult to achieve the target color density as a thin film.

  The resin composition for an ink jet color filter in the present invention can contain a polyfunctional monomer having two or more polymerizable unsaturated bonds as a crosslinkable monomer component. Examples of the polyfunctional monomer include diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol; diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols such as methylolpropane, pentaerythritol, dipentaerythritol or the like, or modified carboxylic acids thereof; polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin, etc. Oligoacrylates or oligomethacrylates of: both ends hydroxypolybutadiene, both ends hydroxypolyisoprene, both ends hydroxypoly Diacrylates or dimethacrylates and the both ends hydroxylated polymer of caprolactone such as, tris (2-acryloyloxyethyl) phosphate, may be mentioned tris (2-methacryloyloxyethyl) phosphate and the like.

  Among these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols or modified carboxylic acids thereof, specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, the following formula (1)

In particular, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferable in terms of high pixel strength and excellent pixel surface smoothness. The said polyfunctional monomer can be used individually or in mixture of 2 or more types. The usage-amount of the polyfunctional monomer in this invention is 500 parts weight or less normally with respect to 100 weight part of binder resins, Preferably it is 20-300 weight part. In this case, when the usage ratio of the polyfunctional monomer exceeds 500 parts by weight, the discharge performance of the resin composition tends to be lowered.

  In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond. Specific examples of such monofunctional monomers include methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, Methoxydipropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, succinic acid 2-acryloyloxyethyl, succinic acid 2- Methacryloyloxyethyl, ω-carbo Sipolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like can be mentioned, and as commercial products, M-5300, M-5400 (trade names, manufactured by Toagosei Chemical Industry Co., Ltd.) and the like can be mentioned. it can. These monofunctional monomers can be used alone or in admixture of two or more. The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer.

  The resin composition for an inkjet color filter in the present invention can impart radiation curability by blending a photopolymerization initiator. Here, the radiation means that containing visible light, ultraviolet rays, far ultraviolet rays, X-rays, electron beams and the like. Examples of the photopolymerization initiator include a compound represented by the following formula (2) (hereinafter referred to as “biimidazole compound (2)”) and a compound represented by the following formula (3) (hereinafter referred to as “biimidazole”). A component containing at least one biimidazole compound selected from the group of “based compound (3)”) is preferable.

〔式（２）において、Ｘは水素原子、ハロゲン原子、シアノ基、炭素数１〜４のアルキル基または炭素数６〜９のアリール基を示し、複数存在するＸは相互に同一でも異なってもよく、Ａは−COOR（但し、R は炭素数１〜４のアルキル基または炭素数６〜９のアリール基を示す。）を示し、複数存在するＡは相互に同一でも異なってもよく、ｍは１〜３の整数であり、ｎは１〜３の整数である。〕

[In Formula (2), X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms, and a plurality of X may be the same or different from each other. A is preferably -COOR (wherein R 1 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms), and a plurality of A's may be the same or different from each other, m Is an integer of 1 to 3, and n is an integer of 1 to 3. ]

〔式（３）において、Ｘ¹ 、Ｘ² およびＸ³ は相互に独立に水素原子、ハロゲン原子、シアノ基、炭素数１〜４のアルキル基または炭素数６〜９のアリール基を示す。但し、Ｘ¹ 、Ｘ² およびＸ³ の２個以上が同時に水素原子をとることはない。〕

[In Formula (3), X < ¹ >, X < ² > and X < ³ > show a hydrogen atom, a halogen atom, a cyano group, a C1-C4 alkyl group, or a C6-C9 aryl group mutually independently. However, two or more of X ¹ , X ² and X ³ do not take a hydrogen atom at the same time. ]

In X, X ¹ , X ² and X ³ in the formulas (2) and (3), examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, etc. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group and t-butyl group. Examples of the 6-9 aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, and a p-tolyl group. Examples of R 1 in —COOR represented by A in Formula (2) include the same groups as the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 9 carbon atoms exemplified for X. Formula (2) and Formula (3) generally represent a structure in which two imidazole units are bonded to each other at the 1-position or 2-position. Therefore, the biimidazole compound (2) and the biimidazole compound (3) are single compounds or a mixture of two or more of compounds whose main skeletons correspond to the following formulas (4) to (6).

  Specific examples of the biimidazole compound (2) and the biimidazole compound (3) are as follows. The biimidazole compound (2) includes 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2 , 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-chlorophenyl)- 4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5 ′ -Tetrakis (4-methoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-Bimi Sol, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis ( 2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4,6- Trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4, 4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole,

  2,2′-bis (2-cyanophenyl) -4,4 ′, 5.5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-cyano) Phenyl) -4,4 ′, 5.5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ′, 5, 5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) ) -1,2′-biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-methylphenyl) -4, ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-ethylphenyl) -4,4', 5,5'-tetrakis (4 -Methoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2' -Biimidazole, 2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-Phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-etoki Carbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-bi Examples include imidazole.

  Further, as the biimidazole compound (3), 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 '-Bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl)- 4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetra Phenyl-1,2′-biimidazole, 2,2′-bis (2,4-dicyanophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′ -Bis (2,4,6-tricyanophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, , 2′-bis (2,4-dimethylphenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trimethylphenyl) ) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-diethylphenyl) -4,4 ′, 5,5′-tetraphenyl -1,2'-biimidazole, 2,2'-bis (2,4,6-triethylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2 '-Bis (2,4-diphenylphenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-triphenylphenyl) And -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

  Among these compounds, the biimidazole compound (2) is particularly 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl)-. 1,2′-biimidazole and 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole are preferred, Further, as the biimidazole compound (3), in particular, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2 '-Biimidazole and 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole are preferred.

  The biimidazole compound (2) and the biimidazole compound (3) are excellent in solubility in solvents, do not generate foreign matters such as undissolved substances and precipitates, and have high sensitivity and irradiation with a small amount of energy. Thus, the curing reaction is sufficiently advanced, the contrast is high, and the curing reaction does not occur in the non-irradiated part, so that an excellent color filter can be formed. In the present invention, the biimidazole compound (2) and the biimidazole compound (3) can be used alone or in admixture of two or more, and the biimidazole compound (2) and the biimidazole compound can be used. Compound (3) can be used in combination. The total use ratio of the biimidazole compound (2) and the biimidazole compound (3) in the present invention is usually 50% with respect to 100 parts by weight of the binder resin when no polyfunctional monomer is used. Part or less, preferably 0.5 to 30 parts by weight, particularly preferably 0.5 to 10 parts by weight. When a polyfunctional monomer is used, it is based on 100 parts by weight of the polyfunctional monomer. The amount is preferably 0.01 to 200 parts by weight, more preferably 1 to 120 parts by weight, and particularly preferably 1 to 50 parts by weight. In this case, by setting the total use ratio of these compounds within the above range, a pixel excellent in pattern shape, adhesion to the substrate, and the like can be formed.

  In the present invention, as a photopolymerization initiator component, together with the biimidazole compound (2) and / or the biimidazole compound (3), other photo radical generators, sensitizers, curing accelerators, etc. One or more photocrosslinking agents or photosensitizers comprising a polymer compound (hereinafter referred to as “polymer photocrosslinking / sensitizer”) may be used in combination. Examples of the other photo radical generator include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, benzophenone, 4,4′-bis (dimethylamino) benzophenone 4,4′-bis (diethylamino) benzophenone, 2,4-diethylthioxanthone, 3, -Dimethyl-4-methoxybenzophenone, 4-azidobenzaldehyde, 4-azidoacetophenone, 4-azidobenzalacetophenone, azidopyrene, 4-diazodiphenylamine, 4-diazo-4'-methoxydiphenylamine, 4-diazo-3-methoxydiphenylamine Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, dibenzoyl, benzoin isobutyl ether, N-phenylthioacridone, triphenylpyrylium perchlorate and the like. These other photo radical generators can be used alone or in admixture of two or more.

  Examples of the sensitizer include 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4 ′ -Diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like. These sensitizers can be used alone or in admixture of two or more. Examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethyl. Examples include chain transfer agents such as aminopyridine. These curing accelerators can be used alone or in admixture of two or more.

  Among the other photo radical generators, sensitizers and curing accelerators, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl- (4-methylthiophenyl) -2-morpholino- 1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (Diethylamino) benzophenone and 2-mercaptobenzothiazole are preferable in that the formed pixels are difficult to drop off from the substrate during development, and the pixel intensity and sensitivity are high.

  In the present invention, as a photopolymerization initiator, in particular, biimidazole compound (2) and / or biimidazole compound (3), benzophenone-based or acetophenone-based other photoradical generator, and thiazole-based curing acceleration. It is preferable to use in combination with at least one selected from the group of agents. Specific examples of the particularly preferable combination include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole / 4,4′-bis ( Diethylamino) benzophenone, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole / 4,4′-bis (diethylamino) benzophenone / 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonyl) Phenyl) biimidazole / 4,4′-bis (diethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone, 2,2′-bis (2-Chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole / 4,4′-bis (dimethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone / 2-mercaptobenzo Thiazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole / 4,4′-bis (diethylamino) benzophenone, 2,2′-bis (2 , 4-Dibromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole / 4,4′-bis (diethylamino) benzophenone / 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) Butan-1-one, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazo 4,4'-bis (diethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenylbiphenyl Examples thereof include imidazole / 4,4′-bis (dimethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone / 2-mercaptobenzothiazole. The use ratio of the other photoradical generator in the present invention is preferably 80% by weight or less of the whole photopolymerization initiator, and the use ratio of the sensitizer and / or the curing accelerator is the whole photopolymerization initiator. It is preferable that it is 80 weight% or less of.

  Further, the polymer photocrosslinking / sensitizing agent is a polymer compound having a functional group capable of functioning as a photocrosslinking agent or a photosensitizer in the main chain and / or side chain. -Condensate of azidobenzaldehyde and polyvinyl alcohol, condensate of 4-azidobenzaldehyde and phenol novolac resin, (co) polymer of 4- (meth) acryloylphenyl cinnamic acid, 1,4-polybutadiene, 1,2 -Polybutadiene etc. can be mentioned. These polymer photocrosslinking / sensitizing agents can be used alone or in admixture of two or more. The proportion of the polymer photocrosslinking / sensitizer used in the present invention is usually 200 parts by weight or less, preferably 180 parts per 100 parts by weight of the biimidazole compound (2) and / or biimidazole compound (3). Less than parts by weight.

  The resin composition for an ink jet color filter in the present invention desirably has a contact angle of 45 degrees or more, preferably 50 degrees or more, with a partition formed from the color filter partition forming resin composition. By having such a contact angle, there is no color mixing of the resin composition between the pixel arrays, and the amount of the resin composition that can be discharged to the light transmission region is increased so as to ensure a sufficient color density of the pixel pattern. It is also possible to do.

[Production method of color filter]
Next, a method for producing a color filter by the inkjet method in the present invention using the resin composition for an inkjet color filter (hereinafter simply referred to as “color filter production method”) will be described. FIG. 6 is a main part longitudinal cross-sectional view illustrating a liquid crystal display device having a color filter manufactured by the color filter manufacturing method of the present invention. As shown in the figure, the color filter 1 basically includes a substrate 101, a partition wall 102, pixel patterns 20 (for example, red), 21 (for example, green) and 22 (for example, blue) for each color, and a protective layer 103 that covers the pixel pattern. These components are light-transmitting except for the partition wall 102, but the partition wall 102 may be light-transmitting or light-blocking. Further, in the liquid crystal display device 6, the polarizing plate 201 is disposed on the outer surface side of the substrate 101, and the common electrode 202, the alignment film 203, the liquid crystal layer 204, the alignment film 205, the pixel electrode 206, the substrate are disposed on the protective layer 103. 207 and polarizing plate 208 are basically laminated.

  As the material of the substrate 101, an appropriate light-transmitting material can be adopted as long as it has heat resistance against heating conditions in the color filter manufacturing process and has a certain level of mechanical strength. Examples thereof include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, norbornene-based ring-opening polymer and hydrogenated products thereof. In addition, the substrate made of these materials may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. You can also. These materials can also be used for the substrate 207, but the materials may be changed between the two substrates depending on circumstances.

  The partition wall 102 is formed of a suitable resin composition for forming a partition wall, and the surface of the substrate 101 is partitioned in a lattice shape in the figure, and the region partitioned by the partition wall 102 has a light transmission region that transmits light. There is no. However, the partition shape by the partition 102 may be changed as desired. Examples of the resin composition used for forming the partition wall 102 include (i) a radiation-sensitive resin composition that contains a binder resin, a polyfunctional monomer, a photopolymerization initiator, and the like and is cured by irradiation with radiation. And (ii) a binder resin, a compound that generates an acid upon irradiation with radiation, a crosslinkable compound that can be crosslinked by the action of an acid generated upon irradiation with radiation, and the like, a radiation-sensitive resin composition that cures upon irradiation Things can be used. These partition wall-forming radiation-sensitive resin compositions are usually prepared as a liquid composition by mixing a solvent when used, and this solvent may be a high-boiling solvent or a low-boiling solvent. As the radiation-sensitive resin composition for forming a partition wall in the present invention, as described in JP-A-10-86456, (a) hexafluoropropylene, unsaturated carboxylic acid (anhydride), and other copolymers A copolymer with a possible ethylenically unsaturated monomer, (b) a compound capable of generating an acid upon irradiation with radiation, (c) a crosslinkable compound capable of crosslinking by the action of an acid generated upon irradiation with radiation, (d A composition containing a fluorine-containing organic compound other than the component (a) and a solvent capable of dissolving the components (a) to (d) is preferable.

  The pixel pattern 20 is formed from a color filter resin composition containing, for example, a red colorant, the pixel pattern 21 is formed from, for example, a color filter resin composition containing a green colorant, and the pixel pattern 22 is For example, it is formed from the resin composition for color filters containing a blue coloring agent, and these pixel patterns are formed by the inkjet system mentioned later. The total number of pixel patterns partitioned by the partition wall 102 is obtained by multiplying the number of pixel patterns of each color in the liquid crystal display device by the number of primary colors (the three primary colors of red, green, and blue in the figure). For example, in the case of a VGA type liquid crystal display device used for an information terminal such as a personal computer, the number of pixel patterns for each color is 640 columns × 480 rows, so that a total of (640 × 480 × 3) pixel patterns Will be composed. The arrangement pitch of the pixel pattern is, for example, 100 μm. In the figure, the number of pixel patterns is reduced to facilitate understanding.

  The material of the protective layer 103 may be a normal material used for forming a protective layer for a color filter, but it can be used by a light or heat action or a light that can use a general-purpose exposure apparatus, a baking furnace or a hot plate. What is hardened | cured by combined use with a heat | fever is preferable, and it becomes possible to aim at the cost reduction and space saving of an installation.

  Furthermore, the common electrode 202 can be formed by processing a conventional material using a material having optical transparency and conductivity, for example, ITO (indium tin oxide). The alignment films 203 and 205 can be formed, for example, by subjecting a film formed from a suitable liquid crystal aligning agent to a rubbing treatment and the like, and have an action of aligning liquid crystal molecules in a certain direction. The liquid crystal layer 204 is composed of polarized liquid crystal molecules, and is configured such that the orientation direction of the liquid crystal molecules can be controlled by applying a voltage. The pixel electrode 206 is arranged corresponding to each pixel pattern of the color filter 1 and connected to the output terminal of the driving means (see FIG. 8). The pixel electrode 206 is also made of a material having optical transparency and conductivity, and the same material as the common electrode 202 can be used as the material, but the material may be changed from that of the common electrode 202 in some cases. Good. As the driving means, for example, a TFT (Thin Film Transistor), a TFD (Thin Film Diode) or the like can be used. Polarizing plates 201 and 208 are attached to the outside of the substrates 101 and 207. These polarizing plates transmit only light in a specific polarization state out of backlight light irradiated from behind the liquid crystal display device 6. These two polarizing plates are arranged such that the polarization direction of light after passing through them is “shifted” by the polarization rotation angle that the liquid crystal molecules give to the light when no voltage is applied to the liquid crystal layer 204, for example. .

Next, with reference to FIGS. 5 and 7, the manufacturing process of the color filter will be described. Here, only the manufacturing process of the color filter 1 in the liquid crystal display device 6 will be described. A known technique can be applied to manufacture the remaining components of the liquid crystal display device 6. FIG. 5 is a longitudinal sectional view of the main part illustrating the manufacturing process of the color filter 1, showing a cut surface corresponding to the AA arrow view of FIG. 7, and FIG. 7 is a plan view of the color filter 1. is there. First, the barrier rib-forming radiation-sensitive resin composition is applied as a solution to the substrate 101 and then pre-baked (PB) to evaporate the solvent to form a coating film. The PB conditions in this case are, for example, a heating temperature of about 50 to 150 ° C. and a heating time of about 30 to 600 seconds. Thereafter, this coating film is irradiated with radiation through a photomask and subjected to post-exposure baking (PEB), and then developed with an alkaline developer to dissolve and remove the unirradiated portions of the coating film. As a result, as shown in FIG. 5A, a plurality of light transmitting regions 105 that transmit light on the surface of the substrate 101 are arranged on the surface of the substrate 101 in which a partition pattern of a predetermined shape partitioned by the partition 102 is arranged according to a predetermined arrangement. A formed substrate is obtained. The PEB conditions in this case are, for example, a heating temperature of about 50 to 150 ° C., a heating time of about 30 to 600 seconds, and a radiation irradiation condition of, for example, about 1 to 500 mJ / cm ² . The developing condition is, for example, about 10 to 300 seconds. As the developing method, for example, a liquid piling method, a dipping method, a vibration dipping method, or the like can be employed. Further, post-baking may be performed after development, and the conditions are, for example, a heating temperature of about 150 to 280 ° C. and a heating time of about 3 minutes to 2 hours.

Next, as shown in FIG. 5B, the resin composition for the ink jet color filter is discharged from the ink jet head 10 to each light transmission region 105, and the upper surface of the resin composition is raised from the upper end of the partition wall 102. Are stored in the respective light transmission regions 105 so as to form the storage layers 21, 22,... Of the resin composition. In addition, 20 has illustrated the state in the middle of discharge of a resin composition. In this case, the discharge speed of the resin composition is, for example, about 0.01 to 100 m / second. Thereafter, as shown in FIG. 5C, the resin composition forming each reservoir layer is subjected to a heat treatment to evaporate the solvent, thereby drying the resin composition, and the pixel patterns 20 and 21 having a predetermined thickness. , 22,... Note that the volume of each reservoir is reduced by such processing. The heat treatment in this case is performed using, for example, a heater, and is performed by heating the whole to a predetermined temperature (for example, about 50 degrees). Thereafter, in some cases, after irradiation with radiation, in order to completely dry and crosslink the resin composition, heating at a predetermined temperature (for example, about 150 to 280 ° C.) for a predetermined time (for example, about 3 minutes to 2 hours) is performed. Do. In this case, the radiation irradiation condition is, for example, about 1 to 500 mJ / cm ² . When forming the pixel patterns 20, 21, 22,..., A red, green, or blue resin composition is sequentially used, for example, so that a pixel array of the three primary colors red, green, and blue is disposed on the substrate 101. be able to.

  Thereafter, as shown in FIG. 5D, a protective layer 103 is formed by using an appropriate resin so as to cover the formed pixel patterns and to flatten the surface of the color filter. Furthermore, the common electrode 202 is formed on the protective layer 103 by using a material having light permeability and conductivity (for example, ITO) by a method such as sputtering or vapor deposition. In the case of forming a pattern on the common electrode 202, the common electrode 202 is etched in accordance with the pattern shape of other components such as the pixel electrode 206. The color filter 1 can be manufactured through the above steps. Next, as shown in FIG. 5E, an alignment film 203, a liquid crystal layer 204, and an alignment film 205 are sequentially formed between the color filter 1 and the substrate 207 on which the pixel electrode 206 is separately arranged, and both outer surfaces thereof Then, the polarizing plates 201 and 208 are attached to the liquid crystal display device 6.

  When the partition wall forming radiation-sensitive resin composition is applied to the substrate 101, an appropriate application method such as spin coating, cast coating, roll coating, or the like can be employed. The coating thickness is usually 0.1 to 10 μm, preferably 0.5 to 3.0 μm, as the film thickness after PB. As the radiation used in forming the partition wall 102 and the pixel patterns 20, 21, 22,. Radiation in the range of 190-450 nm is preferred. Examples of the alkaline developer used for forming the partition wall 102 include sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicon, sodium metasilicon, ammonia water, ethylamine, n-propylamine, diethylamine, Di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0]- An aqueous solution such as 7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene is preferable. For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, after development with an alkaline developer, it is usually washed with water.

  Next, FIG. 8 illustrates an outline of a color filter manufacturing apparatus used in the color filter manufacturing method of the present invention. The color filter manufacturing apparatus includes a control device 2 that controls the inkjet head 10, motors 3 and 4, a position sensor 5, and the like. The inkjet head 10 is for discharging the supplied resin composition for a color filter from its nozzle, and its form is not particularly limited, and a known inkjet method may be used, but in the present invention, the color filter Since the resin composition for use is used, a piezo jet type resin that does not cause heat to act on the resin composition is preferable so as not to damage the material. The piezoelectric jet type inkjet head 10 is provided with N piezoelectric elements 40 (N is an arbitrary number) for discharging the color filter resin composition. In addition, the piezoelectric element 40 is configured so that driving and non-driving can be individually controlled.

  FIG. 9 illustrates a partially cutaway view of the main part of the inkjet head 10. The ink jet head 10 mainly includes a pressure chamber substrate 11, a vibration plate 12 and a nozzle plate 13, and the vibration plate 12 is provided on one surface of the pressure chamber substrate 11. Provided on the other surface. The pressure chamber substrate 11 is formed with a pressure chamber 14, a side wall 15, a reservoir 16, a supply port 17, and the like by etching a silicon substrate, for example, and volume change occurs in the pressure chamber 14 due to deformation of the diaphragm 12. As described above, the piezoelectric elements 40 provided on the diaphragm 12 and the pressure chambers 14 are aligned. The diaphragm 12 is an elastic film made of ceramics or the like, and is provided with the piezoelectric elements 40 arranged so as to be deformed by the distortion of the piezoelectric elements 40. The diaphragm 12 is provided with an ink tank port 18 so that a color filter resin composition stored in an ink tank (not shown) can be supplied into the pressure chamber substrate 11. The color filter resin composition thus made flows through the path of the reservoir 16 → each supply port 17 → each pressure chamber 14. The piezoelectric element 40 is configured by sandwiching a piezoelectric ceramic crystal between electrodes. The nozzle plate 13 is provided with nozzles 19 for discharging the resin composition for color filters, and each nozzle 19 corresponds to each pressure chamber 16. The ink jet heads 10 are provided only for the types of resin compositions for color filters, and actually, for example, the red, green and blue ink jet heads 10 are used. However, only one inkjet head 10 is shown here for easy understanding.

  In such an ink jet head 10, only the piezoelectric element 40 to which a voltage is applied to the drive circuit is distorted, the diaphragm 12 is deformed, and pressure is applied to the pressure chamber 14 corresponding to the piezoelectric element. The resin composition for a color filter is discharged from the nozzle 19. Since the piezoelectric element 40 to which no voltage is applied is not distorted, the resin composition in the corresponding pressure chamber 14 is not discharged. Therefore, one set of the piezoelectric element 40, the pressure chamber 14, and the nozzle 19 constitutes one operating unit.

  Further, FIG. 10 illustrates a plan view of the filter elements on the substrate 101 on which the nozzles 19 in the inkjet head 10 are arranged and the partition wall 102 that is the source of the color filter 1 is formed. Assuming that N nozzle numbers are hn (n is a number from 1 to N), the position Nn (xn, yn) of each nozzle 19 is specified by the relative coordinate x2 axis and y2 axis as shown in the figure. It is like that. The smallest pixel element partitioned by the grid of the partition wall 102 is called a filter element, and for example, a window having a width of about 300 μm in the x1 axis (horizontal) direction and a length of about 100 μm in the y1 axis (vertical) direction is formed. In the substrate on which the partition walls are formed, the position Wm (xm, ym) of each filter element (m is a number from 1 to the maximum number of filter elements) is specified by the relative coordinate x1 axis and the y1 axis. ing. The pitch of each nozzle 19 is set to an integral multiple of the pitch in the x1 axis direction. For example, in the case where 60 nozzles 19 are arranged in the inkjet head 10 and three drops of the color filter resin composition are ejected to one filter element, when the inkjet head 10 is operated at a driving frequency of 14.4 kHz, about 900,000 pixels In the 10 type VGA color filter, the resin composition can be stored at 900,000 pixels × 3 drops / (14400 times / second × 60) = about 3 seconds. However, since it is necessary to consider the moving time of the inkjet head 10, the resin composition can actually be stored in all the filter elements within one minute.

  Such a method for producing a color filter is very advantageous industrially because the production process is simple and the cost is low. The color filter manufactured by the above-described color filter manufacturing method is extremely useful as, for example, a color liquid crystal display device, a color image pickup tube element, a color sensor, and the like as an additive color mixing type and a subtractive color mixing type.

  The resin composition for a color filter of the present invention can be applied to a color resist for a photolithography method, an ink for an ink jet method, or the like as a color material for a color filter.

  Further, according to the present invention, dispersion of fluorescent pigments in field emission displays (FEDs), surface field displays (SEDs), plasma displays (PDPs), etc., and conductive polymers in PEDOTs used in organic EL and organic TFTs, etc. It can also be applied to the dispersion of

  In the present invention, as described above, as the microencapsulated pigment, a pigment having an anionic group on the surface is derived from a cationic polymerizable surfactant having a cationic group, a hydrophobic group, and a polymerizable group. Although a microencapsulated pigment coated with a polymer having a repeating structural unit has been described as a preferred embodiment, a pigment having a cationic group such as an ammonium salt on the surface thereof has at least an anionic group and a hydrophobic group. It may be a microencapsulated pigment coated with a polymer having a repeating structural unit derived from an anionic polymerizable surfactant having a polymerizable group. Such a microencapsulated pigment composed of a pigment having a cationic group on its surface is also obtained in the same manner as the method for producing a microencapsulated pigment composed of a pigment having an anionic group on its surface as described above, Even when this is used, the same effects as those of the color filter resin composition described above can be exhibited.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

Here, the “introduced amount of hydrophilic group on the surface of the pigment particle” shown below was determined by the following method.
"Quantification of the amount of anionic groups introduced (when anionic groups are introduced by a sulfonating agent)"
Pigment particles whose surface has been treated with a sulfonating agent are treated by an oxygen flask combustion method and absorbed in a 0.3% aqueous hydrogen peroxide solution, and then sulfate ions (divalent) are obtained by an ion chromatography method (Dionex Corp .; 2000i). ) Was quantified, and this value was converted to a sulfonic acid group and expressed as a molar amount (mmol / g) per 1 g of pigment.

“Preparation of pigment particles“ P1 ”having an anionic group on the surface”
CI Pigment Red 254: 20 parts are mixed with 500 parts of quinoline, dispersed in Eiger Motor Mill M250 type (manufactured by Eiger Japan) for 2 hours under conditions of a bead filling rate of 70% and a rotational speed of 5000 rpm, The solvent mixture was transferred to an evaporator and heated to 120 ° C. while reducing the pressure to 30 mmHg or less, and water contained in the system was distilled off as much as possible, and then the temperature was controlled at 160 ° C. Next, 20 parts of a sulfonated pyridine complex is added and allowed to react for 8 hours. After completion of the reaction, the resultant is washed several times with excess quinoline, poured into water, and filtered to obtain a pigment having a hydrophilic group (anionic group) on the surface. Particles “P1” were obtained.
The amount of anionic groups introduced into the obtained pigment particles “P1” was 0.06 mmol / g.

"Manufacture of microencapsulated pigment" MCP1 ""
To an aqueous dispersion in which 100 g of pigment particles “P1” having an anionic group on the surface are dispersed in 500 g of ion-exchanged water, 1.25 g of dimethylaminoethyl methyl chloride methacrylate as a cationic polymerizable surfactant is added and mixed. Then, ultrasonic waves were irradiated for 15 minutes. Next, 12 g of benzyl methacrylate, 8 g of dodecyl methacrylate, 3.9 g of anionic polymerizable surfactant Aqualon KH-10, 2.07 g of 2-acrylamido-2-methylpropanesulfonic acid and 50 g of ion-exchanged water as hydrophilic monomers. The mixture was added and mixed, and again irradiated with ultrasonic waves for 30 minutes. This was put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen introduction tube and an ultrasonic generator. After the internal temperature of the reaction vessel was raised to 80 ° C., an aqueous potassium persulfate solution in which 0.6 g of potassium persulfate was dissolved as a polymerization initiator was added dropwise to 20 g of ion-exchanged water. Polymerized for hours. After completion of the polymerization, the pH was adjusted to 8 with a 2 mol / l potassium hydroxide aqueous solution, and the mixture was filtered through a membrane filter having a pore size of 1 μm to remove coarse particles to obtain a dispersion of the desired microencapsulated pigment “MCP1”.

  The volume average particle diameter of the obtained dispersion was measured using a laser Doppler type particle size distribution analyzer Microtrac UPA150 manufactured by Leeds & Northrop Co. As a result, it was 300 nm. The obtained dispersion is diluted 100 times with ion-exchanged water, pretreated, the particles are observed with a scanning electron microscope, and the aspect ratio and Zingg index are obtained by measuring the short diameter, long diameter, and thickness of the particles. As a result, the aspect ratio was 1.0 and the Zingg index was 1.0. The obtained dispersion was dried at room temperature, and the glass transition point of the coated polymer was measured using a thermal scanning calorimeter (differential scanning calorimeter: DSC) DSC200 (manufactured by Seiko Electronics Co., Ltd.). 7 ° C.

“Preparation of resin composition for inkjet color filter”
Based on the composition shown below, an ink jet color filter resin composition (hereinafter referred to as “resin composition (R1)”) of Example 1 colored in red was prepared.
(Composition) (Addition amount)
Microencapsulated pigment: 8% by weight of MCP1 (solid content concentration)
Binder resin: methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 25/65/10, weight average molecular weight = 30,000)
4% by weight
Multifunctional monomer: 4% by weight of dipentaerythritol pentaacrylate
Photopolymerization initiator: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole 0.8% by weight
Same as above: 4,4′-bis (diethylamino) benzophenone 0.8% by weight
Wetting agent: Glycerin 13% by weight
Penetration agent: Diethylene glycol monobutyl ether 5% by weight
Same as above: 1,2-hexanediol 5% by weight
Solid wetting agent: 8% by weight of trimethylolpropane
Polar solvent: 2-pyrrolidone 2% by weight
Surfactant: Olfine E1010 1% by weight
pH adjuster: 0.1% by weight of potassium hydroxide
Preservative: Proxel XL-2 0.05% by weight
Water: Ion exchange water

Separately, a radiation-sensitive resin composition was applied on the surface of a soda glass transparent substrate on which a silica (SiO ₂ ) film that prevents elution of sodium ions was formed on the surface, and then at 110 ° C. on a hot plate. PB was performed for 2 minutes to evaporate the solvent to form a coating film. Thereafter, this coating film was irradiated with radiation through a photomask at 150 mJ / cm ² , subjected to PEB at 110 ° C. for 2 minutes, and then developed with an alkali developer at 25 ° C. for 1 minute. By dissolving and removing the irradiated portion, a partition pattern was formed so as to partition the portion where the pixel pattern was to be formed. Next, the resin composition (R1) is discharged into the partition pattern by an inkjet method at a discharge speed of 7 m / second, and the upper surface of the resin composition (R1) is raised so as to be higher than the height of the partition. PB is performed on the plate at 200 ° C. for 2 minutes to evaporate the solvent, and the rise of the resin composition (R1) is flattened, and further post-baked in an oven at 200 ° C. for 1 hour to obtain a red pixel array Obtained a color filter arranged on the substrate. The obtained color filter was excellent in the surface smoothness of the pixels, the film thickness variation of the pixels was less than 5%, and no color unevenness occurred. Further, the contact angle between the partition wall and the resin composition (R1) at this time (value measured within 1 minute after the resin composition contacted the substrate surface) was about 50 degrees.
The resin composition (R1) used here had good dispersion stability, phase separation did not occur, the film properties during film formation were good, and the resulting color filter pixels had no bias.

"Manufacture of microencapsulated pigment" MCP2 ""
Dimethylaminoethylmethyl methacrylate was used as a cationic polymerizable surfactant in an aqueous dispersion in which 100 g of magenta pigment particles “P1” having an anionic group on the surface prepared in the same manner as in Example 1 was dispersed in 500 g of ion-exchanged water. After adding and mixing 1.25 g of chloride, it was treated by irradiating with ultrasonic waves for 15 minutes. Next, 20 g of isobornyl methacrylate and 0.5 g of 1,6-hexanediol dimethacrylate were mixed and mixed with stirring, and the anionic polymerizable surfactant Aqualon KH-10 previously dissolved in 50 g of ion-exchanged water was used. Was added with 2.07 g of 2-acrylamido-2-methylpropanesulfonic acid as a hydrophilic monomer and treated again by irradiation with ultrasonic waves for 30 minutes. This was put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen introduction tube and an ultrasonic generator. After the internal temperature of the reaction vessel was raised to 80 ° C., an aqueous potassium persulfate solution in which 0.6 g of potassium persulfate was dissolved as a polymerization initiator was added dropwise to 20 g of ion-exchanged water. Polymerized for hours. After completion of the polymerization, the pH was adjusted to 8 with a 2 mol / l aqueous potassium hydroxide solution, and the mixture was filtered through a membrane filter having a pore size of 1 μm to remove coarse particles to obtain a desired microencapsulated pigment “MCP2” dispersion.

  The volume average particle size of the obtained dispersion was measured using a laser Doppler type particle size distribution analyzer Microtrac UPA150 manufactured by Leeds & Northrop Co. As a result, it was 100 nm. The obtained dispersion is diluted 100 times with ion-exchanged water, pretreated, the particles are observed with a scanning electron microscope, and the aspect ratio and Zingg index are obtained by measuring the short diameter, long diameter, and thickness of the particles. As a result, the aspect ratio was 1.0 and the Zingg index was 1.0.

“Preparation of resin composition for inkjet color filter”
Based on the composition shown below, a resin composition for an inkjet color filter of Example 2 colored in red (hereinafter referred to as “resin composition (R2)”) was prepared.
(Composition) (Addition amount)
Microencapsulated pigment: MCP2 5 wt% (solid content concentration)
Polymer fine particles: Polymer fine particles 1 3% by weight
Binder resin: methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 25/65/10, weight average molecular weight = 30,000)
2.5% by weight
Multifunctional monomer: 2.5% by weight of dipentaerythritol pentaacrylate
Wetting agent: Glycerin 13% by weight
Penetration agent: Diethylene glycol monobutyl ether 5% by weight
Same as above: 1,2-hexanediol 3% by weight
Solid wetting agent: 5% by weight of trimethylolpropane
Same as above: 1,2,8-hexanetriol 2% by weight
Surfactant: Olfine E1010 1% by weight
pH adjuster: 0.1% by weight of potassium hydroxide
Preservative: Proxel XL-2 0.05% by weight
Water: Ion exchange water

Here, the production of “polymer fine particles 1” in the above composition is as follows.
A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 90 g of ion-exchanged water and 1 g of anionic polymerizable surfactant Aqualon KH-5, and the temperature was raised to 70 ° C. while purging with nitrogen under stirring. Warm up. After maintaining the internal temperature at 70 ° C. and adding 2 g of potassium persulfate as a polymerization initiator and dissolving, 1 g of anionic polymerizable surfactant AQUALON KH-5 and 43.5 g of styrene are added to 45 g of ion-exchanged water in advance. -An emulsion obtained by stirring 47.5 g of butyl acrylate, 3 g of ethylene glycol dimethacrylate, and 5 g of 2-acrylamido-2-methylpropanesulfonic acid was continuously dropped into the reaction vessel over 3 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours. After cooling the obtained polymer emulsion to room temperature, ion exchange water and 2 mol / l potassium hydroxide aqueous solution were added to adjust the solid content to 35% by weight and pH 8. The concentration of the polymer fine particles of the obtained polymer emulsion was adjusted to 0.1% by weight, and 3 volumes thereof and 1 volume of 1 mol / l magnesium nitrate aqueous solution were contacted in the cell of the spectrophotometer U-3300 (manufactured by Hitachi, Ltd.). The time at which the transmittance at a wavelength of 700 nm was 50% of the initial value was 10 seconds.
Further, the volume average particle size was measured with a laser Doppler type particle size distribution analyzer Microtrac UPA150 manufactured by Leeds & Northrop Co., Ltd., and it was 90 nm. Moreover, when the obtained polymer emulsion was dried at room temperature and the glass transition point was measured using a thermal scanning calorimeter (differential scanning calorimeter: DSC) DSC200 (manufactured by Seiko Electronics Co., Ltd.), it was found to be 8 ° C. Met. The minimum film formation temperature was 20 ° C. Further, the concentration of polymer fine particles in the obtained polymer emulsion was adjusted to 10% by weight, and the contact angle between the polymer fine particle and the Teflon (registered trademark) plate was measured to be 110 °. Moreover, it was 59 * 10 < ^-3 > N / m (59 dyne / cm) when the surface tension of the obtained polymer emulsion was measured with the surface tension meter CBVP-Z (made by Kyowa Interface Science).

Separately, in the same manner as in Example 1, a partition wall pattern was formed on the surface of a soda glass transparent substrate on which a silica (SiO ₂ ) film for preventing elution of sodium ions was formed. Next, using the resin composition (R2), in the same manner as in Example 1, a color filter in which a red pixel array was arranged on the substrate was obtained by an inkjet method. The obtained color filter was excellent in the surface smoothness of the pixels, the film thickness variation of the pixels was less than 5%, and no color unevenness occurred. Further, the contact angle between the partition wall and the resin composition (R2) at this time (value measured within 1 minute after the resin composition contacted the substrate surface) was about 50 degrees.
The resin composition (R2) used here had good dispersion stability, phase separation did not occur, the film properties during film formation were good, and there was no bias in the pixels of the obtained color filter.

Comparative Example 1
100 parts by weight of CI Pigment Red 254, 50 parts by weight of a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 25/65/10, weight average molecular weight = 30,000), polyfunctional monomer As a photopolymer, 50 parts by weight of dipentaerythritol pentaacrylate, and as a photopolymerization initiator, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1 , 2′-biimidazole 10 parts by weight, 4,4′-bis (diethylamino) benzophenone 10 parts by weight, tetraethylene glycol dimethyl ether 1,700 parts by weight, and mixed in red for an ink jet color filter resin composition (Hereinafter referred to as “resin composition (r1)”). Separately, a radiation-sensitive resin composition was applied on the surface of a soda glass transparent substrate on which a silica (SiO ₂ ) film that prevents elution of sodium ions was formed on the surface, and then at 110 ° C. on a hot plate. PB was performed for 2 minutes to evaporate the solvent to form a coating film. Thereafter, this coating film was irradiated with radiation through a photomask at 150 mJ / cm ² , subjected to PEB at 110 ° C. for 2 minutes, and then developed with an alkali developer at 25 ° C. for 1 minute. By dissolving and removing the irradiated portion, a partition pattern was formed so as to partition the portion where the pixel pattern was to be formed. Next, the resin composition (r1) is ejected into the partition pattern by an inkjet method at a discharge speed of 7 m / second, and the resin composition (r1) is raised and discharged so that the upper surface of the resin composition (r1) is higher than the height of the partition. PB was performed on the plate at 200 ° C. for 2 minutes to evaporate the solvent, the resin composition (r1) was flattened, and further post-baked in an oven at 200 ° C. for 1 hour to obtain a red pixel array Obtained a color filter arranged on the substrate.
The obtained color filter had high depolarization and low transmittance and contrast.
The resin composition (r1) used here had unstable dispersibility, and phase separation occurred during drying.

  The present invention relates to a resin composition for a color filter by an ink jet method that prevents occurrence of phase separation by improving dispersion stability and eliminates unevenness and non-uniform film thickness by improving film properties during film formation. The present invention has industrial applicability as a color filter having a pixel pattern formed from the resin composition by an ink jet method and a method for producing a color filter by an ink jet method using the resin composition.

FIG. 3 is a schematic diagram showing a state in which pigment particles having an anionic group on the surface are dispersed in an aqueous solvent and coexist with a cationic polymerizable surfactant and an anionic polymerizable surfactant. FIG. 2 is a schematic diagram showing a state in which a cationic polymerizable surfactant and an anionic polymerizable surfactant are polymerized in the dispersed state shown in FIG. 1. FIG. 3 is a schematic diagram showing a state in which pigment particles having an anionic group on the surface are dispersed in an aqueous solvent and coexist with a cationic polymerizable surfactant and an anionic polymerizable surfactant. It is a schematic diagram which shows the state by which the cationic polymerizable surfactant and the anionic polymerizable surfactant were superposed | polymerized in the dispersion state shown in FIG. It is a principal part longitudinal cross-sectional view which illustrates the manufacturing process of the color filter in this invention, (a) is a partition formation process, (b) is a pixel pattern formation process, (c) is a drying process, (d) is protection. The layer forming step and (e) show the common electrode forming step. It is a principal part longitudinal cross-sectional view which illustrates the liquid crystal display device which has the color filter manufactured by the manufacturing method of the color filter in this invention. It is a top view of the color filter manufactured by the manufacturing method of the color filter in this invention. It is a figure which illustrates the outline | summary of the color filter manufacturing apparatus used for the manufacturing method of the color filter in this invention. It is a partial cross section which illustrates the principal part of the inkjet head used for the manufacturing method of the color filter in this invention. It is a top view which illustrates the arrangement | positioning of each nozzle in the inkjet head used for the manufacturing method of the color filter in this invention, and the filter element in the board | substrate with which the partition was formed.

Explanation of symbols

31 ... Pigment particles, 32 ... Cationic polymerizable surfactant, 33 ... Anionic polymerizable surfactant, 51 ... Cationic group, 52, 52 '... Hydrophobic group, 53,53 '... polymerizable group, 54,54' ... anionic group, 50 ... hydrophobic region, 60,60 '... polymer layer (polymer), 100,100' ... micro Encapsulated pigment, 1 ... color filter, 2 ... control device, 3 ... motor, 4 ... motor, 5 ... position sensor, 6 ... liquid crystal display device, 10 ... inkjet Head, 11 ... Pressure chamber substrate, 12 ... Vibration plate, 13 ... Nozzle plate, 14 ... Pressure chamber, 15 ... Side wall, 16 ... Reservoir, 17 ... Supply port, 18 ... Ink tank port, 19 ... Nozzle, 20 ... Pixel pattern (red ), 21 ... Pixel pattern (green), 22 ... Pixel pattern (blue), 40 ... Piezoelectric element, 101 ... Substrate, 102 ... Partition, 103 ... Protective layer, 105・ ・ ・ Light transmission region, 201... Polarizing plate, 202... Common electrode, 203... Alignment film, 204... Liquid crystal layer, 205. ... Substrate, 208 ... Polarizing plate

Claims (26)

  Inkjet color characterized by containing at least water, a microencapsulated pigment comprising pigment particles, a polymer as a resin component for coating the pigment particles, an ionic group provided on the surface of the polymer, and water Filter resin composition.   Resin composition for ink jet type color filter comprising at least water containing a microencapsulated pigment comprising pigment particles, a polymer as a resin component for coating the pigment particles, an ionic group provided on the surface of the polymer, and water And a contact angle with a partition formed from the partition wall-forming resin composition is 45 degrees or more.   The microencapsulated pigment is a polymer in which pigment particles having an anionic group on the surface thereof have a repeating structural unit derived from a cationic polymerizable surfactant having a cationic group, a hydrophobic group, and a polymerizable group. The resin composition for inkjet color filters according to claim 1 or 2, which is coated.   The microencapsulated pigment polymerizes a cationic polymerizable surfactant having a cationic group, a hydrophobic group, and a polymerizable group in an aqueous dispersion in which pigment particles having an anionic group on the surface are dispersed. The resin composition for inkjet color filters according to claim 1 or 2, wherein the pigment particles are coated with a polymer.   The microencapsulated pigment includes a repeating structural unit in which pigment particles having an anionic group on the surface are derived from a cationic polymerizable surfactant having a cationic group, a hydrophobic group, and a polymerizable group; An anionic polymerizable surfactant having a group, a hydrophobic group and a polymerizable group and / or a polymer having a repeating structural unit derived from a hydrophilic monomer having an anionic group, Item 3. The resin composition for an inkjet color filter according to Item 1 or 2.   The microencapsulated pigment includes a cationic polymerizable surfactant having a cationic group, a hydrophobic group, and a polymerizable group, an anion in an aqueous dispersion in which pigment particles having an anionic group on the surface are dispersed. The pigment particles are coated with a polymer by polymerizing an anionic polymerizable surfactant having an ionic group, a hydrophobic group and a polymerizable group and / or a hydrophilic monomer having an anionic group. Item 3. The resin composition for an inkjet color filter according to Item 1 or 2.   The resin composition for an ink jet color filter according to claim 3, wherein the polymer further has a repeating structural unit derived from a hydrophobic monomer. 8. The polymer according to claim 3, wherein the polymer further has a repeating structural unit derived from a crosslinkable monomer and / or a repeating structural unit derived from a monomer represented by the following general formula (1): A resin composition for an inkjet color filter according to claim 1.

[However, R1 represents a hydrogen atom or a methyl group. R2 is a t-butyl group, an alicyclic hydrocarbon group,
An aromatic hydrocarbon group or a heterocyclic group is represented. m represents an integer of 0 to 3, and n represents an integer of 0 or 1. ]   8. The ink composition color filter resin composition according to claim 1, wherein the pigment constituting the pigment particles is an organic pigment. The anionic group of the pigment particles is a sulfonate anion group (—SO ³⁻ ) and / or a sulfinate anion group (—RSO ²⁻ : R is a C1 to C12 alkyl group or phenyl group or a modified product thereof). The resin composition for inkjet color filters according to any one of claims 3 to 9. The anionic group of the pigment particles, a carboxylic acid anion group (-COO ^-) inkjet type color filter resin composition according to any one of claims 3-9, characterized in that a.   The cationic group of the cationic polymerizable surfactant is selected from the group consisting of a primary amine cation, a secondary amine cation, a tertiary amine cation, and a quaternary ammonium cation. The resin composition for ink-jet color filters according to any one of 3 to 6.   The inkjet system color according to any one of claims 3 to 6, wherein the hydrophobic group of the cationic polymerization surfactant is selected from the group consisting of an alkyl group, an aryl group, and a group in which these are combined. Filter resin composition.   The polymerizable group of the cationic polymerization surfactant is an unsaturated hydrocarbon group capable of radical polymerization, and includes a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinylene group. The resin composition for inkjet color filters according to claim 3, wherein the resin composition is selected from the group consisting of:   2. An ink jet color according to claim 1, comprising an aqueous dispersion containing pigment particles, a polymer as a resin component for coating the pigment particles, and a microencapsulated pigment having an ionic group provided on the surface of the polymer. Filter resin composition. .   2. The polymer fine particle is further contained, the polymer fine particle has an anionic group on a surface thereof, a glass transition temperature is 30 ° C. or less, and a volume average particle diameter is 10 to 200 nm. The resin composition for inkjet type color filters as described in any one of -15.   The resin composition for an inkjet color filter according to claim 16, wherein the anionic group on the surface of the polymer fine particle is the same kind as the anionic group on the surface of the microencapsulated pigment. When the polymer fine particles are brought into contact with 3 volumes of an aqueous emulsion of 0.1% by weight thereof and 1 volume of a divalent metal salt aqueous solution having a concentration of 1 mol / l, the light transmittance at a wavelength of 700 nm is an initial value of 50. The resin for an ink jet type color filter according to claim 16 or 17, which has a reactivity with a divalent metal salt such that the time when the percentage is 1 x 10 ⁴ seconds or less. Composition.   The resin composition for an ink jet color filter according to claim 1, further comprising a water-soluble organic solvent.   The resin composition for an inkjet color filter according to claim 19, wherein the water-soluble organic solvent is a high-boiling water-soluble organic solvent having a boiling point of 180 ° C or higher.   21. The ink composition color filter resin composition according to claim 19 or 20, wherein the water-soluble organic solvent is glycerin.   The water-soluble organic solvent is one or more compounds selected from the group consisting of alkyl ethers of polyhydric alcohols and / or 1,2-alkyl diols. Resin composition for inkjet color filter.   The resin composition for an ink jet color filter according to any one of claims 1 to 22, further comprising a solid wetting agent in an amount of 3 to 20% by weight based on the total weight of the resin composition.   24. The inkjet system according to claim 23, wherein the solid wetting agent is one or more compounds selected from the group consisting of trimethylolpropane, 1,2,6-hexanetriol, sugars, and sugar alcohols. Resin composition for color filter.   A color filter comprising a pixel pattern formed by an inkjet method using the resin composition for an inkjet color filter according to any one of claims 1 to 24. 25. A method for producing a color filter by an ink jet method using the resin composition for an ink jet method color filter according to claim 1, wherein each light transmitting region transmits light of a transparent substrate on which a partition wall is formed in advance. And discharging the resin composition from the inkjet head to store the resin composition in each light transmission region partitioned by the partition, and drying the resin composition stored in each light transmission region to form a pixel pattern And a step of forming a protective layer so as to cover the pixel pattern. A method of manufacturing a color filter by an ink jet method.

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