CN105899717A

CN105899717A - Copolymerized aramid dope-dyed yarn and method for preparing same

Info

Publication number: CN105899717A
Application number: CN201480071976.6A
Authority: CN
Inventors: 李泛薰; 蔡宥利
Original assignee: Kolon Corp
Current assignee: Kolon Industries Inc; Kolon Corp
Priority date: 2013-12-30
Filing date: 2014-12-24
Publication date: 2016-08-24
Anticipated expiration: 2034-12-24
Also published as: JP2017504731A; BR112016015170B1; KR102070137B1; EP3091107A1; JP6185184B2; US20180195207A1; WO2015102297A1; BR112016015170A2; CN105899717B; KR20150079425A; EP3091107A4; EP3091107B1

Abstract

The present invention relates to a copolymerized aramid dope-dyed yarn and a method for preparing the same. When a copolymerized aramid yarn is prepared by adding terephthaloyl dichloride to an organic solvent in which an aromatic diamine having a cyano group is dissolved, followed by a reaction, to polymerize a polymerization solution containing a copolymerized aramid polymer, and then spinning and solidifying the polymerization solution, a copolymerized aramid dope-dyed yarn is prepared by adding a dye having a cation during the polymerization process of the polymerization solution containing the copolymerized aramid polymer. Deterioration in the polymerization degree of the copolymerized aramid polymer or deterioration in the dissolubility of the polymerization solution due to the addition of the dye to the polymerization solution can be effectively prevented. Further, according to the copolymerized aramid dope-dyed yarn and the method, when a copolymerized aramid polymer having a cyano(-CN) group and a dye having a cation are bonded by a hydrogen bond to form a liquid crystal during the polymerization process of the polymerization solution containing the copolymerized aramid polymer, the behavior together with a main chain of the copolymerized aramid polymer is possible, thereby enhancing the color strength, color fastness to light, and color fastness to washing of the copolymerized aramid doped-dyed yarn.

Description

Copolymer aramid solution dyeing yarn and preparation method thereof

Technical field

The present invention relates to a kind of copolymer aramid solution dyeing yarn and preparation method thereof, more particularly, to one Plant when utilizing spinning nozzle that the polymeric solution comprising copolymer aramid polymer carries out spinning by being polymerized In solution, mixing has the pigment of cation and has intensity of colour and the look of excellence without using sulfuric acid to prepare The method of the copolymer aramid solution dyeing yarn of fastness.

Background technology

Aromatic polyamide is commonly called aramid fiber, passes through amide groups (-CONH) including having wherein phenyl ring The p-aramid fiber of the structure that straight line connects and the meta virtue with the attachment structure different from described p-aramid fiber Synthetic fibre.

Described p-aramid fiber has characteristic such as high intensity, high resiliency and the lower shrinkage of excellence.Due to contraposition Aramid fiber has the Thin cable that sufficiently high intensity makes thickness prepared therefrom be about 5mm can promote two tons Vehicle, be therefore widely used in the various application of shellproof and aerospace advanced industry.

Additionally, aramid fiber meeting carbonization and blackening more than 500 DEG C, therefore in the field needing high-fire resistance energy Also focus is become.

Korean patent registration No. 10-0910537 that the preparation method of aramid fiber has had the applicant In illustrate fully.According to this registration patent, mixed by dissolving aromatic diamine preparation in polymer solvent Close solution, then by adding aromatic diacid in above-mentioned solution to prepare aramid fiber polymeric compound.Hereafter, It is dissolved in sulfuric acid solvent to prepare spinning solution by described aramid fiber polymeric compound, by this spinning solution spinning, Carry out the most successively solidifying, cleaning and drying process, be thus finally completed aramid fiber.

But, if preparing aramid fiber, the aramid fiber polymeric compound system of solid state according to above-mentioned operation Standby and it is dissolved in again to prepare spinning solution in sulfuric acid solvent, then it is carried out spinning.Cause This, manufacture process becomes complicated, harmful, and can cause the most durable due to the corrosion of equipment Property reduce problem.

Additionally, due to there is the aramid fiber polymeric compound of high chemical resistance for dissolving and remove after spinning Sulfuric acid solvent often result in environmental pollution, it suitably should be processed after usage.For processing The expense of this type of sulfuric acid consumed generally reduces the economic advantages of aramid fiber.

In order to solve the problems referred to above, Korean patent registration No. 10-171994 discloses one and directly utilizes copolymerization Aramid fiber polymeric solution as spinning solution because of the method preparing aramid fiber without sulfuric acid solvent.

More specifically, in above-mentioned routine techniques, aramid fiber is by joining it by paraphthaloyl chloride In be dissolved with in the organic solvent of p-phenylenediamine and cyano group p-phenylenediamine so that it is react with preparation comprise copolymerization The polymeric solution of aramid fiber polymeric compound, then carries out spinning to this polymeric solution and prepared by solidification.

But, described routine techniques brings following problem: although prepared copolymer aramid fibers has not The advantage using sulfuric acid solvent, but due to highly crystalline performance, there is the dyeability of deterioration.

In order to solve the problems referred to above, Korean patent registration No. 10-067338 discloses one and prepares copolymer aramid The method of fiber, when the method includes preparing copolymer aramid fibers, using polyvinylpyrrolidone as amorphous Property polymer joins in polymeric solution, and this copolymer aramid fibers is by joining it by paraphthaloyl chloride In be dissolved with in the organic solvent of p-phenylenediamine and cyano group p-phenylenediamine, make them react so that comprising The polymeric solution polymerization of copolymer aramid polymer, then, carries out spinning and solidification preparation to it.But, Although improve the dyeability of prepared copolymer aramid fibers, the method still relates to deteriorating polymeric solution Solubility and the problem of fastness of dyeing.

As another routine techniques, have been carried out the preparation method of a kind of copolymer aramid solution dyeing yarn, The method includes: when preparing copolymer aramid fibers, and adding will not be by the cyano group of hydrogen bond with copolymer aramid The specific pigment that (-CN) is bonded, does not the most comprise the pigment of cation, and this copolymer aramid fibers is by will be to benzene Dimethyl chloride is added thereto in the organic solvent being dissolved with p-phenylenediamine and cyano group p-phenylenediamine so that it is anti- Should so that comprise copolymer aramid polymer polymeric solution polymerization, then this polymeric solution is carried out spinning and Solidification preparation.But, the method brings the degree of polymerization of such as copolymer aramid polymer to reduce, polymeric solution Solubility reduce and many problems of color fastness deterioration of prepared solution dyeing yarn.

Summary of the invention

Technical problem

The copolymerization aromatics that it is an object of the present invention to provide a kind of intensity of colour with excellence and color fastness gathers Acid amides solution dyeing yarn and a kind of solubility in the degree of polymerization reduction with polymeric solution that are preventing copolymer aramid The method preparing this copolymer aramid solution dyeing yarn while reduction.

Technical scheme

To achieve these goals, the invention provides a kind of method for preparing copolymer aramid yarn, bag Include: when preparing copolymer aramid yarn, in the polymerization process of the polymeric solution containing copolymer aramid polymer Add content be copolymer aramid polymer weight 0.1 weight % (wt.%) to 5 weight % have sun from The pigment of son, this copolymer aramid yarn has the virtue of cyano group by paraphthaloyl chloride is added thereto dissolving In the organic solvent of fragrant race diamines so that it is reaction is so that the polymerization comprising copolymerization aramid polymer is molten Liquid is polymerized, and then this polymeric solution carries out spinning and solidification preparation.

Beneficial effect

According to the present invention, owing to joining in polymeric solution by pigment, copolymer aramid can be effectively prevented The degree of polymerization of polymer reduces or the solubility of polymeric solution reduces.

Additionally, according to the present invention, in comprising the polymerization process of polymeric solution of copolymer aramid polymer, The copolymer aramid polymer with cyano group (-CN) and the pigment with cation are by hydrogen bonding, and have The pigment of cation is had to be bonded by ionic bond with the cyano group (-CN) on the main chain being positioned at copolymer aramid polymer, And the line position common with main chain can be shown in the forming process of liquid crystal, thus improve described copolymerization Intensity of colour, color fastness to light and the color fastness to washing of aramid fiber solution dyeing yarn.

Detailed description of the invention

Hereinafter, will be described in the present invention.

The embodiment of invention described below is presented to assist in understanding this as illustrative embodiment Bright but be not specially limited claimed subject matter of the present invention.Additionally, those of ordinary skill in the art is come Say and be apparent that and can carry out various modifications and variations in the technical spirit of the present invention and scope.Therefore, The present invention includes the invention described in claim and all modifications in its equivalency range and modification.

First, in the present invention, inorganic salts are dissolved in organic solvent；Then it is added thereto to have The aromatic diamine of cyano group (CN-).

Wherein, the aromatic diamine described in cyano group (CN-) can include the mol ratio with 1:9 to 9:1 The p-phenylenediamine dissolved and the solution of cyano group p-phenylenediamine, or the solution of single cyano group-p-phenylenediamine.

Described organic solvent can include such as, METHYLPYRROLIDONE (NMP), N, N-dimethyl second Acid amides (DMAC), hexamethyl phosphoramide (HMPA), N, N, N ', N '-tetramethylurea (TMU), N, N-diformazan Base formamide (DMF) or their mixture.

Adding inorganic salts is the degree of polymerization in order to increase aromatic polyamide, and inorganic salts can include such as alkali Metal halide salt or alkaline earth metal halide salt, such as CaCl₂, LiCl, NaCl, KCl, LiBr and KBr, They can be individually or with more than two of which being added in combination.

Preferably, the addition of inorganic salts is the 2wt.% to 5wt.% of weight of described organic solvent.

Then, paraphthaloyl chloride join described in comprise the aromatic diamine with cyano group organic solvent In mole identical with the mole of the aromatic diamine with cyano group added and be dissolved in wherein. Copolymer aramid polymer is comprised with preparation additionally, added in described organic solvent by the pigment with cation Polymeric solution.

The described pigment with cation has following typical structure, but is not limited thereto.

There is azo alkaline as C.I. alkali blue 64, the C.I. of pigment precursor (a coloring matter base) Red 22.

C.I. alkali blue 64

The most alkaline red 22

There is azine and the azo compound C.I. basic black 2 as pigment precursor.

C.I. basic black 2

There is azine and the piperazine compound C.I. basic black 7 as pigment precursor.

C.I. basic black 7

There is piperazine as the C.I. alkali blue 10 of pigment precursor, C.I. alkali blue 12, C.I. Blue 74.

C.I. alkali blue 10

C.I. alkali blue 12

C.I. Blue 74

There is thiazine as the C.I. alkali blue 24 of pigment precursor, C.I. alkali blue 25.

C.I. alkali blue 24

C.I. alkali blue 25

There is anthraquinone as the C.I. alkali blue 47 of pigment precursor, C.I. alkali blue 22.

C.I. alkali blue 47

C.I. alkali blue 22

Have that bisazo is red 32 as the C.I. alkalescence of pigment precursor, C.I. alkali red 1:1 11.

The most alkaline red 32

C.I. alkali red 1:1 11

There is the phthalocyanine C.I. alkali blue 140 as pigment precursor.

C.I. alkali blue 140

Preferably, there is described in the weight that addition is copolymer aramid polymer of the pigment of cation 0.1wt.% to 5wt.%.If described addition is less than 0.1wt.%, intensity of colour is weak, and if addition surpasses Crossing 5wt.%, the physical property of fiber can deteriorate.

Then, the polymeric solution of above-mentioned preparation is directly being used as spinning solution and to pass through spinning nozzle After being extruded, fragrant to prepare thread copolymerization by the polymeric solution using coagulator solidification to be extruded Synthetic fibre solution dyeing yarn.

In the polymerization process of the described polymeric solution comprising copolymer aramid polymer, when introducing have cloudy from When the pigment of son replaces the pigment with cation, cyano group (-CN) has strong electronegativity, thus to having the moon The anion sulfo group of the pigment of ion shows repulsive force.Therefore, the pigment with anion can not deposit On polymer but discharge together with solvent, do not show face in coloring level in level of pollution Look and intensity of colour, color fastness to light and the color fastness to washing of copolymer aramid solution dyeing yarn is had the most bad Change.

The example of the described pigment with anion is as follows.

C.I. alkalescence acid blue 25

C.I. alkalescence azogeramine 38

C.I. alkalescence acid black 60

It is any that the copolymer aramid solution dyeing yarn of the present invention can include having above in the pigment of cation A kind of more than or two of which combination.

Described there is cation pigment can be have cation pigment, have cation dyestuff or The pigment with cation and the mixture of the dyestuff with cation.

Can be comprised by prepared according to the methods of the invention copolymer aramid solution dyeing yarn and there is cation Pigment, therefore there is the excellent intensity of colour of at least 50 and the excellent color fastness to light of 4 grades to 5 grades And color fastness to washing.Additionally, described copolymer aramid polymer does not shows the reduction of the degree of polymerization, therefore have There is the high intensity of 28g/d to 35g/d.

Hereinafter, the present invention will be more fully described with reference to embodiment and comparative example.

Embodiment 1

The CaCl of 3wt.% will be comprised₂METHYLPYRROLIDONE (NMP) organic solvent nitrogen injection atmosphere Under reactor in, introduce the p-phenylenediamine of 50mol% and the cyano group of 50mol% the most in the reactor P-phenylenediamine also dissolves to prepare mixed solution.

Then, in the reactor including described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. basic black 2 (relative to the weight of copolymer aramid polymer) of chlorine and 0.3wt.% comprises copolymerization virtue with preparation The polymeric solution of synthetic fibre polymer.

Hereafter, after being extruded by polymeric solution by spinning nozzle, air gap and coagulator order are by spinning Silk spinning head, thus form the multifilament that line density is 3,000 danier.The pressure of filament spinning component is 2,800psi And spinning speed is 600mpm (m/min).

Hereafter, cleaning multifilament, then the drying drum of the temperature by being set as 150 DEG C is dried and stretches institute The multifilament cleaned.The multifilament of drawn through Overheating Treatment and winding, thus prepares copolymer aramid at 250 DEG C Solution dyeing yarn.

The intensity of colour of copolymer aramid solution dyeing yarn prepared by evaluation, fast light and color fastness to washing, and its Result illustrates in Table 1.

Embodiment 2

The CaCl of 3wt.% will be comprised₂METHYLPYRROLIDONE (NMP) organic solvent nitrogen injection atmosphere Under reactor in, introduce the cyano group p-phenylenediamine of 100mol% the most in the reactor and dissolve with system Standby mixed solution.

Then, in the reactor including described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. alkali blue 22 (relative to the weight of copolymer aramid polymer) of chlorine and 1.5wt.% comprises copolymerization with preparation The polymeric solution of aramid fiber polymeric compound.

Embodiment 3

Then, in the reactor including described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. alkali blue 64 (relative to the weight of copolymer aramid polymer) of chlorine and 3wt.% comprises copolymerization virtue with preparation The polymeric solution of synthetic fibre polymer.

Embodiment 4

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% C.I. red 22 (relative to the weight of copolymer aramid polymer) of alkalescence of chlorine and 4.9wt.% comprise copolymerization with preparation The polymeric solution of aramid fiber polymeric compound.

Embodiment 5

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. basic black 7 (relative to the weight of copolymer aramid polymer) of chlorine and 0.3wt.% comprises copolymerization virtue with preparation The polymeric solution of synthetic fibre polymer.

Embodiment 6

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. Blue 74 (relative to the weight of copolymer aramid polymer) of chlorine and 1.5wt.% comprises copolymerization with preparation The polymeric solution of aramid fiber polymeric compound.

Embodiment 7

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. alkali blue 24 (relative to the weight of copolymer aramid polymer) of chlorine and 3wt.% comprises copolymerization virtue with preparation The polymeric solution of synthetic fibre polymer.

Embodiment 8

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. alkali blue 25 (relative to the weight of copolymer aramid polymer) of chlorine and 4.9wt.% comprises copolymerization with preparation The polymeric solution of aramid fiber polymeric compound.

Embodiment 9

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. alkali blue 47 (relative to the weight of copolymer aramid polymer) of chlorine and 1.5wt.% comprises copolymerization with preparation The polymeric solution of aramid fiber polymeric compound.

Embodiment 10

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% C.I. red 32 (relative to the weight of copolymer aramid polymer) of alkalescence of chlorine and 3wt.% comprise copolymerization virtue with preparation The polymeric solution of synthetic fibre polymer.

Embodiment 11

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. alkali red 1:1 11 (relative to the weight of copolymer aramid polymer) of chlorine and 4.9wt.% comprises copolymerization with preparation The polymeric solution of aramid fiber polymeric compound.

Embodiment 12

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. alkali blue 140 (relative to the weight of copolymer aramid polymer) of chlorine and 0.3wt.% comprises copolymerization with preparation The polymeric solution of aramid fiber polymeric compound.

Embodiment 13

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. alkali blue 10 (relative to the weight of copolymer aramid polymer) of chlorine and 0.3wt.% comprises copolymerization with preparation The polymeric solution of aramid fiber polymeric compound.

Embodiment 14

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. alkali blue 12 (relative to the weight of copolymer aramid polymer) of chlorine and 3wt.% comprises copolymerization virtue with preparation The polymeric solution of synthetic fibre polymer.

Comparative example 1

Then, add in the reactor comprising described mixed solution the paraphthaloyl chloride of 100mol% with Preparation comprises the polymeric solution of copolymer aramid polymer.

Hereafter, cleaning multifilament, then the drying drum of the temperature by being set as 150 DEG C is dried and stretches institute The multifilament cleaned.The multifilament of drawn through Overheating Treatment and winding, thus prepares copolymer aramid at 250 DEG C Fiber.

By adding the above-mentioned dye (C.I. of 0.2g in the distilled water of 100ml and the glacial acetic acid of 1.2ml Alkalescence red 22) prepare basic-dyeable fibre, the copolymer aramid fibers of 0.5g prepared as described above is injected and comprises this In the dye bath of basic-dyeable fibre, and dye 1 hour at 100 DEG C, then it be carried out and be dried.

The intensity of colour of the copolymer aramid dyed yarn prepared by evaluation, fast light and color fastness to washing, and its result Illustrate in Table 1.

Comparative example 2

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The polyvinyl pyridine (relative to the weight of copolymer aramid polymer) of chlorine and 57wt.% comprises copolymerization virtue with preparation The polymeric solution of synthetic fibre polymer.

Comparative example 3

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. acid blue 25 (relative to the weight of copolymer aramid polymer) of chlorine and 0.3wt.% comprises copolymerization with preparation The polymeric solution of aramid fiber polymeric compound.

Comparative example 4

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. azogeramine 38 (relative to the weight of copolymer aramid polymer) of chlorine and 2wt.% comprises copolymerization with preparation The polymeric solution of aramid fiber polymeric compound.

Comparative example 5

Then, in the reactor comprising described mixed solution, it is simultaneously introduced the paraphenylene terephthalamide of 100mol% The C.I. acid black 60 (relative to the weight of copolymer aramid polymer) of chlorine and 4wt.% comprises copolymerization virtue with preparation The polymeric solution of synthetic fibre polymer.

[table 1]

The intensity of colour and the color fastness that illustrate in table 1 above are evaluated by following method.

Intensity of colour

Intensity of colour determines by measuring color according to KS K 0205.More specifically, aramid fiber is intensive Be wound on the little card of a size of 7.5cm width and 6.5cm length, then utilize spectrophotometer (Konica-Minolta CM-3600d) measures the color of aramid fiber under d 65 illuminant with the visual angles of 10 degree. Herein, the value measured is the mean value that three values measured at diverse location calculate.

Blue tristimulus value(s)

Green tristimulus value(s)

Red tristimulus value(s)

λ: wavelength

K: absorption coefficient

S: scattering coefficient

R: reflectivity

Color fastness to light

Color fastness to light measures according to 206KS K 0700, and color changes based on utilizing spectrophotometer The mensuration of the color variation grades of KS K ISO 105-A05 determines.

Color fastness to washing

Color fastness to washing measures according to KS K ISO 105-C06, and the face of the textile material after testing Discoloration mensuration based on the color variation grades utilizing spectrophotometer KS K ISO 105-A05 determines.

Commercial Application

Copolymer aramid solution dyeing yarn according to the present invention can effectively serve as protective gloves or protection The raw material of clothes.

Claims

1. a copolymer aramid solution dyeing yarn, this copolymer aramid solution dyeing yarn is by by paraphenylene terephthalamide Chlorine is added thereto in the organic solvent dissolving the aromatic diamine with cyano group so that it is reaction is so that comprising The polymeric solution polymerization of copolymer aramid polymer, then, carries out spinning and solidification is made this polymeric solution It is standby,

Wherein, described yarn comprises the pigment with cation, thus has the intensity of colour of more than 50.

2. yarn as claimed in claim 1, wherein, described in there is cation the content of pigment be described The 0.1wt.% to 5wt.% of the weight of copolymer aramid polymer.

3. yarn as claimed in claim 1, wherein, the color fastness to light of described yarn is 4 grades to 5 grades.

4. yarn as claimed in claim 1, wherein, the color fastness to washing of described yarn is 4 grades to 5 grades.

5. yarn as claimed in claim 1, wherein, described in have the pigment of cation be selected from C.I. alkali Property black 2, C.I. alkali blue 22, C.I. alkali blue 64, C.I. alkalescence is red 22, C.I. basic black 7, C.I. alkalescence Indigo plant 10, C.I. alkali blue 12, C.I. Blue 74, C.I. alkali blue 24, C.I. alkali blue 25, C.I. alkalescence Blue 47, C.I. alkalescence is red 32, at least one in C.I. alkali red 1:1 11 and C.I. alkali blue 140.

6. yarn as claimed in claim 1, wherein, described in have the pigment of cation be to have cation Pigment, there is the dyestuff of cation and there is the pigment of cation and there is dyestuff mixed of cation Compound.

7. for the method preparing copolymer aramid yarn, including: paraphthaloyl chloride is added thereto molten In the organic solvent of the aromatic diamine that solution has cyano group；It is made to react so that comprising copolymer aramid polymer Polymeric solution polymerization, then, this polymeric solution is carried out spinning and solidification,

Wherein, in the polymerization process of the described polymeric solution comprising copolymer aramid polymer, addition has sun The pigment of ion.

8. method as claimed in claim 7, wherein, described in there is cation the addition of pigment be The 0.1wt.% to 5wt.% of the weight of described copolymer aramid polymer.

9. method as claimed in claim 7, wherein, described in have the pigment of cation be selected from C.I. Basic black 2, C.I. alkali blue 22, C.I. alkali blue 64, C.I. alkalescence is red 22, C.I. basic black 7, C.I. Alkali blue 10, C.I. alkali blue 12, C.I. Blue 74, C.I. alkali blue 24, C.I. alkali blue 25, C.I. Alkali blue 47, C.I. alkalescence is red 32, at least one in C.I. alkali red 1:1 11 and C.I. alkali blue 140.

10. method as claimed in claim 7, wherein, described in have the pigment of cation be to have sun The pigment of ion, there is the dyestuff of cation and there is the pigment of cation and there is the dyestuff of cation Mixture.

11. methods as claimed in claim 7, wherein, described dissolving has cyano group in organic solvent Aromatic diamine by p-phenylenediamine and cyano group p-phenylenediamine that mol ratio is 1:9 to 9:1 have been dissolved in Prepared by machine solvent.

12. methods as claimed in claim 7, wherein, described dissolving has cyano group in organic solvent Aromatic diamine by cyano group p-phenylenediamine being separately dissolved in organic solvent preparation.

13. methods as claimed in claim 7, wherein, paraphthaloyl chloride with the virtue with cyano group The mole that the mole of fragrant race diamines is identical is added thereto dissolves the having of aromatic diamine with cyano group In machine solvent.