CN109403075A

CN109403075A - High firmness environmental protection thermal transfer printing technology

Info

Publication number: CN109403075A
Application number: CN201811287134.0A
Authority: CN
Inventors: 陈新玥; 马登云; 杨勇
Original assignee: Huangchuan Shengyu Garment Technology Co Ltd
Current assignee: Huangchuan Shengyu Garment Technology Co Ltd
Priority date: 2018-10-31
Filing date: 2018-10-31
Publication date: 2019-03-01

Abstract

The invention discloses a kind of high firmness environmental protection thermal transfer printing technologies.The high firmness environmental protection thermal transfer printing technology comprises the following steps that: I, design and printing pattern, and according to designed printed patterns, thermal transfer ink is printed on transfer paper by printing machine；Printed patterns on above-mentioned transfer paper are transferred on fabric by II, by conventional caloric transfer printing technology, and PRINTED FABRIC fabric is made；The thermal transfer ink by mass percentage, raw material include: 15-35% disperse dyes mill base, 20-40% emulsion polymerization, 0.2-1% surfactant, 20-40% hygroscopic agent, 0.01-0.5% preservative, 0.1-0.5%pH regulator, surplus be water.The present invention is able to achieve the clean manufacturing of heat transfer printing process, realize trade effluent zero-emission target, and printing effect is good, printing and dyeing color fastness of the disperse dyes on fabric can be effectively improved and prevent disperse dyes from moving in the colour migration of nylon fabric fabric, properties meet market requirement.

Description

High firmness environmental protection thermal transfer printing technology

Technical field

The present invention relates to printing technology fields, and in particular to a kind of high firmness environmental protection thermal transfer printing technology.

Background technique

With the fast development of ink-jet technology, the ink-jet printed new force for having become dyeing, and by people's Extensive concern.Ink-jet printed technique can be divided into two kinds: the first first pre-processes fabric surface, then passes through inkjet printing Directly on the fabric by pattern spray printing；Second then will be printed on first by pattern ink jet printing on special transfer paper The transfer paper of pattern is contacted with fabric surface, transfers a pattern to fabric surface by the pressure and temperature for applying certain.The A kind of method there are processes more, complex process, the disadvantages of production efficiency is lower and transfer effect is poor, and second method (i.e. ink-jet caloric transfer printing technology) is that using heat-transferring printing paper as carrier there is pattern transfer complete display, production efficiency to significantly improve The features such as, most widely used ink-jet printed technology is had become at present.

Thermal transfer is an emerging printing technology, by incoming only 10 years of foreign countries.The technique mode of printing It is divided into transfer film print and transfer processing two large divisions, transfer film printing is using net-point printing (resolution ratio reaches 300dpi), by pattern Film surface is pre-printed, the pattern level of printing is abundant, bright in luster, and ever-changing, color difference is small, and reproducibility is good, can reach The requirement effect of layout person, and be suitble to produce in enormous quantities.By heat transfer machine time processing, (heating adds for transfer processing Pressure) pattern exquisite on transfer film is transferred in product surface, after molding ink layer with product surface is molten is integrated, drift true to nature It is bright, greatly improve the class of product.But since the technology content is higher, many materials are both needed to import.With Conventional decal work Skill is compared, and ink-jet thermal transfer technology can accurately control ink amount with computer, to reduce cost, reduce environmental pollution, is A kind of green printing technique.Ink-jet thermal transfer ink is the key that ink-jet printed technique, and the performance of ink directly influences spray Ink the final mass of flower prod.Ink-jetting process requires ink-jet thermal transfer ink that must have ultra-fine fineness, to prevent from blocking Nozzle；Require the colorant in ink easily can be transferred to fabric surface from transfer paper surface by heat sublimation simultaneously.Traditional coloring Agent is generally divided into dyestuff and two kinds of pigment, and pigmenting power is strong, but there are difficulties in dispersion, fiber affinity is poor the problems such as, therefore The adhesive force that adhesive need to be added to enhance pigment particles to fabric, and this easily causes spray head to block.

Summary of the invention

In view of the above-mentioned deficiencies in the prior art, the present invention provides a kind of high firmness environmental protection thermal transfer printers Skill.

A kind of high firmness environmental protection thermal transfer printing technology, comprises the following steps that:

Thermal transfer ink is printed on transfer paper by I, by printing machine；

Printed patterns are transferred on fabric by II, by gained transfer paper in step I by conventional caloric transfer printing technology, are made Obtain PRINTED FABRIC fabric.

By mass percentage, raw material includes: 15-35% disperse dyes mill base, 20-40% high to the thermal transfer ink Molecularly Imprinted Polymer lotion, 0.2-1% surfactant, 20-40% hygroscopic agent, 0.01-0.5% preservative, 0.1-0.5%pH tune Save agent, surplus is water.

The hygroscopic agent include propylene glycol, isopropanol, glycerol, ethylene glycol, urea, butyl carbitol, oxo diethylene glycol, One of butyrolactam, n-methyl-2-pyrrolidone are a variety of.

The preservative includes potassium sorbate, ethyl-para-hydroxybenzoate, propylparaben, P-hydroxybenzoic acid One of butyl ester is a variety of.

The pH adjusting agent includes citric acid, ammonium sulfate, ammonium chloride, three hydramine, diethanol amine, sodium hydroxide, 2- amino One of ethyl alcohol, sodium tartrate, sodium polyphosphate, sodium citrate are a variety of.

The disperse dyes mill base is prepared by the raw material of following mass percent: 15-35% disperse dyes, 5-25% Dispersing agent, 0.5-5% dispersing aid, surplus are water.

The disperse dyes include one of weld, orchil, blue dyes and dispersed black dye or a variety of.

The dispersing agent includes sodium lignin sulfonate and/or sodium methylene bis-naphthalene sulfonate.

The dispersing aid includes methyl pyrrolidone, ethyl pyrrolidone, diethylene glycol monobutyl ether, dipropylene glycol diformazan One of ether, gamma-butyrolacton, alpha-pyrrolidone are a variety of.

The emulsion polymerization includes acrylate resin emulsion and/or modified polyurethane emulsion.

Preferably, the emulsion polymerization by acrylate resin emulsion, modified polyurethane emulsion in mass ratio (1-6): (1-3) is mixed.

The acrylate resin emulsion the preparation method comprises the following steps:

I, presses (45-55): (20-35): the mass ratio of (500-600), by methyl methacrylate, the positive fourth of methacrylic acid Ester, water mixing, are stirred at 75-85 DEG C, mixed liquor are obtained after mixing, be subsequently added into mixed liquor quality 0.05-0.15% Initiator, maintain temperature and revolving speed it is constant, continue stir 20-40min, obtain mixture A；

II, mixes methyl methacrylate, metering system N-butyl, lauryl sodium sulfate, sodium secondary alkyl sulfonate, water Close, the methyl methacrylate, metering system N-butyl, lauryl sodium sulfate, sodium secondary alkyl sulfonate, water mass ratio be (300-350): (100-130): (1-4): (2-4): (200-300) is stirred at 75-85 DEG C, is mixed after mixing Expect B, mixture B is added dropwise in Xiang Shangshu mixture A, time for adding control continues to protect at 75-85 DEG C after being added dropwise in 3-5h Warm 0.5-1.5h obtains mixture C；

III, mixes methyl methacrylate, methacrylic acid, lauryl sodium sulfate, sodium secondary alkyl sulfonate, water, institute State methyl methacrylate, methacrylic acid, lauryl sodium sulfate, sodium secondary alkyl sulfonate, water mass ratio be (200- 300): (20-30): (1-4): (2-4): (100-200) is stirred at 75-85 DEG C, mixture D is obtained after mixing, upwards Dropwise addition mixture D in mixture C is stated, time for adding control continues to keep the temperature 0.5- at 75-85 DEG C after being added dropwise in 2-5h 1.5h, after being cooled to 45-55 DEG C discharge to get.

The modified polyurethane emulsion the preparation method comprises the following steps:

I, mixes isophorone diisocyanate, polycaprolactone diols, dibutyl tin dilaurate, at 75-85 DEG C Lower reaction 1-4h, is subsequently added into 2,2- dihydromethyl propionic acid, 1,4-butanediol, maintains temperature and revolving speed constant, the reaction was continued 1- 4h obtains multiple emulsion；The isophorone diisocyanate, polycaprolactone diols, dibutyl tin dilaurate, 2,2- bis- Hydroxymethyl propionic acid, 1,4-butanediol mass ratio be (4-5.5): (2-5): (0.05-0.2): (1-1.5): (0.8-2)；

After the above-mentioned multiple emulsion of II, is cooled to 45-55 DEG C, three second of γ-aminopropyl of multiple emulsion quality 15-25% is added Oxysilane reacts 20-40min at 45-55 DEG C, and being adjusted to system pH is 7, remains temperature-resistant, continues to stir 10min, It is cooled to 25-35 DEG C, continuously adds the hydrazine hydrate solution of 4-6 times of multiple emulsion quality, continues to stir 1-4h at 25-35 DEG C, To obtain the final product.

Preferably, the modified polyurethane emulsion the preparation method comprises the following steps:

I, mixes graphene oxide, n,N-Dimethylformamide, is first ultrasonically treated 2-5h, obtains ultrasonic disperse liquid, connect Isophorone diisocyanate is added into ultrasonic disperse liquid, at 75-85 DEG C react 4-8h after, be added phenylhydrazine be placed on 3-7h is reacted at 50-60 DEG C, after suction filtration, washing, drying, obtains modified graphene oxide；The n,N-Dimethylformamide, Graphene oxide, isophorone diisocyanate, phenylhydrazine, methylene chloride mass ratio be 100:(0.5-1.5): (3-6): (1- 4): (600-700)；

II, mixes isophorone diisocyanate, modified graphene oxide, is stirred at 75-85 DEG C, after mixing Polycaprolactone diols, dibutyl tin dilaurate is added, is placed at 75-85 DEG C and reacts 1-4h, continuously add 2,2- dihydroxy first Base propionic acid, 1,4-butanediol maintain temperature and revolving speed constant, the reaction was continued 1-4h to get；The isophorone diisocyanate Ester, modified graphene oxide, polycaprolactone diols, dibutyl tin dilaurate, 2,2- dihydromethyl propionic acid, 1,4-butanediol Mass ratio be (4-5.5): (0.1-0.3): (2-5): (0.05-0.2): (1-1.5): (0.8-2).

It is highly preferred that the modified polyurethane emulsion the preparation method comprises the following steps:

II, mixes isophorone diisocyanate, modified graphene oxide, is stirred at 75-85 DEG C, after mixing Polycaprolactone diols, dibutyl tin dilaurate is added, is placed at 75-85 DEG C and reacts 1-4h, continuously add 2,2- dihydroxy first Base propionic acid, 1,4-butanediol, maintain temperature and revolving speed constant, and the reaction was continued 1-4h obtains multiple emulsion；The isophorone two Isocyanates, modified graphene oxide, polycaprolactone diols, dibutyl tin dilaurate, 2,2- dihydromethyl propionic acid, Isosorbide-5-Nitrae- The mass ratio of butanediol is (4-5.5): (0.1-0.3): (2-5): (0.05-0.2): (1-1.5): (0.8-2)；

After the above-mentioned multiple emulsion of III, is cooled to 45-55 DEG C, three second of γ-aminopropyl of multiple emulsion quality 15-25% is added Oxysilane reacts 20-40min at 45-55 DEG C, and being adjusted to system pH is 7, remains temperature-resistant, continues to stir 10min, It is cooled to 25-35 DEG C, continuously adds the hydrazine hydrate solution of 4-6 times of multiple emulsion quality, continues to stir 1-4h at 25-35 DEG C, To obtain the final product.

The surfactant includes fatty alcohol polyoxyethylene ether, quaternary ammonium salt polyoxyethylene ether trisiloxanes, dodecyl One of phosphate monoester is a variety of.

Preferably, the surfactant is by fatty alcohol polyoxyethylene ether, quaternary ammonium salt polyoxyethylene ether trisiloxanes, 12 Alkyl phosphate monoester (1-6) in mass ratio: (1-6): (1-6) is mixed.

The quaternary ammonium salt polyoxyethylene ether trisiloxanes the preparation method comprises the following steps:

I, press 10:(0.06-0.12): the mass ratio of (5-10), by glycidol ether terminated propenol polyoxyethylene ether, Chloroplatinic acid, toluene mixing, under the protection of nitrogen, are placed at 70-85 DEG C and stir 20-40min, obtain mixture, then to institute The double trimethylsiloxy group methyl-monosilanes for obtaining 0.8-0.95 times of mixture quality of addition in mixture, react 2- at 95-105 DEG C 6h, vacuum distillation obtain polyoxyethylene groups glycidol ether trisiloxanes after removing toluene；

II, presses 1:(0.9-1): the mass ratio of (1-2), by above-mentioned polyoxyethylene groups glycidol ether trisiloxanes, front three Amine hydrochlorate, dehydrated alcohol mixing, are placed at 70-85 DEG C and react 2-6h, be evaporated under reduced pressure, after removing dehydrated alcohol to obtain the final product.

The preparation method of the thermal transfer ink, comprising the following steps:

I, weighs each raw material component by mass percentage；

II, mixes surfactant, hygroscopic agent, preservative, pH adjusting agent, water, stirs 1-5h at 20-35 DEG C, adds Enter emulsion polymerization, maintain temperature and revolving speed constant, continues to stir 1-5h, obtain mixture；

Disperse dyes mill base is added into said mixture by III, stirs 1-5h at 20-35 DEG C, stand to get.

By adopting the above-described technical solution, compared with prior art, the present invention has the following advantages: institute of the present invention Synergistic effect can be generated between the surfactant of use, can preferably reduce surface tension, be conducive to improve thermal transfer ink The stability of water；Using emulsion polymerization used in the present invention, may make and the disperse dyes production in thermal transfer ink Angry body dyestuff is sufficiently spread to the inside unformed area of fabric fibre carries out upper dye, while reducing fabric surface loose colour, makes PRINTED FABRIC color is more full, can after fabric fixation is cooling further, since the filming function of high molecular polymer crosslinking Fabric fibre is tightly coated, the sublimation reliability of disperse dyes is improved, so that fabric can satisfy textile industry to fabric Washing and dry, fastness to wet rubbing requirement.The present invention is able to achieve the clean manufacturing of heat transfer printing process, realizes trade effluent Zero-emission target, and printing effect is good can effectively improve printing and dyeing color fastness of the disperse dyes on fabric and anti- Only disperse dyes are moved in the colour migration of nylon fabric fabric, and properties meet market requirement.

Specific embodiment

Foregoing invention content of the invention is described in further detail With reference to embodiment, but should not be incited somebody to action This range for being interpreted as the above-mentioned theme of the present invention is only limitted to following embodiments.

Each raw material and equipment introduction in embodiment:

Red-1 200 9, No. CAS: 2734-52-3, product number: 26197, it is purchased from Shandong West Asia chemical industry Co., Ltd.

Sodium lignin sulfonate, No. CAS: 8061-51-6, product number: RG84329 has purchased from the smooth scientific and technological share of upper Haitai Limit company.

Dimethyl ether, No. CAS: 111109-77-4, product number: D-83590 thinks biochemical purchased from Tianjin Skien Science and Technology Ltd..

Fatty alcohol polyoxyethylene ether, No. CAS: 68439-50-9, hydroxyl value is 95 ± 5mgKOH/g, HLB value 13.5, model AEO-9 is purchased from BASF Aktiengesellschaft.

Dodecylphosphoric acid monoesters, No. CAS: 12751-23-4, model MA24P are purchased from Nantong Han Sheng Chemical Co., Ltd..

The preparation method of glycidol ether terminated propenol polyoxyethylene ether refers to patent application number 201010264329.0 Chinese patent in preparation method shown in embodiment 1.

Chloroplatinic acid, No. CAS: 16941-12-1, product number: C754M, purchased from the limited public affairs of nine ancient cooking vessels chemical (Shanghai) science and technology Department.

Double trimethylsiloxy group methyl-monosilanes, No. CAS: 873-88-7, product number: H-10150 thinks purchased from Tianjin Skien Biochemical technology Co., Ltd.

Trimethylamine hydrochloride, No. CAS: 593-81-7, product number: T-71875, thinking biochemical technology purchased from Tianjin Skien has Limit company.

Polycaprolactone diols, No. CAS: 36890-68-3, average molecular weight 2000 has purchased from sky farsighted chemical (Shanghai) Limit company.

Dibutyl tin dilaurate, No. CAS: 77-58-7, it is purchased from Shanghai Aladdin biochemical technology limited liability company.

2,2- dihydromethyl propionic acids, No. CAS: 4767-03-7, product number: L14014 changes purchased from AlfaAesar (China) Learn Co., Ltd.

1,4-butanediol, No. CAS: 110-63-4, it is purchased from Shanghai Aladdin biochemical technology limited liability company.

Gamma-aminopropyl-triethoxy-silane, No. CAS: 919-30-2, product number: A10668, purchased from AlfaAesar (in State) Chemical Co., Ltd..

Methyl methacrylate, No. CAS: 80-62-6, product number: A13030 has purchased from AlfaAesar (China) chemistry Limit company.

N-BMA, No. CAS: 97-88-1, product number: A19068 is purchased from AlfaAesar (China) chemistry Co., Ltd.

Lauryl sodium sulfate, No. CAS: 151-21-3, product number: S817788 is purchased from Shanghai Mike woods biochemical technology Co., Ltd.

Sodium secondary alkyl sulfonate, No. CAS: 68411-30-3, model sas-60 are purchased from Guangzhou Sui Xin Chemical Co., Ltd..

Methacrylic acid, No. CAS: 79-41-4, product number: A11543, purchased from the limited public affairs of AlfaAesar (China) chemistry Department.

In the Chinese patent that the preparation method application reference number of graphene oxide is 201710096249.0 shown in embodiment 1 Method be prepared.

Isophorone diisocyanate, No. CAS: 4098-71-9, product number: I811865 is raw purchased from Shanghai Mike woods Change Science and Technology Ltd..

N,N-Dimethylformamide, No. CAS: 4637-24-5, product number: A15350 changes purchased from AlfaAesar (China) Learn Co., Ltd.

Phenylhydrazine, No. CAS: 100-63-0, product number: A11246N is purchased from AlfaAesar (China) Chemical Co., Ltd..

Methylene chloride, No. CAS: 75-09-2, product number: W610942 is purchased from the limited public affairs of Shanghai Mike woods biochemical technology Department.

Hydrazine hydrate, No. CAS: 7803-57-8, product number: A14005, purchased from the limited public affairs of AlfaAesar (China) chemistry Department.

The preparation method of hydrazine hydrate solution: 0.69g hydrazine hydrate and 75.6g deionized water are mixed, after mixing to obtain the final product.

Glycerol, No. CAS: 56-81-5, product number: G810574 is purchased from Shanghai Mike woods biochemical technology Co., Ltd.

Ethylene glycol, No. CAS: 107-21-1, product number: E808734 is purchased from the limited public affairs of Shanghai Mike woods biochemical technology Department.

Potassium sorbate, No. CAS: 590-00-1, product number: HWG24918 is purchased from the limited public affairs of Beijing Hua Weirui section chemical industry Department.

Citric acid, No. CAS: 77-92-9, product number: C805019 is purchased from Shanghai Mike woods biochemical technology Co., Ltd.

Heat-transferring printing paper, technical grade, UPM-Kymmene (Changshu) Paper Industry Co., Ltd..

Fabric is white pure cotton T-shirt, is purchased from Yiwu City Yue Ze clothes firm.

Milling apparatus is MITR-YXQM-12L type nanometer formula planetary ball mill, is purchased from the limited public affairs of Changsha meter Qi instrument and equipment Department.

Ultrasonic device is ZOLLO-S650CT type ultrasonic extraction extraction apparatus, is purchased from Shanghai Zuo Le Instrument Ltd..

Mixing plant is JJ-1A precision reinforcement electric mixer, and 0-3000rpm is purchased from Changzhou Ao Hua Instrument Ltd..

Printing machine is HJ-4182 type digital decorating machine, is purchased from Hongsam Digital Science & Technology Co., Ltd..

Embodiment 1

Thermal transfer ink is printed on transfer paper by I, by printing machine；

The thermal transfer ink is prepared by the raw material of following mass percents: 25% disperse dyes mill base, 30% high Molecularly Imprinted Polymer lotion, 0.1% fatty alcohol polyoxyethylene ether, 0.1% quaternary ammonium salt polyoxyethylene ether trisiloxanes, 0.1% 12 Alkyl phosphate monoester, 10% glycerol, 10% ethylene glycol, 0.1% potassium sorbate, 0.1% citric acid, surplus are deionized water.

The disperse dyes mill base is prepared by the raw material of following mass percent: 25% Red-1 200 9,15% is wooden Plain sodium sulfonate, 1% dimethyl ether, surplus are deionized water.

The disperse dyes mill base the preparation method comprises the following steps: by Red-1 200 9, sodium lignin sulfonate, dimethyl ether point Dissipate, deionized water mixes by mass percentage, be placed in 30 DEG C, ground in the milling apparatus of 300r/min, wherein the ball Mass ratio between material is 2:1, and ball-milling medium is the zirconia ball of diameter 1mm, be ground to partial size be 200nm to get.

The emulsion polymerization is mixed by acrylate resin emulsion, modified polyurethane emulsion by the mass ratio of 1:1 It closes.

I, presses the mass ratio of 50:25:550, and methyl methacrylate, n-BMA, deionized water are mixed, 10min is stirred with the revolving speed of 300r/min at 85 DEG C, mixed liquor is obtained, is subsequently added into the persulfuric acid of mixed liquor quality 0.1% Potassium, maintains temperature and revolving speed constant, and the reaction was continued 30min obtains mixture A；

II, is by methyl methacrylate, metering system N-butyl, lauryl sodium sulfate, sodium secondary alkyl sulfonate, deionization Water mixing, the methyl methacrylate, metering system N-butyl, lauryl sodium sulfate, sodium secondary alkyl sulfonate, deionized water Mass ratio be 300:120:3:4:250,30min is stirred with the revolving speed of 300r/min at 85 DEG C, obtains mixture B, upwards It states and gained mixture B is added dropwise in mixture A, time for adding control continues to keep the temperature 1h at 85 DEG C after being added dropwise, obtain in 3h Mixture C；

III, mixes methyl methacrylate, methacrylic acid, lauryl sodium sulfate, sodium secondary alkyl sulfonate, deionized water Close, the methyl methacrylate, methacrylic acid, lauryl sodium sulfate, sodium secondary alkyl sulfonate, deionized water mass ratio For 250:25:1.5:2.5:150,30min is stirred with the revolving speed of 300r/min at 85 DEG C, mixture D is obtained, to above-mentioned mixing Expect that gained mixture D is added dropwise in C, time for adding control continues to keep the temperature 1h at 85 DEG C after being added dropwise, be cooled to 50 DEG C in 2h After discharge to get.

I, by isophorone diisocyanate, polycaprolactone diols, dibutyl tin dilaurate mix, be placed in 80 DEG C, 1h is reacted under conditions of 230r/min, continuously adds 2,2- dihydromethyl propionic acid, 1,4-butanediol, maintains temperature and revolving speed not Become, the reaction was continued 1.5h obtains multiple emulsion；The isophorone diisocyanate, polycaprolactone diols, tin dilaurate two Butyl tin, 2,2- dihydromethyl propionic acid, 1,4-butanediol mass ratio be 5:3:0.1:1.2:0.9；

After the above-mentioned multiple emulsion of II, is cooled to 50 DEG C, the gamma-aminopropyl-triethoxy silicon of multiple emulsion quality 15% is added Alkane stirs 30min under conditions of 50 DEG C, 500r/min, and it is 7 that triethylamine, which is added, and is adjusted to system pH, remains temperature-resistant, after Continuous stirring 10min, be cooled to 30 DEG C, continuously add 5 times of multiple emulsion quality of hydrazine hydrate solution, in 30 DEG C, 500r/min Under the conditions of stirring 1h to get.

I, presses the mass ratio of 10:0.08:6, by glycidol ether terminated propenol polyoxyethylene ether, chloroplatinic acid, toluene Mixing is placed at 75 DEG C under the protection of nitrogen and stirs 30min with the revolving speed of 300r/min, mixture is obtained, then to gained 0.9 times of mixture quality of double trimethylsiloxy group methyl-monosilanes are added in mixture, under conditions of 100 DEG C, 300r/min React 4h, be then placed in 75 DEG C, absolute pressure be 0.09MPa under conditions of be evaporated under reduced pressure, until liquid be it is light yellow Bright shape obtains polyoxyethylene groups glycidol ether trisiloxanes；

II, press 1:1:1.5 mass ratio, by above-mentioned polyoxyethylene groups glycidol ether trisiloxanes, trimethylamine hydrochloride, Dehydrated alcohol mixing is then placed in 55 DEG C, under conditions of absolute pressure is 0.09MPa in 70 DEG C, the lower reaction 2h of 300r/min Be evaporated under reduced pressure, until liquid be yellowish transparence to get.

I, weighs each raw material component by mass percentage；

II, by fatty alcohol polyoxyethylene ether, quaternary ammonium salt polyoxyethylene ether trisiloxanes, dodecylphosphoric acid monoesters, glycerol, Ethylene glycol, potassium sorbate, citric acid, deionized water mixing, are placed in 30 DEG C, stir 2h under conditions of 400r/min, high score is added Sub- polymer emulsion maintains temperature and revolving speed constant, continues to stir 2h, obtains mixture；

Disperse dyes mill base is added into said mixture by III, is placed in 30 DEG C, stirs 3h under conditions of 400r/min, quiet Set for 24 hours to get.

Embodiment 2

Substantially the same manner as Example 1, difference is only in that: the thermal transfer ink by following mass percents raw material system It is standby to form: 25% disperse dyes mill base, 30% emulsion polymerization, 0.15% fatty alcohol polyoxyethylene ether, 0.15% season Ammonium salt polyoxyethylene ether trisiloxanes, 10% glycerol, 10% ethylene glycol, 0.1% potassium sorbate, 0.1% citric acid, surplus are to go Ionized water.

I, weighs each raw material component by mass percentage；

II, by fatty alcohol polyoxyethylene ether, quaternary ammonium salt polyoxyethylene ether trisiloxanes, glycerol, ethylene glycol, potassium sorbate, Citric acid, deionized water mixing, are placed in 30 DEG C, stir 2h under conditions of 400r/min, emulsion polymerization is added, maintain Temperature and revolving speed are constant, continue to stir 2h, obtain mixture；

Embodiment 3

Substantially the same manner as Example 1, difference is only in that: the thermal transfer ink by following mass percents raw material system It is standby to form: 25% disperse dyes mill base, 30% emulsion polymerization, 0.15% quaternary ammonium salt polyoxyethylene ether trisiloxanes, 0.15% dodecylphosphoric acid monoesters, 10% glycerol, 10% ethylene glycol, 0.1% potassium sorbate, 0.1% citric acid, surplus are to go Ionized water.

I, weighs each raw material component by mass percentage；

II, by quaternary ammonium salt polyoxyethylene ether trisiloxanes, dodecylphosphoric acid monoesters, glycerol, ethylene glycol, potassium sorbate, Citric acid, deionized water mixing, are placed in 30 DEG C, stir 2h under conditions of 400r/min, emulsion polymerization is added, maintain Temperature and revolving speed are constant, continue to stir 2h, obtain mixture；

Embodiment 4

Substantially the same manner as Example 1, difference is only in that: the thermal transfer ink by following mass percents raw material system It is standby to form: 25% disperse dyes mill base, 30% emulsion polymerization, 0.15% fatty alcohol polyoxyethylene ether, 0.15% ten Acidic phosphates monoesters, 10% glycerol, 10% ethylene glycol, 0.1% potassium sorbate, 0.1% citric acid, surplus are deionized water.

I, weighs each raw material component by mass percentage；

II, by fatty alcohol polyoxyethylene ether, dodecylphosphoric acid monoesters, glycerol, ethylene glycol, potassium sorbate, citric acid, go Ionized water mixing is placed in 30 DEG C, stirs 2h under conditions of 400r/min, emulsion polymerization is added, and maintains temperature and turns Speed is constant, continues to stir 2h, obtains mixture；

Embodiment 5

Substantially the same manner as Example 1, difference is only in that: the emulsion polymerization is acrylate cream Liquid.

Embodiment 6

Substantially the same manner as Example 1, difference is only in that: the emulsion polymerization is modified polyurethane emulsion.

Embodiment 7

Substantially the same manner as Example 1, difference is only in that: the modified polyurethane emulsion the preparation method comprises the following steps:

I, mixes graphene oxide, n,N-Dimethylformamide, and 3h, the ultrasonic treatment are first ultrasonically treated at 40 DEG C Ultrasonic power be 200W, supersonic frequency 20kHz obtains ultrasonic disperse liquid, different Fo Er is then added into ultrasonic disperse liquid Ketone diisocyanate reacts 6h under conditions of 80 DEG C, 230r/min, and the item that phenylhydrazine is placed on 50-60 DEG C, 230r/min is added 4h is reacted under part, is filtered, and gained filter cake is washed with methylene chloride, is placed in drying at 40 DEG C and for 24 hours, is obtained modified graphite oxide Alkene；The n,N-Dimethylformamide, graphene oxide, isophorone diisocyanate, phenylhydrazine, methylene chloride mass ratio be 100:0.5:4:2:600；

II, mixes isophorone diisocyanate, modified graphene oxide, stirs under conditions of 80 DEG C, 230r/min 1h is mixed, polycaprolactone diols, dibutyl tin dilaurate are subsequently added into, 80 DEG C is placed in, reacts 1h under conditions of 230r/min, Continuously add 2,2- dihydromethyl propionic acid, 1,4-butanediol, maintain temperature and revolving speed constant, the reaction was continued 1.5h to get；It is described Isophorone diisocyanate, modified graphene oxide, polycaprolactone diols, dibutyl tin dilaurate, 2,2- dihydroxy first Base propionic acid, 1,4-butanediol mass ratio be 5:0.1:3:0.1:1.2:0.9.

Embodiment 8

II, mixes isophorone diisocyanate, modified graphene oxide, stirs under conditions of 80 DEG C, 230r/min 1h is mixed, polycaprolactone diols, dibutyl tin dilaurate are subsequently added into, 80 DEG C is placed in, reacts 1h under conditions of 230r/min, It continuously adds 2,2- dihydromethyl propionic acid, 1,4-butanediol, maintains temperature and revolving speed constant, the reaction was continued 1.5h is obtained compound Lotion；The isophorone diisocyanate, modified graphene oxide, polycaprolactone diols, dibutyl tin dilaurate, 2, 2- dihydromethyl propionic acid, 1,4-butanediol mass ratio be 5:0.1:3:0.1:1.2:0.9；

After the above-mentioned multiple emulsion of III, is cooled to 50 DEG C, the gamma-aminopropyl-triethoxy silicon of multiple emulsion quality 15% is added Alkane stirs 30min under conditions of 50 DEG C, 500r/min, and it is 7 that triethylamine, which is added, and is adjusted to system pH, remains temperature-resistant, after Continuous stirring 10min, be cooled to 30 DEG C, continuously add 5 times of multiple emulsion quality of hydrazine hydrate solution, in 30 DEG C, 500r/min Under the conditions of stirring 1h to get.

Comparative example 1

Substantially the same manner as Example 1, difference is only in that: the thermal transfer ink by following mass percents raw material system It is standby to form: 25% disperse dyes mill base, 30% emulsion polymerization, 10% glycerol, 10% ethylene glycol, 0.1% sorbic acid Potassium, 0.1% citric acid, surplus are deionized water.

I, weighs each raw material component by mass percentage；

II, mixes glycerol, ethylene glycol, potassium sorbate, citric acid, deionized water, is placed in the condition of 30 DEG C, 400r/min Emulsion polymerization is added in lower stirring 2h, maintains temperature and revolving speed constant, continues to stir 2h, obtains mixture；

Comparative example 2

Substantially the same manner as Example 1, difference is only in that: high molecular polymer cream is not added in the thermal transfer ink Liquid.

Test case 1

Surface tension test: by method described in standard QBT2730.2-2005, heat used in the present invention is turned at 25 DEG C The surface tension of printing ink is tested, and each sample test 5 times, is averaged, and specific test result is shown in Table 1.

Table 1: surface tension test result table

Group	Surface tension/(mNm^-1)
		Embodiment 1	25.6
Embodiment 2	30.2
		Embodiment 3	29.6
Embodiment 4	30.9
		Embodiment 5	27.4
Embodiment 6	27.1
		Embodiment 7	24.8
Embodiment 8	23.6
		Comparative example 1	33.4

Surface tension is to influence one of the principal element of thermal transfer stability of ink, reduces surface in thermal transfer ink system Tension is conducive to the stability for improving thermal transfer ink.By test result it is found that thermal transfer ink is using fat in embodiment 1 The surfactant that alcohol polyoxyethylene ether, quaternary ammonium salt polyoxyethylene ether trisiloxanes, dodecylphosphoric acid monoesters combine, surface Tension (uses fatty alcohol polyoxyethylene ether, three silicon oxygen of quaternary ammonium salt polyoxyethylene ether significantly lower than thermal transfer ink in embodiment 2-4 Alkane, dodecylphosphoric acid monoesters combine any two kinds of surfactant) and using the comparative example 1 of surfactant.

Test case 2

Degree of fixation, fastness to soaping measurement: according to standard GB/T 2391-2006 " measurement of reactive dye degree of fixation " It is high to the present invention is used with test method specified in GB/T 3921-2008 " textile color stability test fastness to soaping " Firmness environmental protection thermal transfer printing technology prepares degree of fixation, the fastness to soaping of gained PRINTED FABRIC fabric, wherein color fastness Test result is divided into 5 grades, wherein 1 grade minimum, 5 grades of highests, specific test result is shown in Table 2.

Table 2: degree of fixation, fastness to soaping measurement result table

Group	Degree of fixation/%	Fastness to soaping/grade
			Embodiment 1	92.2	5
Embodiment 2	87.9	5
			Embodiment 3	88.5	5
Embodiment 4	88.1	5
			Embodiment 5	84.6	4.5
Embodiment 6	85.3	4.5
			Embodiment 7	93.8	5
Embodiment 8	99.4	5
			Comparative example 2	80.5	4

By test result it is found that thermal transfer ink is added to acrylate resin emulsion, modified polyurethane cream in embodiment 1 The emulsion polymerization of liquid combination, degree of fixation, fastness to soaping are all better than in embodiment 5-6 thermal transfer ink (only It is added to one of acrylate resin emulsion, modified polyurethane emulsion) and it is not added with the comparison of emulsion polymerization Example 2；And embodiment 8 is composite modified to polyaminoester emulsion progress, for embodiment 1, further improves thermal transfer ink The degree of fixation of water.

The above described is only a preferred embodiment of the present invention, limitation in any form not is done to the present invention, therefore The equivalent or simple change that all principles described according to the invention patent design are done, is included in the scope of protection of the patent of the present invention It is interior；Those skilled in the art can make various modifications or additions to the described embodiments Or be substituted in a similar manner, without departing from structure of the invention or beyond the scope defined by this claim, It is within the scope of protection of the invention.

Claims

1. a kind of high firmness environmental protection thermal transfer printing technology, which is characterized in that comprise the following steps that:

I, design and printing pattern, and according to designed printed patterns, thermal transfer ink is printed by transfer paper by printing machine On；

Printed patterns on above-mentioned transfer paper are transferred on fabric by II, by conventional caloric transfer printing technology, and PRINTED FABRIC is made Fabric.

By mass percentage, raw material includes: 15-35% disperse dyes mill base, 20-40% macromolecule to the thermal transfer ink Polymer emulsion, 0.2-1% surfactant, 20-40% hygroscopic agent, 0.01-0.5% preservative, 0.1-0.5%pH are adjusted Agent, surplus are water.

2. high firmness environmental protection thermal transfer printing technology as described in claim 1, which is characterized in that the disperse dyes mill base by The raw material of following mass percent is prepared: 15-35% disperse dyes, 5-25% dispersing agent, 0.5-5% dispersing aid, remaining Amount is water；

The disperse dyes include one of weld, orchil, blue dyes and dispersed black dye or a variety of；

The dispersing agent includes sodium lignin sulfonate and/or sodium methylene bis-naphthalene sulfonate；

The dispersing aid include methyl pyrrolidone, ethyl pyrrolidone, diethylene glycol monobutyl ether, dimethyl ether, One of gamma-butyrolacton, alpha-pyrrolidone are a variety of.

3. high firmness environmental protection thermal transfer printing technology as described in claim 1, which is characterized in that the high molecular polymer cream Liquid includes acrylate resin emulsion and/or modified polyurethane emulsion.

4. high firmness environmental protection thermal transfer printing technology as claimed in claim 3, which is characterized in that the acrylate cream Liquid the preparation method comprises the following steps:

I, press (45-55): (20-35): the mass ratio of (500-600), by methyl methacrylate, n-BMA, Water mixing, is stirred at 75-85 DEG C, mixed liquor is obtained after mixing, be subsequently added into drawing for mixed liquor quality 0.05-0.15% Agent is sent out, maintains temperature and revolving speed constant, continues to stir 20-40min, obtains mixture A；

II, mixes methyl methacrylate, metering system N-butyl, lauryl sodium sulfate, sodium secondary alkyl sulfonate, water, institute State methyl methacrylate, metering system N-butyl, lauryl sodium sulfate, sodium secondary alkyl sulfonate, water mass ratio be (300- 350): (100-130): (1-4): (2-4): (200-300) is stirred at 75-85 DEG C, mixture B is obtained after mixing, to Mixture B is added dropwise in above-mentioned mixture A, time for adding control continues to keep the temperature 0.5- at 75-85 DEG C after being added dropwise in 3-5h 1.5h obtains mixture C；

III, mixes methyl methacrylate, methacrylic acid, lauryl sodium sulfate, sodium secondary alkyl sulfonate, water, the first Base methyl acrylate, methacrylic acid, lauryl sodium sulfate, sodium secondary alkyl sulfonate, water mass ratio be (200-300): (20-30): (1-4): (2-4): (100-200) is stirred at 75-85 DEG C, mixture D is obtained after mixing, mixes to above-mentioned It closes and mixture D is added dropwise in material C, time for adding control continues to keep the temperature 0.5-1.5h at 75-85 DEG C after being added dropwise in 2-5h, After being cooled to 45-55 DEG C discharge to get.

5. high firmness environmental protection thermal transfer printing technology as claimed in claim 3, which is characterized in that the modified polyurethane emulsion The preparation method comprises the following steps:

I, mixes isophorone diisocyanate, polycaprolactone diols, dibutyl tin dilaurate, anti-at 75-85 DEG C 1-4h is answered, is subsequently added into 2,2- dihydromethyl propionic acid, 1,4-butanediol, maintains temperature and revolving speed constant, the reaction was continued 1-4h is obtained To multiple emulsion；The isophorone diisocyanate, polycaprolactone diols, dibutyl tin dilaurate, 2,2- dihydroxy first Base propionic acid, 1,4-butanediol mass ratio be (4-5.5): (2-5): (0.05-0.2): (1-1.5): (0.8-2)；

After the above-mentioned multiple emulsion of II, is cooled to 45-55 DEG C, the gamma-aminopropyl-triethoxy of multiple emulsion quality 15-25% is added Silane reacts 20-40min at 45-55 DEG C, and being adjusted to system pH is 7, remains temperature-resistant, continues to stir 10min, cooling To 25-35 DEG C, continuously add the hydrazine hydrate solution of 4-6 times of multiple emulsion quality, continue at 25-35 DEG C stir 1-4h to get.

6. high firmness environmental protection thermal transfer printing technology as claimed in claim 5, which is characterized in that the modified polyurethane emulsion The preparation method comprises the following steps:

I, by graphene oxide, n,N-Dimethylformamide mix, be first ultrasonically treated 2-5h, obtain ultrasonic disperse liquid, then to Isophorone diisocyanate is added in ultrasonic disperse liquid, after reacting 4-8h at 75-85 DEG C, phenylhydrazine is added and is placed on 50-60 3-7h is reacted at DEG C, after suction filtration, washing, drying, obtains modified graphene oxide；The n,N-Dimethylformamide, oxidation Graphene, isophorone diisocyanate, phenylhydrazine, methylene chloride mass ratio be 100:(0.5-1.5): (3-6): (1-4): (600-700)；

II, mixes isophorone diisocyanate, modified graphene oxide, is stirred at 75-85 DEG C, is added after mixing Polycaprolactone diols, dibutyl tin dilaurate are placed at 75-85 DEG C and react 1-4h, continuously add 2,2- dihydroxymethyl third Acid, 1,4-butanediol maintain temperature and revolving speed constant, the reaction was continued 1-4h to get；The isophorone diisocyanate changes Property graphene oxide, polycaprolactone diols, dibutyl tin dilaurate, 2, the matter of 2- dihydromethyl propionic acid, 1,4-butanediol Amount is than being (4-5.5): (0.1-0.3): (2-5): (0.05-0.2): (1-1.5): (0.8-2).

7. high firmness environmental protection thermal transfer printing technology as claimed in claim 5, which is characterized in that the modified polyurethane emulsion The preparation method comprises the following steps:

II, mixes isophorone diisocyanate, modified graphene oxide, is stirred at 75-85 DEG C, is added after mixing Polycaprolactone diols, dibutyl tin dilaurate are placed at 75-85 DEG C and react 1-4h, continuously add 2,2- dihydroxymethyl third Acid, 1,4-butanediol, maintain temperature and revolving speed constant, and the reaction was continued 1-4h obtains multiple emulsion；Two isocyanide of isophorone Acid esters, modified graphene oxide, polycaprolactone diols, dibutyl tin dilaurate, 2,2- dihydromethyl propionic acid, Isosorbide-5-Nitrae-fourth two The mass ratio of alcohol is (4-5.5): (0.1-0.3): (2-5): (0.05-0.2): (1-1.5): (0.8-2)；

After the above-mentioned multiple emulsion of III, is cooled to 45-55 DEG C, the gamma-aminopropyl-triethoxy of multiple emulsion quality 15-25% is added Silane reacts 20-40min at 45-55 DEG C, and being adjusted to system pH is 7, remains temperature-resistant, continues to stir 10min, cooling To 25-35 DEG C, continuously add the hydrazine hydrate solution of 4-6 times of multiple emulsion quality, continue at 25-35 DEG C stir 1-4h to get.

8. high firmness environmental protection thermal transfer printing technology as described in claim 1, which is characterized in that the surfactant includes One of fatty alcohol polyoxyethylene ether, quaternary ammonium salt polyoxyethylene ether trisiloxanes, dodecylphosphoric acid monoesters are a variety of.

9. high firmness environmental protection thermal transfer printing technology as claimed in claim 8, which is characterized in that the quaternary ammonium salt polyoxyethylene Ether trisiloxanes the preparation method comprises the following steps:

I, presses 10:(0.06-0.12): the mass ratio of (5-10), by glycidol ether terminated propenol polyoxyethylene ether, chlorine platinum Acid, toluene mixing, under the protection of nitrogen, are placed at 70-85 DEG C and stir 20-40min, obtain mixture, then mixed to gained The double trimethylsiloxy group methyl-monosilanes for closing 0.8-0.95 times of mixture quality of addition in material, react 2-6h at 95-105 DEG C, Vacuum distillation obtains polyoxyethylene groups glycidol ether trisiloxanes after removing toluene；

II, presses 1:(0.9-1): the mass ratio of (1-2), by above-mentioned polyoxyethylene groups glycidol ether trisiloxanes, front three amine salt Hydrochlorate, dehydrated alcohol mixing, are placed at 70-85 DEG C and react 2-6h, be evaporated under reduced pressure, after removing dehydrated alcohol to obtain the final product.

10. high firmness environmental protection thermal transfer printing technology as described in claim 1, which is characterized in that the thermal transfer ink Preparation method, comprising the following steps:

I, weighs each raw material component by mass percentage；

II, mixes surfactant, hygroscopic agent, preservative, pH adjusting agent, water, and 1-5h is stirred at 20-35 DEG C, is added high Molecularly Imprinted Polymer lotion maintains temperature and revolving speed constant, continues to stir 1-5h, obtains mixture；