JPS5917744B2 - Water-soluble polymer dye with strong cationic group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a water-soluble polymer dye having a strong cationic group.

Generally, dyes are in an associated state in an aqueous solution, and this is particularly noticeable when the dye is in a concentrated solution.

Therefore, when a dye core is introduced into the side chain or main chain of a polymer, even if the starting polymer is sufficiently water-soluble, the resulting polymer dye may be mixed with the same or other polymers. As a result of association of the pigmented bone nuclei introduced into the chain, the water solubility tends to decrease significantly. Therefore, it is not possible to increase the introduction rate of pigmented bone nuclei. This invention was made based on the above circumstances, and by introducing a strong cationic group into the polymer chain, it prevents the association of pigment bone nuclei with each other and exhibits water solubility in a wide range of pH ranges. The purpose is to provide polymeric dyes.

In the broadest sense, the polymer dye of this invention has the general formula (in the above formula, R1 is a hydrocarbon group having a quaternary nitrogen cation in the side chain, R2 and R* are each a hydrocarbon group, and A is a hydrocarbon group). Pigmented bone core, and Z is the content of each unit and is expressed as x+y+ZlOO).

As mentioned above, R1 is a hydrocarbon group having a quaternary nitrogen cation in its side chain.

In this specification and claims, "hydrocarbon group" refers to pure hydrocarbon groups such as alkyl groups, aralkyl groups, phenyl groups, etc., and these hydrocarbon groups substituted with groups other than carbon and hydrogen, such as -0 group. This is a general expression of the group. A specific example of such R1 is CHCH2O
CHCH2 CHCH2 In these formulas, R3 is a hydrocarbon group and X is an anion.

This R1 is a group that imparts water solubility, and therefore R3
It is preferable that the group has a small bulk such as a methyl group. Further, X excludes ClO4 and is generally a halogen atom. R
2 is generally a hydrocarbon group derived from a group containing an active halogen or epoxy group that can react with active hydrogen in the dye.

To give a specific example of this R2, -CHCH2- -0C
HCH21I pigment bone core A is derived by reacting a pigment containing an active hydrogen-containing group such as an OH group, -NH2 group, =NH group, -COOH group, etc. with the halogen group or epoxy group.

These pigments include a wide range of pigments such as quinoneimine pigments (thiazine pigments, azine pigments), indigo pigments, xanthine pigments, as well as anthraquinone pigments, carbonium pigments, azo pigments, phthalocyanine pigments, and methine pigments. chosen from the group. Specific examples of pigmented bone nuclei derived from such pigments include R4, R5, R6, and R7.
, R8 and R9 are hydrogen or a hydrocarbon group, RlO is hydrogen or a halogen, Y is COOH or a salt thereof, z is or 0, . W is N(CH3)2 or X is as described above.

It doesn't matter if Z is O.

In particular, this invention provides strong cationic groups having the general formula (where R1 represents -CHCH2 or the content of R1 and R2 units, respectively, exceeds O, and x+y=100: X is a halogen). The present invention provides a water-soluble polymer dye having the following properties.

The water-soluble polymeric dye of the present invention is obtained by copolymerizing the unit having a strong cationic side group and the unit having an active halogen or active epoxy group together with an appropriate R* unit according to the case by a conventional method. It is obtained by first synthesizing a copolymer as a base material, and then reacting this copolymer with an excess amount of a dye having active hydrogen.

This reaction is a dehydrohalogenation reaction or a ring-opening reaction of an epoxy group. Generally, the difficulty level of the reaction between the active halogen group or epoxy group of the copolymer and the active hydrogen of the dye is as follows.

It is the quickest.

The preferable equivalent relationship between this active halogen group or active epoxy group and the active hydrogen of the dye is that the active hydrogen of the dye is 10
It is as if it exists in excess of more than twice as much. If the amount is less than 10 times, and the dye has two or more active hydrogens, the polymer chains will be crosslinked by the pigment bone core, and an insoluble portion will be generated.

The polymer dye of the present invention has a unit having the cationic side chain group and R2 unit into which the dye has been introduced in advance.The water-soluble polymer dye of the present invention described above has (1) good water solubility in all pH ranges (2) maintains water solubility even when the introduction rate of pigmented bone nuclei increases; (3) has good stability in a solution state, is particularly stable against light, and has a long lifespan. has.

Such polymeric dyes can be used as (1) components of dye photoredox photovoltaic cells, (2) ultraviolet or visible light filters, (3) pH or redox indicators, and (4) components of direct dyeing or similar dyeing methods. It can be applied to other uses.

EXAMPLES Examples of the present invention will be described below, but first, examples of synthesis of a copolymer, which is a basic material, will be described.

Synthesis Example 1 Obtained by copolymerizing 10 grams of p-chloromethylstyrene with 300 grams of pure trimethylamine at room temperature* in a pressure tube, optionally with R* units.

In the polymer dye of the present invention, the polymer chains are stretched out due to the repulsion between the strong cationic groups present, and as a result, collisions between the introduced dye bone nuclei are extremely unlikely to occur.

Therefore, there is little deterioration of the pigmented bone nucleus as shown in the following formula, and the life span is long even when irradiated with light in an aqueous solution state. The mixture was reacted for 24 hours under vacuum to obtain a white needle-like solid.

This was collected under drying conditions, and N-N-N-N-trimethyl (
p-vinylbenzyl) ammonium chloride (TBA)
was obtained with a yield of 98%. Dissolve 3.36 grams of this TBA and 0.43 grams of glycidyl methacrylate (GMA) in 50 ml of dimethylformamide (DMF), and add about 6.6X of azobisisobutyronitrile (AIBN) to the solution.
10-2 grams were added and radical copolymerization was carried out at 60° C. for 7 hours according to a conventional method. This reaction mixture was reprecipitated twice in ether to obtain a white copolymer (BGA) with a yield of 62%. A part of this BGA was dialyzed from an aqueous solution, dried, and then subjected to elemental analysis to obtain the following results. C (%)/N
(%): 12.505 C1: 14.50% From these results, it was found that BGA had the following structure.

The molecular weight was approximately 25,000. Synthesis Example 2 10 grams of commercially available polyepichlorohydrin having a degree of polymerization of about 170 was dispersed in about 120 ml of a 50% DMF' aqueous solution, 60 grams of trimethylamine was added thereto, the mixture was charged into a pressure tube, and the mixture was reacted at 120° C. for 48 hours.

The solvent was distilled off from this reaction mixture under reduced pressure, the residue was dried under reduced pressure, and then dissolved in methanol. This methanol solution was poured into ether twice, and the product was purified by reprecipitation and dried. This product will be referred to as QE. Elemental analysis C (
%)/N(%)-14.816, C1 (%)=32.
68, QE was found to have the following structure. <
Dissolve 9.1 grams of acrylic acid chloride and 5.6 grams of TBA in 50ml of DMF, and add AIBN6.6X to this.
2 grams of IO was added and radical copolymerization was carried out by a conventional method to obtain a DMF solution of the desired copolymer.

A portion of this copolymer was hydrolyzed, dialyzed, the solvent was distilled off under reduced pressure, and then dried. When this sample was measured by a light scattering method, it was found that Mw=15,000. Example
1 DM 15 grams of thionine (Th) and gram of BGAl
It was dissolved in Fl5Ome and reacted at 60°C for 10 hours.

After removing DMF under reduced pressure, the reaction mixture was dissolved in water. On the other hand, crush the sawami into small pieces and make a diameter 3 (V7l, length 2m)
The aqueous solution was packed in a column, and the aqueous solution was subjected to column fractionation. 1 per minute
When developed at a rate of 5 ml, an aqueous solution of the desired polymer dye was obtained in the second outflow section. After concentrating this aqueous solution and purifying it by dialysis, water was distilled off under reduced pressure and dried to obtain C (%)/N (%).
A polymer thionin of -7.731 having the following structure was obtained. The yield was 65%. Moreover, this polymeric thionin was blue in color and had a maximum absorption λMax of 605 nm. Example 2 The same procedure as in Example 1 was performed except that 18 grams of safranin (Saf) was used instead of thionine, and C.
A polymer safranin having the following structure and having a composition of (%)/N (%) = 7.601 was obtained.

The yield was 72%. Moreover, this polymer safranin was red in color and had a λMax of 508 nm. Example
3Th15.0 grams and QEO. 5 grams and DMF6
1 gram of triethylamine was added thereto, and the mixture was reacted at 60° C. for 48 hours.

Thereafter, perform the same operation as in Example 1 to obtain C(%)/N(
A polymeric thionin having the following structure and having a composition of %)=4.769 was obtained. The yield was 57%. Moreover, this polymeric thionin was blue in color and had a λMax of 603 nm. Example 4 Azure Bl8. instead of Th. The same operation as in Example 3 was performed except that O-gram was used, and C(%)/N(%
Polymer Azur B having the following ε structure and having a composition of )=4.763 was obtained.

The yield was 62%. Moreover, this polymer Azur B was blue-green in color and had a λMax of 615 nm. Example 5 Copolymer solution 5 of fluorescein JO ram and synthesis example 3
m1 was reacted in 50 ml of DMF in the same manner as in Example 1.

Claims (1)

[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R^1 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
- or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼; R^2 is ▲ There are ▲ mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼; A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ x and y indicate the content of R^1 units and R^2 units, respectively, and are strongly cationic, exceeding 0 and represented by x + y = 100; X is halogen) A water-soluble polymer dye with a group.