CN103224765A - Fluorine-silicon-modified acrylate adhesive, preparation method and application thereof - Google Patents
Fluorine-silicon-modified acrylate adhesive, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorine-silicon-modified acrylate adhesive which is prepared by the following raw materials by weight parts: 50 parts of water, 0.1-1 part of an anionic emulsifier, 10-20 parts of acrylate polymerizable monomers, 0.2-1 part of acrylic acid, 0.5-5 parts of fluorine containing organosilicon monomers, 0.1-2 parts of co-emulsifier and 0.1-1 part of an initiator. The fluorine-silicon-modified acrylate adhesive is a stable fluorine-silicon-modified acrylate emulsion, can be used for pigment printing, is soft in touch, high is color fastness, good in system stability and stable in product quality, and effectively solves problems of incompatible touch and fastness, and hot sticking and cold shortness existing in present acrylate adhesives. The invention further discloses a preparation method of the fluorine-silicon-modified acrylate adhesive. According to the method, stable fluorine-silicon-modified acrylate emulsion is prepared through miniemulsion polymerization. The method is simple in preparation, easy to implement and operate, and easy for industrial production, and has wide application prospect.
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 as the application of pigment printing binding agent.
Background technology
Pigment printing is a kind ofly will fiber not to be anchored at fabric face with having affinity and reactive paint machine by tackiness agent, only needs fixation, need not washing.Therefore, have advantages such as energy-conservation, water saving, reduction of discharging,, also listed in textile industry simultaneously and carry out one of technology of cleaner production by State Economic and Trade Commission by vast printing and dyeing enterprise widespread use.
And 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 the polyacrylate(s) pigment printing binding agent, and it has characteristics such as good film-forming property, cohesive strength height, heat-resisting, resistance to oxidation, but exist that hardness is big, problem such as hot sticky cold crisp, feel and fastness are difficult to get both.And, be cross-linking monomer how with the N hydroxymethyl acrylamide, high temperature bakes and can discharge in a large number human body and the deleterious free formaldehyde of environment, and the physical and mechanical properties of textile fiber is sustained damage.
Therefore, research and development environment-protection coating printing adhesive soft, high color fastness has crucial meaning.
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, the preparation method comprises: (1) makes organosilicon pre-polymerization emulsion with silane monomer, coupling agent, modified monomer catalyzer, emulsifying agent and deionized water pre-polymerization; (2) with this organosilicon pre-polymerization emulsion and basic monomer emulsification, make the intermediate pre-emulsion; (3) with intermediate pre-emulsion, basic monomer catalyzer and deionized water polymerization, make environment-friendly type organosilicon modified acrylic ester binding agent.In this technical scheme, mainly be that the silica segment of silane monomer is longer, cause it to have stronger water repellency, be difficult to realize this process of monomeric migration in the ordinary emulsion polymerization, make that organosilyl final transformation efficiency is not high.
Summary of the invention
The invention provides a kind of fluorinated silicone modified acrylic binder, fluorinated silicone modified acrylic ester emulsion for stable can be used for pigment printing, and is soft, the colour fastness height has solved the feel of existing acrylate adhesive existence effectively and fastness contradicts and the problem of hot sticky cold crisp.
A kind of fluorinated silicone modified acrylic binder, make by the raw material of following weight part:
50 parts in water;
0.1～1 part of anionic emulsifier;
10～20 parts of acrylic ester polymerization monomers;
0.2～1 part in vinylformic acid;
0.5～5 part of fluorine-containing organosilane monomer;
0.1～2 part of assistant for emulsifying agent;
0.1～1 part of initiator;
Described acrylic ester polymerization monomer be in butyl acrylate, Hydroxyethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, the glycidyl methacrylate one or more.
As preferably, described fluorinated silicone modified acrylic binder, make by the raw material of following weight part:
50 parts in water;
0.1～0.9 part of anionic emulsifier;
10.5～15.1 parts of acrylic ester polymerization monomers;
0.4～0.8 part in vinylformic acid;
0.5～4 part of fluorine-containing organosilane monomer;
0.2～1.5 part of assistant for emulsifying agent;
0.1～0.9 part of initiator.
This fluorinated silicone modified acrylic binder is applied to pigment printing, and feel is more soft, and colour fastness is higher,
Anionic emulsifier attached to the emulsion particle surface, produces electrostatic repulsion owing to electronegative each other, therefore, can avoid making minor comonomer to collide into big drop mutually, thereby play the effect of stablizing 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 the raw material, this is because the carboxyl in the acrylic molecules is strong polar group (electronegative), can make the emulsion particle skin have static charge, and emulsion particle is difficult for assembling because of electrostatic repulsion, thereby improves the stability of emulsion.Vinylformic acid can significantly improve the film forming properties of tackiness agent as cross-linking monomer simultaneously, increases the magnetism to fiber, improves bonding force, and cross-linking set can also be provided, and plays self-catalysis, so can improve the pigment printing fastness.Therefore, adopt vinylformic acid, can improve the stability of emulsion and the printing fastness that improves coating.
As preferably, described fluorine-containing organosilane monomer is the fluorinated polysiloxane of ethenyl blocking, is the compound of formula I structure;
Formula I;
Wherein, n is a mean polymerisation degree, n=3～50.
Fluorine-containing organosilane monomer (being the fluorinated polysiloxane of ethenyl blocking), contain the silicone macromolecule of vinyl and small molecules vinyl monomer and carry out copolymerization by the method for radical polymerization and obtain, the fluorine-containing organosilane monomer that adopts formula I structure is to acrylate modified.
Assistant for emulsifying agent can form the interface obstacle on the drop surface, reduces monomer droplet and degrades because of Ostwald (Ostwald) slaking, delays monomer from the migration of small droplets to big drop, thereby improves the stability of emulsion.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 the stability of emulsion better.
Described initiator is oil-soluble initiator or water soluble starter, can decompose the generation free radical, thereby causes the free-radical polymerized of vinyl monomer.As preferably, oil-soluble initiator is a Diisopropyl azodicarboxylate, and Diisopropyl azodicarboxylate mainly is present in the monomer droplet, and all monomer droplets cause simultaneously during the reaction beginning, and polymerization rate is very fast; Water soluble starter is ammonium persulphate or Potassium Persulphate, and ammonium persulphate or Potassium Persulphate mainly are present in aqueous phase, and monomer droplet is by catching the free radical polymerization of aqueous phase, and polymerization process is more steady, the implode phenomenon can not occur.Be that described initiator is Diisopropyl azodicarboxylate, ammonium persulphate or Potassium Persulphate.
The present invention also provides a kind of preparation method of fluorinated silicone modified acrylic binder, has prepared stable fluorinated silicone modified acrylic ester emulsion by mini-emulsion polymerization, and preparation is simple, and is easy to implement.
A kind of preparation method of fluorinated silicone modified acrylic binder may further comprise the steps:
1) anionic emulsifier and water are mixed the preparation pre-emulsion;
2) acrylic ester polymerization monomer, vinylformic acid, fluorine-containing organosilane monomer, assistant for emulsifying agent and initiator are mixed, be added drop-wise to then in the pre-emulsion, after dripping off, mix, obtain emulsion, obtain thin emulsion through ultrasonication again;
3) thin emulsion was reacted 1～8 hour at 50 ℃～90 ℃, obtain fluorinated silicone modified acrylic ester emulsion, promptly fluorinated silicone modified acrylic binder.
In the step 1), as preferably, with anionic emulsifier and water at rotating speed 500r/min～1500r/min(rev/min) stir down and mixed in 5～30 minutes, can make that anionic emulsifier and water thorough mixing are even.
Step 2) in, as preferably, it is 3min～10min that acrylic ester polymerization monomer, vinylformic acid, fluorine-containing organosilane monomer, assistant for emulsifying agent and initiator mix the time that is added drop-wise to pre-emulsion, make acrylic ester polymerization monomer, vinylformic acid, fluorine-containing organosilane monomer, assistant for emulsifying agent and initiator mix the mixed solution that forms, evenly spread in the pre-emulsion.
As preferably, after dripping off, under rotating speed 500r/min～1500r/min, stir and mixed in 5～30 minutes, obtain emulsion, make that each component thorough mixing is even in the emulsion, obtain stable emulsion.
As preferably, emulsion adopts ice-water bath can absorb a large amount of heats that produce in the ultrasonic procedure through ice-water bath ultrasonication 5～20 minutes, makes monomer stable, thereby makes the submicron monomer droplet of formation more stable.
In the step 3),, thin emulsion was reacted 1～6 hour at 60 ℃～80 ℃ as preferably, can specifically select water bath with thermostatic control for use, temperature of reaction is too low to be difficult to the trigger monomer polymerization, and too high reaction is too fast, the implode phenomenon takes place easily, and above-mentioned reaction conditions can make polyreaction successfully carry out.
Carry out under the described atmosphere that is reflected at shielding gas, 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 may further comprise the steps:
(1) printing paste prescription (weight part): 2 parts of pigment, 10～20 parts of fluorinated silicone modified acrylic binders, 1～2 part of thickening material, 20～40 parts in water.
(2) printing technology: stamp → preliminary drying (80 ℃, 5 minutes) → bake (160 ℃, 3 minutes).
Compared with prior art, the present invention has following advantage:
The fluorinated silicone modified acrylic binder of the present invention is stable fluorinated silicone modified acrylic ester emulsion, and system has good stability, constant product quality.In embodiment 1, emulsion particle diameter is distributed in about 1 at 60～70nm, and the size distribution of emulsion particle is even.Latex film second-order transition temperature after fluorinated silicone modified drops to-15 ℃, can reach 102 ° to the contact angle of water.The situation of other embodiment is basic consistent with embodiment 1.
The present invention carries out modification by fluorine-containing organosilane monomer to the polyacrylate(s) pigment printing binding agent, and adjust other components and content accordingly, make when the fluorinated silicone modified acrylic binder of the present invention is used 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 the K/S value can reach more than 13.5, the colour fastness height, 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 large-scale industrialization production, has broad application prospects.
Description of drawings
Fig. 1 is the size distribution figure of the fluorinated silicone modified acrylic ester emulsion of embodiment 1 preparation;
Fig. 2 is differential scanning calorimetric (DSC) spectrogram that the fluorinated silicone modified acrylic ester emulsion of embodiment 1 preparation forms latex film;
Fig. 3 is that the fluorinated silicone modified acrylic ester emulsion of embodiment 1 preparation forms the contact angle figure of latex film to water.
Embodiment
Following embodiment further specifies of the present invention, but the invention is not restricted to following embodiment.
Embodiment 1
(1) emulsifier sodium lauryl sulfate (SDS) with 0.3 gram is dissolved in 50 gram deionized water high speeds (1000r/min) stirrings 10 minutes, mixes, and makes pre-emulsion;
(2) with 6 gram butyl acrylates, 2.5 gram methyl methacrylate, 0.6 gram Hydroxyethyl acrylate, 0.6 gram Isooctyl acrylate monomer, 0.9 gram glycidyl methacrylate, 0.4 gram vinylformic acid, 1.5 restrain fluorine-containing organosilane monomer (formula I structure, mean polymerisation degree n is 8, utilizing existing anionic polymerisation process to synthesize obtains), 0.6 gram n-hexadecane and 0.15 gram Diisopropyl azodicarboxylate, slowly be added drop-wise in the pre-emulsion after mixing, the dropping time is 5min, (1000r/min) stirred 20 minutes at a high speed, obtained thin emulsion in 8 minutes with the ultrasonic disintegrator processing again in ice-water bath;
(3) above-mentioned thin emulsion is poured in the four-hole boiling flask that has stirring arm, thermometer and prolong, logical 30 minutes excluding airs of high purity nitrogen, 70 ℃ of waters bath with thermostatic control afterwards added thermal-initiated polymerization 3 hours, obtained fluorinated silicone modified acrylic ester emulsion, promptly fluorinated silicone modified acrylic binder.
Formula I
The size distribution figure of the fluorinated silicone modified acrylic ester emulsion of embodiment 1 preparation, as shown in Figure 1, the particle diameter of the emulsion particle in the emulsion is distributed in about 1 at 60～70nm.
The preparation method of latex film is: the fluorinated silicone modified acrylic binder (being fluorinated silicone modified acrylic ester emulsion) that takes by weighing an amount of present embodiment preparation is applied in the tetrafluoro plate, after envrionment temperature (10～25 ℃) is placed 7 days down, under 150 ℃, bake 3min, form latex film.
The fluorinated silicone modified acrylic ester emulsion of embodiment 1 preparation forms differential scanning calorimetric (DSC) spectrogram of latex film, as shown in Figure 2, as can be seen from Figure 2 designed consistent of the second-order transition temperature of the acrylate after fluorinated silicone modified and experimental formula is for about-15 ℃.
The fluorinated silicone modified acrylic ester emulsion of embodiment 1 preparation forms the contact angle figure of latex film to 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 present embodiment forms has the excellent hydrophobicity energy.
Embodiment 2
(1) emulsifier sodium lauryl sulfate (SDS) with 0.3 gram is dissolved in 50 gram deionized water high speeds (1000r/min) stirrings 10 minutes, mixes, and makes pre-emulsion;
(2) with 6 gram butyl acrylates, 2.5 gram methyl methacrylate, 0.6 gram Hydroxyethyl acrylate, 0.6 gram Isooctyl acrylate monomer, 0.9 gram glycidyl methacrylate, 0.4 gram vinylformic acid, 1.5 restrain fluorine-containing organosilane monomer (formula I structure, mean polymerisation degree n is 16, utilizing existing anionic polymerisation process to synthesize obtains), 0.6 gram n-hexadecane and 0.15 gram ammonium persulphate, slowly be added drop-wise in the emulsifier aqueous solution after mixing, the dropping time is 5min, (1000r/min) stirred 20 minutes at a high speed, obtained thin emulsion in 8 minutes with the ultrasonic disintegrator processing again in ice-water bath;
(3) above-mentioned thin emulsion is poured in the four-hole boiling flask that has stirring arm, thermometer and prolong, logical 30 minutes excluding airs of high purity nitrogen, 70 ℃ of waters bath with thermostatic control afterwards added thermal-initiated polymerization 3 hours, obtained fluorinated silicone modified acrylic ester emulsion, promptly fluorinated silicone modified acrylic binder.
Formula I
Fluorinated silicone modified acrylic ester emulsion according to the present embodiment preparation forms the contact angle figure of latex film to water, and as can be known, the latex film that the fluorinated silicone modified acrylic binder of present embodiment forms has the excellent hydrophobicity energy.
Embodiment 3
(1) emulsifier sodium lauryl sulfate (SDS) with 0.3 gram is dissolved in 50 gram deionized water high speeds (1000r/min) stirrings 10 minutes, mixes, and makes pre-emulsion;
(2) with 7 gram butyl acrylates, 2.5 gram methyl methacrylates, 1 gram glycidyl methacrylate, 0.8 gram vinylformic acid, the fluorine-containing organosilane monomer of 1.5 grams (formula I structure, mean polymerisation degree n is 32, utilize that existing anionic polymerisation process is synthetic to be obtained), 0.6 gram n-hexadecane and 0.15 gram Diisopropyl azodicarboxylate, slowly be added drop-wise in the emulsifier aqueous solution after mixing, the dropping time is 5min, (1000r/min) stirred 20 minutes at a high speed, in ice-water bath, handled 8 minutes again, obtain thin emulsion with ultrasonic disintegrator;
(3) above-mentioned thin emulsion is poured in the four-hole boiling flask that has stirring arm, thermometer and prolong, logical 30 minutes excluding airs of high purity nitrogen, 70 ℃ of waters bath with thermostatic control afterwards added thermal-initiated polymerization 3 hours, obtained fluorinated silicone modified acrylic ester emulsion, promptly fluorinated silicone modified acrylic binder.
Formula I
Fluorinated silicone modified acrylic ester emulsion according to the present embodiment preparation forms the contact angle figure of latex film to water, and as can be known, the latex film that the fluorinated silicone modified acrylic binder of present embodiment forms has the excellent hydrophobicity energy.
Embodiment 4
(1) emulsifier sodium lauryl sulfate (SDS) of 0.3 gram is dissolved in the 50 gram deionized waters stirred 10 minutes, mix, make pre-emulsion with 1000r/min;
(2) with 6 gram butyl acrylates, 2.5 gram methyl methacrylate, 0.6 gram Hydroxyethyl acrylate, 0.6 gram Isooctyl acrylate monomer, 0.9 gram glycidyl methacrylate, 0.4 gram vinylformic acid, 1.5 restrain fluorine-containing organosilane monomer (formula I structure, mean polymerisation degree n is 50, utilizing existing anionic polymerisation process to synthesize obtains), 0.6 gram n-hexadecane and 0.15 gram Diisopropyl azodicarboxylate, mixing back 5min slowly is added drop-wise in the pre-emulsion, the dropping time is 5min, (1000r/min) stirred 20 minutes at a high speed, in ice-water bath, handled 8 minutes again, obtain thin emulsion with ultrasonic disintegrator;
(3) above-mentioned thin emulsion is poured in the four-hole boiling flask that has stirring arm, thermometer and prolong, logical 30 minutes excluding airs of high purity nitrogen, 70 ℃ of waters bath with thermostatic control afterwards added thermal-initiated polymerization 3 hours, obtained fluorinated silicone modified acrylic ester emulsion, promptly fluorinated silicone modified acrylic binder.
Formula I
Fluorinated silicone modified acrylic ester emulsion according to the present embodiment preparation forms the contact angle figure of latex film to water, and as can be known, the latex film that the fluorinated silicone modified acrylic binder of present embodiment forms has the excellent hydrophobicity energy.
Embodiment 5
(1) emulsifier sodium lauryl sulfate (SDS) of 0.3 gram is dissolved in the 50 gram deionized waters stirred 10 minutes, mix, make pre-emulsion with 1000r/min;
(2) with 6.5 gram butyl acrylates, 2.5 gram methyl methacrylate, 0.6 gram Hydroxyethyl acrylate, 0.6 gram Isooctyl acrylate monomer, 0.9 gram glycidyl methacrylate, 0.4 gram vinylformic acid, the fluorine-containing organosilane monomer of 1 gram (formula I structure, mean polymerisation degree n is 13.6, utilizing existing anionic polymerisation process to synthesize obtains), 0.6 gram n-hexadecane and 0.15 gram Diisopropyl azodicarboxylate, mixing back 5min slowly is added drop-wise in the pre-emulsion, the dropping time is 5min, (1000r/min) stirred 20 minutes at a high speed, in ice-water bath, handled 8 minutes again, obtain thin emulsion with ultrasonic disintegrator (600W);
(3) above-mentioned thin emulsion is poured in the four-hole boiling flask that has stirring arm, thermometer and prolong, logical 30 minutes excluding airs of high purity nitrogen, 70 ℃ of waters bath with thermostatic control afterwards added thermal-initiated polymerization 3 hours, obtained fluorinated silicone modified acrylic ester emulsion, promptly fluorinated silicone modified acrylic binder.
Formula I
Fluorinated silicone modified acrylic ester emulsion according to the present embodiment preparation forms the contact angle figure of latex film to water, and as can be known, the latex film that the fluorinated silicone modified acrylic binder of present embodiment forms has the excellent hydrophobicity energy.
Embodiment 6
(1) the emulsifying agent sodium laurylsulfonate (SDS) with 0.9 gram is dissolved in 50 gram deionized water high speeds (1500r/min) stirrings 25 minutes, mixes, and makes pre-emulsion;
(2) with 8 gram butyl acrylates, 4 gram methyl methacrylates, 0.9 gram Hydroxyethyl acrylate, 0.9 gram Isooctyl acrylate monomer, 1.3 gram glycidyl methacrylate, 0.7 gram vinylformic acid, the fluorine-containing organosilane monomer of 4 grams (formula I structure, mean polymerisation degree n is 8, utilizing existing anionic polymerisation process to synthesize obtains), 1.5 gram n-hexadecane and 0.9 gram Diisopropyl azodicarboxylate, slowly be added drop-wise in the pre-emulsion after mixing, the dropping time is 10min, (1500r/min) stirred 20 minutes at a high speed, obtained thin emulsion in 15 minutes with the ultrasonic disintegrator processing again in ice-water bath;
(3) above-mentioned thin emulsion is poured in the four-hole boiling flask that has stirring arm, thermometer and prolong, logical 30 minutes excluding airs of high purity nitrogen, 60 ℃ of waters bath with thermostatic control afterwards added thermal-initiated polymerization 6 hours, obtained fluorinated silicone modified acrylic ester emulsion, promptly fluorinated silicone modified acrylic binder.
Formula I
Fluorinated silicone modified acrylic ester emulsion according to the present embodiment preparation forms the contact angle figure of latex film to water, and as can be known, the latex film that the fluorinated silicone modified acrylic binder of present embodiment forms has the excellent hydrophobicity energy.
Embodiment 7
(1) emulsifier sodium lauryl sulfate (SDS) with 0.1 gram is dissolved in 50 gram deionized water high speeds (500r/min) stirrings 5 minutes, mixes, and makes pre-emulsion;
(2) with 6 gram butyl acrylates, 2.5 gram methyl methacrylate, 0.6 gram Hydroxyethyl acrylate, 0.6 gram Isooctyl acrylate monomer, 0.9 gram glycidyl methacrylate, 0.4 gram vinylformic acid, 0.5 restrain fluorine-containing organosilane monomer (formula I structure, mean polymerisation degree n is 8, utilizing existing anionic polymerisation process to synthesize obtains), 0.2 restrain positive hexadecanol and 0.1 gram Diisopropyl azodicarboxylate, slowly be added drop-wise in the pre-emulsion after mixing, the dropping time is 3min, (500r/min) stirred 20 minutes at a high speed, obtained thin emulsion in 5 minutes with the ultrasonic disintegrator processing again in ice-water bath;
(3) above-mentioned thin emulsion is poured in the four-hole boiling flask that has stirring arm, thermometer and prolong, logical 30 minutes excluding airs of high purity nitrogen, 80 ℃ of waters bath with thermostatic control afterwards added thermal-initiated polymerization 2 hours, obtained fluorinated silicone modified acrylic ester emulsion, promptly fluorinated silicone modified acrylic binder.
Formula I
Fluorinated silicone modified acrylic ester emulsion according to the present embodiment preparation forms the contact angle figure of latex film to water, and as can be known, the latex film that the fluorinated silicone modified acrylic binder of present embodiment forms has the excellent hydrophobicity energy.
Comparative Examples 1
(1) emulsifier sodium lauryl sulfate (SDS) with 0.3 gram is dissolved in 50 gram deionized water high speeds (1000r/min) stirrings 10 minutes, mixes, and makes pre-emulsion;
(2) with 6 gram butyl acrylates, 2.5 gram methyl methacrylates, 0.6 gram Hydroxyethyl acrylate, 0.6 gram Isooctyl acrylate monomer, 0.9 gram glycidyl methacrylate, 0.4 gram vinylformic acid, 0.6 gram n-hexadecane and 0.15 gram Diisopropyl azodicarboxylate, slowly be added drop-wise in the pre-emulsion after mixing, the dropping time is 5min, (1000r/min) stirred 20 minutes at a high speed, obtained thin emulsion in 8 minutes with the ultrasonic disintegrator processing again in ice-water bath;
(3) above-mentioned thin emulsion is poured in the four-hole boiling flask that has stirring arm, thermometer and prolong, logical 30 minutes excluding airs of high purity nitrogen, 70 ℃ of waters bath with thermostatic control afterwards added thermal-initiated polymerization 3 hours, obtained acrylic ester emulsion, i.e. acrylic binder.
Application examples
The printing technology of pigment printing:
(1) printing paste prescription: blue 2 grams of coating, adopt the tackiness agent 15 of embodiment 1～7 and Comparative Examples 1 preparation to restrain respectively, thickening material 1.5 grams, water 31.5 grams amount to 50 grams.
(2) printing technology: stamp → preliminary drying (80 ℃, 5 minutes) → bake (160 ℃, 3 minutes).
Adopt the printing quality of synthetic pigment printing of the present invention,, fastness to wet rubbing dried according to GB/T3920-1997 " textile color stability test colour fastness to rubbing " measurement of test method with tackiness agent; Adopt LLY-01 type electronics stiffness instrument 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, after acrylic binder (being the fluorinated silicone modified acrylic binder of the present invention) after process different molecular weight and different content are fluorinated silicone modified is used for pigment printing, the dry fastness of PRINTED FABRIC all can reach 4～5 grades, fastness to wet rubbing all can reach more than 3 grades, be higher than the acrylic binder that does not have modification, therefore, the fluorinated silicone modified acrylic binder colour fastness of the present invention height, and the fluorinated silicone modified acrylic binder stiffness of the present invention reduces, feel limbers up, and stamp K/S value increases.
Claims (10)
1. a fluorinated silicone modified acrylic binder is characterized in that, is made by the raw material of following weight part:
50 parts in water;
0.1～1 part of anionic emulsifier;
10～20 parts of acrylic ester polymerization monomers;
0.2～1 part in vinylformic acid;
0.5～5 part of fluorine-containing organosilane monomer;
0.1～2 part of assistant for emulsifying agent;
0.1～1 part of initiator;
Described acrylic ester polymerization monomer be in butyl acrylate, Hydroxyethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, the glycidyl methacrylate one or more.
2. fluorinated silicone modified acrylic binder according to claim 1 is characterized in that, described anionic emulsifier is sodium lauryl sulphate or sodium laurylsulfonate.
3. fluorinated silicone modified acrylic binder according to claim 1 is characterized in that, described fluorine-containing organosilane monomer is the fluorinated polysiloxane of ethenyl blocking, is the compound of formula I structure;
Formula I;
Wherein, n is a mean polymerisation degree, n=3～50.
4. fluorinated silicone modified acrylic binder according to claim 1 is characterized in that, described assistant for emulsifying agent is n-hexadecane or positive hexadecanol.
5. fluorinated silicone modified acrylic binder according to claim 1 is characterized in that, described initiator is Diisopropyl azodicarboxylate, ammonium persulphate or Potassium Persulphate.
6. according to the preparation method of each described fluorinated silicone modified acrylic binder of claim 1～5, it is characterized in that, may further comprise the steps:
1) anionic emulsifier and water are mixed the preparation pre-emulsion;
2) acrylic ester polymerization monomer, vinylformic acid, fluorine-containing organosilane monomer, assistant for emulsifying agent and initiator are mixed, be added drop-wise to then in the pre-emulsion, after dripping off, mix, obtain emulsion, obtain thin emulsion through ultrasonication again;
3) thin emulsion was reacted 1～8 hour at 50 ℃～90 ℃, obtain fluorinated silicone modified acrylic ester emulsion, promptly fluorinated silicone modified acrylic binder.
7. the preparation method of fluorinated silicone modified acrylic binder according to claim 6 is characterized in that, in the step 1), anionic emulsifier and water stirred under rotating speed 500r/min～1500r/min mixed in 5～30 minutes.
8. the preparation method of fluorinated silicone modified acrylic binder according to claim 6 is characterized in that step 2) in, emulsion is through ice-water bath ultrasonication 5～20 minutes.
9. the preparation method of fluorinated silicone modified acrylic binder according to claim 6 is characterized in that, in the step 3), thin emulsion is reacted 1～6 hour at 60 ℃～80 ℃.
10. according to of the application of each described fluorinated silicone modified acrylic binder of claim 1～5 as pigment printing binding agent.
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| CN103952105A (en) * | 2014-03-28 | 2014-07-30 | 广东达美新材料有限公司 | Fluorosilicone modified aqueous pressure-sensitive adhesive used for polyethylene protection film, and preparation method thereof |
| CN105625043A (en) * | 2016-03-11 | 2016-06-01 | 浙江七色彩虹印染有限公司 | Three-proofing finishing agent containing fluorine and stable emulsifying technology thereof |
| CN105755864A (en) * | 2016-02-29 | 2016-07-13 | 广西大学 | Method for preparing printing coating adhesive |
| CN106010379A (en) * | 2015-08-18 | 2016-10-12 | 江苏景宏新材料科技有限公司 | Water-based acrylate pressure sensitive adhesive for battery labels and preparation method thereof |
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| CN105755864A (en) * | 2016-02-29 | 2016-07-13 | 广西大学 | Method for preparing printing coating adhesive |
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| CN107988822A (en) * | 2017-10-27 | 2018-05-04 | 浙江理工大学 | The high dyestuff of disperse dyes Non-water washing stamp carries passing property adhesive and preparation method |
| CN107988822B (en) * | 2017-10-27 | 2022-06-28 | 浙江理工大学 | High-dye-carrying-property adhesive for washing-free printing of disperse dye and preparation method thereof |
| CN109517110A (en) * | 2018-11-26 | 2019-03-26 | 宁德师范学院 | The preparation method of the siliceous fluorinated monomer lotion of textile printing coating |
| CN110642999A (en) * | 2019-10-28 | 2020-01-03 | 浙江理工大学 | Preparation method and application of fluorosilicone modified acrylate emulsion |
| CN113265888A (en) * | 2021-05-13 | 2021-08-17 | 苏州联胜化学有限公司 | High-fastness pigment printing adhesive and preparation method thereof |
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