CN103224765B - A kind of fluorinated silicone modified acrylic binder and its preparation method and application - Google Patents
A kind of fluorinated silicone modified acrylic binder and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of fluorinated silicone modified acrylic binder, be made up of the raw material of following weight part: the initiator of 50 parts of water, 0.1 ~ 1 part of anionic emulsifier, 10 ~ 20 parts of olefin(e) acid polyisocyanate polyaddition monomers, 0.2 ~ 1 part of vinylformic acid, 0.5 ~ 5 part of fluorine-containing organic silicon monomer, 0.1 ~ 2 part of assistant for emulsifying agent and 0.1 ~ 1 part.The fluorinated silicone modified acrylic binder of the present invention is stable fluorine silicon-modified acrylic ester emulsion, can be used for pigment printing, soft, colour fastness is high, system stability is good, constant product quality, efficiently solves the feel of existing acrylate adhesive existence and fastness contradicts and the problem of hot sticky cold crisp.The invention also discloses a kind of preparation method of fluorinated silicone modified acrylic binder, prepared stable fluorine silicon-modified acrylic ester emulsion by mini-emulsion polymerization, preparation is simple, easy to implement and operation, be easy to industrialization scale operation, have broad application prospects.
Description
Technical field
The present invention relates to adhesive field, what be specifically related to is fluorinated silicone modified acrylic binder of a kind of environment-friendly type and preparation method thereof and the application as pigment printing binding agent.
Background technology
Pigment printing is that one will not anchor at fabric face with having affinity and reactive paint machine to fiber by tackiness agent, only needs fixation, without the need to washing.Therefore, there is the advantages such as energy-conservation, water saving, reduction of discharging, by vast printing and dyeing enterprise widespread use, also listed in textile industry by State Economic and Trade Commission simultaneously and carry out one of technique of cleaner production.
And the wear behavior such as the feel of pigment printing fabric, crock fastness depend on the performance of pigment printing binding agent to a great extent.At present, what China was most widely used is polyacrylate(s) pigment printing binding agent, the features such as good film-forming property, cohesive strength are high, heat-resisting, resistance to oxidation that it has, but also exists that hardness is large, hot sticky cold crisp, feel and fastness are difficult to problems such as getting both.And be cross-linking monomer mainly with N hydroxymethyl acrylamide, high temperature bakes the free formaldehyde that can discharge in a large number to human body and bad environmental, and the physical and mechanical properties of textile fiber also can be made to sustain damage.
Therefore, research and develop environment-protection coating printing adhesive tool that is soft, high color fastness to be of great significance.
Publication number is the preparation method that the Chinese invention patent application of CN101423734A discloses a kind of organosilicon modified acrylic ester binding agent, raw material comprises: basic monomer, silane monomer, coupling agent, modified monomer catalyzer, basic monomer catalyzer, emulsifying agent and deionized water, wherein, basic monomer comprises hard monomer, soft monomer and cross-linking monomer, preparation method comprises: (1), by silane monomer, coupling agent, modified monomer catalyzer, emulsifying agent and deionized water pre-polymerization, obtains organosilicon pre-polymerization emulsion; (2) by this organosilicon pre-polymerization emulsion and basic monomer emulsification, obtained intermediate pre-emulsion; (3) intermediate pre-emulsion, basic monomer catalyzer and deionized water are polymerized, obtained environment-friendly type organosilicon modified acrylic ester binding agent.In this technical scheme, mainly the silica segment of silane monomer is longer, causes and makes it have stronger water repellency, is difficult to this process of migration realizing monomer in general emulsion polymerization, makes organosilyl final transformation efficiency not high.
Summary of the invention
The invention provides a kind of fluorinated silicone modified acrylic binder, for stable fluorine silicon-modified acrylic ester emulsion, can be used for pigment printing, soft, colour fastness is high, efficiently solve existing acrylate adhesive exist feel and fastness contradicts and the problem of hot sticky cold crisp.
A kind of fluorinated silicone modified acrylic binder, be made up of the raw material of following weight part:
50 parts, water;
Anionic emulsifier 0.1 ~ 1 part;
Acrylic ester polymerization monomer 10 ~ 20 parts;
0.2 ~ 1 part, vinylformic acid;
Fluorine-containing organic silicon monomer 0.5 ~ 5 part;
Assistant for emulsifying agent 0.1 ~ 2 part;
Initiator 0.1 ~ 1 part;
Described acrylic ester polymerization monomer be in butyl acrylate, Hydroxyethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, glycidyl methacrylate one or more.
As preferably, described fluorinated silicone modified acrylic binder, be made up of the raw material of following weight part:
50 parts, water;
Anionic emulsifier 0.1 ~ 0.9 part;
Acrylic ester polymerization monomer 10.5 ~ 15.1 parts;
0.4 ~ 0.8 part, vinylformic acid;
Fluorine-containing organic silicon monomer 0.5 ~ 4 part;
Assistant for emulsifying agent 0.2 ~ 1.5 part;
Initiator 0.1 ~ 0.9 part.
This fluorinated silicone modified acrylic binder is applied to pigment printing, and feel is more soft, and colour fastness is higher,
Anionic emulsifier, due to electronegative, be attached to emulsion particle surface, produce electrostatic repulsion each other, therefore, can avoid making minor comonomer mutually collide into large drop, thus play the effect of stable miniemulsion.As preferably, described anionic emulsifier is sodium lauryl sulphate or sodium laurylsulfonate, and above-mentioned two kinds of anionic emulsifier can play the effect of stablizing miniemulsion better.
Adopt vinylformic acid in raw material, this is because the carboxyl in acrylic molecules is strong polar group (electronegative), emulsion particle skin can be made with static charge, and emulsion particle is not easily assembled because of electrostatic repulsion, thus improves emulsion intercalation method.Vinylformic acid is as cross-linking monomer simultaneously, can significantly improve the film forming properties of tackiness agent, increase the magnetism to fiber, improve bonding force, can also provide cross-linking set, play self-catalysis, so can improve pigment printing fastness.Therefore, adopt vinylformic acid, emulsion intercalation method can be improved and improve the printing fastness of coating.
As preferably, described fluorine-containing organic silicon monomer is the fluorinated polysiloxane of ethenyl blocking, is the compound of formula I structure;
Formula I;
Wherein, n is mean polymerisation degree, n=3 ~ 50.
Fluorine-containing organic silicon monomer (i.e. the fluorinated polysiloxane of ethenyl blocking), carry out copolymerization containing the silicone macromolecule of vinyl and small molecules vinyl monomer by the method for radical polymerization to obtain, adopt the fluorine-containing organic silicon monomer of formula I structure to acrylate modified.
Assistant for emulsifying agent can form interface obstacles on drop surface, reduces monomer droplet and degrades because of Ostwald's (Ostwald) slaking, delay monomer from small droplets to the migration of large drop, thus improve emulsion intercalation method.As preferably, described assistant for emulsifying agent is n-hexadecane or positive hexadecanol, and above-mentioned two kinds of assistant for emulsifying agents can improve emulsion intercalation method better.
Described initiator is oil-soluble initiator or water soluble starter, can decompose generation free radical, thus causes the free-radical polymerized of vinyl monomer.As preferably, oil-soluble initiator is Diisopropyl azodicarboxylate, and Diisopropyl azodicarboxylate is mainly present in monomer droplet, and when reaction starts, all monomer droplets cause simultaneously, and polymerization rate is very fast; Water soluble starter is ammonium persulphate or Potassium Persulphate, and ammonium persulphate or Potassium Persulphate are mainly present in aqueous phase, and monomer droplet is by catching the free radical polymerization in aqueous phase, and polymerization process is comparatively steady, there will not be implode phenomenon.Namely described initiator is Diisopropyl azodicarboxylate, ammonium persulphate or Potassium Persulphate.
Present invention also offers a kind of preparation method of fluorinated silicone modified acrylic binder, prepared stable fluorine silicon-modified acrylic ester emulsion by mini-emulsion polymerization, preparation is simple, easy to implement.
A preparation method for fluorinated silicone modified acrylic binder, comprises the following steps:
1) anionic emulsifier and water are mixed, prepare pre-emulsion;
2) acrylic ester polymerization monomer, vinylformic acid, fluorine-containing organic silicon monomer, assistant for emulsifying agent and initiator are mixed, be then added drop-wise in pre-emulsion, after dripping off, mix, obtain emulsion, then obtain fine crankshaft liquid through ultrasonication;
3) fine crankshaft liquid is reacted 1 ~ 8 hour at 50 DEG C ~ 90 DEG C, obtain fluorine silicon-modified acrylic ester emulsion, i.e. fluorinated silicone modified acrylic binder.
In step 1), as preferably, by anionic emulsifier and water at rotating speed 500r/min ~ 1500r/min(rev/min) under stir and mix for 5 ~ 30 minutes, anionic emulsifier and water can be made fully to mix.
Step 2) in, as preferably, it is 3min ~ 10min that acrylic ester polymerization monomer, vinylformic acid, fluorine-containing organic silicon monomer, assistant for emulsifying agent and initiator mix the time being added drop-wise to pre-emulsion, the mixed solution that acrylic ester polymerization monomer, vinylformic acid, fluorine-containing organic silicon monomer, assistant for emulsifying agent and initiator are mixed to form, evenly spreads in pre-emulsion.
As preferably, after dripping off, stir under rotating speed 500r/min ~ 1500r/min and mix for 5 ~ 30 minutes, obtain emulsion, each component in emulsion is fully mixed, obtains stable emulsion.
As preferably, emulsion, through ice-water bath ultrasonication 5 ~ 20 minutes, adopts ice-water bath can absorb the amount of heat produced in ultrasonic procedure, makes monomer stabilization, thus make the submicron monomer droplet of formation more stable.
In step 3), as preferably, by fine crankshaft liquid 60 DEG C ~ 80 DEG C reactions 1 ~ 6 hour, specifically can select water bath with thermostatic control, temperature of reaction is too low is difficult to trigger monomer polymerization, and too high reaction is too fast, easy generation implode phenomenon, above-mentioned reaction conditions can make polyreaction successfully carry out.
Described reaction is carried out under the atmosphere of shielding gas, and described shielding gas is nitrogen or rare gas element.
Described fluorinated silicone modified acrylic binder is as the application of pigment printing binding agent, and concrete application comprises the following steps:
(1) printing paste prescription (weight part): pigment 2 parts, fluorinated silicone modified acrylic binder 10 ~ 20 parts, thickening material 1 ~ 2 part, 20 ~ 40 parts, water.
(2) printing technology: stamp → preliminary drying (80 DEG C, 5 minutes) → bake (160 DEG C, 3 minutes).
Compared with prior art, tool of the present invention has the following advantages:
The fluorinated silicone modified acrylic binder of the present invention is stable fluorine silicon-modified acrylic ester emulsion, and system stability is good, constant product quality.In embodiment 1, emulsion particle diameter, at 60 ~ 70nm, is distributed in about 1, the even particle size distribution of emulsion particle.Latex film second-order transition temperature after fluorinated silicone modified drops to-15 DEG C, can reach 102 ° to the contact angle of water.The situation of other embodiments is basic consistent with embodiment 1.
The present invention carries out modification by fluorine-containing organic silicon monomer to polyacrylate(s) pigment printing binding agent, and corresponding other components of adjustment and content, when the fluorinated silicone modified acrylic binder of the present invention is applied as pigment printing binding agent, gained PRINTED FABRIC dry fastness can reach 4 ~ 5 grades, fastness to wet rubbing can reach 3 ~ 4 grades, and K/S value can reach more than 13.5, and colour fastness is high, soft, formaldehydeless release.
The fluorinated silicone modified acrylic binder preparation method of the present invention, preparation is simple, and easy to implement and operation, is easy to industrialization scale operation, has broad application prospects.
Accompanying drawing explanation
Fig. 1 is the grain size distribution of fluorine silicon-modified acrylic ester emulsion prepared by embodiment 1;
Fig. 2 is means of differential scanning calorimetry (DSC) spectrogram of fluorine silicon-modified acrylic ester emulsion formation latex film prepared by embodiment 1;
Fig. 3 is that fluorine silicon-modified acrylic ester emulsion prepared by embodiment 1 forms latex film to the contact angle figure of water.
Embodiment
Following embodiment further illustrates of the present invention, but the invention is not restricted to following embodiment.
Embodiment 1
(1) emulsifier sodium lauryl sulfate (SDS) of 0.3 gram is dissolved in 50 grams of deionized water high speeds (1000r/min) and stirs 10 minutes, mix, make pre-emulsion;
(2) by 6 grams of butyl acrylates, 2.5 grams of methyl methacrylates, 0.6 gram of Hydroxyethyl acrylate, 0.6 gram of Isooctyl acrylate monomer, 0.9 gram of glycidyl methacrylate, 0.4 gram of vinylformic acid, 1.5 grams of fluorine-containing organic silicon monomer (formula I structures, mean polymerisation degree n is 8, utilize existing anionic polymerisation process to synthesize to obtain), 0.6 gram of n-hexadecane and 0.15 gram of Diisopropyl azodicarboxylate, mix rear being slowly added drop-wise in pre-emulsion, time for adding is 5min, (1000r/min) stirs 20 minutes at a high speed, within 8 minutes, fine crankshaft liquid is obtained with ultrasonic disintegrator process again in ice-water bath,
(3) above-mentioned fine crankshaft liquid is poured in the four-hole boiling flask with stirring arm, thermometer and prolong, logical High Purity Nitrogen 30 minutes excluding airs, 70 DEG C of waters bath with thermostatic control afterwards add thermal-initiated polymerization 3 hours, obtain fluorine silicon-modified acrylic ester emulsion, i.e. fluorinated silicone modified acrylic binder.
Formula I
The grain size distribution of fluorine silicon-modified acrylic ester emulsion prepared by embodiment 1, as shown in Figure 1, the particle diameter of the emulsion particle in emulsion, at 60 ~ 70nm, is distributed in about 1.
The preparation method of latex film is: take fluorinated silicone modified acrylic binder (i.e. fluorine silicon-modified acrylic ester emulsion) prepared by appropriate the present embodiment and be applied in tetrafluoro plate, place under envrionment temperature (10 ~ 25 DEG C) after 7 days, at 150 DEG C, bake 3min, form latex film.
Fluorine silicon-modified acrylic ester emulsion prepared by embodiment 1 forms means of differential scanning calorimetry (DSC) spectrogram of latex film, as shown in Figure 2, the second-order transition temperature of the acrylate as can be seen from Figure 2 after fluorinated silicone modified and consistent designed by experimental formula, be about-15 DEG C.
Fluorine silicon-modified acrylic ester emulsion prepared by embodiment 1 forms latex film to the contact angle figure of water, as shown in Figure 3, can reach 102 ° to the contact angle of water, shows that the latex film that the fluorinated silicone modified acrylic binder of the present embodiment is formed has excellent hydrophobic performance.
Embodiment 2
(1) emulsifier sodium lauryl sulfate (SDS) of 0.3 gram is dissolved in 50 grams of deionized water high speeds (1000r/min) and stirs 10 minutes, mix, make pre-emulsion;
(2) by 6 grams of butyl acrylates, 2.5 grams of methyl methacrylates, 0.6 gram of Hydroxyethyl acrylate, 0.6 gram of Isooctyl acrylate monomer, 0.9 gram of glycidyl methacrylate, 0.4 gram of vinylformic acid, 1.5 grams of fluorine-containing organic silicon monomer (formula I structures, mean polymerisation degree n is 16, utilize existing anionic polymerisation process to synthesize to obtain), 0.6 gram of n-hexadecane and 0.15 gram of ammonium persulphate, mix rear being slowly added drop-wise in emulsifier aqueous solution, time for adding is 5min, (1000r/min) stirs 20 minutes at a high speed, within 8 minutes, fine crankshaft liquid is obtained with ultrasonic disintegrator process again in ice-water bath,
(3) above-mentioned fine crankshaft liquid is poured in the four-hole boiling flask with stirring arm, thermometer and prolong, logical High Purity Nitrogen 30 minutes excluding airs, 70 DEG C of waters bath with thermostatic control afterwards add thermal-initiated polymerization 3 hours, obtain fluorine silicon-modified acrylic ester emulsion, i.e. fluorinated silicone modified acrylic binder.
Formula I
Form latex film to the contact angle figure of water according to fluorine silicon-modified acrylic ester emulsion prepared by the present embodiment, known, the latex film that the fluorinated silicone modified acrylic binder of the present embodiment is formed has excellent hydrophobic performance.
Embodiment 3
(1) emulsifier sodium lauryl sulfate (SDS) of 0.3 gram is dissolved in 50 grams of deionized water high speeds (1000r/min) and stirs 10 minutes, mix, make pre-emulsion;
(2) by 7 grams of butyl acrylates, 2.5 grams of methyl methacrylates, 1 gram of glycidyl methacrylate, 0.8 gram of vinylformic acid, 1.5 grams of fluorine-containing organic silicon monomer (formula I structures, mean polymerisation degree n is 32, utilize existing anionic polymerisation process to synthesize to obtain), 0.6 gram of n-hexadecane and 0.15 gram of Diisopropyl azodicarboxylate, mix rear being slowly added drop-wise in emulsifier aqueous solution, time for adding is 5min, (1000r/min) stirs 20 minutes at a high speed, again in ice-water bath with ultrasonic disintegrator process 8 minutes, obtain fine crankshaft liquid;
(3) above-mentioned fine crankshaft liquid is poured in the four-hole boiling flask with stirring arm, thermometer and prolong, logical High Purity Nitrogen 30 minutes excluding airs, 70 DEG C of waters bath with thermostatic control afterwards add thermal-initiated polymerization 3 hours, obtain fluorine silicon-modified acrylic ester emulsion, i.e. fluorinated silicone modified acrylic binder.
Formula I
Form latex film to the contact angle figure of water according to fluorine silicon-modified acrylic ester emulsion prepared by the present embodiment, known, the latex film that the fluorinated silicone modified acrylic binder of the present embodiment is formed has excellent hydrophobic performance.
Embodiment 4
(1) emulsifier sodium lauryl sulfate (SDS) of 0.3 gram is dissolved in 50 grams of deionized waters stirs 10 minutes with 1000r/min, mix, make pre-emulsion;
(2) by 6 grams of butyl acrylates, 2.5 grams of methyl methacrylates, 0.6 gram of Hydroxyethyl acrylate, 0.6 gram of Isooctyl acrylate monomer, 0.9 gram of glycidyl methacrylate, 0.4 gram of vinylformic acid, 1.5 grams of fluorine-containing organic silicon monomer (formula I structures, mean polymerisation degree n is 50, utilize existing anionic polymerisation process to synthesize to obtain), 0.6 gram of n-hexadecane and 0.15 gram of Diisopropyl azodicarboxylate, mix rear 5min to be slowly added drop-wise in pre-emulsion, time for adding is 5min, (1000r/min) stirs 20 minutes at a high speed, again in ice-water bath with ultrasonic disintegrator process 8 minutes, obtain fine crankshaft liquid,
(3) above-mentioned fine crankshaft liquid is poured in the four-hole boiling flask with stirring arm, thermometer and prolong, logical High Purity Nitrogen 30 minutes excluding airs, 70 DEG C of waters bath with thermostatic control afterwards add thermal-initiated polymerization 3 hours, obtain fluorine silicon-modified acrylic ester emulsion, i.e. fluorinated silicone modified acrylic binder.
Formula I
Form latex film to the contact angle figure of water according to fluorine silicon-modified acrylic ester emulsion prepared by the present embodiment, known, the latex film that the fluorinated silicone modified acrylic binder of the present embodiment is formed has excellent hydrophobic performance.
Embodiment 5
(1) emulsifier sodium lauryl sulfate (SDS) of 0.3 gram is dissolved in 50 grams of deionized waters stirs 10 minutes with 1000r/min, mix, make pre-emulsion;
(2) by 6.5 grams of butyl acrylates, 2.5 grams of methyl methacrylates, 0.6 gram of Hydroxyethyl acrylate, 0.6 gram of Isooctyl acrylate monomer, 0.9 gram of glycidyl methacrylate, 0.4 gram of vinylformic acid, 1 gram of fluorine-containing organic silicon monomer (formula I structure, mean polymerisation degree n is 13.6, utilize existing anionic polymerisation process to synthesize to obtain), 0.6 gram of n-hexadecane and 0.15 gram of Diisopropyl azodicarboxylate, mix rear 5min to be slowly added drop-wise in pre-emulsion, time for adding is 5min, (1000r/min) stirs 20 minutes at a high speed, 8 minutes are processed with ultrasonic disintegrator (600W) again in ice-water bath, obtain fine crankshaft liquid,
(3) above-mentioned fine crankshaft liquid is poured in the four-hole boiling flask with stirring arm, thermometer and prolong, logical High Purity Nitrogen 30 minutes excluding airs, 70 DEG C of waters bath with thermostatic control afterwards add thermal-initiated polymerization 3 hours, obtain fluorine silicon-modified acrylic ester emulsion, i.e. fluorinated silicone modified acrylic binder.
Formula I
Form latex film to the contact angle figure of water according to fluorine silicon-modified acrylic ester emulsion prepared by the present embodiment, known, the latex film that the fluorinated silicone modified acrylic binder of the present embodiment is formed has excellent hydrophobic performance.
Embodiment 6
(1) the emulsifying agent sodium laurylsulfonate (SDS) of 0.9 gram is dissolved in 50 grams of deionized water high speeds (1500r/min) and stirs 25 minutes, mix, make pre-emulsion;
(2) by 8 grams of butyl acrylates, 4 grams of methyl methacrylates, 0.9 gram of Hydroxyethyl acrylate, 0.9 gram of Isooctyl acrylate monomer, 1.3 grams of glycidyl methacrylate, 0.7 gram of vinylformic acid, 4 grams of fluorine-containing organic silicon monomer (formula I structures, mean polymerisation degree n is 8, utilize existing anionic polymerisation process to synthesize to obtain), 1.5 grams of n-hexadecanes and 0.9 gram of Diisopropyl azodicarboxylate, mix rear being slowly added drop-wise in pre-emulsion, time for adding is 10min, (1500r/min) stirs 20 minutes at a high speed, within 15 minutes, fine crankshaft liquid is obtained with ultrasonic disintegrator process again in ice-water bath,
(3) above-mentioned fine crankshaft liquid is poured in the four-hole boiling flask with stirring arm, thermometer and prolong, logical High Purity Nitrogen 30 minutes excluding airs, 60 DEG C of waters bath with thermostatic control afterwards add thermal-initiated polymerization 6 hours, obtain fluorine silicon-modified acrylic ester emulsion, i.e. fluorinated silicone modified acrylic binder.
Formula I
Form latex film to the contact angle figure of water according to fluorine silicon-modified acrylic ester emulsion prepared by the present embodiment, known, the latex film that the fluorinated silicone modified acrylic binder of the present embodiment is formed has excellent hydrophobic performance.
Embodiment 7
(1) emulsifier sodium lauryl sulfate (SDS) of 0.1 gram is dissolved in 50 grams of deionized water high speeds (500r/min) and stirs 5 minutes, mix, make pre-emulsion;
(2) by 6 grams of butyl acrylates, 2.5 grams of methyl methacrylates, 0.6 gram of Hydroxyethyl acrylate, 0.6 gram of Isooctyl acrylate monomer, 0.9 gram of glycidyl methacrylate, 0.4 gram of vinylformic acid, 0.5 gram of fluorine-containing organic silicon monomer (formula I structure, mean polymerisation degree n is 8, utilize existing anionic polymerisation process to synthesize to obtain), 0.2 gram of positive hexadecanol and 0.1 gram of Diisopropyl azodicarboxylate, mix rear being slowly added drop-wise in pre-emulsion, time for adding is 3min, (500r/min) stirs 20 minutes at a high speed, within 5 minutes, fine crankshaft liquid is obtained with ultrasonic disintegrator process again in ice-water bath,
(3) above-mentioned fine crankshaft liquid is poured in the four-hole boiling flask with stirring arm, thermometer and prolong, logical High Purity Nitrogen 30 minutes excluding airs, 80 DEG C of waters bath with thermostatic control afterwards add thermal-initiated polymerization 2 hours, obtain fluorine silicon-modified acrylic ester emulsion, i.e. fluorinated silicone modified acrylic binder.
Formula I
Form latex film to the contact angle figure of water according to fluorine silicon-modified acrylic ester emulsion prepared by the present embodiment, known, the latex film that the fluorinated silicone modified acrylic binder of the present embodiment is formed has excellent hydrophobic performance.
Comparative example 1
(1) emulsifier sodium lauryl sulfate (SDS) of 0.3 gram is dissolved in 50 grams of deionized water high speeds (1000r/min) and stirs 10 minutes, mix, make pre-emulsion;
(2) by 6 grams of butyl acrylates, 2.5 grams of methyl methacrylates, 0.6 gram of Hydroxyethyl acrylate, 0.6 gram of Isooctyl acrylate monomer, 0.9 gram of glycidyl methacrylate, 0.4 gram of vinylformic acid, 0.6 gram of n-hexadecane and 0.15 gram of Diisopropyl azodicarboxylate, mix rear being slowly added drop-wise in pre-emulsion, time for adding is 5min, (1000r/min) stirs 20 minutes at a high speed, then within 8 minutes, obtains fine crankshaft liquid with ultrasonic disintegrator process in ice-water bath;
(3) pour in the four-hole boiling flask with stirring arm, thermometer and prolong by above-mentioned fine crankshaft liquid, logical High Purity Nitrogen 30 minutes excluding airs, 70 DEG C of waters bath with thermostatic control afterwards add thermal-initiated polymerization 3 hours, obtain acrylic ester emulsion, i.e. acrylic binder.
Application examples
The printing technology of pigment printing:
(1) printing paste prescription: blue 2 grams of coating, adopts 15 grams, tackiness agent prepared by embodiment 1 ~ 7 and comparative example 1 respectively, thickening material 1.5 grams, 31.5 grams, water, amounts to 50 grams.
(2) printing technology: stamp → preliminary drying (80 DEG C, 5 minutes) → bake (160 DEG C, 3 minutes).
Adopt the printing quality of the pigment printing tackiness agent of the present invention's synthesis, fastness to wet rubbing dry according to GB/T3920-1997 " textile color stability test colour fastness to rubbing " measurement of test method; LLY-01 type electronics hardometer is adopted to measure stiffness; Adopt the color depth (K/S value) of DatacolorSF600 type computer color measurement and color match instrument test stamp product, the printing quality of detection is as shown in table 1.
Table 1
As can be seen from Table 1, through different molecular weight and different content fluorinated silicone modified after acrylic binder (i.e. the fluorinated silicone modified acrylic binder of the present invention) for pigment printing after, the dry fastness of PRINTED FABRIC all can reach 4 ~ 5 grades, fastness to wet rubbing all can reach more than 3 grades, higher than the acrylic binder not having modification, therefore, the present invention's fluorinated silicone modified acrylic binder colour fastness is high, and the fluorinated silicone modified acrylic binder stiffness of the present invention reduces, feel limbers up, and stamp K/S value increases.
Claims (4)
1. fluorinated silicone modified acrylic binder is as an application for pigment printing binding agent, it is characterized in that, described fluorinated silicone modified acrylic binder is made up of the raw material of following weight part:
Described acrylic ester polymerization monomer be in butyl acrylate, Hydroxyethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, glycidyl methacrylate one or more;
Described fluorine-containing organic silicon monomer is the fluorinated polysiloxane of ethenyl blocking, is the compound of formula I structure;
Wherein, n is mean polymerisation degree, n=3 ~ 50;
The preparation method of described fluorinated silicone modified acrylic binder, comprises the following steps:
1) anionic emulsifier and water are mixed, prepare pre-emulsion;
Anionic emulsifier and water are stirred under rotating speed 500r/min ~ 1500r/min and within 5 ~ 30 minutes, mixes;
2) acrylic ester polymerization monomer, vinylformic acid, fluorine-containing organic silicon monomer, assistant for emulsifying agent and initiator are mixed, be then added drop-wise in pre-emulsion, after dripping off, mix, obtain emulsion, then obtain fine crankshaft liquid through ultrasonication;
Emulsion is through ice-water bath ultrasonication 5 ~ 20 minutes;
3) fine crankshaft liquid is reacted 1 ~ 6 hour at 60 DEG C ~ 80 DEG C, obtain fluorine silicon-modified acrylic ester emulsion, i.e. fluorinated silicone modified acrylic binder.
2. application according to claim 1, is characterized in that, described anionic emulsifier is sodium lauryl sulphate or sodium laurylsulfonate.
3. application according to claim 1, is characterized in that, described assistant for emulsifying agent is n-hexadecane or positive hexadecanol.
4. application according to claim 1, is characterized in that, described initiator is Diisopropyl azodicarboxylate, ammonium persulphate or Potassium Persulphate.
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| CN110642999B (en) * | 2019-10-28 | 2022-06-03 | 浙江理工大学 | Preparation method and application of fluorosilicone modified acrylate emulsion |
| CN113265888B (en) * | 2021-05-13 | 2023-01-17 | 苏州联胜化学有限公司 | High-fastness pigment printing adhesive and preparation method thereof |
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