CN110028808A

CN110028808A - A kind of high preparation method for turning photoinitiator dye of degree of fixation

Info

Publication number: CN110028808A
Application number: CN201910362031.4A
Authority: CN
Inventors: 许博成
Original assignee: Individual
Current assignee: Individual
Priority date: 2019-04-30
Filing date: 2019-04-30
Publication date: 2019-07-19

Abstract

The present invention relates to a kind of high preparation methods for turning photoinitiator dye of degree of fixation, belong to technical field of dye.The present invention regard ester based quaternary ammonium salt softening agent and Dye Fixative S H-96 compounding as color fixing agent, organosilicon as film forming substance, color fixing agent TX as crosslinking agent, in conjunction with pigment (phthalocyanine blue, fluorescein, vat red etc.) prepare a kind of degree of fixation it is high turn photoinitiator dye；The washing fastness of dyed fabric not only can be improved as film forming substance in organosilicon, can also improve crock fastness, especially fastness to wet rubbing；Dye Fixative S H-96 is a polycationic fixing agent, this handles coloured fibre with them, not only there is strong binding force to the reactive dye (including the hydrolised dye on fiber) on fiber, to improving, the wet fastness of dyeing product cationic fixing agent simpler than structure is good, long-chain ester group hydrophobic part can form one layer of oiliness film in fiber surface, to generate soft effect, so that the fiber degree of fixation after dyeing is high and soft.

Description

A kind of high preparation method for turning photoinitiator dye of degree of fixation

Technical field

The present invention relates to a kind of high preparation methods for turning photoinitiator dye of degree of fixation, belong to technical field of dye.

Background technique

As luminescent material is in the extensive use of modern science and technology, application of the luminescent material in clothes is also paid close attention to, Dress ornament containing luminescent material starts to play the part of important in fields such as traffic, fire-fighting, antiultraviolet, dress designing, stage performances Role.On fabric, excitation light source or intelligence electricity can be passed through using with the addition of electroluminescent, photoexcitation characteristic luminescent material Sub- device control fabric color and brightness.Photic, electroluminescent fabric the special performance of intelligence is pushing the wearable display of intelligence Possess great potential in the realization and development process of apparatus field.But from the point of view of present Research, luminescent material is in clothes Using still in exploitation initial stage, not only product category negligible amounts, but also comfort level is also all to be improved.It uses now Small organic molecule fluorescent dye light emission luminance is well below metal complex luminescent material.And in the wearability of luminescent material In, luminescent fibre fabric or fluorescent powder, long afterglow comfort of fabric are substantially better than other application mode, but luminescent material how It is upper that contaminate, adhere to, being fixed on garment material be the problem of research at present.Print is passed through using metal complex luminescent material Luminous fabric prepared by the modes such as flower, original liquid coloring is increasingly becoming the direction of future studies development.

Capable of emitting fluorescence of the about 617nm with distinct characteristic of rare-earth europium ion in novel light conversion agent, colour purity height, The advantages that half-peak breadth is less than 10nm, and fluorescence lifetime is long.The ligand p-aminobenzoic acid of selection is that synthesis is medical important with dyestuff Intermediate can form complex with many metal ions.Carboxylic acid is multi-functional ligand, has monodentate, chelates diversified forms Bridging ability.It is link base in dye field amino, is connect by diazonium reactant salt with active group.Cyanuric Chloride is usually as work Property dyestuff active group, under proper condition can with fiber-reactive formed Covalent bonding together.With the novel of a variety of groups Light conversion agent has ultraviolet light to be converted into red fluorescence, forms the multifrequency natures such as covalent bond, weaker water solubility with fabric.

In active dye printing processing, to ensure high washing fastness and reducing staining of the hydrolised dye to cotton fabric, one As select the reactive dye of high-dissolvability, low substantivity, but this is also dyestuff dye-uptake and the low reason of utilization rate, in order to promote It is contaminated on dyestuff, a kind of method is that a large amount of neutral electrolytes are added in dyeing；Another method is short liquor dyeing.But both Method all has some limitations.Dyeing is reduced at present to the mode of water resource ground contamination, is mainly contaminated by novel active Material molecular structure is modified, cellulose fibre is multi-functional handles, improves upper dye using the methods of solvent-recoverable dyeing, electrochemistry Rate reduces dyeing water pollution.

The definition of light conversion agent also prematurity now, ununified definition, name is roughly the same, it is applied to agricultural earliest It is that the high levels light beams such as the ultraviolet light of wave bands a variety of in sunlight or blue light can be converted into red by one kind in light conversion agent The film application auxiliary agent of light or sodium yellow.Generally, it is considered that light conversion agent is one kind using rare earth ion as center particle, Duo Zhongyou Machine object is the polynary cyclic structure organic matter that ligand complex is formed, and having can be by a variety of wave band ultraviolet lights, blue light and height Energy level light is converted to the ability of the low-lying levels light such as feux rouges, yellow light.Wherein as the rare earth ion of activator, there are europium (Eu), samarium (Sm) etc. a variety of lanthanide atoms allow to issue because lanthanide metal atom has the special ability of f-f orbital electron transition The characteristic spectrum of specific atoms has the function of ultraviolet turn of red, blue or green light.In addition, light conversion agent structure removes activator and matrix, Also there is the inert sensitizer of fluorescence with another kind, and use rare earth element as the sensitizer of light conversion agent knot, such as yttrium (Y) Sensitizer main function is enhancing fluorescence intensity and delay light decay and other effects.

China's research initial to light conversion agent is in agriculture field, and research report has every year later first appeared in nineteen ninety The research of agricultural light conversion agent and conversion film is reported.With the continuous development of society, light conversion agent turns increasingly by the reuse of people Photo etching all presents higher practical value in each field.Light conversion agent actually belongs to embedded photoluminescent material, is that a kind of performance is excellent Good, without any power supply energy self-luminescence material.Embedded photoluminescent material also obtains mature application, novel storage in weaving Light type luminescent material is to mix rare earth metal using alkali earth metal aluminate as matrix and other elements are closed through high temperature solid state reaction At.Printing pigment, luminescent fibre etc. are had been used at present.However light conversion agent in weaving using document report that is less, can finding Road is rarely seen.Not long ago Sinopec Group and Donghua University invented a kind of rareearth phototransformation non-woven fabric and its Preparation method, this non-woven cloth are mutually multiple by the high molecular materials such as polypropylene and rare earth organic light conversion agents and other effective auxiliary agents Match and manufactured functionalization turns light non-woven cloth, the ultraviolet light of 200 ~ 400nm can be absorbed, emit the feux rouges of 600 ~ 620nm, as Covering material improves 15 DEG C than plain polypropylene non-woven cloth heat insulating ability after sunlight irradiates 5min.With the continuous hair of society Exhibition, light conversion agent are especially arranged in UV resistance using upper increasingly by the reuse of people.

In recent years, luminous fabric becomes research hotspot, and luminous fabric mostly uses luminescent material to pass through stamp, original liquid coloring etc. It is prepared by mode.The novel photoinitiator dye that turns can prepare luminous fabric by way of dip dyeing in conjunction with fabric, make its intelligent wearing, The fields such as field relief, antiultraviolet, anti-counterfeiting for clothing have huge application value.

The novel fluorescence for turning the capable of emitting about 617nm of rare-earth europium ion in photoinitiator dye and there is distinct characteristic, colour purity The advantages that high, half-peak breadth is less than 10nm, and fluorescence lifetime is long.The ligand p-aminobenzoic acid of selection is the weight of synthesis medicine and dyestuff Intermediate is wanted, complex can be formed with many metal ions.Carboxylic acid is multi-functional ligand, has monodentate, chelating diversified forms Bridging ability.It is link base in dye field amino, is connect by diazonium reactant salt with active group.Cyanuric Chloride usually as The active group of reactive dye can form Covalent bonding together with fiber-reactive under proper condition.With the new of a variety of groups Type, which turns photoinitiator dye, to be had ultraviolet light to be converted into red fluorescence, forms the multifrequency natures such as covalent bond, weaker water solubility with fabric.Cause It is not high for solubility in water, in dyestuff low concentration, dye strength and fiber contacts can not be being promoted to a certain degree When, dyestuff is gradually adsorbed on fiber surface, but cannot move to fibrous inside, and the dye-uptake for causing aqueous solvent to dye is lower.Water Solvent dyeing degree of fixation is poor, the reason is that dyestuff only forms covalent bond with the dye seat of fiber surface, dyestuff is poor in water Solubility cause dyestuff that can not migrate to fibrous inside, and exist and be adsorbed on the dye that surface does not form covalent bond with fiber Material leads to falling off for during soaping dyestuff.As the dyestuff of fiber surface increases, the dyestuff to fall off after soaping can also increase It is more.Therefore it is directed to existing the problem of turning photoinitiator dye technology, it is high to develop a kind of dye-uptake, good color fastness, and environmentally protective The photoinitiator dye that turns be particularly important.

Summary of the invention

The technical problems to be solved by the invention: for turning, photoinitiator dye dye fixing rate is poor, causes in the process soaped The problem of falling off of middle dyestuff provides a kind of high preparation method for turning photoinitiator dye of degree of fixation.

In order to solve the above technical problems, the technical solution adopted by the present invention is that:

(1) ester based quaternary ammonium salt softening agent and deionized water are mixed, stir process is to get mixed liquor, and in mass ratio 1: 3 by fixation Agent SH-96 and mixed liquor mixing, after continuing 10~20min of stirring, are cooled to 30~40 DEG C to get color fixing agent；

(2) taking methyl p-aminobenzoate, dehydrated alcohol, mass fraction is 98% hydrazine hydrate, by methyl p-aminobenzoate and nothing Water-ethanol mixing, stir process is to get reaction solution A, and it is 98% hydrazine hydrate that mass fraction is added in reaction solution A, back flow reaction, Up to reaction solution B, it is dry 3~4h at 60~70 DEG C that reaction solution B, which is placed in temperature, is cooled to room temperature to get crude product；

It (3) is that 98% salicylide, crude product and dehydrated alcohol mix by triethylamine, mass fraction, back flow reaction is cooled to room temperature, and is used Dehydrated alcohol recrystallizes up to filler A；

(4) Cyanuric Chloride, filler A and tetrahydrofuran are mixed, after stir process, filters up to filter residue, filter residue is washed And be dried, it is cooled to room temperature up to presoma；

(5) organic siliconresin, presoma, color fixing agent, pigment, fatty alcohol polyoxyethylene ether silane type dispersing agent WA, color fixing agent are taken TX mixes organic siliconresin, presoma, pigment and fatty alcohol polyoxyethylene ether silane type dispersing agent WA, quick stir process, Up to matrix object, color fixing agent and color fixing agent TX are added in matrix object, continues 20~30min of stirring and turns to get degree of fixation is high Photoinitiator dye, the pigment are preferably phthalocyanine blue or fluorescein or vat red.

Stir process step described in step (1) are as follows: in mass ratio 1: 5 mixes ester based quaternary ammonium salt softening agent and deionized water It closes, is 70~80 DEG C in temperature, mixing speed is to stir 20~30min under 400~500r/min.

The ratio of methyl p-aminobenzoate, dehydrated alcohol, mass fraction between 98% hydrazine hydrate described in step (2) It is respectively as follows: according to parts by weight, weighs 2~5 parts of methyl p-aminobenzoates, 20~30 parts of dehydrated alcohols, 0.5~0.7 respectively Part mass fraction is 98% hydrazine hydrate.

Stir process step described in step (2) are as follows: mix methyl p-aminobenzoate and dehydrated alcohol, in stirring speed Degree is that 10~20min is stirred under 300~400r/min.

Back flow reaction step described in step (2) are as follows: it is 98% hydrazine hydrate that mass fraction, which is added, in reaction solution A, in temperature It is 6~8h of back flow reaction at 75~80 DEG C.

Back flow reaction step described in step (3) are as follows: in mass ratio 1: 2: 2: 20 by triethylamine, mass fraction be 98% water Poplar aldehyde, crude product and dehydrated alcohol mixing, 7~8h of back flow reaction at being 70~80 DEG C in temperature.

Stir process step described in step (4) are as follows: in mass ratio 3: 6: 100 by Cyanuric Chloride, filler A and tetrahydrofuran Mixing, in a nitrogen atmosphere, low whipping speed are that 8~9h is stirred under 500~600r/min.

Washing described in step (4) is simultaneously dried step are as follows: is washed with deionized filter residue 2~4 times, is placed in temperature To dry in 50~60 DEG C of baking ovens to constant weight.

Organic siliconresin described in step (5), presoma, color fixing agent, pigment, the dispersion of fatty alcohol polyoxyethylene ether silane type Ratio between agent WA, color fixing agent TX is respectively as follows: according to parts by weight, weighs 30~40 parts of organic siliconresins, 50~60 respectively Part presoma, 5~15 parts of color fixing agent, 50~60 parts of pigment, 1~10 part of fatty alcohol polyoxyethylene ether silane type dispersing agent WA, 1~ 5 parts of color fixing agent TX.

Quick stir process step described in step (5) are as follows: by organic siliconresin, presoma, pigment and fatty alcohol polyoxy Vinethene silane type dispersing agent WA mixing, low whipping speed are quickly to stir 10~20min under 800~1000r/min.

The present invention is compared with other methods, and advantageous effects are:

(1) present invention regard ester based quaternary ammonium salt softening agent and Dye Fixative S H-96 compounding as color fixing agent, and organosilicon is as film forming object Matter, color fixing agent TX prepare a kind of high turn of degree of fixation as crosslinking agent, in conjunction with pigment (phthalocyanine blue, fluorescein, vat red etc.) Photoinitiator dye；The washing fastness of dyed fabric not only can be improved as film forming substance in organosilicon, can also improve friction jail Degree, especially fastness to wet rubbing；Dye Fixative S H-96 is a polycationic fixing agent, this kind of cationic fixing agent molecular mass Greatly, there are multiple cationic bases in molecule, handle coloured fibre with them, not only to reactive dye (including the fiber on fiber On hydrolised dye) have strong binding force, and it is also strong to the adsorption capacity of fiber, compare structure to the wet fastness of dyeing product is improved Simple cationic fixing agent is good, and after ester based quaternary ammonium salt softening agent is adsorbed on fiber surface, long-chain ester group hydrophobic part can be Fiber surface forms one layer of oiliness film, so that soft effect is generated, so that the fiber degree of fixation after dyeing is high and soft；

(2) the color fixing agent TX in the present invention is as crosslinking agent, and color fixing agent TX is a kind of polyethers crosslinking color fixing agent, and there are two its tools Epoxy group can crosslink reaction with fiber, hydrolised dye, and anchor at them on fiber, so that colour fixation is significantly It improves；On the one hand film forming high-molecular compound passes through Coulomb attraction, hydrogen bond, covalent bond in conjunction with not fixed dyestuff, prevent They fall down when washing, and cause to fade；On the other hand, they improve interfibrous obvolvent after fabric surface film forming Power reduces frictional force (having lubricating action), and yarn can be prevented by frictionally damage, prevent the fibrous dust young pilose antler of coloring Got off by friction；Therefore, after they are coated on outside fiber, the effects of improving washing and crock fastness can be played significantly；

(3) chief active composition formula of the ester based quaternary ammonium salt as softening agent in the present invention, mainly by single, double and three esters mixed Object composition is closed, wherein by the most prominent with the softness of dibasic acid esters；Diester quaternary ammonium not only has softness, also quiet with resisting Electrically, shorten the functions such as drying time, be easy the fabric of washing smooth；Containing one or several length in the structure of softening agent Alkyl chain, for softening agent Molecular Adsorption in fiber surface, the substance of this backbone can assign textile with soft feel； In addition, containing groups such as the stronger epoxy group of some reactivities, hydroxyls in soft agent molecule, and can be with ionic forces, quiet Groups, these groups such as quaternary ammonium salt ion of the electric attraction in conjunction with fabric surface are combined with textile fiber, are made it have excellent Good softness, while these softening agents also have antistatic, waterproof, anti-recontamination, and it is equivalent to improve lubricity, tearing brute force Fruit.

Specific embodiment

In mass ratio 1: 5 mixes ester based quaternary ammonium salt softening agent and deionized water, is 70~80 DEG C in temperature, mixing speed Dye Fixative S H-96 and mixed liquor are mixed to get mixed liquor, in mass ratio 1: 3 to stir 20~30min under 400~500r/min It closes, after continuing 10~20min of stirring, is cooled to 30~40 DEG C to get color fixing agent；According to parts by weight, 2~5 parts are weighed respectively Methyl p-aminobenzoate, 20~30 parts of dehydrated alcohols, 0.5~0.7 part of mass fraction are 98% hydrazine hydrate, by p-aminophenyl first Sour methyl esters and dehydrated alcohol mixing, low whipping speed be under 300~400r/min 10~20min of stirring to get reaction solution A, It is 98% hydrazine hydrate that mass fraction is added in reaction solution A, at being 75~80 DEG C in temperature 6~8h of back flow reaction to get reaction solution B, It is dry 3~4h at 60~70 DEG C that reaction solution B, which is placed in temperature, is cooled to room temperature to get crude product；In mass ratio 1: 2: 2: 20 will Triethylamine, mass fraction be 98% salicylide, crude product and dehydrated alcohol mixing, temperature be 70~80 DEG C at back flow reaction 7~ 8h is cooled to room temperature, and is recrystallized with dehydrated alcohol up to filler A；In mass ratio 3: 6: 100 by Cyanuric Chloride, filler A and tetrahydro Furans mixing, in a nitrogen atmosphere, low whipping speed are to filter up to filter residue, use after stirring 8~9h under 500~600r/min Deionized water is washed filter residue 2~4 times, is placed in the baking oven that temperature is 50~60 DEG C and is dried to constant weight, is cooled to room temperature to obtain the final product Presoma；According to parts by weight, weigh respectively 30~40 parts of organic siliconresins, 50~60 parts of presomas, 5~15 parts of color fixing agent, 50~60 parts of pigment, 1~10 part of fatty alcohol polyoxyethylene ether silane type dispersing agent WA, 1~5 part of color fixing agent TX, by organosilicon tree Rouge, presoma, pigment and fatty alcohol polyoxyethylene ether silane type dispersing agent WA mixing, low whipping speed are 800~1000r/min Color fixing agent and color fixing agent TX is added to get matrix object in lower quickly 10~20min of stirring in matrix object, continue stirring 20~ 30min to get degree of fixation it is high turn photoinitiator dye, the pigment is preferably phthalocyanine blue or fluorescein or vat red.

In mass ratio 1: 5 mixes ester based quaternary ammonium salt softening agent and deionized water, is 70 DEG C in temperature, mixing speed is 20min is stirred under 400r/min to mix Dye Fixative S H-96 and mixed liquor to get mixed liquor, in mass ratio 1: 3, continues to stir After 10min, 30 DEG C are cooled to get color fixing agent；According to parts by weight, 2 parts of methyl p-aminobenzoates, 20 parts of nothings are weighed respectively Water-ethanol, 0.5 part of mass fraction are 98% hydrazine hydrate, methyl p-aminobenzoate and dehydrated alcohol are mixed, low whipping speed is 10min is stirred under 300r/min to get reaction solution A, it is 98% hydrazine hydrate that mass fraction is added in reaction solution A, is 75 in temperature For back flow reaction 6h to get reaction solution B, it is dry 3h at 60 DEG C that reaction solution B, which is placed in temperature, at DEG C, is cooled to room temperature to get thick Product；Triethylamine, mass fraction are 98% salicylide by mass ratio 1: 2: 2: 20, crude product and dehydrated alcohol mix, and are 70 in temperature Back flow reaction 7h at DEG C, is cooled to room temperature, and is recrystallized with dehydrated alcohol up to filler A；In mass ratio 3: 6: 100 by three polychlorostyrene Cyanogen, filler A and tetrahydrofuran mixing, in a nitrogen atmosphere, low whipping speed are to filter after stirring 8h under 500r/min up to filtering Slag is washed with deionized filter residue 2 times, is placed in the baking oven that temperature is 50 DEG C and dries to constant weight, is cooled to room temperature up to before Drive body；According to parts by weight, 30 parts of organic siliconresins, 50 parts of presomas, 5 parts of color fixing agent, 50 parts of pigment, 1 part of rouge are weighed respectively Fat alcohol polyoxyethylene ether silane type dispersing agent WA, 1 part of color fixing agent TX, by organic siliconresin, presoma, pigment and fatty alcohol polyoxy Vinethene silane type dispersing agent WA mixing, low whipping speed are quickly to stir 10min to get matrix object, in base under 800r/min Color fixing agent and color fixing agent TX are added in body object, continue to stir 20min to get degree of fixation it is high turn photoinitiator dye, the pigment is excellent It is selected as phthalocyanine blue or fluorescein or vat red.

In mass ratio 1: 5 mixes ester based quaternary ammonium salt softening agent and deionized water, is 75 DEG C in temperature, mixing speed is 25min is stirred under 450r/min to mix Dye Fixative S H-96 and mixed liquor to get mixed liquor, in mass ratio 1: 3, continues to stir After 15min, 35 DEG C are cooled to get color fixing agent；According to parts by weight, 4 parts of methyl p-aminobenzoates, 25 parts of nothings are weighed respectively Water-ethanol, 0.6 part of mass fraction are 98% hydrazine hydrate, methyl p-aminobenzoate and dehydrated alcohol are mixed, low whipping speed is 15min is stirred under 350r/min to get reaction solution A, it is 98% hydrazine hydrate that mass fraction is added in reaction solution A, is 78 in temperature For back flow reaction 7h to get reaction solution B, it is dry 3.5h at 65 DEG C that reaction solution B, which is placed in temperature, at DEG C, be cooled to room temperature to get Crude product；Triethylamine, mass fraction are that 98% salicylide, crude product and dehydrated alcohol mix by mass ratio 1: 2: 2: 20, are in temperature 7~8h of back flow reaction, is cooled to room temperature at 75 DEG C, is recrystallized with dehydrated alcohol up to filler A；In mass ratio 3: 6: 100 by three Polychlorostyrene cyanogen, filler A and tetrahydrofuran mixing, in a nitrogen atmosphere, low whipping speed are filtering after stirring 8.5h under 550r/min It up to filter residue, is washed with deionized filter residue 3 times, is placed in the baking oven that temperature is 55 DEG C and dries to constant weight, be cooled to room temperature Up to presoma；According to parts by weight, 35 parts of organic siliconresins, 55 parts of presomas, 10 parts of color fixing agent, 55 parts of face are weighed respectively Material, 5 parts of fatty alcohol polyoxyethylene ether silane type dispersing agent WA, 3 parts of color fixing agent TX, by organic siliconresin, presoma, pigment and rouge Fat alcohol polyoxyethylene ether silane type dispersing agent WA mixing, low whipping speed are to stir 15min quickly under 900r/min to get matrix Color fixing agent and color fixing agent TX is added in object in matrix object, continue to stir 25min to get degree of fixation it is high turn photoinitiator dye, it is described Pigment is preferably phthalocyanine blue or fluorescein or vat red.

In mass ratio 1: 5 mixes ester based quaternary ammonium salt softening agent and deionized water, is 80 DEG C in temperature, mixing speed is 30min is stirred under 500r/min to mix Dye Fixative S H-96 and mixed liquor to get mixed liquor, in mass ratio 1: 3, continues to stir After 20min, 40 DEG C are cooled to get color fixing agent；According to parts by weight, 5 parts of methyl p-aminobenzoates, 30 parts of nothings are weighed respectively Water-ethanol, 0.7 part of mass fraction are 98% hydrazine hydrate, methyl p-aminobenzoate and dehydrated alcohol are mixed, low whipping speed is 20min is stirred under 400r/min to get reaction solution A, it is 98% hydrazine hydrate that mass fraction is added in reaction solution A, is 80 in temperature For back flow reaction 8h to get reaction solution B, it is dry 4h at 70 DEG C that reaction solution B, which is placed in temperature, at DEG C, is cooled to room temperature to get thick Product；Triethylamine, mass fraction are 98% salicylide by mass ratio 1: 2: 2: 20, crude product and dehydrated alcohol mix, and are 80 in temperature Back flow reaction 8h at DEG C, is cooled to room temperature, and is recrystallized with dehydrated alcohol up to filler A；In mass ratio 3: 6: 100 by three polychlorostyrene Cyanogen, filler A and tetrahydrofuran mixing, in a nitrogen atmosphere, low whipping speed are to filter after stirring 9h under 600r/min up to filtering Slag is washed with deionized filter residue 4 times, is placed in the baking oven that temperature is 60 DEG C and dries to constant weight, is cooled to room temperature up to before Drive body；According to parts by weight, 40 parts of organic siliconresins, 60 parts of presomas, 15 parts of color fixing agent, 60 parts of pigment, 10 parts are weighed respectively Fatty alcohol polyoxyethylene ether silane type dispersing agent WA, 5 parts of color fixing agent TX, by organic siliconresin, presoma, pigment and poly alkyl alcohol Ethylene oxide ether silane type dispersing agent WA mixing, low whipping speed are that 20min is quickly stirred under 1000r/min to get matrix object, Color fixing agent and color fixing agent TX are added in matrix object, continue to stir 30min to get degree of fixation it is high turn photoinitiator dye, the pigment Preferably phthalocyanine blue or fluorescein or vat red.

By degree of fixation prepared by the present invention it is high turn photoinitiator dye and it is commercially available commonly turn photoinitiator dye and detect, specific detection knot Fruit such as following table table 1:

Test method:

(1) colour fastness to rubbing is tested

The method that colour fastness to rubbing is tested in GB/T3920-2008 according to national standards is tested.

Fastness to soaping is tested the method that fastness to soaping is tested in GB/T3921-2008 according to national standards and is carried out Test.

Colour fasteness to sunlight is tested the method that colour fasteness to sunlight is tested in GB/T8427-2008 according to national standards and is carried out Test.

Ultraviolet permeability test is referring to GB/T18830-2009 " evaluation of ultraviolet resistance of fabric ", using ultraviolet light UV-R(280-400nm) light source and corresponding ultraviolet receiving sensor, between devices by cloth specimen folder, test cloth specimen blocks ultraviolet Light ability.

1 degree of fixation of table it is high turn photoinitiator dye performance characterization

What degree of fixation prepared by the present invention was high as shown in Table 1 turns photoinitiator dye, and crock fastness is soaped, light fastness reaches up to 5 grades 4 grades and 5 grades.Cloth specimen UPF numerical value reaches 37.6, has preferable uvioresistant ability.

Claims

1. a kind of high preparation method for turning photoinitiator dye of degree of fixation, it is characterised in that specific preparation step are as follows:

2. a kind of high preparation method for turning photoinitiator dye of degree of fixation according to claim 1, it is characterised in that: step (1) The stir process step are as follows: in mass ratio 1: 5 mixes ester based quaternary ammonium salt softening agent and deionized water, temperature be 70~ 80 DEG C, mixing speed is that 20~30min is stirred under 400~500r/min.

3. a kind of high preparation method for turning photoinitiator dye of degree of fixation according to claim 1, it is characterised in that: step (2) Ratio of the methyl p-aminobenzoate, dehydrated alcohol, mass fraction between 98% hydrazine hydrate is respectively as follows: by weight Number meter, weighing 2~5 parts of methyl p-aminobenzoates, 20~30 parts of dehydrated alcohols, 0.5~0.7 part of mass fraction respectively is 98% Hydrazine hydrate.

4. a kind of high preparation method for turning photoinitiator dye of degree of fixation according to claim 1, it is characterised in that: step (2) The stir process step are as follows: mix methyl p-aminobenzoate and dehydrated alcohol, low whipping speed is 300~400r/ 10~20min is stirred under min.

5. a kind of high preparation method for turning photoinitiator dye of degree of fixation according to claim 1, it is characterised in that: step (2) The back flow reaction step are as follows: in reaction solution A be added mass fraction be 98% hydrazine hydrate, temperature be 75~80 DEG C next time 6~8h of stream reaction.

6. a kind of high preparation method for turning photoinitiator dye of degree of fixation according to claim 1, it is characterised in that: step (3) The back flow reaction step are as follows: triethylamine, mass fraction are 98% salicylide, crude product and anhydrous by mass ratio 1: 2: 2: 20 Ethyl alcohol mixing, 7~8h of back flow reaction at being 70~80 DEG C in temperature.

7. a kind of high preparation method for turning photoinitiator dye of degree of fixation according to claim 1, it is characterised in that: step (4) The stir process step are as follows: in mass ratio 3: 6: 100 mix Cyanuric Chloride, filler A and tetrahydrofuran, in nitrogen atmosphere Under, low whipping speed is that 8~9h is stirred under 500~600r/min.

8. a kind of high preparation method for turning photoinitiator dye of degree of fixation according to claim 1, it is characterised in that: step (4) The washing is simultaneously dried step are as follows: is washed with deionized filter residue 2~4 times, is placed in the baking that temperature is 50~60 DEG C It dries in case to constant weight.

9. a kind of high preparation method for turning photoinitiator dye of degree of fixation according to claim 1, it is characterised in that: step (5) The organic siliconresin, presoma, color fixing agent, pigment, fatty alcohol polyoxyethylene ether silane type dispersing agent WA, color fixing agent TX it Between ratio be respectively as follows: according to parts by weight, weigh 30~40 parts of organic siliconresins, 50~60 parts of presomas, 5~15 parts respectively Color fixing agent, 50~60 parts of pigment, 1~10 part of fatty alcohol polyoxyethylene ether silane type dispersing agent WA, 1~5 part of color fixing agent TX.

10. a kind of high preparation method for turning photoinitiator dye of degree of fixation according to claim 1, it is characterised in that: step (5) The quick stir process step are as follows: disperse organic siliconresin, presoma, pigment and fatty alcohol polyoxyethylene ether silane type Agent WA mixing, low whipping speed are quickly to stir 10~20min under 800~1000r/min.