JP2013032441A - Sulfonate group-containing block copolymer, method for production thereof, pigment dispersant, pigment colorant composition, resin-treated pigment composition, method for production thereof, and pigment colorant composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel A-B block copolymer which can have the function of highly and finely dispersing a micronized pigment and enables the preparation of a pigment colorant composition excellent in long-term stability; and to provide a pigment dispersant, a method for the production thereof, and a pigment colorant composition using the same.SOLUTION: The sulfonate group-containing block copolymer is an A-B block copolymer at least 90 mass% of which is constituted of a methacrylic acid monomer and is characterized in that only one of polymer blocks A and B is formed from a methacrylate as a structural component and has a structural moiety represented by formula [1] in which a benzenesulfonic acid group is bonded to the polymer block through an ester bond.

Description

  The present invention has a specific structural portion in which a benzenesulfonic acid group is bonded via an ester bond only to one of the polymer blocks AB, in which 90% by mass or more is composed of a methacrylic acid monomer. And a novel sulfonic acid group-containing block copolymer. More specifically, the structure described above can be obtained by a novel polymerization method that uses a material that is easy to polymerize, has a good yield, is inexpensive and has a low environmental impact, and does not require any special compound. Novel sulfonic acid group-containing block copolymer, pigment dispersant based on the block copolymer, pigment colorant composition containing the pigment dispersant, or resin-treated pigment treated with the block copolymer The present invention relates to a technique for providing a composition, a pigment coloring composition obtained by dispersing the resin-treated pigment, and a pigment colorant composition for a color filter using these pigment colorant compositions.

  With the recent rapid development of information devices, liquid crystal color displays are widely used as information display members for information devices. Applications of liquid crystal color displays include, for example, televisions, projectors, personal computers, mobile information devices, monitors, car navigation systems, mobile phones, display screens of electronic computers and electronic dictionaries, information bulletin boards, guidance bulletin boards, function display boards, Examples include signs and other displays, and digital camera and video camera shooting screens. The liquid crystal color display used for such various uses is equipped with a color filter. The color filter is required to have excellent image characteristics such as fineness, color density, light transmission, and contrast, and color characteristics and optical characteristics.

  A color stabilizer for a color filter (hereinafter also referred to as “color for color filter”) used for the three primary color pixels of a conventional color filter uses a dispersion stabilizer together with a pigment. Examples of the dispersion stabilizer include (a) a dye derivative (hereinafter referred to as “dye”) having a skeleton similar to a pigment, generally referred to as “synergist”, and having an acid group such as a sulfonic acid group introduced into the skeleton. Derivatives ”are also simply referred to as“ synergists ”), and (b) a combination of a basic polymer type pigment dispersant having an amino group paired with the acidic group of this synergist is often used (for example, Patent Document 1). By using such a combination of (a) a synergist and (b) a polymer type pigment dispersant, not only can the dispersion stability of the pigment in an organic solvent be improved, but also the viscosity of the pigment ink obtained. Can be improved, and the long-term storage stability of the ink can be improved.

  However, for color filters for liquid crystal color televisions, for example, color display performance (pixel performance) such as color density, light transmission, and contrast ratio is required to be improved, and the prior art is sufficient. Not done. In order to improve the performance of the pixel in response to the above requirements, the particle diameter of the pigment used tends to be reduced to ultrafine particles. As a result, the ultrafine pigment has an increased number of particles and an increased surface area even if the mass of the pigment is the same as that of the non-ultrafine pigment. For this reason, it is difficult for the conventional technology to sufficiently maintain the dispersion stability of the ultrafine pigment.

  On the other hand, there is a method of increasing the use amount of a synergist having an acidic group and a pigment dispersant in order to stably disperse the ultrafine pigment (for example, see Patent Document 2). However, in this case, since the pigment density relatively decreases, the color density (high color density of the pixel) cannot be satisfied. That is, it is very difficult to provide an ink that satisfies both the requirement of increasing the pigment content in order to increase the color density of the pixel to obtain an appropriate pixel coating composition and the dispersion stability of the pigment.

  In order to improve the relative decrease in the pigment concentration, a method of introducing an acidic group into the molecular structure of the pigment dispersant is conceivable (for example, see Patent Document 3). However, this method is difficult to apply to basic pigment dispersants having amino groups. In a combination of a synergist having an acidic group and a basic polymer type pigment dispersant having an amino group, if an acidic group is introduced into the molecular structure of the pigment dispersant, the acidic group and amino group This is because the group may be ionically bonded. When the acidic group and the amino group are ionically bonded, the pigment dispersant may be gelled in the organic solvent. Even if the pigment dispersant does not gel, an ionic bond exists in the molecule of the pigment dispersant or between molecules, so that the pigment dispersant and the synergist are difficult to ion bond. For this reason, the pigment dispersant having an ionic bond may not function sufficiently as a pigment dispersant.

  By the way, color filters are usually coated with color filter color on glass, exposed to only necessary parts using a photomask, etc. and insolubilized, and then unexposed parts (unnecessary parts) are removed with an alkaline developing aqueous solution. It is manufactured by the method. For example, a developing polymer having an acidic group such as a carboxyl group is added to the color for a color filter. For this reason, the acidic group of the developing polymer is neutralized with an aqueous alkaline developing solution, and the developing polymer is solubilized in water and removed. However, a basic pigment dispersant having an amino group cannot be dissolved in an alkaline developing aqueous solution because an acidic group cannot be introduced into its molecular structure. For this reason, it has been a cause of deteriorating developability such as a long development time or a sharp pixel edge.

  On the other hand, as pigment colorants, in addition to pigment dispersions obtained by dispersing pigments with pigment dispersants, pigments that have been subjected to various surface treatments in order to increase the dispersibility of the pigment and easily disperse it. It is used. In particular, pigments that have been surface-treated by resin treatment are useful. As a method for treating the pigment with this resin, there are various treatment methods as described below. For example, after adding a monomer to a pigment dispersion prepared in advance, a method of generating a resin on the pigment surface with a polymerization initiator (for example, see Patent Document 4), or after dispersing the pigment with a resin-type pigment dispersant There is a method in which a poor solvent of a pigment dispersant is added to the dispersion, or conversely added to a large amount of a poor solvent, and the pigment dispersant is precipitated and treated (see, for example, Patent Document 5). Also, using a neutralized water-soluble dispersant, after dispersing in an aqueous medium, adjusting the pH to precipitate the dispersant as water-insoluble and treating the pigment, or with a dispersant If the dispersed pigment dispersion is precipitated by a change in the temperature of the dispersant, a method of depositing using the temperature change of the dispersion, a method of combining a resin emulsion and a pigment, or a reaction with each other There is a method in which a reactive group reacts by being dispersed in a resin having a group to be heated and heated to crosslink and encapsulate a pigment (for example, see Patent Document 6). In addition, a group capable of polymerizing on the pigment surface or a group that initiates polymerization is introduced, and a monomer is added for polymerization to form a resin on the pigment surface to obtain a resin-treated pigment (for example, see Non-Patent Document 1). There are methods. These methods take a plurality of steps in order to treat the resin on the pigment surface. However, it is preferable that the method is simpler, and that the pigment is more reliably treated with the resin. It is rare.

  Under such circumstances, in recent years, a method for producing a block copolymer by living radical polymerization has been developed, and various polymerization methods that can easily control the structure and molecular weight using the same have been developed. As specific examples, the methods listed below have been developed, and extensive research and development has been conducted. Nitroxide mediated polymerization (NMP method) using dissociation and bonding of amine oxide radicals (see Non-Patent Document 2). Atom transfer radical polymerization (ATRP method) in which a heavy metal such as copper, ruthenium, nickel, and iron and a ligand that forms a complex therewith are used as a starting compound (Atom transfer radical polymerization: ATRP method) (See Patent Document 8 and Non-Patent Document 3). Reversible addition-fragmentation chain transfer (RAFT method) in which dithiocarboxylic acid ester or xanthate compound is used as the starting compound and polymerized using an addition polymerizable monomer and a radical initiator (Patent Literature) 9) and Macromolecular Design via Interchange of Xanthate (MADIX method) (see Patent Document 10). A method using a heavy metal such as organic tellurium, organic bismuth, organic antimony, antimony halide, organic germanium, or germanium halide (Degenerative transfer: DT method) (see Patent Document 11 and Non-Patent Document 4).

JP-A-9-176511 JP 2001-240780 A JP 2008-298967 A JP 2001-240780 A JP 2008-298967 A JP 2000-191974 A Special Table 2000-500516 JP 2000-514479 A Special Table 2000-515181 International Publication No. 1999-05099 Pamphlet JP 2007-277533 A

Paint Engineering (2011) 46, p49 Chemical Review (2001) 101, p3661 Chemical Review (2001) 101, p3689 Journal of American Chemical Society (2002) 124 p2874, (2002) 124 p13666, (2003) 125 p8720

  The present invention has been made in view of the above problems existing in the prior art, and the problem is that the finely divided pigment can be highly finely dispersed and has excellent long-term storage stability. It is another object of the present invention to provide a novel pigment dispersant capable of preparing a pigment colorant composition and a method for producing the same. Another object of the present invention is to provide a pigment colorant composition having excellent coating properties and long-term storage stability.

Another object of the present invention is to provide a resin-treated pigment that can be easily resin-treated and is reliably resin-treated on the pigment surface. Another object of the present invention is to provide the above excellent pigment colorant composition by dispersing the resin-treated pigment.
Furthermore, the subject of the present invention is a liquid crystal color television having excellent coating characteristics and long-term storage stability, and excellent optical characteristics such as pixel color density, definition, contrast, and transparency. An object of the present invention is to provide a pigment colorant composition for a color filter, which can produce a color filter equipped in an information display device such as the above.

  Although the structure and molecular weight of the resin can be easily controlled, the living radical polymerization listed above has the following practical problems, and the subject of the present invention is a pigment dispersant. It is an object to provide a technique for obtaining a novel AB block copolymer that can function as a manufacturing method that does not cause such problems. For example, in the NMP method, a tetramethylpiperidine oxide radical is used. In this case, a high polymerization temperature of 100 ° C. or higher is required. Furthermore, in order to increase the polymerization rate, it is necessary to polymerize the monomer alone without using a solvent, so that the polymerization conditions become severe. In this polymerization method, the polymerization of the methacrylate monomer generally does not proceed. On the other hand, it is possible to lower the polymerization temperature or to polymerize the methacrylate monomer, but in that case, it is necessary to use a special nitroxide compound.

  In the ATRP method, it is necessary to use heavy metal, and after polymerization, it is necessary to remove the heavy metal from the polymer and purify the polymer even if it is a trace amount. Further, when purifying the polymer, since heavy metals with high environmental load are contained in the waste water and waste solvent in the refining treatment, it is necessary to remove the heavy metals and purify them. In addition, in the ATRP method using copper, it is necessary to perform polymerization in an inert gas. This is because, when oxygen is present in the polymerization atmosphere, the monovalent copper catalyst is oxidized to divalent copper, and the catalyst is deactivated. In that case, there is a method to restore the copper by adding a reducing agent such as stannic compound or ascorbic acid, but there is a possibility that the polymerization may stop in the middle, and oxygen is sufficiently removed from the polymerization atmosphere. It is essential to do.

  Furthermore, in the method of forming a complex using an amine compound as a ligand and polymerizing it, if an acidic substance is present in the polymerization system, the formation of the complex is inhibited, so that it is difficult to polymerize an addition polymerizable monomer having an acid group. It is. In order to introduce an acid group into the polymer by this method, polymerization must be performed while the acid group of the monomer is protected, and after the polymerization, the protecting group must be eliminated. It ’s not easy.

  From the above, since the methods described in Patent Document 1 and Patent Document 2 described above as the prior art use copper, it is necessary to remove the copper after polymerization and purify the polymer. In addition, when an acid that inhibits the complex formation of copper and a ligand is present, polymerization does not proceed. Therefore, the techniques described in these documents cannot directly polymerize a monomer having an acid group.

  Furthermore, in the RAFT method and the MAGIX method, it is necessary to synthesize and use a special compound such as a dithiocarboxylic acid ester or a xanthate compound. In addition, since a sulfur-based compound is used, the resulting polymer has a sulfur-based unpleasant odor and also has coloration, and it is necessary to remove these odors and color from the polymer. Since the DT method uses heavy metals in the same manner as the ATRP method, it is necessary to remove heavy metals from the polymer, and if removed, there is a problem of purification of waste water containing heavy metals.

  As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have achieved the present invention as follows. The basic structure of the resin that characterizes the present invention is an AB block copolymer having a solvent-soluble chain and an acidic chain having a benzenesulfonic acid group that is an acid group. Furthermore, the block copolymer is not the conventional living radical polymerization listed above, but the resulting polymer has no odor or coloration, and does not have the problem of using heavy metals or the cost. It can be easily obtained by reaction with 2-sulfobenzoic anhydride having high reactivity with. In addition, by using the sulfonic acid group-containing block copolymer having the above-described configuration as a pigment dispersant, a highly stable pigment dispersion in which a pigment is highly finely dispersed can be obtained. Furthermore, by simply mixing the pigment treated with a pigment derivative having a basic group and the sulfonic acid group-containing block copolymer in water or a polyhydric alcohol, the basic group and sulfonic acid group on the pigment surface are ionically bonded. Thus, the resin is completely coated and deposited on the surface, and the resin-treated pigment can be easily obtained.

  More specifically, when the present inventors use a novel sulfonic acid group-containing AB block copolymer designed to have a structure specific to only one polymer block as a pigment dispersant, finely divided pigments are obtained. A pigment colorant composition that can be highly finely dispersed and excellent in long-term storage stability can be prepared. In addition, a resin-treated pigment obtained simply by mixing with a pigment produces the same effect. These pigment dispersions are found in the alkali development step in the color filter production process, and the dispersant itself exhibits alkali developability, which leads to a reduction in development time and an increase in pigment concentration, thereby completing the present invention. It came to.

  Each of the conventional living radical polymerizations listed above has problems. The production method of the block copolymer of the present invention uses an iodine compound as a polymerization initiating compound and, if necessary, a living radical polymerization using an organic compound having active phosphorus, nitrogen, oxygen, and carbon atoms as a catalyst. Thus, it is possible to solve the problems of the prior art and easily obtain a block copolymer having a narrow molecular weight distribution (hereinafter referred to as PDI) and having the above excellent properties. Furthermore, a block copolymer is obtained using this production method, and then 2-sulfobenzoic anhydride is reacted, whereby the sulfonic acid group-containing block capable of exhibiting the above-described excellent operational effects whose structure is reliably controlled Copolymers can be easily obtained. And it came to develop the pigment dispersant, the resin treatment pigment, and the pigment colorant composition which can solve the conventional subject by making this block copolymer into a pigment dispersant.

That is, this invention provides resin shown below which can solve an above-described subject.
[1] Benzene, which is an AB block copolymer in which 90% by mass or more is composed of a methacrylic acid monomer, and only one of the polymer blocks is formed by using methacrylate as a constituent component. A sulfonic acid group-containing block copolymer having a structural portion represented by the following formula 1 in which a sulfonic acid group is bonded via an ester bond.

[2] As a preferred embodiment of the present invention, B is a polymer block having a structural portion represented by the formula 1 and A is a polymer block having no structural portion represented by the formula 1 in the structure. In this case, the sulfonic acid group-containing block copolymer of [1], in which the polymer block of A includes at least a methacrylate having a carboxyl group and the acid value thereof is 30 to 200 mgKOH / g.

Moreover, according to this invention, the manufacturing method of the sulfonic acid group containing block copolymer shown below is provided.
[3] 90% by mass from a polymer block of A that does not have a structural portion represented by the following formula 1 and does not have a hydroxyl group, and a polymer block of C that contains at least a hydroxyl group as a constituent component The step of synthesizing an AC block copolymer composed of a methacrylic acid monomer as described above, and reacting 2-sulfobenzoic anhydride represented by the following formula 2 with the hydroxyl group to the synthesized AC block copolymer And a step of synthesizing the AB block copolymer according to [1] or [2], which is a method for producing a sulfonic acid group-containing block copolymer.

The following are mentioned as a preferable form of the manufacturing method of the sulfonic acid group containing block copolymer of this invention.
[4] The method for producing a sulfonic acid group-containing block copolymer according to [3], wherein the polymer block of A includes a methacrylate having at least a carboxyl group as a constituent component and an acid value of 30 to 200 mgKOH / g.
[5] The number average molecular weight of the polymer block A is 3,000 to 20,000, and the molecular weight distribution (weight average molecular weight / number average molecular weight) is 1.6 or less. The molecular weight is 500 to 3,000, the number average molecular weight of the AC block copolymer synthesized from these polymer blocks is 4,000 to 23,000, and the molecular weight distribution is 1.6 or less. [3] The method for producing a sulfonic acid group-containing block copolymer according to [4].
[6] The method for producing a sulfonic acid group-containing block copolymer according to [4] or [5], wherein the methacrylate having a carboxyl group is methacrylic acid.

[7] The sulfonic acid group-containing block according to any one of [3] to [6], wherein in the step of synthesizing the AC block copolymer, at least an iodine compound is used as a polymerization initiating compound, and a methacrylate monomer is living radically polymerized. A method for producing a copolymer.
[8] Phosphorus halides, phosphorous compounds that are phosphite compounds and phosphinate compounds; nitrogen compounds that are imide compounds; oxygen compounds that are phenol compounds; diphenylmethane compounds and cyclopentadiene compounds The method for producing a sulfonic acid group-containing block copolymer according to [7], wherein at least one selected from the group consisting of hydrocarbons is used as a catalyst.
[9] The method for producing a sulfonic acid group-containing block copolymer according to [7] or [8], wherein the synthesis temperature is 30 to 70 ° C.

Furthermore, according to the present invention, the following pigment dispersant and pigment colorant composition are provided as uses of the sulfonic acid group-containing block copolymer.
[10] A pigment dispersant characterized in that the main component is the sulfonic acid group-containing block copolymer according to [1] or [2].
[11] A pigment colorant composition comprising the pigment dispersant according to [10] and a pigment having an average particle size of 10 to 150 nm.
[12] The pigment colorant composition according to [11], further including a dye derivative having a basic functional group.

Furthermore, according to the present invention, the following resin-treated pigment and pigment colorant composition using the sulfonic acid group-containing block copolymer are provided.
[13] 10 to 100 parts of the sulfonic acid group-containing block copolymer described in [1] or [2] and 5 to 100 parts of a pigment derivative having a basic functional group are used with respect to 100 parts of the pigment. A resin-treated pigment composition characterized by
[14] The pigment is treated in a treatment solution containing the sulfonic acid group-containing block copolymer according to [1] or [2], a pigment derivative having a basic group, water and / or a polyhydric alcohol as essential components. This is a method for producing a resin-treated pigment composition.
[15] A pigment colorant composition comprising the resin-treated pigment composition according to [13].

In addition, according to the present invention, there is provided a pigment colorant composition comprising any one of the above-described pigment colorant compositions and further containing an alkali-developable polymer.
[16] Further, an alkali-developable polymer is contained, and the alkali-developable polymer does not have a structural portion represented by the following formula 1 and does not have a hydroxyl group: 90% by mass or more of an AC block copolymer composed of a methacrylic acid monomer synthesized from a hydroxyl group-containing methacrylate as a constituent component, or the AC block copolymer, The pigment coloring composition according to any one of [11], [12] and [15], which is an unsaturated bond-containing block copolymer obtained by reacting a (meth) acrylate having a glycidyl group and an isocyanate group.

  In addition, according to the present invention, there is provided a pigment colorant composition for a color filter obtained by using any one of the above-described pigment colorant compositions.

  The sulfonic acid group-containing block copolymer of the present invention comprises a polymer block having no sulfonic acid group in its structure (hereinafter referred to as a polymer block of A for convenience) and a polymer having a benzenesulfonic acid group in its structure. It is an AB block copolymer composed of 90% by mass or more of a methacrylic acid monomer, which comprises a block (hereinafter referred to as a polymer block of B for convenience). As described above, the polymer block of A is a polymer block that is compatible with a dispersion medium that can be dissolved, affinity, dispersed, and melted in a solvent, and the polymer block of B is a strongly acidic sulfonic acid group. Since it is a polymer block having, various uses such as an ion exchange resin are conceivable as its use, but a pigment dispersant is particularly suitable. That is, the sulfonic acid group-containing block copolymer of the present invention has a structure controlled as described above, and the basic group of the pigment treated with the basic group and the sulfonic acid group of the polymer block of B are strong. When the sulfonic acid group-containing block copolymer of the present invention is adsorbed to the pigment by ionic bonding and the sulfonic acid group-containing block copolymer of the present invention is used as a resin-treated pigment by this ionic bonding, it is ensured. The pigment is treated with a resin to give a resin-treated pigment. By these actions, the sulfonic acid group-containing block copolymer of the present invention can highly finely disperse the finely divided pigment, and can prepare a pigment colorant composition having excellent long-term storage stability. Can be. In addition, by using the pigment dispersant containing the sulfonic acid group-containing block copolymer of the present invention as a main component, it is possible to highly finely disperse the finely divided pigment and to provide a pigment colorant having excellent long-term storage stability. Compositions and resin-treated pigments can be easily produced.

  Furthermore, the pigment colorant composition provided by the present invention has a low viscosity that is stably maintained for a long period of time and has excellent coating properties. The pigment colorant composition of the present invention can be used for a variety of purposes in paints, inks, coating agents, stationery, toners, plastics, and the like, but is particularly preferably a pigment colorant for color filters. The pigment colorant composition for a color filter of the present invention is excellent in coating characteristics and long-term storage stability, and is excellent in optical characteristics such as pixel color density, fineness, contrast, and transparency. It can manufacture color filters equipped in information display devices such as televisions. In addition, if the pigment colorant composition for a color filter of the present invention is used, a color filter resist having excellent developability during alkali development can be obtained.

  The sulfonic acid group-containing block copolymer of the present invention cannot be obtained by conventionally known radical polymerization. This is because, in conventional radical polymerization, side reactions such as recombination and disproportionation occur, and the polymerization stops, and a block copolymer with a controlled structure cannot be obtained. In contrast, living radical polymerization was invented, but as described above, the conventional methods have various problems. If the novel sulfonic acid group-containing block copolymer of the present invention is produced by using the novel living radical polymerization developed by the present inventors, it is not necessary to purify the polymer without using a heavy metal compound. It is not necessary to synthesize such a compound, and the target product can be easily obtained using only relatively inexpensive materials on the market. Further, there are advantages listed below. The polymerization conditions are mild and can be carried out under the same conditions as in the conventional radical polymerization method, no special equipment is required, and the conventional radical polymerization equipment can be used, and oxygen, water can be used during the polymerization. And is not affected by light. Moreover, since it is not necessary to refine | purify the monomer, solvent, etc. to be used, the monomer which has various functional groups can be used, Therefore Various functional groups desired can be introduce | transduced in a polymer. Furthermore, the polymerization rate is very high, and the block copolymer of the present invention can be easily produced in large quantities.

Next, the present invention will be described in more detail with reference to preferred embodiments for carrying out the present invention.
(1) Structure and action of sulfonic acid group-containing block copolymer The sulfonic acid group-containing block copolymer of the present invention is an AB block copolymer comprising 90% by mass or more of a methacrylic acid monomer, Only the polymer block has a structural part represented by the following formula 1 in which a benzenesulfonic acid group is bonded via an ester bond, which is formed by using methacrylate as a constituent component. Furthermore, the polymer block of A that does not have a structural portion represented by the following formula 1 in its structure contains at least a methacrylate having a carboxyl group, and its acid value is 30 to 200 mgKOH / g. A sulfonic acid group-containing block copolymer is more preferable.

  The structure of the sulfonic acid group-containing block copolymer of the present invention is an AB block copolymer, and as the function of the structure, the polymer block of A functions as a polymer block that dissolves and is compatible with the medium to be dispersed, Since the other polymer block of B has a sulfonic acid group bonded in its structure, the sulfonic acid group is treated with a pigment, preferably a pigment containing a basic-containing dye derivative (hereinafter referred to as pigment) Both the pigment itself and the pigment surface-treated with a basic dye derivative). This adsorption is due to hydrogen bonds between active hydrogen (hydroxyl, amide group, carboxyl group, thiol group, urethane group, etc.) and sulfonic acid groups in the structure of the pigment, pigments with a basic structure, and basic group-containing dyes. This is done by ionic bonding between the basic group of the pigment treated with the derivative and the sulfonic acid group. Due to the unique structure of this AB block copolymer and its action, the polymer block of B is adsorbed on the surface of the finely divided pigment by ionic bonds, and the polymer block of A is dissolved or compatible with the medium. In addition, the present invention has the function of enhancing the fine dispersion and storage stability of the finely divided pigment by preventing aggregation between particles by steric repulsion and electrical repulsion of the polymer block of A. It is a big feature.

  In addition, as described below, it is also useful to apply the pigment colorant composition using the sulfonic acid group-containing block copolymer of the present invention to a color filter manufacturing process. In this case, since alkali development is performed, it is effective to blend an alkali-developable polymer so that the pigment colorant composition of the present invention is dissolved in an alkaline aqueous solution. This alkali-developable polymer has an acid group in the structure, most of which is a lucaboxyl group. The carboxyl group is neutralized with an aqueous alkali solution to become water-soluble and can be developed with an alkali. That is, it is considered that some alkali-developable polymers also have acid groups and have an ionic bond with the pigment on the basic surface. However, since the sulfonic acid group-containing block copolymer of the present invention has a strong sulfonic acid group present in its structure, for example, even if a carboxylic acid group coexists as described above, Since it selectively ionically bonds with the basic group on the pigment surface, high dispersibility can be imparted even if other acid groups are contained.

  Moreover, as a more preferable form, by using a methacrylate having a carboxyl group as a material for forming the polymer block of A, the polymer block of A is ionized and dissolved in water when neutralized with an alkali. Another major feature is that it can be developed by alkali development in the production process.

  It should be noted that the structure having an acid group that is a carboxyl group in the polymer block of A and an acid group that is a sulfonic acid group in the polymer block of B is not limited as long as the acid group is ion-bonded to the pigment. There may be an idea that ionic bond adsorption may be performed after neutralization. However, as described above, the sulfonic acid group is a much stronger acid than the carboxyl group, that is, the pKa value is known to be low, so that the sulfonic acid is selectively adsorbed on the pigment. To do.

  The amount of the carboxyl group introduced into the polymer block A is preferably 30 to 200 mgKOH / g so that alkali development can be performed. If it is less than 30 mgKOH / g, it will not dissolve even if it is neutralized with alkali, or dissolution will be slow, which is not preferable. On the other hand, when it is more than 200 mgKOH / g, the water resistance is poor, and when producing a color filter, it is exposed and cured, but the affinity for water comes out to this exposed and cured part, and an alkaline developing aqueous solution is used. This is not preferable because the water resistance deteriorates and the pixel may become messy. More preferably, it is 50-150 mgKOH / g.

  What is more characteristic is that the aqueous solution of the polymer is usually ionized by neutralizing an acid group such as a carboxyl group or a basic group such as an amino group or a nonionic group such as a polyethylene glycol group. The sulfonic acid group-containing block copolymer of the present invention is dissolved, dispersed or emulsified as it is in water or a polyhydric alcohol even if it is not neutralized by introducing a sulfonic acid group into the structure. . This is considered to be due to the hydrogen bond between the high polarity of the sulfonic acid group and the solvent. The water solubility varies depending on the amount of the sulfonic acid group and other monomers to be copolymerized. Therefore, the amount of the sulfonic acid group introduced is not limited, but is preferably 5 to 30% by mass in the block copolymer. is there. By this action, the sulfonic acid group and the basic group are ion-bonded and insolubilized and precipitated only by mixing with the pigment on the basic surface in water or polyhydric alcohol. That is, if the block polymer of the present invention is used, a pigment treated with a resin can be obtained with certainty.

(2) Method for Producing a Sulfonic Acid Group-Containing Block Copolymer The introduction of the structural portion having a sulfonic acid group represented by the above formula 1 that constitutes the polymer block B can be easily carried out, for example, as follows. The That is, 2-sulfobenzoic anhydride represented by the following formula 2 is known to react with a hydroxyl group to become a carboxylic acid ester and a sulfonic acid. Using this, first, an AC block copolymer having a polymer block of C having a hydroxyl group-containing methacrylate as a constituent component is synthesized, and 2-sulfobenzoic anhydride of the following formula is reacted with the copolymer. Thus, the AB block copolymer of the present invention can be easily obtained.

  As a method for introducing a sulfonic acid group into a polymer structure, for example, a method of polymerizing an addition polymerizable monomer having a sulfonic acid group (hereinafter, “addition polymerizable monomer” is also simply referred to as “monomer”). There is. A monomer having a sulfonic acid group is considered to have reactivity with an unsaturated bond. For this reason, the sulfonic acid group in the monomer is usually in a salt state such as a metal salt or an amine salt, or in an ester state in many cases. A monomer having a sulfonic acid group in a salt state does not dissolve in most organic solvents. For this reason, it is difficult to polymerize a monomer having a sulfonic acid group in a salt state to produce a sulfonic acid group-containing polymer in an organic solvent. Further, since the sulfonic acid group is in a salt state, the monomer may contain water or may be an aqueous solution. For this reason, when it superposes | polymerizes using the monomer which has a sulfonic acid group in a salt state, it is necessary to remove a water | moisture content after superposition | polymerization. Further, after polymerization, the sulfonate must be returned to the sulfonic acid, and the ester needs to be hydrolyzed, which is complicated.

  There are also monomers having sulfonic acid groups, but such monomers are generally very poorly soluble in organic solvents. A specific example of the monomer having a sulfonic acid group is dimethylpropanesulfonic acid acrylamide. This dimethylpropanesulfonic acid acrylamide is slightly soluble in alcohol and the like, but hardly dissolved in general organic solvents other than alcohol.

  In addition to the above, as a method for introducing a sulfonic acid group into an acrylic polymer, there is a method in which a polymer is reacted with a sulfonating agent such as chlorosulfonic acid, sulfuric acid, or sulfur dioxide. However, when these sulfonating agents are used, the polymer may be decomposed. Thus, there are various problems in other methods, and the sulfonic acid group-containing block copolymer of the present invention cannot be easily obtained. It is characterized by reacting a hydroxyl group in a polymer block of C with 2-sulfobenzoic anhydride via an AC block copolymer having a polymer block of C having a hydroxyl group-containing methacrylate as a constituent component. The method for producing a sulfonic acid group-containing block copolymer of the present invention is extremely useful.

  Since 2-sulfobenzoic anhydride used in the method for producing a sulfonic acid group-containing block copolymer of the present invention is an acid anhydride obtained by dehydration condensation of a sulfonic acid group and a carboxyl group, the solubility in an organic solvent is sufficiently high. . Moreover, 2-sulfobenzoic anhydride has high reactivity with a hydroxyl group. For this reason, it can be easily made into a sulfonic acid group-containing AB block copolymer by reacting a hydroxyl group-containing A-C block copolymer with 2-sulfobenzoic anhydride.

  It is also conceivable to produce a sulfonic acid group-containing AB block copolymer by polymerizing a sulfonic acid group-containing monomer obtained by reacting a hydroxyl group-containing methacrylate with 2-sulfobenzoic anhydride. However, as described above, since the sulfonic acid group-containing monomer is difficult to dissolve in an organic solvent, even when the sulfonic acid group-containing monomer is polymerized, the polymerization reaction is not completed or a side reaction tends to occur. It is in. On the other hand, by reacting a hydroxyl group-containing AC block copolymer with 2-sulfobenzoic anhydride, a sulfonic acid group AB block copolymer can be obtained easily and in high yield.

  The reaction of 2-sulfobenzoic anhydride with a hydroxyl group is carried out by a conventionally known method and is not particularly limited. The reaction is preferably carried out in an organic solvent at a reaction temperature in the range of -20 to 100 ° C. Moreover, since 2-sulfobenzoic anhydride has high reaction activity, it is not necessary to use a catalyst. However, if necessary, an acidic catalyst such as sulfuric acid or p-toluenesulfonic acid; a basic catalyst such as triethylamine, pyridine, or 1,8-diazabicyclo [5,4,0] -7-undecene may be used.

  In the AB block copolymer of the present invention, it is necessary to introduce the structural portion represented by the formula 1 having a sulfonic acid group into the polymer block of B. As described above, first, as shown in FIG. An AC block copolymer having the following polymer block is synthesized, and 2-sulfobenzoic anhydride is reacted with the hydroxyl group of the C polymer block of the copolymer. For this reason, an AC block copolymer is prepared so that it becomes the AB block copolymer of this invention after reaction. That is, in the AC block copolymer, 90% by mass or more is composed of a methacrylic acid monomer, the polymer block of A is a polymer block having no hydroxyl group, and the polymer block of C has a methacrylate having at least a hydroxyl group. Prepare to consist of polymer blocks. More preferably, 90% by mass or more is an AC block copolymer composed of a methacrylic acid-based monomer, and the polymer block of A has at least a methacrylate having a hydroxyl group and a carboxyl group as its acid component. It is prepared so as to be composed of a polymer block of C having a value of 30 to 200 mg KOH / g and having a methacrylate having at least a hydroxyl group in the polymer block of B. By making 2-sulfobenzoic anhydride react with the AC block copolymer having such a structure, the AB block copolymer of the present invention can be easily obtained.

(3) Constituent component of sulfonic acid group-containing AB block copolymer The sulfonic acid group-containing AB block copolymer of the present invention is 90% or more of the constituent components, preferably all constituent components are methacrylic acid monomers. is there. This is because the methacrylic acid monomer is particularly suitable for the polymerization method used in the production method of the present invention. For other vinyl monomers such as styrene, acrylate monomers, vinyl ether monomers, etc., the terminal iodine May be overstabilized and may require temperature to dissociate or may not dissociate. For this reason, when these monomers are used, it is a block copolymer having a specific structure, which is the object of the present invention, and the molecular weight distribution may not be uniform. Moreover, since it has a strong acid called a sulfonic acid group, there is a possibility of being decomposed in the case of vinyl ester type or acrylic type. On the other hand, since methacrylate is a tertiary ester, it is relatively strong in degradability. Further, the above-described problems of the present invention can be sufficiently achieved with a methacrylic acid monomer. However, monomers such as the above-described vinyl monomers may be used within a range that does not contradict the intended purpose, if necessary. Below, each structural component of the sulfonic acid group containing AB block copolymer of this invention is demonstrated.

  As described above, the sulfonic acid group-containing AB block copolymer of the present invention includes an AC block copolymer having a polymer block of C having a hydroxyl group-containing methacrylate as a constituent, and 2-sulfobenzoic anhydride. It can be easily obtained by reacting.

  Examples of the hydroxyl group-containing methacrylate constituting the C polymer block used in this case include conventionally known ones, and are not particularly limited. For example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, glyceryl monomethacrylate, poly (n = 2 or more) ethylene glycol monomethacrylate, poly (n = 2 or more) propylene glycol monomethacrylate And polyalkylene glycol monomethacrylate. Furthermore, it is obtained by reacting a compound having an active hydrogen such as a carboxyl group or an amino group with a methacrylate having an epoxy group such as glycidyl methacrylate or an oxetanyl group such as 3-methyl-3-oxetanylmethyl methacrylate. Hydroxyl groups can also be used.

  In this case, after a monomer such as glycidyl methacrylate is reacted to form a hydroxyl group, it may be introduced by the polymerization of the present invention, or after glycidyl methacrylate is copolymerized, a compound having active hydrogen is reacted. Thus, a hydroxyl group may be generated. This hydroxyl group-containing methacrylate must not be used as a constituent of the polymer block of A. This is because, in addition to the adsorbing B polymer block, a sulfonic acid group is also introduced into the A polymer block, which is different from the structure of the sulfonic acid group-containing AB block copolymer of the present invention.

  The polymer block of C may be a homopolymer of these hydroxyl group-containing methacrylates, but other methacrylates may be used as copolymerization components. What is necessary is just to become a polymer block which has a hydroxyl group.

  Other methacrylates include conventionally known ones and are not particularly limited. For example, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-methylpropane methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate , Isodecyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, octadecyl methacrylate, behenyl methacrylate, isostearyl methacrylate, cyclohexyl methacrylate, t-butylcyclohexyl methacrylate, isobornyl methacrylate, trimethylcyclohexyl methacrylate, cyclodecyl methacrylate , Cyclodecylmethyl methacrylate, tricyclodecyl methacrylate, benzyl methacrylate, phenyl methacrylate, naphthyl methacrylate, allyl methacrylate and other alkyls, cycloalkyl methacrylates, (poly) ethylene glycol monomethyl ether methacrylate, (poly) ethylene glycol monolauryl ether methacrylate (Glycol monoalkyl ether methacrylates such as (poly) propylene glycol monomethyl ether methacrylate;

Glycidyl group-containing methacrylates such as glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, methacryloyloxyethyl glycidyl ether, methacryloyloxyethoxyethyl glycidyl ether;
Isocyanate group-containing methacrylates such as (meth) acryloyloxyethyl isocyanate, 2- (2-isocyanatoethoxy) ethyl methacrylate, and monomers of which isocyanate is blocked with ε-caprolactone, MEK oxime, pyrazole and the like;
Cyclic methacrylates such as tetrahydrofurfuryl methacrylate, oxetanylmethyl methacrylate;
Halogen-containing methacrylates such as octafluorooctyl methacrylate and tetrafluoroethyl methacrylate;
Methacrylates that absorb ultraviolet light, such as 2- (4-benzoxy-3-hydroxyphenoxy) ethyl methacrylate, 2- (2′-hydroxy-5-methacryloyloxyethylphenyl) -2H-benzotriazole;
Examples thereof include monomers such as a silicon atom-containing methacrylate having a trimethoxysilyl group or a dimethylsilicone chain. Moreover, the macromonomer etc. which are obtained by introduce | transducing a (meth) acryl group into the one terminal of the oligomer obtained by superposing | polymerizing these monomers can also be used.

  In the present invention, it is only necessary that 2-sulfobenzoic anhydride reacts with a hydroxyl group in the structure of the polymer block of C to introduce a sulfonic acid group, and the monomer having an acid group may be contained in the polymer block of C. . For example, methacrylic acid, methacrylate obtained by reacting 2-hydroxyethyl methacrylate with dibasic acid such as phthalic acid, glycidyl methacrylate reacted with phthalic acid and methacrylate having hydroxyl group and carboxyl group, ethyl methacrylate phosphoric acid, etc. Can be mentioned.

  However, methacrylates having amino groups, such as dimethylaminoethyl methacrylate, are ionically bonded to carboxyl groups or sulfonic acid groups, causing gelation or the like, or inhibiting the adsorptivity with the basic groups of pigments. Should not do.

  Next, components of the polymer block A constituting the sulfonic acid group-containing AB block copolymer of the present invention will be described. The polymer block of A can use one or more of the above-mentioned methacrylates, and is optimized to give an affinity for the medium. Preferably, the polymer block of A is copolymerized with methacrylate having a carboxyl group as described above. As described above for the methacrylate having a carboxyl group used in this case, methacrylic acid, methacrylate obtained by reacting 2-hydroxyethyl methacrylate with a dibasic acid such as phthalic acid, and glycidyl methacrylate are reacted with phthalic acid. And methacrylates having a hydroxyl group and a carboxyl group. Particularly preferred is methacrylic acid having a low molecular weight and good polymerizability. This is because other monomers have a large molecular weight and may remain without being polymerized. Here, the AC block copolymer having a carboxyl group in the polymer block of A is referred to as A-C1 block copolymer.

  The AB block copolymer of the present invention can be easily obtained by reacting 2-sulfobenzoic anhydride with an AC block copolymer having a hydroxyl group containing the above-described monomer as a constituent component. The molecular weight of the AC block copolymer used in this case is such that the number average molecular weight of the polymer block of A is 3,000 to 20,000, the molecular weight distribution is 1.6 or less, and the molecular weight of the polymer block of C is 500 to The number average molecular weight of the AC block copolymer is 4,000 to 23,000, and the molecular weight distribution is preferably 1.6 or less.

  The polymer block A is a polymer block that is soluble and compatible with the medium, and the number average molecular weight is preferably 3,000 to 20,000. If it is 3,000 or less, there is a possibility that the steric repulsion of the A polymer block of the AB block copolymer adsorbed with the pigment does not act and lacks stability, and if it is 20,000 or more, it is dissolved. In some cases, the portion increases, the viscosity increases, and the developability may deteriorate. Preferably, it is 4,000-10,000.

  The molecular weight distribution of the polymer block A is preferably 1.6 or less. According to the living radical polymerization used in the present invention, such a molecular weight distribution can be achieved. This 1.6 or less means that the molecular weight is uniform, that is, if it is wide, it will contain a molecular weight outside the above-mentioned molecular weight range, 3,000 or less and 20,000 or more, and stable. Property, developability, and viscosity may be deteriorated. A more preferable molecular weight distribution is 1.5 or less.

  The polymer block of C has a hydroxyl group, and 2-sulfobenzoic anhydride is reacted with the group to form a polymer block of B having a sulfonic acid group introduced therein. The molecular weight of the C polymer block represents a molecular weight obtained by subtracting the number average molecular weight of the A polymer block from the number average molecular weight of the AC block copolymer. The molecular weight of the polymer block of C is 300 to 3,000. Since this group is a polymer block that adsorbs pigments, if it is smaller than 300, the adsorption may be weak and lack stability, and if it is 3,000 or more, the molecular weight is too large and adsorption between pigment particles occurs, resulting in stability. May be lacking. More preferably, the molecular weight of the polymer block of C is 600 to 2,000.

  The number average molecular weight of the resulting AC block copolymer is 4,000 to 23,000. Further, the molecular weight distribution is preferably 1.6 or less, more preferably 1.5 or less.

(4) Polymerization Method for Obtaining Block Copolymer Next, a method for obtaining the AC block copolymer used in the present invention with the components as described above will be described. Although this method can be obtained by the above-described conventional living radical polymerization method, it is preferably obtained by a novel living radical polymerization without the above-mentioned problems.

  The novel living radical polymerization is synthesized by living radical polymerization starting from at least an iodine compound. This is because the iodine radical is dissociated from the polymerization initiator compound by heat or light, the monomer is inserted in the dissociated state, and the iodine radical is immediately combined with the polymer terminal radical to stabilize and prevent termination reaction. This is a living radical polymerization method.

  Although it does not specifically limit as an iodine compound which is this polymerization initiating compound, For example, alkyl iodides, such as 2-iodo-1-phenylethane and 1-iodo-1-phenylethane, 2-cyano-2-iodo Examples include cyano group-containing iodides such as propane, 2-cyano-2-iodobutane, 1-cyano-1-iodocyclohexane, and 2-cyano-2-iodovaleronitrile.

  Moreover, although these compounds can use a commercial item as it is, they can also be obtained by a conventionally well-known method. For example, it can be obtained by reacting an azo compound with iodine such as azobisisobutyronitrile. Alternatively, an organic halide obtained by substituting other halogen atoms such as bromide or chloride in place of iodine of the organic iodide described above, and using an iodide salt such as quaternary ammonium iodide or sodium iodide, a halogen exchange reaction Thus, an organic iodide used in the present invention can be obtained. They are not particularly limited.

  In the present invention, a catalyst capable of extracting the iodine can be used. Examples of the catalyst include phosphorus halides which are phosphorus halides, phosphite compounds and phosphinate compounds; nitrogen compounds which are imide compounds; oxygen compounds which are phenol compounds; diphenylmethane compounds and cyclopentadiene compounds. And at least one selected from them is used as a catalyst.

Although it will not specifically limit if it is these compounds, For example, phosphorus triiodide, diethyl phosphite, dibutyl phosphite, ethoxyphenyl phosphinate, phenylphenoxy phosphinate etc. are mentioned as a phosphorus compound.
Examples of nitrogen compounds include succinimide, 2,2-dimethylsuccinimide, maleimide, phthalimide, N-iodosuccinimide, and hydantoin.
Examples of the oxygen-based compound include phenol, hydroquinone, methoxyhydroquinone, t-butylphenol, catechol, and di-t-butylhydroxytoluene.
Examples of the hydrocarbon having active carbon include cyclohexadiene and diphenylmethane.

  The amount of this catalyst is less than the number of moles of the polymerization initiator. If the number of moles is too large, the polymerization is too controlled and the polymerization does not proceed, which is not preferable.

  Next, regarding polymerization conditions, in particular, in the polymerization of methacrylic acid used in the present invention, the synthesis temperature is preferably 30 to 70 ° C. This is because when the temperature is high, the iodine group at the polymerization terminal is decomposed by the acid of methacrylic acid, the terminal is not stable, and living polymerization may not be performed.

  In addition, an initiator for generating radicals is added to the polymerization of the present invention. A conventionally well-known thing is used for this initiator, an azo type initiator and a peroxide type initiator are used, and it is not specifically limited. Particularly preferably, as described above, since the polymerization temperature is preferably 30 to 70 ° C., an initiator capable of generating radicals sufficiently in that range is preferable. For example, 2,2′-azobis (4 -Methoxy-2,4-dimethylvaleronitrile).

  The amount of the initiator is 0.001 to 0.1 mol times, more preferably 0.002 to 0.05 mol times based on the number of moles of monomers. This is because if the amount is less than the above range, the polymerization does not proceed sufficiently, and if it is too large, a normal radical polymerization that is not a living radical polymerization may proceed as a side reaction.

  The polymerization conditions are not particularly limited. Bulk polymerization without using an organic solvent may be performed, but solution polymerization using a solvent is preferable. Any solvent that dissolves the iodide, catalyst, monomer, and initiator used in the present invention may be used. A group capable of reacting with sulfobenzoic anhydride, such as an alcohol having a hydroxyl group, can be used. After obtaining an AC block copolymer, it is purified to remove alcohol and then reacted with sulfobenzoic anhydride. This is because it can be reacted with sulfobenzoic anhydride in a solvent having no such group.

Although the organic solvent used in this case is not specifically limited, the following can be illustrated.
Hydrocarbon solvents such as hexane, octane, decane, isodecane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene;
Alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, hexanol, benzyl alcohol, cyclohexanol;
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, diglyme, triglyme, dipropylin glycol dimethyl ether, butyl carbitol, butyl Glycol solvents such as triethylene glycol, methyl dipropylene glycol, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, dipropylene glycol butyl ether acetate, diethylene glycol monobutyl ether acetate;

Ether solvents such as diethyl ether, dipropyl ether, methylcyclopropyl ether, tetrahydrofuran, dioxane, anisole;
Ketone solvents such as methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, acetophenone;
Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl butyrate, ethyl butyrate, caprolactone, methyl lactate, ethyl lactate;
Halogenated solvents such as chloroform and dichloroethane;
Amide solvents such as dimethylformamide, dimethylacetamide, pyrrolidone, N-methylpyrrolidone, caprolactam;
Examples thereof include dimethyl sulfoxide, sulfolane, tetramethylurea, ethylene carbonate, propylene carbonate, dimethyl carbonate, and the like, and these are used as a single type or a mixed solvent of two or more types.

  However, since a purification step is disadvantageous in terms of cost, it is preferable to use a solvent that does not react with 2-sulfobenzoic anhydride. More preferably, since the sulfonic acid group generated by the reaction with 2-sulfobenzoic anhydride is a strong acid, there is a risk of decomposing an ester group, etc., so hydrocarbon-based, ether-based, dialkylene glycol dialkyl ether Good.

  In the solution polymerization, the solid content (monomer concentration) of the polymerization solution is not particularly limited, but is preferably 5 to 80% by mass, more preferably 20 to 60% by mass. If the solid content is less than 5% by mass, the monomer concentration may be too low and polymerization may not be completed. On the other hand, in 80% by mass to bulk polymerization, the viscosity of the polymerization solution becomes too high and stirring becomes difficult. The polymerization yield may be deteriorated.

  The polymerization time is preferably continued until the monomer runs out, but is not particularly limited. For example, the polymerization time is 0.5 to 48 hours, and the substantial time is 1 to 24 hours.

  The polymerization atmosphere is not particularly limited and may be polymerized as it is, that is, oxygen may be present in the system within a normal range, and if necessary, performed under a nitrogen stream to remove oxygen. May be.

  Moreover, although the material used for superposition | polymerization may remove an impurity with distillation, activated carbon, or an alumina, a commercial item can be used as it is. Further, the polymerization may be performed under light shielding, and there is no problem even if it is performed in a transparent container such as glass. The block copolymer of the present invention can be obtained under the above polymerization conditions.

  Further, the polymerization may be performed by polymerizing from the polymer block of A to obtain the polymer block of C, or polymerizing the polymer block of C and then polymerizing the polymer block of A. However, it is essential that the polymer block of C has a hydroxyl group and the polymer block of A does not have a hydroxyl group. Therefore, it is necessary to polymerize the A polymer block in a state where the hydroxyl group-containing methacrylate of the C polymer block does not completely remain. Alternatively, after polymerizing the block copolymer of C, only the polymer block of C is taken out and produced, and then the polymer block of A may be polymerized again. However, in order to make it simpler, there is no problem whether a monomer that forms the polymer block of A or a methacrylate having a carboxyl group is introduced into the polymer block of C. It is better to form a polymer block of C by polymerizing the polymer block and polymerizing completely or at a polymerization rate of 50% or more, more preferably 80% or more, and then adding a methacrylate having a hydroxyl group.

  In the polymerization method used in the present invention, the molecular weight of the polymer can be controlled by the amount of the starting compound. That is, by setting the number of moles of the monomer with respect to the number of moles of the starting compound, it is possible to control the arbitrary molecular weight or the molecular weight. For example, when 1 mol of the starting compound is used and 500 mol of the monomer having a molecular weight of 100 is used for polymerization, a theoretical molecular weight of 1 × 100 × 500 = 50,000 is given. That is, the set molecular weight can be calculated by the formula [1 mol of starting compound × monomer molecular weight × monomer to starting compound molar ratio].

  However, the polymerization method used in the present invention may involve a bimolecular termination or a disproportionation side reaction, and may not achieve the above theoretical molecular weight. Polymers without these side reactions are preferred, but they can be coupled to increase molecular weight or stopped to decrease molecular weight. Further, the polymerization rate may not be 100%, and after obtaining a desired block copolymer, a polymerization initiator or a catalyst may be added to polymerize the remaining monomers to be completed. The block copolymer used in the present invention may be produced and contained, and there is no problem even if each polymer block unit is included.

Moreover, although iodine is used in the polymerization method used in the present invention, it may be used in a state in which the iodine is bound, but it is preferable to remove it from the polymer so that the iodine can be removed. The method is a conventionally known method and is not particularly limited, but may be desorbed by heating while flowing air, or may be desorbed by adding an acid or alkali, and sodium thiosulfate or the like is added. And may be disassembled. It may be used as it is without desorption, or may be removed by passing through an iodine adsorbent such as activated carbon or alumina after decomposition.
The AC block copolymer used in the present invention can be obtained as described above, and then the AB block copolymer of the present invention can be easily obtained by reacting with 2-sulfobenzoic anhydride. Can do.

(5) Use of sulfonic acid group-containing block copolymer Since the sulfonic acid group-containing block copolymer of the present invention has a sulfonic acid group, various uses can be considered. In the present invention, a pigment dispersant or a resin treatment is used. It is preferably used as a resin component for pigments.

(5-1) Use as a pigment dispersant First, when the sulfonic acid group-containing block copolymer of the present invention is used as the main component of the pigment dispersant, the pigment treated with a basic pigment or a basic group-containing dye derivative The basic group and the sulfonic acid group in the structure of the block copolymer are strongly adsorbed, thereby increasing the dispersibility. Since the pigment is dispersed by this action, the pigment to be used is not particularly limited, and organic pigments, inorganic pigments, metal pigments such as metal powders or fine particles, inorganic fillers, and the like can be used. Specific examples of pigments include quinacridone pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, perylene pigments, phthalocyanine blue pigments, phthalocyanine green pigments, isoindolinone pigments, indigo / thioindigo pigments, dioxazine pigments. , Quinophthalone pigment, nickel azo pigment, insoluble azo pigment, soluble azo pigment, high molecular weight azo pigment, carbon black pigment, composite oxide black pigment, iron oxide black pigment, titanium oxide black pigment, and azomethine azo black pigment And red, green, blue, yellow, orange, purple, black, and white pigments selected from the group consisting of titanium oxide pigments.
Examples of metal pigments include copper powder and aluminum flakes, and examples of fillers include mica pigments, natural minerals, and silica.

In particular, organic pigments and black matrix inorganic pigments are used for color filters, and it is preferable to select pigments used for color filters. Examples of the red pigment include color index (hereinafter, CI) pigment red (PR) 56, 58, 122, 166, 168, 176, 177, 178, 224, 242, 254, and 255. Examples of green pigments include C.I. I. Pigment green (PG) 7, 36, 58, poly (14-16) bromo copper phthalocyanine, poly (12-15) bromo-poly (4-1) chloro copper phthalocyanine. Examples of blue pigments include C.I. I. Pigment blue 15: 1, 15: 3, 15: 6, 60, 80, and the like.
Moreover, the following can be mentioned as a complementary color pigment with respect to said pigment, or a multicolor type pixel pigment. Examples of yellow pigments include C.I. I. Pigment Yellow (PY) 12, 13, 14, 17, 24, 55, 60, 74, 83, 90, 93, 126, 128, 138, 139, 150, 154, 155, 180, 185, 216, 219, C . I. Pigment violet (PV) 19, 23 can be used. Examples of black pigments for black matrix include C.I. I. Pigment black (PBK) 6, 7, 11, 26, copper-manganese-iron-based composite oxide can be used.

  The average particle diameter of the pigment is 10 to 150 nm, and preferably 20 to 80 nm. By thus finely dispersing the pigment, high transparency and high contrast can be achieved even when the pigment colorant composition is used in a color filter. The pigment colorant composition of the present invention contains the above-described pigment dispersant capable of highly finely dispersing finely divided pigments. Therefore, in the pigment colorant composition of the present invention, the extremely fine pigment as described above is dispersed in a good state and excellent in long-term storage stability.

  The pigment colorant composition of the present invention preferably contains a basic dye derivative having a basic functional group so as to be ion-bonded and adsorbed with a sulfonic acid group constituting the pigment dispersant. This dye derivative has a basic functional group introduced into the dye skeleton. As the dye skeleton, a skeleton that is the same as or similar to that of the pigment and a skeleton that is the same as or similar to the compound used as the raw material of the pigment are preferable. Specific examples of the dye skeleton include azo dye skeleton, phthalocyanine dye skeleton, anthraquinone dye skeleton, triazine dye skeleton, acridine dye skeleton, and perylene dye skeleton.

The basic functional group introduced into the dye skeleton is preferably an amino group. The amino group to be introduced may be any of primary, secondary, and tertiary amino groups, and may be a quaternary ammonium salt. A basic functional group such as an amino group may be directly bonded to the dye skeleton, but may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, ether, sulfonamide, or urethane bond. It may be bonded. From the viewpoint of synthesis and bond strength, a sulfonamide is preferable.
As described above, a pigment dispersion can be obtained using the block copolymer of the present invention as a pigment dispersant.

(5-2) Use as a resin for resin-treated pigments The sulfonic acid group-containing block copolymer of the present invention is characterized by having an action of dissolving, dispersing, and emulsifying in water or a polyhydric alcohol by the sulfonic acid group. is there. Using this solubility, an aqueous solution of the sulfonic acid group-containing block copolymer of the present invention in a state where a pigment, a basic pigment, and a basic group-containing dye derivative are mixed and stirred in water and / or a polyhydric alcohol. Alternatively, when a dispersion or an emulsion is added, the basic group on the pigment surface and the sulfonic acid form an ionic bond, and the resin becomes insoluble and precipitates. This means that the adsorption in the pigment dispersion is an adsorption action of ionic bond between the pigment and the resin, which means that the block copolymer of the present invention is acting on the pigment, which greatly increases the certainty of the dispersibility. It is work. Unlike the resin treatment described above, there is no need to take a plurality of steps, and this is a very simple method that can produce a resin-treated pigment simply by mixing.

  Examples of the solvent that can be used include water and / or polyhydric alcohols. Examples thereof include water, lower alcohols such as methanol and ethanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, alkyl ethers thereof, and glycerin. , Diglycerin, etc., used in one or more.

  The ratio of these pigments, basic group-containing dye derivatives, and block copolymers of the present invention is 10 to 100 parts by weight of the sulfonic acid group-containing block copolymer and 100% by weight of the pigment derivative having a basic functional group. 5 to 100 parts by mass. If the block copolymer is less than 10 parts by mass, sufficient dispersibility cannot be exhibited, and if it is more than 100 parts by mass, a resin that does not contribute to dispersion may be generated. More preferably, it is 10-50 mass parts. With respect to the dye derivative, if the amount is less than 5 parts by mass, there are few basic groups covering the surface and there is a possibility that sufficient adsorption may not be achieved. May result in the target hue not being achieved. More preferably, it is 10-30 mass parts.

  The method for this treatment is not particularly limited. To illustrate, it is only necessary to prepare a slurry having a solid content of 1 to 10% by mass of a pigment and a dye derivative, and add a block copolymer solution previously diluted with water. This step may be stirring alone or while dispersing. After the addition, the particles may be heated to aggregate the particles.

  It can also be used when the pigment is refined. During or after kneading, the block copolymer of the present invention is added, and ion adsorption is performed by the kneading. The kneading method is not particularly limited. For example, the kneading method is preferably 30 minutes to 60 hours at room temperature or heated by a conventionally known kneader such as a kneader, an extruder, a ball mill, a two-roll, a three-roll, or a flasher. Knead for 1 to 12 hours. In addition, if necessary, carbonate, chloride salt, etc. can be used in combination as fine media for refining the pigment in the mixture, and in order to impart lubricity, glycerin, ethylene glycol, diethylene glycol It is preferable to use a viscous organic solvent together. Since the block copolymer of the present invention is dissolved in this viscous organic solvent, the pigment can be processed without precipitation. The salt is used in an amount of 1 to 30 times, preferably 2 to 20 times the weight of the pigment. The amount of the viscous organic solvent used is adjusted according to the viscosity at the time of pigment kneading. Moreover, after desalting, it may be used as a water paste, or may be pulverized and used as a powder. The obtained resin-treated pigment can be dispersed in a liquid medium to form a pigment dispersion.

(5-3) Pigment Colorant Composition As described above, pigment coloration, which is a pigment dispersion obtained by using the block copolymer of the present invention as a pigment dispersant or a pigment dispersion obtained by dispersing a resin-treated pigment, is used. The composition will be described.

  As described above, this pigment colorant composition is obtained by dispersing a pigment, the block copolymer of the present invention, and, if necessary, a basic group-containing dye derivative in a liquid medium. If necessary, an alkali-developable polymer may be added as a component as a colorant for the color filter. The sulfonic acid group-containing block copolymer that is a pigment dispersant of the present invention is characterized by being capable of alkali development because it is neutralized and ionized when it has a carboxyl group and becomes soluble in water. The pigment colorant composition preferably contains an alkali developable binder which is a polymer having a carboxyl group which is an alkali developable polymer.

  As this alkali-developable polymer, a polymer having a photosensitive group (unsaturated bond group) or a non-photosensitive polymer is used. Specific examples of the photosensitive resin include a photosensitive cyclized rubber resin and a photosensitive phenol. Resin, photosensitive polyacrylate resin, photosensitive polyamide resin, photosensitive polyimide resin, unsaturated polyester resin, polyester acrylate resin, polyepoxy acrylate resin, polyurethane acrylate resin, polyether acrylate resin And polyol acrylate resins. Specific examples of the non-photosensitive resin polymer include cellulose acetate resin, nitrocellulose resin, styrene (co) polymer, polyvinyl butyral resin, amino alkyd resin, polyester resin, amino resin modified polyester resin, Polyurethane resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, hydroxyethyl cellulose, styrene-maleic acid ester copolymer, (meth) acrylic acid Examples include ester-based (co) polymers. These alkali-developable polymers can be used alone or in combination of two or more.

  Particularly preferably, as the alkali-developable polymer, an A-C1 block copolymer which is an AC block copolymer having a carboxyl group in the polymer block of A used in the present invention, or a glycidyl group, an isocyanate is added to the A-C1 polymer. An unsaturated bond-containing block copolymer obtained by reacting a (meth) acrylate having a group is preferable. This is because the polymer is the same as the AB block copolymer used in the present invention, so that the compatibility is good. If the compatibility is poor, it may lead to a decrease in resistance or turbidity due to separation of the membrane, and may be inferior in transparency and physical properties as a color filter membrane. By using the same kind of polymer, the physical properties of the membrane are not inhibited.

  In addition, for unsaturated group-containing block copolymers reacted with (meth) acrylates having a glycidyl group or an isocyanate group, the dispersant also becomes a film component as a film component during photocuring of the color filter, and resistance such as strength is improved. It can be improved and has the effect of contributing to solvent resistance after pixel edges and pixel formation. The unsaturated bond is preferably an acryl group or a methacryl group, and this introduction is performed by a conventionally known method.

A (meth) acrylate monomer having a group capable of reacting with a carboxyl group or a hydroxyl group can be reacted and introduced into an AC block copolymer having a carboxyl group or a hydroxyl group. The carboxyl group or the group that reacts with a hydroxyl group is preferably a glycidyl group or an isocyanate group in the case of a carboxyl group, and is preferably an isocyanate group in the case of a hydroxyl group.
Although it does not specifically limit as a monomer which has this glycidyl group, Glycidyl methacrylate, (meth) acrylic acid epoxy cyclohexyl, glycidyl ethoxyethyl acrylate, etc. are mentioned. Examples of the monomer having an isocyanate include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, and an isocyanate block body thereof.

  These reactions are not particularly limited, and are carried out at 70 ° C. or higher, preferably 80 ° C. or higher, with a polymerization inhibitor such as hydroquinone added, and preferably in an air stream. In the case of a glycidyl group, a quaternary ammonium salt or triphenylphosphine is used as a catalyst. In the case of an isocyanate group, a titanium catalyst, a zirconia catalyst, a bismuth catalyst, or a tin catalyst is used as a catalyst. used. In order to perform alkali development, since it must have a carboxyl group, if the molar amount of the glycidyl group and the isocyanate group with respect to the carboxyl group is equimolar, the carboxyl group disappears in A. The molar amount should be in excess of the molar amount of glycidyl groups. Further, it may be used in combination with the above-mentioned photosensitive polymer or non-photosensitive polymer.

  As a liquid medium of the pigment colorant composition of the present invention, an organic solvent, water, or a mixed solvent of water and a hydrophilic organic solvent can be used as a medium. As the medium, an organic solvent is preferably used. Specific examples of the organic solvent include hydrocarbon solvents such as hexane and toluene; alcohol solvents such as butanol; ester solvents such as propyl acetate and butyl acetate; ketone solvents such as cyclohexanone and methyl isobutyl ketone; diethylene glycol monobutyl ether Glycol solvents such as propylene glycol monomethyl ether; glycol ester or ether solvents such as propylene glycol monomethyl ether acetate and dipropylene glycol dibutyl ether; amide solvents such as N-methylpyrrolidone and dimethylacetamide; ethylene carbonate and propion carbonate And carbonate-based solvents. These organic solvents can be used singly or in combination of two or more.

  A conventionally known additive may be further added to the pigment colorant composition of the present invention. Examples of the additive include an ultraviolet absorber, a leveling agent, an antifoaming agent, a photopolymerization initiator, and the like, or a monomer having an unsaturated bond such as methacrylate or acrylate may be added as a reactive diluent. Good.

  Next, the method for producing the pigment colorant composition of the present invention will be described. The pigment, the pigment dispersant, and the dye derivative may be added separately. It is also preferable to use a pigment (surface-treated pigment) whose surface is made basic by adding a dye derivative when the pigment raw material is made into a pigment or when the pigment is made finer. Further, in the resin-treated pigment, a liquid medium, and if necessary, a material such as an alkali-developable polymer is added and dispersed. If necessary, other pigment dispersants can be added without any problem.

  As described above, the pigment colorant composition of the present invention contains at least a pigment dispersant and a pigment, preferably further contains a dye derivative, more preferably contains an alkali-developable polymer, and if necessary. An organic solvent and an additive are added to disperse the pigment. The ratio of the pigment contained in the pigment colorant composition is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on 100% by mass as a whole. Moreover, the amount of the pigment dispersant contained in the pigment colorant composition is preferably 5 to 300 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the pigment. The amount of the pigment derivative contained in the pigment colorant composition is preferably 1 to 50 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the pigment. The amount of the alkali-developable binder is preferably 5 to 300 parts by mass, and more preferably 10 to 100 parts by mass.

  The method for dispersing the pigment is not particularly limited as long as it is a conventionally known method. Examples of the apparatus used for dispersing the pigment include vertical and horizontal media mills, sand mills, attritors, microfluidizers, ultrasonic dispersers, and three rolls. It is preferable to use these apparatuses to disperse the pigment until a predetermined average particle diameter is obtained.

  The pigment colorant composition of the present invention can be used as a colorant for various articles, and can be used as gravure ink, offset ink, UV inkjet ink, and the like. In particular, it is suitable as a pigment colorant composition for color filters (colorant for color filters) because it can reduce viscosity and increase the fineness of pigments and has good long-term storage stability. The use as a colorant for the color filter is not particularly limited.

  Next, the present invention will be described in more detail with specific examples. Hereinafter, “part” and “%” in the text are based on mass unless otherwise specified.

[Synthesis Example 1]
In a 2-liter separable flask equipped with a reflux tube, a gas introduction device, a thermometer, and a stirring device, 260 parts of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMAc), 4.5 parts of iodine, 2,2′-azobis (4 -Methoxy-2,4-dimethylvaleronitrile) (hereinafter abbreviated as V-70) 22.1 parts, methyl methacrylate (hereinafter abbreviated as MMA) 64.8 parts, butyl methacrylate (hereinafter abbreviated as BMA) 64.8 Parts, 2-ethylhexyl methacrylate (hereinafter abbreviated as EHMA) 32.4 parts, methoxypolyethylene glycol methacrylate (n = 3 to 5) (hereinafter abbreviated as PME200), 32.4 parts, benzyl methacrylate (hereinafter abbreviated as BzMA) 16.2 parts, 22.5 parts of methacrylic acid (hereinafter abbreviated as MAA), 0.75 part of diphenylmethane (hereinafter abbreviated as DPM) And polymerized at 40 ° C. for 7 hours while flowing nitrogen to obtain a polymer block solution of A. The polymerization rate calculated from the solid content of the obtained polymer block solution was 87.2%. Moreover, when the molecular weight was measured by GPC, Mn was 5,300, PDI was 1.31, and peak top molecular weight was 7,100. Moreover, it was 62.7 mgKOH / g when the acid value was measured. The polymer block A is a polymer block having a carboxyl group derived from methacrylic acid.

  Next, in the polymer block solution of A obtained above, 13.5 parts of MMA, 48.7 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), and 0.5 part of V-70 were mixed. And polymerized for another 5 hours to form a polymer block of C. Next, the flow of nitrogen was stopped, and the mixture was heated to 80 ° C. to remove iodine as a terminal. After confirming that iodine was liberated by becoming a brown transparent liquid, 402 parts of PGMAc was added to obtain a solution of an AC block copolymer.

  This polymer solution had a solid content of 31.6%, and it was confirmed that the polymerization rate was almost 100%. Mn was 7,000, PDI was 1.35, and the peak top molecular weight was 10,200. It was considered that the block copolymer was formed from the fact that it was confirmed that the molecular weight was shifted to the higher molecular weight side than when the polymer block of A was formed. The molecular weight of the polymer block of C can be calculated as a value obtained by subtracting the polymer block of A from the molecular weight of the AC block copolymer, and was calculated as 1,700. Hereinafter, the molecular weight of the polymer block of C is calculated by this method. Moreover, it was 49.7 mgKOH / g when the acid value was measured.

  Furthermore, 25 g of carborane (Nippon EnviroChemicals) was added as activated carbon, stirred at room temperature for 12 hours to adsorb iodine, filtered through a filter to remove the activated carbon, and a lemon-colored transparent liquid Got. When the molecular weight was measured, Mn was 7,000, PDI was 1.34, the peak top molecular weight was 10,200, the acid value was 50.9 mgKOH / g, and the solid content was 31.1%. Further, in the measurement with an infrared spectrophotometer (hereinafter abbreviated as IR), no change in peak was observed, and it was confirmed that the polymer was not removed by activated carbon. The obtained AC block copolymer solution is referred to as P-1.

Next, 150 parts of P-1 was charged into a reactor similar to the above, and heated to 50 ° C. while flowing nitrogen. Then, 8.4 parts of 2-sulfobenzoic anhydride (hereinafter abbreviated as SBA) was added and reacted for 3.5 hours to obtain a polymer. When 1,800 cm ⁻¹ , which is the peak of carboxylic acid sulfonic acid anhydride, was confirmed by IR, it was not detected at all and it was confirmed that all reacted with hydroxyl groups. The elimination of the sulfonic acid carboxylic acid anhydride is known to cause a strong acid to be a free radical. In fact, it was confirmed that the peak of carboxylic acid did not increase in IR. The sulfonic acid cannot be confirmed in the peak. When the solid content of the obtained polymer was measured, it was 34.2%, and the molecular weight by GPC was Mn 4,700, PDI 1.37, peak top molecular weight 6,600, It has become smaller than the polymer. This is probably because the measurement was not possible due to column adsorption of sulfonic acid.

  Surprisingly, the polymer obtained was dissolved when added to water. Although the polymer (P-1) before the reaction was insoluble in water, it is considered that the hydrophilicity increased by introducing a large amount of sulfonic acid, and the polymer (P-1) was dissolved by introducing a highly polar group. As described above, sulfonic acid was introduced into an AC block copolymer of an A polymer block having a carboxyl group and a C polymer block having a hydroxyl group to obtain an AB block copolymer of the present invention. The acid value was 89.6 mgKOH / g. This is referred to as PSB-1.

[Synthesis Example 2]
In the same reactor as in Synthesis Example 1, 377 parts PGMAc, 4.5 parts iodine, 22.1 parts V-70, 97.2 parts MMA, 97.2 parts BMA, 48.6 EHMA Part, 48.6 parts of PME200, 24.3 parts of BzMA, 33.8 parts of MAA, and 0.75 parts of DPM, and polymerize at 40 ° C. for 7 hours while flowing nitrogen, and the solution of polymer block of A Got. The polymerization rate calculated from the solid content of the obtained polymer block solution was 90.1%. Moreover, when the molecular weight was measured by GPC, Mn was 7,700, PDI was 1.34, and the peak top molecular weight was 10,100. The acid value was 63.2 mgKOH / g.

  Next, a mixture of 13.5 parts of MMA, 48.7 parts of HEMA, and 0.5 part of V-70 was added to the polymer block solution of A obtained above, and the mixture was further polymerized for 5 hours. A polymer block was formed. Subsequently, it heated at 80 degreeC, flowing air, and the iodine which is a terminal was desorbed. Thereafter, 646 parts of PGMAc was added to obtain an AC block copolymer solution. The solid content of this polymer solution was 31.7%, and it was confirmed that the polymerization rate was almost 100%. The Mn was 9,400, the PDI was 1.36, and the peak top molecular weight was 12,600. The molecular weight of the polymer block of C was calculated as 1,700. The acid value was 44.7 mgKOH / g.

  Furthermore, 25 g of carborane was added as activated carbon, and the mixture was stirred at room temperature for 12 hours to adsorb iodine, and then filtered through a filter to remove the activated carbon. When the molecular weight was measured, Mn was 9,300, PDI was 1.35, the peak top molecular weight was 12,400, the acid value was 48.1 mgKOH / g, and the solid content was 31.6%. The resulting AC block copolymer solution is referred to as P-2.

Next, 150 parts of P-2 was charged into the same reaction apparatus as described above, and heated to 50 ° C. while flowing nitrogen. Then, 5.7 parts of SBA was added and reacted for 3.5 hours. When 1,800 cm ⁻¹ , which is the peak of carboxylic acid sulfonic acid anhydride, was confirmed by IR, it was not detected at all and it was confirmed that all reacted with hydroxyl groups. The obtained AB block copolymer had a solid content of 34.7%, and the molecular weight by GPC was Mn of 5,200, PDI of 1.40, peak top molecular weight of 6,700, and acid value. Was 83.2 mg KOH / g. This is referred to as PSB-2.

[Synthesis Example 3]
In the same reactor as in Synthesis Example 1, 253 parts of PGMAc, 4.5 parts of iodine, 22.1 parts of V-70, 59.2 parts of MMA, 59.2 parts of BMA and 29.6 of EHMA Part, 29.6 parts of PME200, 14.8 parts of BzMA, 33.7 parts of MAA, and 0.75 parts of DPM, and polymerize at 40 ° C. for 7 hours while flowing nitrogen, and the solution of polymer block of A Got. The polymerization rate calculated from the solid content of the obtained polymer block solution was 91.1%. Moreover, when the molecular weight was measured by GPC, Mn was 5,000, PDI was 1.28, and the peak top molecular weight was 6,500. The acid value was 96.2 mgKOH / g.

  Next, a mixed solution of 13.5 parts of MMA, 48.7 parts of HEMA and 0.5 part of V-70 is added to the polymer block solution of A obtained above, and further polymerized for 5 hours to form a polymer block of C. did. Subsequently, it heated at 80 degreeC, flowing air, and the iodine which is a terminal was desorbed. 420 parts of PGMAc was added to obtain an AC block copolymer solution. The solid content of this polymer solution was 31.5%, and it was confirmed that the polymerization rate was almost 100%. Mn was 6,900, PDI was 1.30, and the peak top molecular weight was 9,000. The molecular weight of the C polymer block calculated from this was 1,900. Moreover, it was 77.3 mgKOH / g when the acid value was measured.

  Furthermore, 25 g of carborane was added as activated carbon, and the mixture was stirred at room temperature for 12 hours to adsorb iodine, and then filtered through a filter to remove the activated carbon. When molecular weight was measured, Mn was 6,800, PDI was 1.30, and peak top molecular weight was 8,900. Moreover, the acid value was 77.0 mgKOH / g and solid content was 31.3%. The obtained AC block copolymer solution is referred to as P-3.

Next, 150 parts of P-3 was charged into the same reaction apparatus as described above, and heated to 50 ° C. while flowing nitrogen. Subsequently, 7.7 parts of SBA was added and reacted for 3.5 hours. When 1,800 cm ⁻¹ , which is the peak of carboxylic acid sulfonic acid anhydride, was confirmed by IR, it was not detected at all and it was confirmed that all reacted with hydroxyl groups. The solid content of the obtained AB block copolymer was measured to be 34.1%. The molecular weight by GPC was 4,300 for Mn, 1.37 for PDI, and 5,500 for the peak top molecular weight. It was. The acid value was 113.1 mgKOH / g. This is referred to as PSB-3.

[Synthesis Example 4]
In the same reactor as in Synthesis Example 1, 260 parts of PGMAc, 4.5 parts of iodine, 22.1 parts of V-70, 64.8 parts of MMA, 64.8 parts of BMA, 32.4 of EHMA Part, 32.4 parts of PME200, 16.2 parts of BzMA, 22.5 parts of MAA and 0.75 parts of DPM, and polymerizing at 40 ° C. for 7 hours while flowing nitrogen, the polymer block solution of A Obtained. The polymerization rate calculated from the solid content of the obtained polymer block solution was 87.1%. Moreover, when the molecular weight was measured by GPC, Mn was 5,300, PDI was 1.27, and the peak top molecular weight was 6,700. Moreover, it was 62.9 mgKOH / g when the acid value was measured.

  Next, 9.5 parts of MMA, 34.1 parts of HEMA, and 0.4 part of V-70 were added to the polymer block solution of A obtained above, and the mixture was further polymerized for 5 hours. A polymer block was formed. Subsequently, it heated at 80 degreeC, flowing air, and the iodine which is a terminal was desorbed. Thereafter, 395 parts of PGMAc was added to obtain an AC block copolymer solution. The solid content of this polymer was 31.2%, and it was confirmed that the polymerization rate was almost 100%. Moreover, Mn was 6,200, PDI was 1.30, and the peak top molecular weight was 8,000. The molecular weight of the polymer block of C was calculated as 900. The acid value was 60.3 mgKOH / g.

  Furthermore, 25 g of carborane was added as activated carbon, and the mixture was stirred at room temperature for 12 hours to adsorb iodine, and then filtered through a filter to remove the activated carbon. When the molecular weight was measured, Mn was 6,200, PDI was 1.30, and the peak top molecular weight was 8,100. Moreover, the acid value was 60.1 mgKOH / g and solid content was 31.3%. This AC block copolymer solution is referred to as P-4.

Next, 150 parts of P-4 was charged into the same reaction apparatus and heated to 50 ° C. while flowing nitrogen. Next, 6.0 parts of SBA was added and reacted for 3.5 hours. When 1,800 cm ⁻¹ , which is the peak of carboxylic acid sulfonic acid anhydride, was confirmed by IR, it was not detected at all and it was confirmed that all reacted with hydroxyl groups. The solid content of the obtained AB block copolymer was measured and found to be 33.5%. The molecular weight by GPC was 4,400 for Mn, 1.38 for PDI, and 5,600 for the peak top molecular weight. It was. The acid value was 83.4 mgKOH / g. This is referred to as PSB-4.

[Synthesis Example 5]
In the same reactor as in Synthesis Example 1, 242 parts of PGMAc, 4.5 parts of iodine, 22.1 parts of V-70, 74.8 parts of MMA, 74.8 parts of BMA, 42.4 parts of EHMA 22.5 parts of MAA and 0.75 parts of DPM were charged and polymerized at 40 ° C. for 7 hours while flowing nitrogen to obtain a polymer block solution of A. The polymerization rate calculated from the solid content of the obtained polymer block solution was 92.0%. When the molecular weight was measured by GPC, Mn was 4,900, PDI was 1.25, and the peak top molecular weight was 6,400. The acid value was measured and found to be 67.7 mgKOH / g.

  Next, a mixture of 13.5 parts of MMA, 48.7 parts of HEMA, and 0.5 part of V-70 was added to the polymer block solution of A obtained above, and the mixture was further polymerized for 5 hours. A polymer block was formed. Subsequently, it heated at 80 degreeC, flowing air, and the iodine which is a terminal was desorbed. 404 parts of PGMAc was added to obtain an AC block copolymer solution. The solid content of this polymer solution was 31.5%, and it was confirmed that the polymerization rate was almost 100%. The Mn was 8,000, the PDI was 1.28, and the peak top molecular weight was 10,400. The molecular weight of the C polymer block was calculated to be 1,600. The acid value was 74.1 mgKOH / g.

  Furthermore, 25 g of carborane was added as activated carbon, and the mixture was stirred at room temperature for 12 hours to adsorb iodine, and then filtered through a filter to remove the activated carbon. When the molecular weight was measured, Mn was 8,000, PDI was 1.28, and the peak top molecular weight was 10,200. The acid value was 74.2 mgKOH / g and the solid content was 31.3%. This block copolymer solution is referred to as P-5.

Next, 150 parts of P-5 was charged in the same reaction apparatus as described above, and heated to 50 ° C. while flowing nitrogen. Subsequently, 8.7 parts of SBA was added and reacted for 3.5 hours. When 1,800 cm ⁻¹ , which is the peak of carboxylic acid sulfonic acid anhydride, was confirmed by IR, it was not detected at all and it was confirmed that all reacted with hydroxyl groups. The solid content of the obtained AB block copolymer was measured and found to be 34.3%. The molecular weight by GPC was Mn of 4,600, PDI of 1.39, and peak top molecular weight of 5,900. It was. The acid value was 94.5 mgKOH / g. This is referred to as PSB-5.

[Reference Synthesis Example 1]
In a 1-liter separable flask equipped with a reflux tube, a gas introduction device, a thermometer, and a stirring device, 125 parts of PGMAc, 4.5 parts of iodine, 22.1 parts of V-70, 32.4 parts of MMA, Charge 32.4 parts of BMA, 16.2 parts of EHMA, 16.2 parts of PME200, 8.1 parts of BzMA, 11.3 parts of MAA, and 0.75 parts of DPM, 40 ° C. while flowing nitrogen. For 7 hours to obtain a polymer block solution of A. The polymerization rate calculated from the solid content of the obtained polymer block solution was 92.5%. Moreover, when molecular weight was measured by GPC, Mn was 2,400, PDI was 1.21, and peak top molecular weight was 3,000. The acid value was measured and found to be 63.0 mgKOH / g.

  Next, a mixture of 13.5 parts of MMA, 48.7 parts of HEMA, and 0.5 part of V-70 was added to the polymer block solution of A obtained above, and the mixture was further polymerized for 5 hours. A polymer block was formed. Subsequently, it heated at 80 degreeC, flowing air, and the iodine which is a terminal was desorbed. 292 parts of PGMAc was added to obtain a solution of the AC block copolymer. The solid content of this polymer solution was 31.5%. The Mn was 4,200, the PDI was 1.23, and the peak top molecular weight was 5,200. The molecular weight of the polymer block of C was calculated as 1,800. The acid value was 40.7 mgKOH / g.

  Furthermore, 25 g of carborane was added as activated carbon, and the mixture was stirred at room temperature for 12 hours to adsorb iodine and filtered through a filter to remove the activated carbon. When the molecular weight was measured, the Mn was 4,100, the PDI was 1.23, the peak top molecular weight was 5,200, the acid value was 40.1 mgKOH / g, and the solid content was 31.6%. This AC block copolymer solution is referred to as P-6.

Next, 150 parts of P-6 was charged into the same reaction apparatus as described above, and heated to 50 ° C. while flowing nitrogen. Subsequently, 13.3 parts of SBA was added and reacted for 3.5 hours. When 1,800 cm ⁻¹ , which is the peak of carboxylic acid sulfonic acid anhydride, was confirmed by IR, it was not detected at all and it was confirmed that all reacted with hydroxyl groups. The solid content of the obtained AB block copolymer was measured to be 34.4%. The molecular weight by GPC was 2,700 for Mn, 1.44 for PDI, and 3,900 for the peak top molecular weight. It was. The acid value was 103.0 mgKOH / g. This is referred to as HSB-1. This HSB-1 has a Mn value of 2,700, which is smaller than those obtained in Synthesis Examples 1 to 5, compared with Mn of 3,000 or more, particularly 4,000 or more.

[Reference Synthesis Example 2]
In the same reactor as in Synthesis Example 1, 260 parts of PGMAc, 4.5 parts of iodine, 22.1 parts of V-70, 64.8 parts of MMA, 64.8 parts of BMA, 32.4 of EHMA Part, PME200 32.4 parts, BzMA 16.2 parts, MAA 22.5 parts, DPM 0.75 parts, polymerized at 40 ° C. for 7 hours while flowing nitrogen, and a polymer block solution of A Got. The polymerization rate calculated from the solid content of the obtained polymer block solution was 88.4%. Moreover, when the molecular weight was measured by GPC, Mn was 5,000, PDI was 1.30, and the peak top molecular weight was 6,800. The acid value was measured and found to be 62.6 mgKOH / g.

  Next, a mixed solution of 27.0 parts of MMA, 97.4 parts of HEMA, and 1.0 part of V-70 was added to the polymer block solution of A obtained above, and the mixture was further polymerized for 5 hours. A polymer block was formed. Subsequently, it heated at 80 degreeC, flowing air, and the iodine which is a terminal was desorbed. 583 parts of PGMAc was added to obtain an AC block copolymer solution. This polymer solution had a solid content of 31.7%. Mn was 9,000, PDI 1.35, and the peak top molecular weight was 12,700. The molecular weight of the polymer block of C was calculated to be 4,000. Moreover, it was 45.6 mgKOH / g when the acid value was measured.

  Furthermore, 25 g of carborane was added as activated carbon, and the mixture was stirred at room temperature for 12 hours to adsorb iodine, and then filtered through a filter to remove the activated carbon. When the molecular weight was measured, Mn was 9,000, PDI was 1.35, and the peak top molecular weight was 12,400. The acid value was 45.2 mgKOH / g and the solid content was 31.6%. This solution of the AC block copolymer is referred to as P-7.

Next, 150 parts of P-7 was charged into the same reaction apparatus as described above, and heated to 50 ° C. while flowing nitrogen. Then, 17.1 parts of SBA was added and reacted for 3.5 hours. When 1,800 cm ⁻¹ , which is the peak of carboxylic acid sulfonic acid anhydride, was confirmed by IR, it was not detected at all and it was confirmed that all reacted with hydroxyl groups. When the solid content of the obtained AB block copolymer was measured, it was 36.5%, and the molecular weight by GPC was Mn of 5,200, PDI of 1.40, and peak top molecular weight of 6,700. It was. The acid value was 102.5 mgKOH / g. This is referred to as HSB-2. In the HSB-2, the molecular weight of the polymer block of C used for synthesis is 4,000, and the molecular weight of those used in Synthesis Examples 1 to 5 is 3,000 or less, particularly 2,000 or less. large.

  The compositions and physical properties of the polymers obtained in the respective synthesis examples are shown in Table 1 for Synthesis Examples 1 to 5 and in Table 2 for Reference Synthesis Examples 1 and 2.

[Synthesis Example 6]
In the same reactor as in Synthesis Example 1, 253 parts of PGMAc, 4.5 parts of iodine, and 13.4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) (hereinafter abbreviated as V-65) , 72.0 parts MMA, 72.0 parts BMA, 36.0 parts EHMA, 36.0 parts PME200, 18.0 parts BzMA, 0.75 parts DPM, Polymerization was carried out at 7 ° C. for 7 hours to obtain a polymer block solution of A. The polymerization rate calculated from the solid content of the polymer solution obtained above was 95.3%. Moreover, when the molecular weight was measured by GPC, Mn was 5,200, PDI was 1.25, and the peak top molecular weight was 6,500.

  Subsequently, a mixed solution of 13.5 parts of MMA, 48.7 parts of HEMA and 0.4 part of V-65 was added to the polymer block solution of A obtained above, and the mixture was further polymerized for 5 hours. The polymer block was formed. Subsequently, it heated at 80 degreeC, flowing air, and the iodine which is a terminal was desorbed. Thereafter, 438 parts of PGMAc was added to obtain an AC block copolymer solution. The solid content of this polymer solution was 31.1%, and it was confirmed that the polymerization rate was almost 100%. Moreover, Mn was 7,000, PDI was 1.28, and the peak top molecular weight was 8,900. The molecular weight of the polymer block of C was calculated as 1,800.

  Furthermore, 25 g of carborane was added as activated carbon, and the mixture was stirred at room temperature for 12 hours to adsorb iodine, and then filtered through a filter to remove the activated carbon. When the molecular weight was measured, Mn was 7,000, PDI was 1.28, and the peak top molecular weight was 9,000. The solid content was 31.2%. This solution of the AC block copolymer is referred to as P-8.

Next, 150 parts of P-8 was charged into the same reaction apparatus, and heated to 50 ° C. while flowing nitrogen. Next, 8.5 parts of SBA was added and reacted for 3.5 hours. When 1,800 cm ⁻¹ , which is the peak of carboxylic acid sulfonic acid anhydride, was confirmed by IR, it was not detected at all and it was confirmed that all reacted with hydroxyl groups. The obtained AB block copolymer had a solid content of 34.5%, and the molecular weight by GPC was 4,800 for Mn, 1.38 for PDI, and 6,600 for the peak top molecular weight. The acid value was 49.5 mgKOH / g. This is referred to as PSB-6.

[Synthesis Example 7] (Binder Synthesis 1)
In a 1-liter separable flask equipped with a reflux tube, a gas introduction device, a thermometer, and a stirring device, 253 parts of PGMAc, 4.5 parts of iodine, 22.1 parts of V-70, 59.2 parts of MMA, Charge 59.2 parts of BMA, 29.6 parts of EHMA, 29.6 parts of PME200, 14.8 parts of BzMA, 33.7 parts of MAA, and 0.75 parts of DPM, 40 ° C. while flowing nitrogen. Was polymerized for 9 hours to obtain a polymer solution. The polymerization rate calculated from the solid content of the polymer solution obtained above was 98.2%. Moreover, when the molecular weight was measured by GPC, Mn was 5,100, PDI was 1.27, and the peak top molecular weight was 6,400. The acid value was measured and found to be 96.6 mgKOH / g. Subsequently, the mixture was heated to 80 ° C. while flowing air to desorb iodine as a terminal. Thereafter, 275 parts of PGMAc was added to obtain a polymer solution.

  Furthermore, 25 g of carborane was added as activated carbon, and the mixture was stirred at room temperature for 12 hours to adsorb iodine, and then filtered through a filter to remove the activated carbon. When molecular weight was measured, Mn was 5,100, PDI was 1.27, and peak top molecular weight was 6,400. The acid value was 96.6 mgKOH / g, and the solid content was 31.6%. This polymer is referred to as BP-1.

[Synthesis Example 8] (Binder Synthesis 2)
In the same reactor as in Synthesis Example 6, 265 parts of PGMAc, 4.5 parts of iodine, 22.1 parts of V-70, 59.2 parts of MMA, 59.2 parts of BMA, 29.6 of EHMA Part, 29.6 parts of PME200, 14.8 parts of BzMA, 45.0 parts of MAA, and 0.75 parts of DPM were polymerized at 40 ° C. for 9 hours while flowing nitrogen to obtain a polymer solution. The polymerization rate calculated from the solid content of the polymer solution obtained above was 98.5%. When the molecular weight was measured by GPC, Mn was 4,800, PDI was 1.26, and the peak top molecular weight was 6,200. It was 123.3 mgKOH / g when the acid value was measured. Subsequently, the mixture was heated to 80 ° C. while flowing air to desorb iodine as a terminal. Thereafter, 289 parts of PGMAc was added to obtain a polymer solution.

  Furthermore, 25 g of carborane was added as activated carbon, and the mixture was stirred at room temperature for 12 hours to adsorb iodine, and then filtered through a filter to remove the activated carbon. When the molecular weight was measured, Mn was 4,700, PDI was 1.26, and the peak top molecular weight was 6,100. The acid value was 123.1 mgKOH / g, and the solid content was 31.6%. This polymer solution is referred to as P-9.

Next, 150 parts of this P-9 was charged in the same reaction apparatus, and heated to 70 ° C. while flowing air. Subsequently, 4.1 parts of glycidyl methacrylate (hereinafter abbreviated as GMA) and 1 part of triphenylphosphine as a catalyst were added and reacted for 5 hours. It was confirmed by IR that a peak derived from a hydroxyl group was 3,500 cm ⁻¹ and a peak derived from an unsaturated group was 1,650 cm ⁻¹ . When the solid content was measured and found to be 33.1%, it is considered that almost all GMA was added to the carboxyl group. The molecular weight by GPC was 5,900 for Mn, 1.45 for PDI, and 8,700 for the peak top molecular weight. The acid value was 78.3 mgKOH / g. This polymer is referred to as BP-2.

Examples 1 to 6: Pigment colorant composition
(A) Pigment Refinement Treatment PR254, PG58, PY138, PY150, PB15-6, and PV23 were prepared as color filter pigments and subjected to the refinement treatment according to the method described below.
100 parts of each pigment, 400 parts of sodium chloride, and 130 parts of diethylene glycol were charged into a kneader equipped with a pressure lid. Premixing was performed until a uniformly moist mass was formed in the kneader. The pressure lid was closed and kneading and grinding were performed for 7 hours while pressing the contents at a pressure of 6 kg / cm ² . The obtained ground product was put into 3,000 parts of 2% sulfuric acid and stirred for 1 hour. After filtering to remove sodium chloride and diethylene glycol, each was sufficiently washed with water, dried and pulverized to obtain each pigment powder. The average particle diameter of the obtained pigment powder was about 30 nm.

(B) Preparation of pigment colorant composition “Materials used” shown in Table 5 were blended in the amounts (parts) shown in Table 5 and stirred with a dissolver for 2 hours. After confirming the absence of the pigment mass, the pigment was dispersed using a horizontal media disperser to prepare a pigment colorant composition. “Synergist 1”, “Synergist 2”, and “Synergist 3” in Table 5 are pigment derivatives having an amino group, each represented by the following structure. The obtained pigment colorant composition was used as a “pigment dispersion” for each color of the pigment used.

  In addition, “acrylic resin” in Table 5 has a monomer composition of BzMA / MAA = 80/20, Mn by GPC measurement of 5,500, and PDI of 2.02. This “acrylic resin” was used as a PGMAc solution (solid content concentration: 30%).

  Table 6 shows the measurement results of the number average particle diameter of the pigment contained in the obtained pigment dispersion. Table 6 shows the measurement results of the initial viscosity of the pigment dispersion and the viscosity after standing at 45 ° C. for 3 days (after storage).

As shown in Table 6, the average particle diameters of the pigments contained in the pigment dispersions of the respective colors obtained in Examples 1 to 6 are all about 50 nm, and the refined pigment is sufficiently finely dispersed. Turned out to be. In addition, any of the pigment dispersions has an initial viscosity of 10 mPa · s or less, and it is clear that the change in viscosity is small when the initial viscosity and the viscosity after storage are compared. For this reason, the pigment dispersion was found to have sufficient stability.
On the other hand, when compared with Example 1, the red pigment dispersions obtained in Reference Examples 1 and 2 have a large average particle size, are not sufficiently finely dispersed, and greatly increase in viscosity after storage. As a result, it was found that the dispersion stability was insufficient. From the above, the AB block polymer used has a molecular weight of the polymer block of A that is too small as in Reference Example 1, or the molecular weight of the polymer block of C as in Reference Example 2 (molecular weight of the polymer block of B ) Is too large, it has been confirmed that it is difficult to achieve stable pigment dispersion without change over time.

(Examples 7 to 9: Pigment colorant composition for color filter)
(C) Preparation of pigment colorant composition for color filter The “materials used” shown in Table 7 are blended in the amounts (parts) shown in Table 7 and mixed thoroughly with a mixer, and then the colorant pigment colorant for each color filter. A composition (color resist) was obtained. The obtained color resist was used as a “pigment ink” for each color.

  The “photosensitive acrylic resin varnish” in Table 7 is a varnish containing an acrylic resin obtained by reacting glycidyl methacrylate with a BzMA / MAA copolymer. Mn of this acrylic resin was 6,000, PDI was 2.38, and the acid value was 110 mgKOH / g. “TMPTA” represents trimethylolpropane triacrylate, “HEMPA” represents 2-hydroxyethyl-2-methylpropionic acid, and “DEAP” represents 2,2-diethoxyacetophenone.

(D-1) Preparation of red, green and blue glass substrates A glass substrate treated with a silane coupling agent was set on a spin coater. The red pigment ink-1 obtained in Example 7 was spin coated on a glass substrate at 300 rpm for 5 seconds. After pre-baking at 80 ° C. for 10 minutes, exposure was performed with a light amount of 100 mJ / cm ² using an ultrahigh pressure mercury lamp to produce a red glass substrate. Similarly, a green glass substrate and a blue glass substrate were produced using the green pigment ink-1 obtained in Example 8 and the blue pigment ink-1 obtained in Example 9, respectively.

  Each of the obtained glass substrates (color glass substrates) of each color had excellent spectral curve characteristics and excellent fastness such as light resistance and heat resistance. In addition, all the color glass substrates were excellent in optical properties such as light transmittance and contrast ratio.

(Examples 10 to 15: pigment colorant composition for color filter)
A color filter pigment of each color in the same manner as in Example 7 except that BP-1 and -2 obtained in Synthesis Examples 7 and 8 were used instead of the photosensitive acrylic resin varnish used in Example 7, respectively. A colorant composition (color resist) was obtained. Table 8 shows the blending results.

(D-2) Preparation of red, green and blue glass substrates A glass substrate treated with a silane coupling agent was set on a spin coater. The red pigment inks-2 and 3 obtained in Examples 10 and 13 were spin-coated on a glass substrate at 300 rpm for 5 seconds. After pre-baking at 80 ° C. for 10 minutes, exposure was performed with a light amount of 100 mJ / cm ² using an ultrahigh pressure mercury lamp to produce a red glass substrate. Similarly, a green glass substrate and a blue glass substrate are manufactured using the green pigment inks-2 and 3 obtained in Examples 11 and 14 and the blue pigment inks 2 and 3 obtained in Examples 12 and 15, respectively. did.

  Each of the obtained glass substrates (color glass substrates) of each color had excellent spectral curve characteristics and excellent fastness such as light resistance and heat resistance. In addition, all the color glass substrates were excellent in optical properties such as light transmittance and contrast ratio. Even if BP-1 and -2 which are the dispersion resin of this invention are used, it is thought that compatibility with the pigment dispersant of this invention is favorable, and this dispersion resin is considered useful. From the above, it was found that the pigment inks obtained in Examples 10 to 15 are extremely useful as inks for forming the pixels of the color filter.

(Examples 16 to 24: alkali developability test)
A 0.1N tetramethylammonium hydroxide aqueous solution was spotted every 5 seconds on a color glass substrate manufactured using the pigment inks obtained in Examples 7 to 15, and “the exposed part of the coating film dissolved after several seconds. A development test was conducted.

(Comparative Examples 1 and 2)
(1) Instead of “PSB-5”, a polyester-based dispersant having no sulfonic acid group (condensate of polyε-caprolactone and polyethyleneimine, starting with 12-hydroxystearic acid, Mn: 12, 000, amine value: 12 mg KOH / g), and (2) in the same manner as in Example 1 except that monosulfonated diketopyrrolopyrrole was used instead of “synergist 1”. A red pigment dispersion was prepared. In addition, (1) The above-described polyester dispersant was used instead of “PSB-3”, and (2) Monosulfonated PY-138 was used instead of “Synergist 2”. A yellow pigment dispersion for comparison was prepared in the same manner as in Example 3.

  Using these prepared comparative pigment dispersions, a comparative red pigment ink and a yellow pigment ink were prepared in the same manner as in Example 7, and a comparative red color was prepared using these pigment inks. A glass substrate and a yellow glass substrate were produced.

Table 9 shows the alkali developability test results of Examples 16 to 24 and Comparative Examples 3 and 4.

After 10 seconds to 15 for the red glass substrate, 20 to 25 seconds for the green glass substrate, and 10 to 15 seconds for the blue glass substrate, the coating film of the exposed portion was dissolved. In any of Examples 16 to 24, no film-like residue was generated, and good developability was exhibited. Furthermore, when the edge part (edge) of the coating film which remained without melt | dissolving was observed with the microscope, it has confirmed respectively that it was sharp. That is, if the pigment inks obtained in Examples 16 to 24 are used, the development time can be shortened and the productivity can be improved.
Further, in Examples 19 to 24, the dispersion resin of the present invention is used, the composition is the same as that of the pigment dispersant, the compatibility is good, and the PDI is narrow and the molecular weight is uniform. From this, it is considered that the dissolution time was slightly faster.

  For the manufactured comparative red glass substrate and yellow glass substrate, it took 50 seconds or more to completely eliminate the exposed portion of the coating film. This is thought to be because the development time was long because the pigment dispersant cannot be alkali-developed. Further, in any glass substrate, the exposed portion of the coating film was detached in a film shape, and debris was generated. This is presumably because the pigment dispersant is not alkali-soluble. From the above, it was found that the coating film formed using the pigment dispersant of the present invention is excellent in developability.

(Example 25: Application to resin-treated pigment)
In a 2,000 mL glass beaker, 45 parts of PR254, 5 parts of Synergist-1 and 450 parts of ion-exchanged water used in Example 1 were put and peptized with a dissolver at 2,000 rpm for 30 minutes to obtain a red pigment slurry. .
In another 1,000 mL glass beaker, 43.5 parts of PSB-6 obtained in Synthesis Example 8 and 456.5 parts of ion-exchanged water were added to dissolve the resin. The sulfonic acid group in the B block has a strong affinity for water and dissolved even without neutralization with alkali. This resin solution was added to the red pigment slurry while stirring with a dissolver, and stirred at 2,000 rpm for 30 minutes to obtain an aqueous red dispersion-1.
The obtained aqueous red dispersion-1 was heated to 70 ° C. to aggregate the pigment particles, and then subjected to suction filtration while hot, and then washed three times with 1 L of ion-exchanged water to obtain a paste. This was dried with a dryer at 70 ° C. for 24 hours. When the weight of the obtained powder was weighed, it was almost the same as the theoretical amount calculated from the charged amount. From this, it was confirmed that almost all PSB-6 was adsorbed to the pigment, and it was not washed away even by washing with ion-exchanged water. Subsequently, the obtained powder was pulverized by a pulverizer and passed through 200 mesh to obtain a resin-treated red pigment-1.

(Example 26)
Resin-treated green pigment-1 was obtained in the same manner as in Example 25 except that PR254 of Example 25 was used in Example 2 and PG-58 was used instead of Synergist-2.

(Example 27)
Resin-treated blue pigment-1 was obtained in the same manner as in Example 25 except that PR254 of Example 25 was replaced with PB15-6 used in Example 5 and Synergist-1 was replaced with Synergist-3.

(Examples 28 to 30)
The resin-treated pigments obtained in Examples 25 to 27 were blended in the amounts (parts) shown in Table 10, and stirred with a dissolver for 2 hours. After confirming the absence of the pigment mass, the pigment was dispersed using a horizontal media disperser to prepare a pigment colorant composition. The “acrylic resin” in Table 10 was the same as that used in Examples 1 to 6 and Comparative Examples 1 and 2.

  Table 11 shows the measurement results of the number average particle diameter of the pigment contained in the obtained pigment dispersion. In addition, Table 11 shows the measurement results of the initial viscosity of the pigment dispersion and the viscosity after standing at 45 ° C. for 3 days (after storage).

  First, it was confirmed that when the resin-treated pigment obtained in the present invention was used, it was possible to sufficiently reduce the size without adding a dispersant during dispersion. In addition, as shown in Table 11, the average particle diameter of the pigments contained in the pigment dispersion liquids of the respective colors obtained in Examples 28 to 30 is 50 nm or less, and the refined pigment is sufficiently finely dispersed. Turned out to be. Further, any of the pigment dispersions had an initial viscosity of 10 mPa · s or less, and it was revealed that the change in viscosity was small when the initial viscosity and the viscosity after storage were compared. For this reason, the pigment dispersion was found to have sufficient stability.

(Examples 31 to 33: Pigment colorant composition for color filter)
Preparation of Color Filter Pigment Colorant Composition “Use Materials” shown in Table 12 are blended in the amounts (parts) shown in Table 12 and mixed thoroughly with a mixer, and each color filter pigment colorant composition ( Color resist) was obtained. The obtained color resist was used as a “pigment ink” for each color.

(D-3) Preparation of red, green and blue glass substrates A glass substrate treated with a silane coupling agent was set on a spin coater. The red pigment ink-4 obtained in Example 31 was spin-coated on a glass substrate at 300 rpm for 5 seconds. After pre-baking at 80 ° C. for 10 minutes, exposure was performed with a light amount of 100 mJ / cm ² using an ultrahigh pressure mercury lamp to produce a red glass substrate. Similarly, a green glass substrate and a blue glass substrate were produced using the green pigment ink-4 obtained in Example 32 and the blue pigment ink-4 obtained in Example 33, respectively.

  The obtained glass substrates (color glass substrates) for each color are not hue-adjusted, so they cannot be said to be reliable filter hues, but all have excellent spectral curve characteristics, light resistance, heat resistance, etc. Excellent robustness. In addition, all the color glass substrates were excellent in optical properties such as light transmittance and contrast ratio.

  Moreover, even if it pigment-treated using PSB-1-5 obtained by the synthesis examples 1-5, it turned out that the same result as mentioned above is obtained.

  The polymer provided by the present invention is an AB block copolymer comprising an A polymer block having an affinity for a solvent and a B polymer block containing a sulfonic acid group having an affinity for a pigment. Excellent pigment dispersibility as a pigment dispersant. Further, by using such a pigment dispersant, a pigment colorant composition having low viscosity and excellent long-term storage stability can be prepared. And since the pigment ink obtained using this pigment colorant composition is excellent in coating properties and developability, the optical properties such as fineness, color density, light transmittance, and contrast are improved. It is useful as a material for producing a color filter. In addition, the pixel display device including the color filter manufactured in this way is excellent in image performance such as definition, color density, light transmission, and contrast.

Claims (17)

A benzenesulfonic acid group in which 90% by mass or more is an AB block copolymer composed of a methacrylic acid-based monomer, and only one of the polymer blocks AB is formed with methacrylate as a constituent component. Has a structural moiety represented by the following formula 1 bonded through an ester bond:

  When the polymer block having the structural part represented by Formula 1 is B and the polymer block having no structural part represented by Formula 1 is A in the structure, the polymer block of A is carboxyl. 2. The sulfonic acid group-containing block copolymer according to claim 1, comprising at least a methacrylate having a group as a constituent component and having an acid value of 30 to 200 mg KOH / g. A polymer block of A that does not have a structural portion represented by the following formula 1 and does not have a hydroxyl group;
A step of synthesizing an AC block copolymer in which 90% by mass or more is composed of a methacrylic acid monomer from a polymer block of C having at least a hydroxyl group-containing methacrylate as a constituent component;
3. The step of synthesizing the AB block copolymer according to claim 1 or 2 by reacting the synthesized AC block copolymer with 2-sulfobenzoic anhydride represented by the following formula 2 with the hydroxyl group. A process for producing a sulfonic acid group-containing block copolymer.

  4. The method for producing a sulfonic acid group-containing block copolymer according to claim 3, wherein the polymer block A comprises at least a methacrylate having a carboxyl group as a constituent component and has an acid value of 30 to 200 mgKOH / g. The number average molecular weight of the polymer block of A is 3,000 to 20,000, and the molecular weight distribution (weight average molecular weight / number average molecular weight) is 1.6 or less,
The molecular weight of the polymer block C is 500 to 3,000,
The sulfonic acid according to claim 3 or 4, wherein the number average molecular weight of the AC block copolymer synthesized from these polymer blocks is 4,000 to 23,000, and the molecular weight distribution is 1.6 or less. A method for producing a group-containing block copolymer.   The method for producing a sulfonic acid group-containing block copolymer according to claim 4 or 5, wherein the methacrylate having a carboxyl group is methacrylic acid.   The sulfonic acid group-containing block copolymer according to any one of claims 3 to 6, wherein in the step of synthesizing the AC block copolymer, at least an iodine compound is used as a polymerization initiating compound, and a methacrylate monomer is subjected to living radical polymerization. Method.   Phosphorus halides, phosphorus compounds that are phosphite compounds and phosphinate compounds; nitrogen compounds that are imide compounds; oxygen compounds that are phenol compounds; diphenylmethane compounds and hydrocarbons that are cyclopentadiene compounds The method for producing a sulfonic acid group-containing block copolymer according to claim 7, wherein at least one selected from the group consisting of the following groups is used as a catalyst.   The method for producing a sulfonic acid group-containing block copolymer according to claim 7 or 8, wherein the synthesis temperature is 30 to 70 ° C.   A pigment dispersant characterized in that the main component is the sulfonic acid group-containing block copolymer according to claim 1 or 2.   A pigment colorant composition comprising the pigment dispersant according to claim 10 and a pigment having an average particle size of 10 to 150 nm.   The pigment colorant composition according to claim 11, further comprising a pigment derivative having a basic functional group.   A resin comprising 10 to 100 parts of the sulfonic acid group-containing block copolymer according to claim 1 or 5 and 5 to 100 parts of a pigment derivative having a basic functional group with respect to 100 parts of the pigment. Treated pigment composition.   The pigment is treated in a treatment solution containing the sulfonic acid group-containing block copolymer according to claim 1 or 2, a pigment derivative having a basic group, water and / or a polyhydric alcohol as essential components. A method for producing a resin-treated pigment composition.   A pigment colorant composition comprising the resin-treated pigment composition according to claim 13. Furthermore, comprising an alkali developable polymer,
The alkali-developable polymer does not have a structural portion represented by the following formula 1, and has a polymer block A having no hydroxyl group, and a polymer block having C having at least a hydroxyl group as a constituent component 90% by weight or more of an A-C block copolymer synthesized from a methacrylic acid monomer, or
The pigment coloring composition according to any one of claims 11, 12, and 15, which is an unsaturated bond-containing block copolymer obtained by reacting the AC block copolymer with a (meth) acrylate having a glycidyl group or an isocyanate group. object.

  A pigment colorant composition for a color filter, which is obtained by using the pigment colorant composition according to any one of claims 11 to 13 and claims 15 and 16.