JP2005350648A - Crystalline aqueous coloring material and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-based aqueous coloring material capable of substantially withstanding use as a pigment and excellent in crystallinity and to provide a method for simply producing the aqueous coloring material. <P>SOLUTION: The crystalline aqueous coloring material is composed of a polyion complex in which an anion (Y) of a salt composed of a polymer (X) having a cationic hydrophilic segment (X1) and the anion (Y) having a fluorine atom, a nitrogen atom or an oxygen atom is ion-exchanged with a coloring compound (Z) having an anionic functional group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a crystalline water-based coloring material and a method for producing the same, and more particularly to a crystalline water-based coloring material useful for various paints such as water-based inks such as inkjet inks and gravure inks and automobile paints, and a method for producing the same. .

  There are many technologies that impart to pigments fastness, water resistance, and light resistance while maintaining the variety of colors of dyes, the vividness of colors, and the high saturation of water-based colorant dispersions. Appearance is awaited in the field. As means for solving this problem, there is a polyion complex (PIC) method. (See, for example, Non-Patent Document 1.) The polyion complex (PIC) method is an electrostatic process between a polar functional group of a dye that mainly causes dispersion and a polymer having a charged functional group. In addition, a strong attractive force is generated, and the dye molecule is solidified (pigmented) by the interaction of π-π stacking between aromatic rings of the dye molecule.

  For example, an anionic dye having a sulfonic acid group neutralized with an alkali metal or the like can be solidified using a salt of a cationic compound such as a polyamine compound. However, a practical production method is limited to a method in which anionic groups of dyes are ion-exchanged with various amine hydrochlorides to be solidified. However, the polyion complex (PIC) produced by this method has low crystallinity of the solid deposited from the dye, is substantially amorphous, and cannot be used as a pigment.

  The reason for this is that when chlorine ions are used as the counter anion of the polyamine, the anions move away from the polyamine all at once during the ion exchange. It is considered that hydrophobic aggregates are caused to form irregular aggregates.

C. F. J. et al. Faul, M.M. Antonietti, Chem. Eur. J. et al. , 2002, no. 12, p 2764-2768

  The problem to be solved by the present invention is to provide a dye-based crystalline aqueous coloring material excellent in crystallinity that can substantially withstand use as a pigment, and a simple method for producing the crystalline aqueous coloring material. There is.

  As a result of intensive studies, the present inventors made a salt of a hydrophilic cation polymer and an anion containing a fluorine atom, a nitrogen atom or an oxygen atom, and ion-exchanged these anion with another anionic coloring compound. It has been found that if a polyion complex is produced, a solid crystalline aqueous coloring material having high crystallinity can be produced, and the present invention has been completed.

  Further, as a result of intensive studies, the present inventors have found an aqueous coloring material in which an anion is substituted with an anion of a coloring compound in a salt comprising a hydrophilic cationic polymer and an anion having a fluorine atom, a nitrogen atom, or an oxygen atom. The present inventors have found that it has high crystallinity and have completed the present invention.

  That is, the present invention provides an anionic functional group in which the anion in a salt comprising a polymer (X) having a cationic hydrophilic segment (X1) and an anion (Y) having a fluorine atom, a nitrogen atom or an oxygen atom is present. There is provided a crystalline aqueous coloring material comprising a polyion complex ion-exchanged with a coloring compound (Z) having

  Further, a polymer (X) having a cationic hydrophilic segment (X1) having an anion (Y) having a fluorine atom, a nitrogen atom or an oxygen atom as a counter anion is mixed with water or a mixed solvent of water and a hydrophilic solvent. A coloring compound (Z) having an anionic functional group is added to an aqueous solution dissolved in the solution, and a fluorine atom or a nitrogen atom which is a counter anion of the polymer (X) having the cationic hydrophilic segment (X1) Or a method for producing a crystalline aqueous coloring material comprising ion-exchanging a part or all of an anion (Y) having an oxygen atom with a coloring compound (Z) having an anionic functional group.

  The crystalline water-based coloring material of the present invention has not only a similar coloring power compared to a dye in which molecules are isolated, but also has a significantly long durability time due to crystallization, water and organic matter. Color fastness to solvents can be provided. Therefore, it can be suitably used for water-based paints, printing water-based inks, paints and the like as well as ink-jet inks. Moreover, it can use suitably also for a photo-alignment film | membrane, a color filter etc. as a raw material relevant to an optical device.

  The crystalline water-based coloring material of the present invention is an anion in a salt comprising a cationic polymer (X) having a cationic hydrophilic segment (X1) and an anion (Y) having a fluorine atom, a nitrogen atom, or an oxygen atom. Is made of a polyion complex ion-exchanged with a coloring compound (Z) having an anionic functional group.

  It is essential that the cationic polymer (X) used in the present invention has a cationic hydrophilic segment (X1). Here, the cationic hydrophilic segment (X1) refers to a segment composed of a polymer skeleton in which structural units having a cationic group appear continuously concentrated. As such a cationic hydrophilic segment (X1), a protonated and cationized structural unit in a polymer having a structural unit that exhibits cationicity by protonation can be used, and an amine structure can be used. A segment in which the amine structure in the polymer having cation is cationized can be particularly preferably used.

  Examples of polymers having an amine structure constituting such cationic hydrophilic segment (X1) are polylysine, chitosan, polyallylamine, polydiallylamine, polydimethylaminoethyl (meth) acrylate, polydiethylaminoethyl (meth). Examples thereof include polyamines such as acrylate, polypropyleneimine, polystyreneimine, polyethyleneimine, polyallylamine, polyvinylamine, poly (4-vinylpyridine), poly (2-vinylpyridine), and copolymers thereof.

  In addition, a polymer having an amine structure does not necessarily have a structure in which only structural units having an amine structure are continuous. For example, poly (N-acylethyleneimine) partially hydrolyzed polyethyleneimine-poly (N-acylethyleneimine) random copolymer or block copolymer, (meth) acrylic acid amine monomer, Random copolymers of dimethylamino (meth) acrylate, 4-vinylpyridine and the like with other monomers such as methyl (meth) acrylate and hydroxyethyl (meth) acrylate are also cationic hydrophilic segments in the present invention. It can be used as (X1).

  In the cationic hydrophilic segment (X1), the weight of the structural unit having an amine structure is preferably 30% by weight or more, more preferably 50% by weight, and 70% by weight or more. Is most preferred. When the proportion of the structural unit having an amine structure is in the above range, the crystallinity of the obtained water-based coloring material is improved, and as a result, light resistance, water resistance, and color fastness can be provided.

  Furthermore, the polymer (X) may have a nonionic hydrophilic segment (X2) separately from the cationic hydrophilic segment (X1). In this way, by creating a structure in which the separate nonionic hydrophilic segment (X2) is chemically bonded to the cationic hydrophilic segment (X1), there is a possibility that the coloring material can be finely dispersed compared to other systems. There is. Examples of such nonionic hydrophilic segment (X2) include polyethers such as polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol random copolymer, and polyoxazolines such as polymethyloxazoline and polyethyloxazoline. Its copolymers, starches, polysaccharides such as cellulose and their alkyl-substituted products, polymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meta ) Poly (meth) acrylic esters such as acrylate, polyvinyl alcohols such as polyvinyl alcohol and vinyl alcohol-vinyl acetate copolymer, polydimethyl (meta Polyacrylamides such as polyacrylamide, polylactic acid, polyesters such as polyglycolic acid, poly aspartic acid derivatives, polypeptides such as polyglutamic acid derivatives and the like.

  The polymer (X) in the present invention is characterized in that the cationic hydrophilic segment (X1) which is an essential component is chemically bonded to the nonionic hydrophilic segment (X2) in some cases. There are various ways to combine these. Examples include block copolymers, multi-block copolymers, graft copolymers, star copolymers having a block copolymer structure in a branch, star copolymers having two or more types of branches, etc. Can be mentioned.

  In the case of having a nonionic hydrophilic segment (X2), the amount of the nonionic hydrophilic segment (X2) in the polymer (X) is within a range in which the obtained coloring material has good dispersibility and crystallinity. Any value can be used as long as it is present, but the mass of the nonionic hydrophilic segment (X2) is preferably 70% by mass or less with respect to the total mass of the polymer (X). When the amount of the nonionic hydrophilic segment (X2) in the polymer (X) is within this range, the crystalline aqueous coloring material obtained has high crystallinity, and when heated or in an organic solvent In addition to good dispersion stability, it is possible to maintain the water resistance and color fastness of the produced crystalline aqueous coloring material.

  In addition, the polymer (X) having a hydrophobic segment (X3) in addition to the hydrophilic portion of the cationic hydrophilic segment (X1) and the nonionic hydrophilic segment (X2) can also be preferably used. Since the polymer (X) having such a hydrophobic segment (X3) has both a hydrophilic portion and a hydrophobic portion, it tends to form a micelle structure in water. As a result, even when the crystallinity of the coloring compound (Z) having an anionic functional group is low, it is easy to form micelles incorporating this. As such a hydrophobic part, styrene such as styrene, α-methylstyrene, p-methylstyrene and derivatives thereof, phenyl (meth) acrylate, benzyl (meth) acrylate, β-phenethyl (meth) acrylate, α-phenethyl (meta ) (Meth) acrylic acid esters such as acrylate and octadecyl (meth) acrylate, oxazoline derivatives such as phenyloxazoline ring-opening polymer and benzyloxazoline ring-opening polymer, and the like.

  In the case of having the hydrophobic segment (X3), the amount of the hydrophobic segment (X3) in the polymer (X) is not particularly limited as long as the crystalline aqueous coloring material of the present invention can be obtained. The mass of the hydrophobic segment (X3) is preferably 50% by mass or less based on the total mass of the polymer (X). When the amount of the hydrophobic segment (X3) in the polymer (X) is within this range, the resulting crystalline aqueous coloring material can have good dispersibility.

  The weight average molecular weight (Mw) of the polymer (X) is preferably 3000 or more and 100,000 or less, and more preferably 8000 or more and 50000 or less. By using the polymer (X) having a weight average molecular weight within this range, the size of the obtained crystalline aqueous coloring material can be made suitable for use as a coloring material, Since a good crystalline aqueous coloring material can be obtained, it is excellent in light resistance and fastness after coloring.

  As the anion (Y) having a fluorine atom, nitrogen atom or oxygen atom used in the present invention, any water-soluble general anion can be used. Inorganic having oxygen atoms such as phosphate anion, diphosphate anion, phosphite anion, monohydrogen phosphate anion, dihydrogen phosphate anion, polyphosphate anion, carbonate anion, hydrogen carbonate anion, sulfite anion, sulfate anion Examples thereof include inorganic anions having fluorine atoms such as anions, fluorine anions, hexafluorosilicate anions, hexafluorophosphate anions, and inorganic anions having nitrogen atoms such as cyanate anions. In addition, as anions of metal oxides, boron, aluminum, silicon, titanium, vanadium, chromium, manganese, iron, cobalt, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, tin, antimony, barium, tantalum, Anions such as oxides of tungsten, rhenium, iridium, lead and the like can be mentioned.

  In addition, organic anions having an oxygen atom, a nitrogen atom, a fluorine atom, etc. can also be used. For example, acetate anion, propionate anion, butyrate anion, valerate anion, glycolate anion, lactate anion , Hydroxymethanesulfonate anion, methanesulfonate anion, trifluoromethanesulfonate anion, benzenesulfonate anion, toluenesulfonate anion, nitrobenzoate anion, cyanoacetate anion, oxalate anion, succinate anion, methylphosphonate anion, glycine Anion, alanine anion, polyphosphate anion, polybenzenesulfonate anion, sulfanilate anion, valproate anion and the like can be mentioned.

The anion (Y) as exemplified above is a counter anion of the cationic hydrophilic segment (X1). The counter anion as used herein means a pair formed with the cationic hydrophilic segment (X1) before introducing the coloring compound (Z) having an anionic functional group. By using the anion (Y), a hydrogen bond is formed between the anion (Y) and the cationic hydrophilic segment (X1) by the action of the oxygen atom, nitrogen atom, or fluorine atom of the anion (Y). It can be made. The following two effects can be given as the effect of this hydrogen bond.
(1) The coloring compound (Z) having an anionic functional group as a result of the rate at which the anion (Y) is desorbed from the cationic hydrophilic segment (X1) during the production of the crystalline aqueous coloring material of the present invention is slow. The crystal formation rate is suppressed, and the crystallinity is increased.
(2) As a result of being able to draw two or more cationic hydrophilic segments (X1) through an anion (Y), a complex of polymer (X) -coloring compound (Z) having an anionic functional group The crystallinity of can be improved. Due to these effects, as a result, the crystalline aqueous coloring material of the present invention has high crystallinity.

  Among these anion species containing a fluorine atom, a nitrogen atom, or an oxygen atom, an anion having an oxygen atom and a fluoride ion can be preferably used. In addition, when the dissociation constant of the first step of the conjugated acid is K, it is particularly preferable to select the acid having a value of −log K of −2 or more. By selecting such an anion, the polymer (X) can be provided with the necessary water solubility, particularly in a salt state.

  When such an anion is used, the interaction between the cation and the anion is relatively weak while hydrogen-bonding with the cationic hydrophilic segment (X1), and the salt is completely dissolved in water, or is heated and cooled. Some of them dissolve reversibly. Such an anion is more preferable as an anion (Y), and examples thereof include a fluorine ion, a carbonate ion, a hydrogen carbonate ion, a phosphate ion, a phosphate hydrogen ion, a phosphate dihydrogen ion, a diphosphate ion, A polyphosphate ion etc. can be mentioned.

  Among them, it has been found that salts such as diphosphate ions, fluorine ions, and polyphosphate ions have high solubility in water, and precipitation hardly occurs at a concentration of 1 to 10% by weight, for example. When a polyion complex is prepared using such a salt, the desorption rate of the anion (Y) becomes appropriate, and the crystallinity can be increased while incorporating a large amount of the coloring compound (Z). Is preferred.

  Next, the coloring compound (Z) having an anionic functional group is obtained from a general dye having a salt structure of an acidic functional group such as a sulfonate structure, a phosphate structure, or a carboxylate structure. Any anion can be used. Classifying this mainly includes acid dyes, acid mordant dyes, direct dyes, reactive dyes and the like. Examples of the dye that gives the coloring compound (Z) having an anionic functional group are the color index numbers: Acid Black 1, Acid Black 194, Acid Black 182, Acid Black 3, Food Black 2, Acid Blue 1, Acid Blue 15, Acid Blue 175, Acid Blue 182, Acid Blue 249, Acid Blue 29, Acid Blue 3, Acid Blue 5, Acid Blue 61, Acid Blue 7, Acid Blue 74, Acid Blue 80, Acid Blue 9, Acid Blue 93 , Direct Blue 1, Direct Blue 199, Acid Brown 126, Acid Brown 237, Acid Brown 289, Acid Brown 362, Acid Green 1, Acid Green 25, Acid Green 3, Acid Green 5, Acid Green 81, Acid Orange 10, Acid Orange 20, Acid Orange 24, Acid Orange 7, Acid Red 18, Acid Red 115, Acid Red 131, Acid Red 154, Acid Red 186, Acid Red 249 Acid Red 26, Acid Red 254, Acid Red 265, Acid Red 27, Acid Red 33, Acid Red 51, Acid Red 52, Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 94, Acid Red 95, Direct Red 28, Acid Violet 126, Acid Violet 43, Acid Violet 48, Acid Violet 66, Acid Violet 9 Acid Yellow 1, Acid Yellow 2, Acid Yellow 11, Acid Yellow 17, Acid Yellow 184, Acid Yellow 23, Acid Yellow 29, Acid Yellow 3, Acid Yellow 36, Acid Yellow 40, Acid Yellow 42, Acid Yellow 49, Acid Yellow 49 7, Acid Yellow 73, Acid Yellow 99, Direct Yellow 86, and the like.

  In addition, pigment molecules with functional groups that can easily generate negative ions such as sulfonic acid, such as tetrasodium salt of copper phthalocyanine tetrasulfonate and quinacridone sulfonate, and raw materials for some lake pigments Can be used even those with low hydrophilicity such as

  In the crystalline aqueous coloring material of the present invention, it is not necessary that all of the anions (Y) are ion-exchanged at the time of ion exchange. The anion (Y) having a fluorine atom, a nitrogen atom, or an oxygen atom and the coloring compound (Z) having the anionic functional group may comprise a polyion complex in which an ion pair is formed.

  When the crystalline aqueous coloring material of the present invention comprises a polymer (X), an anion (Y) containing a fluorine atom, a nitrogen atom or an oxygen atom, and an anionic coloring agent (Z), the anion ( When the amount of Y) is y (equivalent) and the amount of anion of the anionic colorant (Z) is z (equivalent), the ratio y / z is preferably in the range of 1/99 to 95/5. It is further desirable that the ratio is 1/99 to 30/70. Actually, it is easy to make the value of y / z larger than this, but as a result of the reduction of the ratio of components that substantially work for coloring, there is a possibility that coloring power may be weakened when used as a coloring material. Moreover, since the production process becomes troublesome and the production on an industrial scale may become complicated, it is particularly preferable to make it smaller than this range.

  In addition, the sum of the number of cationized basic groups and non-cationized basic groups in the polymer (X) is x (equivalent) of the anion (Y) having a fluorine atom, a nitrogen atom, or an oxygen atom. When the number of anionic groups is y (equivalent) and the number of anionic groups in the coloring compound (Z) having an anionic functional group is z (equivalent), the value of x / (y + z) is 0. Desirably, it is between 2 and 5, more preferably between 0.5 and 1.5. When the value is larger than this, the number of the coloring compound (Z) having an anionic functional group contained in the polymer becomes very small, resulting in faint coloring, or the obtained crystalline aqueous coloring The crystallinity of the material may be lowered, and the color fastness and light resistance when used as a coloring material may be lowered. On the other hand, if the value is smaller than this, the amount of the coloring compound (Z) having an anionic functional group is large, but the ratio of crystallization is low, and the color fastness and light resistance tend to be low. Therefore, it is desirable that x / (y + z) be a value between these.

Here, the ratio of the sizes of x, y, and z can be determined by titration, elemental analysis, a method such as making a solution as it is or decomposing it by adding acid or alkali and measuring ¹ H-NMR. .

  In the crystalline aqueous coloring material of the present invention, by using the anion (Y) as a counter anion, a crystalline aqueous coloring material having higher crystallinity can be obtained as compared with the case of using halogen or the like as a counter anion. Moreover, since the number average particle diameter can be controlled to a particle diameter of 150 nm or less, preferably 100 nm or less, the crystalline water-based coloring material having such a fine particle diameter is particularly excellent in dispersibility.

  Next, a method for producing the crystalline aqueous coloring material of the present invention will be described. The crystalline aqueous coloring material of the present invention is obtained by adding an anionic coloring agent (Z) to an aqueous solution obtained by dissolving the cationic polymer (X) in which the anion (Y) is a counter anion in an aqueous medium. The counter anion of X) can be produced by ion exchange with the anionic coloring compound (Z).

  These coloring materials can be produced, for example, by the following two-stage method. The first stage is the preparation of the polymer (X) in which the anion (Y) is a counter anion, and the second stage is the preparation of a crystalline aqueous coloring material having the coloring compound (Z) as a counter anion. .

First, the preparation of the polymer (X) having an anion (Y) having a fluorine atom, a nitrogen atom, or an oxygen atom in the first stage as a counter anion will be described. The polymer (X) having the anion (Y) used in the above production method as a counter anion can be produced, for example, using the method described below.
(1) Cationic (neutralization reaction) by reacting a hydrophilic polymer (A1) having a cationizable hydrophilic segment (for example, polyamine having a free amino group) with the acid of the anion (Y). How to do the
(2) Hydrophilic polymer (A2) having a hydrophilic segment that cannot be cationized (for example, poly (N-acylethyleneimine)) is hydrolyzed with the acid of the anion (Y) to be cationized and neutralized. A method for producing a salt which is a product,
(3) Hydrophilic polymer (A2) having a hydrophilic segment that cannot be cationized (eg, poly (N-acylethyleneimine)) is hydrolyzed with alkali to enable cationization, and then the anion (Y ) And neutralizing with acid to form a salt,
(4) Using a salt (A2) of a polymer (X) having an anion (B) having no fluorine atom, nitrogen atom or oxygen atom as a counter anion (for example, polyamine hydrogen halide salt), the anion ( A method in which B) is subjected to an ion exchange reaction with an anion (Y) having a fluorine atom, a nitrogen atom, or an oxygen atom.

In the method of (4) above, as a method of ion-exchanging an anion (B) having no fluorine atom, nitrogen atom or oxygen atom with an anion (Y) having a fluorine atom, nitrogen atom or oxygen atom,
(4-1) A polymer having a water-soluble salt of an anion (Y) having a fluorine atom, a nitrogen atom, or an oxygen atom, and an anion (B) having no fluorine atom, nitrogen atom, or oxygen atom as a counter anion (X ) And then removing the anion (B) by dialysis or filtration washing,
(4-2) A half solution of an aqueous solution of an anion (Y) having a fluorine atom, a nitrogen atom, or an oxygen atom and a polymer (X) having an anion (B) having no fluorine atom, a nitrogen atom, or an oxygen atom A method of ion exchange by contacting through a permeable membrane,
Etc. can be mentioned.

  In the reaction (4), the amount of the anion (Y) having a fluorine atom, nitrogen atom or oxygen atom is represented by y ′ (equivalent), and a counter anion having no fluorine atom, nitrogen atom or oxygen atom ( Adjust the amount of salt to be added in the range where the value of y ′ / x ′ is 1 to 3000 when the amount of the cationic group of the polymer (X) having B) is x ′ (equivalent). It is more preferable to add in the range of 1-30. In particular, the above method (4-1) requires a relatively small amount of a water-soluble salt of an anion (Y) having a fluorine atom, a nitrogen atom, or an oxygen atom, and is more preferable as an ion exchange system. Is.

  The above (1) to (4) exemplify elementary reactions, and a system in which these are caused simultaneously may be constructed. Examples thereof include a system in which a poly (alkyloxazoline) -polyethyleneimine random copolymer is reacted with a strong acid containing an oxygen atom such as nitric acid to cause hydrolysis and neutralization at the same time.

  Therefore, the polymer (X) exemplified above can be obtained from any hydrophilic polymer such as an ionic one and a nonionic one, and the ionic portion and the nonionic portion have a random structure or block. What has copolymerized with a structure may be used for a raw material. In the above (1) to (4), hydrolysis, neutralization, or ion exchange reaction can be performed in water or water and a hydrophilic solvent.

  In the production method of the present invention, the polymer (X) having an anion (Y) having a fluorine atom, a nitrogen atom, or an oxygen atom obtained by the above method as a counter anion is added to water, a hydrophilic solvent, or a mixed solvent thereof. Dissolve to make an aqueous solution.

  Examples of hydrophilic solvents that can be used here include aprotic polar solvents such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, hexamethylphosphorous triamide, dimethylimidazolidinone, and N-methylpyrrolidone. , Alcohols such as methanol, ethanol, normal propanol, isopropanol, ethylene glycol, propylene glycol, acetylenediethanol, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate, ethyl acetate, isopropyl acetate, diethylene glycol, triethylene glycol , Tetraethylene glycol, dimethoxyethane, diglyme, triglyme, tetraglyme, methyl cellosolve, etc. Such as ethers can be mentioned with.

When a mixed solvent is used as the solvent, the amount of the hydrophilic solvent in the mixed solvent is preferably 70% or less. If the amount of the hydrophilic solvent is larger than this, the waste is unnecessarily increased.
.

  Next, the preparation of a polyion complex color material having a dye as a counter anion in the second stage will be described. In the production method of the present invention, the coloring compound (Z) having an anionic functional group is added to the aqueous solution, and the anion having a fluorine atom, a nitrogen atom, or an oxygen atom, which is a counter anion of the polymer (X). A part of (Y) is ion-exchanged with the coloring compound (Z) having an anionic functional group. The coloring compound (Z) having an anionic functional group may be in the form of a solution or dispersion in water or a mixed solvent of water and a hydrophilic solvent, even if a solid salt is added. In order to cause smooth ion exchange, it is preferable to add the anionic colorant (Y) in a solution in an aqueous medium.

  The amount of (Z) added is a fluorine atom, a nitrogen atom or an oxygen atom in the polymer (X) in the polymer (X) having the anion (Y) having a fluorine atom, a nitrogen atom or an oxygen atom as a counter anion. When the number of anionic groups in the anion (Y) has y ″ (equivalent) and the number of anionic groups in the coloring compound (Z) having an anionic functional group is z ″ (equivalent), It is preferable to use such an amount that the ratio of equivalents represented by z ″ / y ″ is in the range of 0.5 to 50, preferably 1 to 30.

  The method for ion-exchanging a part of the anion (Y) having a fluorine atom, a nitrogen atom, or an oxygen atom, which is a counter anion of the polymer (X), with the coloring compound (Z) having an anionic functional group is as described above ( In the method 2), the counter anion (B) having no fluorine atom, nitrogen atom or oxygen atom is ion-exchanged with the anion (Y) having a fluorine atom, nitrogen atom or oxygen atom. I can do it.

  The crystalline aqueous coloring material obtained by the production method of the present invention can be dehydrated after washing by various methods to obtain a powdery one. First, in order to obtain a dye aggregate that has been completely dried by dehydration, it is often necessary to completely remove various salts or coloring compounds (Z) that are excessive or liberated. For this purpose, it is necessary to remove these in advance by techniques such as dialysis, centrifugation, filtration washing, and ultrafiltration. Furthermore, methods for actually drying to obtain a powdered coloring material include, for example, distillation under reduced pressure, distillation, azeotropic dehydration, freeze drying, spray drying and the like.

  The crystalline aqueous coloring material of the present invention comprises a cationic hydrophilic segment (X1) in the polymer (X) and an anionic group in the coloring compound (Z) having an anionic functional group that is mainly a dye. By electrostatic interaction, the coloring compound (Z) having an anionic functional group gathers in the vicinity of the polymer (X), and this is the π electron of the coloring compound (Z) molecule having an anionic functional group. It was crystallized by the interaction of to form a hydrophobic aggregate. When the polymer (X) has a nonionic hydrophilic segment (X2), the periphery of the aggregate is covered with the nonionic hydrophilic segment (X2), and crystallinity in the form of a polyion complex dispersion is obtained. A dispersion of an aqueous coloring material is easily obtained.

  Furthermore, when the polymer (X) has a hydrophobic segment (X3), there is an advantage that a micelle structure can be easily formed around the hydrophobic segment (X3). When a polymer having a hydrophobic segment (X3), a nonionic hydrophilic segment (X2), and a cationic hydrophilic segment (X1) is used for forming an aggregate of a coloring compound (Z) having an anionic functional group, Even when the crystalline form of the coloring compound (Z) molecule having an anionic functional group is not firm, the micelles of the aggregate can be easily formed.

  The micellar crystalline aqueous coloring material has good water dispersibility without using a dispersant because the periphery of the colored hydrophobic association portion is covered with a hydrophilic portion, and further, hydrophobic The meeting part exhibits good colorability. Moreover, in the hydrophobic association part, the coloring compound (Z) molecule having an anionic functional group and the cationic hydrophilic segment (X1) are ionically bonded to each other so that the coloring has a large number of anionic functional groups. The active compound (Z) molecules are concentrated along the polymer chain. In the concentrated state, strong π-π stacking occurs between the coloring compound (Z) molecules having an anionic functional group, and the coloring compound (Z) having an anionic functional group is not a molecular dispersion but constant. To form a regular assembly structure. Therefore, the obtained coloring material has excellent water resistance and weather resistance.

  The particle size of the micellar crystalline aqueous coloring material can be easily adjusted by adjusting the degree of polymerization of the polymer (X) used and the composition of the cationic hydrophilic segment (X1) in the polymer (X). The particle size tends to increase as the degree of polymerization increases or as the content of the cationic hydrophilic segment (X1) increases. The degree of polymerization and the composition of the cationic hydrophilic segment (X1) need to be appropriately adjusted depending on the type of polymer used, but the number average particle size of the micellar crystalline aqueous coloring material is about 20 nm to 5 μm. The range can be controlled.

  Such a micellar crystalline aqueous coloring material can also be made into a powdery coloring material that is easy to handle by evaporating water as a dispersion medium.

  As described above, the crystalline aqueous coloring material of the present invention has high crystallinity by taking the form of a polyion complex dispersion. Therefore, it has not only a similar coloring power but also a dye in which molecules are isolated. In addition, since crystallization occurs, it is possible to have a significantly long durability time and fastness to coloring with respect to water and organic solvents. In the case of a micellar shape, the particle size can be easily controlled, it has good dispersibility without using a dispersant, and is excellent in water resistance and weather resistance. Therefore, the crystalline water-based coloring material of the present invention can be suitably used for ink-jet inks, water-based paints, printing water-based inks, paints and the like. Moreover, it can use suitably also for a photo-alignment film | membrane, a color filter etc. as a raw material relevant to an optical device.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present embodiment does not limit the scope of the present invention to the embodiment. In the following examples, “parts” represents parts by weight.

[Synthesis Example 1] (Synthesis of polyethyleneimine hydrochloride)
In a container equipped with a reflux condenser, a thermometer, and a stirring rod, 15.68 parts of poly (2-ethyloxazoline) (manufactured by Aldrich, weight average molecular weight 50000) and 5N hydrochloric acid were charged and completely dissolved. Here, 5N hydrochloric acid is charged and reacted so that the number of moles of hydrogen chloride is 7.1 times the number of moles of N-propionylethyleneimine unit in poly (2-ethyloxazoline). It was. This was heated to 110 ° C. and stirred for 8 hours. The solution was clear at first but became cloudy after 8 hours. This was poured into 400 parts of acetone with vigorous stirring and precipitated. This was filtered and washed with acetone to obtain a white powder. The yield was almost quantitative.

[Synthesis Example 2] (Synthesis of polyethyloxazoline-polyethyleneimine hydrochloride random copolymer)
In a container equipped with a reflux condenser, a thermometer, and a stirring rod, 10 parts of poly (2-ethyloxazoline) (manufactured by Aldrich, weight average molecular weight 50000) and 300 parts of 5N hydrochloric acid were charged and completely dissolved. Here, 5N hydrochloric acid was charged so that the number of moles of hydrogen chloride was 3 times the number of moles of N-propionylethyleneimine units in poly (2-ethyloxazoline). This was heated to 80 ° C. and stirred for 12 hours. The solution was clear at first but became cloudy after 8 hours. This was poured into 400 parts of acetone with vigorous stirring and precipitated. This was filtered and washed with acetone to obtain a white powder. When the proton NMR spectrum of this was measured in heavy water, the molar content of the ethyleneimine hydrochloride unit relative to the sum of the ethyleneimine hydrochloride unit and the 2-ethyloxazoline unit was 59 mol%. The yield was almost quantitative.

[Synthesis Example 3] (Synthesis of polyethyleneimine)
10 parts of polyethyleneimine hydrochloride prepared in Synthesis Example 1 was dissolved in 100 parts of water, and a 1N aqueous solution of potassium hydroxide was added and stirred well. In addition, potassium hydroxide was calculated and added so that polyethyleneimine hydrochloride could be neutralized 100%. This was dialyzed for 24 hours in pure water using a dialysis membrane having a molecular weight cut off of 14,000. This was put into acetone, filtered and then dried to obtain a white powder. The yield was almost quantitative.

[Synthesis Example 4] (Polyethylene glycol (PEG) -polyethyleneimine (PEI) hydrochloride block polymer synthesis)

  Chloroform (20 parts) containing 7.15 parts of p-toluenesulfonic acid chloride in a mixed solution of 15.0 parts of methoxypolyethylene glycol [Mn = 2,000], 6.0 parts of pyridine, and 20 parts of chloroform under a nitrogen atmosphere. The solution was added dropwise for 30 minutes with ice cooling and stirring. Here, the molar ratio of methoxypolyethylene glycol, pyridine and p-toluenesulfonic acid chloride was 1: 10: 5. After completion of dropping, the mixture was further stirred at a bath temperature of 40 ° C. for 4 hours. After completion of the reaction, 40 parts of chloroform was added to dilute the reaction solution. Subsequently, the mixture was washed successively with 50 parts of a 5% hydrochloric acid aqueous solution, a saturated aqueous sodium hydrogen carbonate solution, and a saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained solid was washed several times with hexane, filtered, and dried under reduced pressure at 80 ° C. to obtain 15.1 parts of a tosylated product.

The results of 1H-NMR measurement (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained product are shown below.
1H-NMR (CDCl3) measurement results:
δ (ppm): 7.82 (d), 7.28 (d), 3.74-3.54 (bs), 3.41 (s), 2.40 (s)

  3.0 parts of a methoxypolyethylene glycol compound having a p-toluenesulfonyloxy group at the end, 6.8 parts of 2-methyloxazoline and 40 parts of N, N-dimethylacetamide synthesized above were added at 100 ° C. under a nitrogen atmosphere. Stir for 24 hours. At this time, the molar ratio of the added methoxypolyethylene glycol compound and 2-methyloxazoline was 1:50. To the obtained reaction mixture, 300 parts of an ethyl acetate / hexane mixed solution (volume ratio = 1: 2) was added, and after vigorous stirring at room temperature, the product solid was filtered. The solid was washed twice with 100 parts of a mixed solution of ethyl acetate / hexane (volume ratio = 1: 2) and then dried under reduced pressure to obtain 8.7 parts of a block polymer solid of polyethylene glycol and polymethyloxazoline. Obtained.

The results of 1H-NMR measurement (manufactured by JEOL Ltd., AL300, 300 MHz) of the obtained block polymer are shown below.
1H-NMR (CDCl3) measurement results:
δ (ppm): 7.71 (d), 7.18 (d), 3.50 to 3.30 (bs), 3.45 (s), 2.36 (s), 2.22 to 2. 08 (m)

  4.3 parts (0.69 mmol) of the polyethylene glycol and polymethyloxazoline block polymer obtained above were stirred at 90 ° C. for 6 hours in 14.0 parts of 5N aqueous hydrochloric acid to conduct a hydrolysis reaction. After standing to cool, the reaction mixture solution containing white precipitate formed over time is added to about 150 parts of acetone and stirred at room temperature for about 30 minutes, and then the solid product is filtered, washed twice with acetone, and dried under reduced pressure. As a result, 3.9 parts of a white solid was obtained. From the analysis by 1H-NMR, there was no side chain acetyl hydrogen (δ: 2.22 to 2.08 ppm) derived from poly (N-acetylethyleneimine) by hydrolysis reaction, and the obtained solid was obtained from polyethylene glycol and It is recognized as a double hydrophilic block polymer composed of polyethyleneimine. From the 1H-NMR spectrum, it was considered that the polyethylene glycol moiety was a 44-mer and the polyethyleneimine moiety was a 46-mer.

1H-NMR (manufactured by JEOL Ltd., AL300, 300 MHz) measurement results of the obtained block polymer are shown below.
1H-NMR (DMSO) measurement results:
δ (ppm): 3.49 (s), 3.31 to 3.19 (bs)

[Synthesis Example 5] (Synthesis of PEG-PEI hydrochloride block polymer)
In Example 4, the amount of 2-methyloxazoline to be reacted with methoxypolyethylene glycol having a p-toluenesulfonyloxy group was changed from 6.8 parts to 3.4 parts, and the polyethylene glycol-polyethyleneimine block copolymer was exactly the same. Synthesis of the coalesced was performed. 1H-NMR gave exactly the same results as in Example 4. From this result, it was considered that the polyethylene glycol moiety was a 44-mer and the polyethyleneimine moiety was a 23-mer.

[Synthesis Example 1A] Preparation of polyethyleneimine phosphate A solution of 79 parts of polyethyleneimine hydrochloride prepared in Synthesis Example 1 in 790 parts of water was dissolved in 19000 parts of trisodium phosphate decahydrate in 190000 parts of water. The solution was brought into contact with the solution through a dialysis membrane having a molecular weight cut-off of 14,000 and dialyzed for 24 hours. After 24 hours, polymer was observed to precipitate from the solution. This was further dialyzed with water for 24 hours and then dialyzed, washed, filtered and dried with methanol to obtain a white powder.

[Synthesis Examples 1B to 1H]
19000 parts of trisodium phosphate decahydrate used in Synthesis Example 1A were changed to Salt 1 and Amount 1, respectively, and the amount of water in which Salt 1 was dissolved was changed to Amount 1-2, and exactly the same procedure as in Synthesis Example 1A Each salt was synthesized by

[Synthesis Example 2A]
A solution prepared by dissolving 137 parts of the polyethyleneimine-polyethyloxazoline random copolymer prepared in Synthesis Example 2 in 1370 parts of water, an aqueous solution of 14000 parts of trisodium phosphate decahydrate and 140000 parts of water, and a molecular weight cutoff The contact was made through 14,000 dialysis membranes, and dialysis was performed for 24 hours. The polymer solution was initially homogeneous, but after dialysis, polymer precipitation from the solution was observed. This was further dialyzed with water for 24 hours and then dialyzed, washed, filtered and dried with methanol to obtain a white powder.

[Synthesis Examples 2B to 2F]
14,000 parts of trisodium phosphate decahydrate used in Synthesis Example 2A were changed to salt 2 and amount 2, respectively, and 140000 parts of water in which salt 2 was dissolved were changed to amount 2-2. Each salt was synthesized by simple procedure

[Synthesis Example 3A]
43 parts of polyethyleneimine synthesized in Synthesis Example 3 was suspended in 430 parts of water and mixed with 500 parts of 2N phosphoric acid while being uniformly dissolved at about 70 ° C. Excess salt was expelled to the outside through a dialysis membrane having a molecular weight cut off of 14,000 to prepare a resin salt. The polymer was precipitated, washed with methanol, filtered and dried to obtain a white powder.

[Synthesis Examples 3B to 3F]
430 parts of phosphoric acid used in Synthesis Example 3A was changed to Acid 3 and Amount 3, and the amount of water for diluting Acid 3 was changed to Amount 3-2 to prepare each salt in the same procedure as in Synthesis Example 3A. .

[Synthesis Example 4A]
5.55 parts of the polyethylene glycol-polyethyleneimine hydrochloride block copolymer synthesized in Synthesis Example 4 was dissolved in 30 parts of water, and this was dissolved in an aqueous solution consisting of 36.7 parts by weight of sodium diphosphate and 300 parts by weight of water. Added and stirred. Here, the molar ratio of the polyethyleneimine hydrochloride unit to sodium diphosphate was 1: 3. This was passed through a dialysis membrane having a molecular weight cut off of 3,500 and contacted with distilled water for 1 week, and then dried under reduced pressure to obtain a white powder of a block copolymer of polyethylene glycol-polyethyleneimine diphosphate.

[Synthesis Example 5A]
The polyethylene glycol-polyethyleneimine hydrochloride block copolymer obtained in Synthesis Example 5 (3.72 parts) was dissolved in 30 parts of water, and this was an aqueous solution comprising 36.7 parts by weight of sodium diphosphate and 300 parts by weight of water. And stirred. Here, the molar ratio of the polyethyleneimine hydrochloride unit to sodium diphosphate was 1: 3. This was passed through a dialysis membrane having a molecular weight cut off of 3,500 and contacted with distilled water for 1 week, and then dried under reduced pressure to obtain a white powder of a block copolymer of polyethylene glycol-polyethyleneimine diphosphate.

[Example 1A]
75 parts of polyethyleneimine phosphate synthesized in Synthesis Example 1A was dissolved in 750 parts of water, and C.I. I. Acid red 265 314.7 parts was mixed with a solution of 944.2 parts water. The mixed solution was brought into contact with water through a cellulose ester dialysis membrane having a molecular weight cut off of 14,000. This operation was continued until the water was not colored at all while changing the water. This was centrifuged and then filtered to separate the solid, which was then vacuum dried at room temperature to obtain a reddish brown crystalline aqueous colored material powder.

[Examples 1B to 3F]
The polymer used in Example 1A was changed to a polymer obtained from polyethyleneimine and the salt shown in the respective salt 4 as shown in Synthesis Examples 1B to 1F, 2A to 2F, 3A to 3D. The amount of water in which the polymer is dissolved is 4-2, C.I. I. A crystalline aqueous coloring material was obtained in exactly the same procedure as in Example 1A, except that Acid Red 265 was used in an amount of 4-3 and water in which the acid red 265 was dissolved was 4-4.

[Example 4A]
An aqueous solution obtained by dissolving 48.6 parts of the polyethylene glycol-polyethyleneimine diphosphate block copolymer obtained in Synthesis Example 4A in 3600 parts of water, and dissolving 187.0 parts of sodium copper phthalocyanine tetrasulfonate in 8500 parts of water. Was slowly dropped. The obtained dispersion was brought into contact with distilled water through a dialysis membrane having a molecular weight cut off of 30,000. This operation was continued until no coloration of water was seen while changing the water. The obtained polycation-dye complex was filtered to obtain a water-containing solid of a blue polycation-dye complex. Distilled water was added thereto, and the mixture was stirred and sonicated to obtain an aqueous dispersion of a polycation-dye complex. When the particle size of the obtained crystalline aqueous coloring material was measured by “Microtrac UPA150” manufactured by Leeds & Northrup, the number average particle size was 102 nm.

[Example 5A]
An aqueous solution in which 50.8 parts of the polyethylene glycol-polyethyleneimine diphosphate block copolymer obtained in Synthesis Example 5A are dissolved in 3320 parts of water, and 146.7 parts of copper phthalocyanine tetrasulfonate are dissolved in 4230 parts of water. Was slowly dropped. The obtained dispersion was brought into contact with distilled water through a dialysis membrane having a molecular weight cut off of 30,000. This operation was continued until no coloration of water was seen while changing the water. The obtained polycation-dye complex was filtered to obtain a water-containing solid of a blue polycation-dye complex. Distilled water was added thereto, and the mixture was stirred and sonicated to obtain an aqueous dispersion of a polycation-dye complex. When the particle size of the obtained crystalline aqueous coloring material was measured by “Microtrac UPA150” manufactured by Leeds & Northrup, the number average particle size was 115 nm.

[Comparative Example 1]
79.5 parts of polyethyleneimine hydrochloride obtained in Synthesis Example 1 was dissolved in 795 parts of water, and C.I. I. Acid Red 265 315.7 parts was mixed with a solution of 945 parts water. The mixed solution was brought into contact with water through a cellulose ester dialysis membrane having a molecular weight cut off of 14,000. This operation was continued until no coloration of water was seen while changing the water. The obtained polycation-dye complex was filtered, washed with water, and vacuum-dried to obtain a reddish brown polycation-dye complex powder.

[Comparative Example 2]
81 parts of the polyethyloxazoline-polyethyleneimine hydrochloride random copolymer obtained in Synthesis Example 2 was dissolved in 810 parts of water; I. A mixed solution of 317.8 parts of Acid Red 265 in 954 parts of water was mixed. The mixed solution was brought into contact with water through a cellulose ester dialysis membrane having a molecular weight cut off of 14,000. This operation was continued until no coloration of water was seen while changing the water. The obtained polycation-dye complex was filtered, washed with water, and vacuum-dried to obtain a reddish brown polycation-dye complex powder.

  Wide-angle X-ray scattering spectra of the crystalline aqueous coloring materials prepared in Examples 1A to 1F, 2A to 2F, and 3A to 3F and the polycation-dye complexes prepared in Comparative Examples 1 to 2 were measured to evaluate crystallinity. did. The evaluation results are as shown in Table 5. In Comparative Examples 1 and 2, polyethyleneimine hydrochloride-C.I. I. The crystallinity of the low-crystallinity polycation-dye complex powder prepared from Acid Red 265 is indicated by Δ, the crystallinity higher than this is indicated by ◯, and the crystallinity particularly high is indicated by ◎.

  As shown in Table 5, the polycation-dye complex used as a comparative example was amorphous with low crystallinity, but the crystalline aqueous coloring materials of Examples 1A to 3D were all excellent. It had a crystallinity.

  In addition, 3 parts of the crystalline aqueous coloring material prepared in Examples 1A to 1F, 2A to 2F, and 3A to 3F are sampled, and 100 parts of water is added and suspended therein, and this is dropped onto a glass plate. And let it dry naturally. This film had a red color and was recognized as a good color.

  On the other hand, when the polycation-dye complex obtained in Comparative Examples 1 and 2 was treated and observed in the same manner, a black film was formed and good color development could not be achieved.

From Examples 4A and 5A, the crystalline aqueous coloring material of the present invention had a small particle size and good dispersibility.

Claims (18)

Coloring compound in which the anion in a salt comprising a polymer (X) having a cationic hydrophilic segment (X1) and an anion (Y) having a fluorine atom, a nitrogen atom or an oxygen atom has an anionic functional group A crystalline aqueous coloring material comprising a polyion complex ion-exchanged with (Z). In the cationic hydrophilic segment (X1) in the polymer (X), an anion (Y) having a fluorine atom, a nitrogen atom or an oxygen atom, and a coloring compound (Z) having an anionic functional group are ionized. The crystalline aqueous coloring material of claim 1 bound. The number of moles of the anionic group of the anion (Y) having the fluorine atom, nitrogen atom, or oxygen atom ion-bonded to the cationic hydrophilic segment (X1) in the polymer (X) is y, and the anionic group The crystalline aqueous coloring material according to claim 2, wherein y / z is in the range of 1/99 to 95/5, where z is the number of moles of the anionic group of the coloring compound (Z) having a functional group. . The crystalline aqueous coloring material according to any one of claims 1 to 3, wherein the polymer (X) has a nonionic hydrophilic segment (X2). The crystalline aqueous coloring material according to any one of claims 1 to 4, wherein the polymer (X) has a hydrophobic segment (X3). The cationic hydrophilic segment (X1) in the polymer (X) is a segment composed of at least one selected from polyallylamine, polyethyleneimine, polyvinylamine, or polyvinylpyridine. The crystalline aqueous coloring material described in 1. The crystalline aqueous coloring material according to claim 1, wherein the anion (Y) is an anion having an oxygen atom. The anion having an oxygen atom is a nitrate anion, a phosphate anion, a phosphate hydrogen anion, a phosphate dihydrogen anion, a phosphate anion, a diphosphate anion, a carbonate anion, a bicarbonate anion, a sulfate anion or a sulfite anion. The crystalline aqueous coloring material according to claim 7, which is at least one selected from the group consisting of The crystalline aqueous coloring material according to claim 7, wherein the anion having an oxygen atom is an anion of a metal oxide. The crystalline aqueous coloring material according to any one of claims 1 to 9, wherein the polymer (X) has a weight average molecular weight (Mw) in the range of 3000 to 100,000. The number of cationic groups in the polymer (X) is x (equivalent), and the number of anionic groups in the anion (Y) having a fluorine atom, nitrogen atom, or oxygen atom is y (equivalent), and the anion. The molar ratio represented by x / (y + z) is in the range of 0.2-5, where z (equivalent) is the number of anionic groups in the coloring compound (Z) having a functional group. Item 11. The crystalline aqueous coloring material according to any one of Items 1 to 10. The crystalline aqueous coloring material according to any one of claims 1 to 11, having a number average particle diameter of 150 nm or less. A polymer (X) having a cationic hydrophilic segment (X1) having an anion (Y) having a fluorine atom, nitrogen atom, or oxygen atom as a counter anion is dissolved in water or a mixed solvent of water and a hydrophilic solvent. In the aqueous solution, a coloring compound (Z) having an anionic functional group is added, and a fluorine atom, a nitrogen atom, or a counter anion of the polymer (X) having the cationic hydrophilic segment (X1) A method for producing a crystalline aqueous coloring material, comprising ion-exchanging a part or all of an anion (Y) having an oxygen atom with a coloring compound (Z) having an anionic functional group. The method for producing a crystalline aqueous coloring material according to claim 13, wherein the polymer (X) is a polymer in which at least one selected from the group consisting of polyallylamine, polyethyleneimine, polyvinylpyridine, or polyvinylamine is cationized. The method for producing a crystalline aqueous coloring material according to claim 13 or 14, wherein the anion (Y) is an anion having an oxygen atom. The anion having an oxygen atom is a nitrate anion, a phosphate anion, a phosphate hydrogen anion, a phosphate dihydrogen anion, a phosphate anion, a diphosphate anion, a carbonate anion, a bicarbonate anion, a sulfate anion or a sulfite anion. The method for producing a crystalline aqueous coloring material according to claim 15, which is at least one selected from the group consisting of: The method for producing a crystalline aqueous coloring material according to claim 15, wherein the anion having an oxygen atom is a metal oxide. The method for producing a crystalline aqueous coloring material according to any one of claims 13 to 17, wherein the polymer (X) has a weight average molecular weight (Mw) in the range of 3000 to 100,000.