CN115124721B - Modified gelatin for coating printing and dyeing adhesive as well as preparation method and application thereof - Google Patents
Modified gelatin for coating printing and dyeing adhesive as well as preparation method and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
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- D06P1/5292—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds containing Si-atoms
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Abstract
The application belongs to the field of gelatin application, and in particular relates to modified gelatin for a coating printing and dyeing adhesive, and a preparation method and application thereof, wherein the modified gelatin is prepared by modifying gelatin by using epoxy polysiloxane (PDMS-E) emulsion drops, the average particle size of the epoxy polysiloxane emulsion drops is 500-750 nm, and the mass ratio of the gelatin to the PDMS-E is 1:0.75 to 0.80; the viscosity of the modified gelatin is 1.10-1.12 mPa.s, the primary amino conversion rate of the gelatin is 11-13% (mole percent), and the epoxy group consumption in PDMS-E is 22-24% (mole percent). The modified gelatin provided by the application is used as a coating printing and dyeing adhesive to play a role in supporting between a fabric and a coating, so that the problems of uneven coating and excessive adhesive coating caused by excessive viscosity of gelatin are solved; and increases the heat resistance, flexibility and color fastness of the fabric.
Description
The application relates to a divisional application of application No. 202110325823.1 (application date 2021-03-26, the application name is a modified gelatin for coating printing and dyeing adhesive, and a preparation method and application thereof)
Technical Field
The application belongs to the field of gelatin application, and relates to modified gelatin for a coating printing and dyeing adhesive, and a preparation method and application thereof.
Background
The pigment dyeing has the advantages of wide fiber adaptation range, complete color spectrum, convenient color matching, small water consumption, energy saving, consumption reduction and the like, and is therefore widely promoted in the dyeing and finishing industry. Unlike dyes, the paint has no affinity with the fiber fabric, and an adhesive is required to fix the paint on the surface of the fabric, so the preparation technology of the adhesive is one of key technologies for developing paint dyeing. The binders currently used for pigment printing are basically oil/water type emulsions of polymers, and under certain process conditions, the binders are treated on the surface of the fabric, and the binders form films to fix the pigment on the fabric. Gelatin is an extremely important protein biomass material, and is now widely used in various fields, especially in the fields of food, medicine and chemical industry, and is also a high-value adhesive raw material.
Gelatin has a long history of being used as an adhesive, and has the advantages of short setting time of a glue layer, good adhesive force to wood and the like, high adhesive strength, simple glue mixing, no need of adding other auxiliary agents and the like. However, the single gelatin adhesive has the defects of high viscosity, difficult brushing and leveling, poor stability, large change of viscosity along with environment, extremely strong hydrophilicity of gelatin, low film forming fastness and the like. Therefore, when gelatin is used as a binder, it needs to be modified. The molecular structure of the gelatin mainly contains amino (-NH) 2 ) The presence of carboxyl groups (-COOH), hydroxyl groups (-OH), mercapto groups (-SH), etc., provides the possibility of modification of gelatin.
Chinese patent document CN106833455A (201710079034.8) provides a preparation method of a modified gelatin-acrylic resin adhesive, which comprises initiating by potassium persulfate at 75-90 ℃ and polymerizing to complete the reaction to obtain a yellow transparent adhesive body with solid content of 45% and viscosity of 200-300 mPas. However, when the modified gelatin is used for a pigment-dyed adhesive, the viscosity of the gelatin is preferably less than 100 mPas, and the modified gelatin has a problem that the structure of the gelatin is easily damaged and denaturation or gelation is easily caused due to a high modification temperature.
Chinese patent document CN106192473A (201610674824.6) discloses a polylysine gelatin composite paint dyeing adhesive, which belongs to the field of printing and dyeing, and is prepared by mixing polylysine and gelatin according to a weight ratio of 1:150-170, wherein the preparation method comprises the steps of mixing a polylysine alcohol preparation with gelatin according to the weight ratio, and stirring for 20-30 hours under ultraviolet irradiation; after the irradiation is finished, the mixture is put into a refrigerator for 24 to 36 hours and is kept at a low temperature, and the mixture is immediately dried at a high temperature after being taken out of the refrigerator; the composite pigment dyeing adhesive and the pigment are mixed according to the weight ratio of 1:3-5 and applied to textiles, so that the pigment dyeing color depth can be obviously improved, the rubbing fastness and washing fastness of dyed fabrics are improved, and the influence on the handfeel of the fabrics is small. However, the polylysine and gelatin composite material in the patent is crosslinked through ultraviolet irradiation, the polylysine has strong hygroscopicity, and the modified gelatin has no hydrophobicity; and in the use process, acidic polysaccharides, hydrochloride, phosphate, copper ions and the like can be combined with the acidic polysaccharides to reduce the activity.
Disclosure of Invention
In order to solve the problems of high viscosity, instability, difficult use and the like of gelatin when the gelatin is used for a pigment printing and dyeing adhesive, the application provides modified gelatin for the pigment printing and dyeing adhesive, and a preparation method and application thereof.
In order to achieve the above purpose, the present application adopts the following technical scheme:
the modified gelatin for the coating printing and dyeing adhesive is prepared by modifying gelatin by using epoxy polysiloxane (PDMS-E) emulsion drops, wherein the average particle size of the epoxy polysiloxane emulsion drops is 500-750 nm, and the mass ratio of the gelatin to the PDMS-E is 1:0.75 to 0.80; the viscosity of the modified gelatin is 1.10-1.12 mPa.s, the primary amino conversion rate of the gelatin is 11-13% (mole percent), and the epoxy group consumption in PDMS-E is 22-24% (mole percent).
The secondary structure content of the modified gelatin is as follows: beta-sheet 30-31%; random coil is 26.2-27.5%; the alpha-helical structure is 21.4 to 23.5 percent; the beta-turning angle is 19.8-20.2%.
Preferably, the molecular weight (Mw) of the gelatin is 1.40X10 5 g/mol, mw/Mn of 1.43, primary amino group content in gelatin of 4.95×10 -4 g mol -1 . The micro morphology of the modified gelatin is a shell-core structure which is uniformly distributed.
The application adopts grafted PDMS-E emulsion drop modified gelatin, which not only can keep main properties of main chain of gelatin matrix, but also can obtain new properties from grafted side chain. The modified gelatin of the present application is used to treat the surface of fabric to form a film to fix the coating to the fabric. The existence of the anionic surfactant makes the polymer have strong adhesive capacity, and simultaneously endows the material with the properties of hydrophobicity, heat resistance, flexibility and the like. The unreacted primary amino groups can form hydrogen bonds with other polar compounds added in the fabric, the unreacted epoxy groups can open loops to generate hydroxyl groups, and further hydrogen bonds can be formed, so that the paint and the fabric are combined more tightly.
The application also provides a preparation method of the modified gelatin, which comprises the following steps:
(1) Synthesis of Mono Si-H terminated polysiloxane (PDMS-H): with hexamethylcyclotrisiloxane (D) 3 ) Is monomer, n-butyllithium (C) 4 H 9 Li) as initiator, benzene as solvent, tetrahydrofuran (THF) as promoter, and dimethyl-hydrosilyl-chlorane (C) 2 H 7 ClSi) is used as a capping agent, and PDMS-H is synthesized by living anionic polymerization;
the reaction equation:
n is 6-14;
(2) Preparation of epoxy polysiloxane (PDMS-E): under the action of a catalyst chloroplatinic acid, performing hydrosilylation reaction on Allyl Glycidyl Ether (AGE) and PDMS-H to obtain epoxy polysiloxane (PDMS-E);
the reaction equation is:
(3) Preparation of monodisperse PDMS-E emulsion particles:
PDMS-E is taken as a disperse phase, passes through the membrane pores of an SPG membrane emulsifier under the pressure of nitrogen, and is added into deionized water containing Sodium Dodecyl Sulfate (SDS), sodium Dodecyl Benzene Sulfonate (SDBS) and glacial acetic acid to form PDMS-E oil-in-water emulsion;
(4) The monodisperse PDMS-E emulsion particles react with gelatin to modify the gelatin: and (3) regulating the pH value of the gelatin solution to 10.0+/-0.2, dropwise adding the PDMS-E emulsion prepared in the step (3) into the gelatin solution, and stirring to obtain the monodisperse PDMS-E emulsion particle modified gelatin.
Preferably, the specific method of the step (1) is as follows: first C is carried out 4 H 9 Li is dissolved in benzene, D dissolved in benzene is added under the condition of decompressing and introducing argon 3 After a period of reaction, THF is added for a period of time, and then C is injected 2 H 7 Stopping the reaction after ClSi; the product was then filtered, distilled under reduced pressure and purified to give PDMS-H.
Further preferably, D 3 /C 4 H 9 Li/C 2 H 7 The molar ratio of ClSi is 1.9-2.1:3.9-4.1:1.
Further preferably, C 4 H 9 The volume of Li is 2.3 to 2.5 times that of benzene; the volume of THF is 4.8-5.2 times that of benzene.
Further preferably, D is added 3 Post-reaction for 28-32 min; after THF is added, the reaction is continued for 7.5 to 8.5 hours.
Preferably, the specific method of the step (2) is as follows: argon is introduced into the AGE, and chloroplatinic acid is added after 25 to 35 minutes; heating to 78-82 ℃, dropwise adding PDMS-H, heating to 108-112 ℃ after the dropwise adding, reacting for 5.5-6.5H, and purifying the product by reduced pressure distillation to obtain the product epoxy polysiloxane (PDMS-E).
Further preferably, the mass ratio of AGE to chloroplatinic acid is 1: 0.011-0.012.
It is further preferred that the molar ratio of PDMS-H to AGE is 1.5 to 1.7:1.
Preferably, in step (3), the SDS/SDBS ratio (w/w) is 0.43-0.54, and the total concentration of the surfactant in the deionized water is 0.35-0.40 wt%.
Preferably, in step (3), the SPG membrane has an average pore size of 0.5.+ -. 0.1. Mu.m.
Preferably, in the step (3), the concentration of glacial acetic acid in the deionized water is 2-3 mol/L.
Preferably, in the step (3), the mass fraction of PDMS-E in the oil-in-water emulsion is 0.95-1.05%.
Preferably, the specific method of the step (4) is as follows:
dissolving gelatin in distilled water to prepare gelatin solution, and heating the gelatin solution to 49-51 ℃ after 2.5-3.5 h to ensure that gelatin is completely dissolved; subsequently, the pH of the gelatin solution was adjusted to 10.0.+ -. 0.2 using sodium hydroxide solution; then, the PDMS-E emulsion prepared in the step (3) is mixed with the water according to the proportion of 19-21 mL.min -1 Is added to the gelatin solution and stirred at 49-51 c for 5-6 hours.
It is further preferred that the concentration of the sodium hydroxide solution in the step (4) is 1.8 to 2.2mol L -1 。
It is further preferred that the mass percentage of gelatin in the gelatin solution in step (4) is 4.95 to 5.05wt%.
The application also provides application of the modified gelatin in paint printing and dyeing.
Preferably, the application provides the use of the modified gelatin as described above as a binder in the printing and dyeing of coatings.
The modified printing and dyeing coating containing the modified gelatin comprises the modified gelatin and the coating, wherein the mass ratio of the modified gelatin to the coating is 1:1.5-2.
Preferably, the paint is a conventional dyeing paint in the textile field, and comprises one or more of hydroxyethyl acrylate, sodium hydroxymethyl cellulose, polymethyl vinyl ether and acrylonitrile.
The use method of the modified printing and dyeing paint comprises the steps of 0.03-0.035 g/cm of the printing and dyeing paint 2 Is applied to the textile; the base material of the textile is white-blank pure cotton fabric.
The dyeing paint also comprises pigment, auxiliary agent and the like.
The pigment is a common pigment in the field of printing and dyeing.
The auxiliary agent comprises one or more of an antioxidant, a polymerization inhibitor and a defoaming agent.
The antioxidant, the polymerization inhibitor and the defoamer are all conventional products in the textile printing and dyeing field. Such as antioxidant 1010, chemical name: pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionate ]; antioxidant 168, chemical name: tris (2, 4-di-t-butylphenyl) phosphite; antioxidant 1076, chemical name is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, etc.
The polymerization inhibitor comprises a common polymerization inhibitor such as a polyhydric phenol polymerization inhibitor, a quinone polymerization inhibitor, an arylamine polymerization inhibitor and the like, such as hydroquinone, p-tert-butylcatechol, p-toluidine and the like. The defoamer is organic silicon defoamer, the active ingredients are polysiloxane and silicone resin, and the defoamer is organic silicon defoamer DF-933NS.
A textile fabric with good color fastness contains 0.03-0.035 g/cm 2 The printing and dyeing paint; the glass transition temperatures Tg are 129℃and 187.6 ℃. Preferably, the thermal decomposition temperature of the textile is 273.8 ℃.
Preferably, the substrate of the textile is white-blank pure cotton fabric.
Preferably, the textile fabric tested according to the common standard GB/T3920 for rubbing color fastness is 4-5, the wet-hot fastness tested according to GB/T3921-2008 "textile color fastness to soaping" is 4, and the perspiration fastness tested according to the textile perspiration fastness test method (GB/T3922-1995) is 4.
The application has the following technical effects:
1. the modified gelatin has the modification temperature of 50 ℃ and mild conditions, and compared with the prior art (the reaction temperature of other methods is above 60 ℃), the modified gelatin has the advantages that the structural integrity of the gelatin can be ensured, and the denaturation or the gel change is not easy to occur.
2. The emulsion disclosed by the application has good stability, emulsion particles can be uniformly dispersed along with the increase of the reaction time, the particle size can not be continuously increased along with the reaction time, and aggregation and demulsification phenomena generated by long-time placement can be avoided. The emulsion with good stability can maintain uniform dispersion and uniform structure, and the modified gelatin has uniform properties when in use and can not generate uneven coating phenomenon.
3. The modified material used in the application uses the PDMS-E latex particles which are nontoxic and pollution-free, and can not cause harm to human health;
4. the gelatin/PDMS-E latex polymer (modified gelatin) prepared by the application has uniform and stable morphology, and the defect that gelatin is easy to deteriorate is overcome; the existence of anionic surfactants (SDS, SDBS) makes the polymer have strong adhesion capability, and the PDMS-E endows the material with properties such as hydrophobicity, heat resistance, flexibility and the like.
5. The modified gelatin with the viscosity of 1.10-1.12 mPas is obtained by using the emulsion particles with the particle size of 500-750 nm, and the modified gelatin has the viscosity suitable for being used as a coating printing and dyeing adhesive to play a role in supporting between fabrics and coatings, so that the problems of uneven coating and excessive thick adhesive coating caused by excessive viscosity can be avoided. The modified gelatin provided by the application is used as an adhesive for printing and dyeing of the coating, so that the heat resistance, flexibility and hydrophobicity of the fabric are improved, and the coating and the fabric are more easily tightly combined in the printing and dyeing process.
Drawings
FIG. 1 is an optical microscope image and particle size distribution diagram of monodisperse emulsion particles of example 1;
FIG. 2 is an optical microscope image and particle size distribution diagram of monodisperse emulsion particles of example 2;
FIG. 3 is an optical microscope image and particle size distribution diagram of monodisperse emulsion particles of comparative example 4;
FIG. 4 is an optical microscope image and a particle size distribution diagram of monodisperse emulsion particles of comparative example 5;
FIG. 5 is a graph of the microtopography of the modified gelatin of example 1;
FIG. 6 is a graph of the micro-morphology of the modified gelatin of comparative example 1;
FIG. 7 is a thermogravimetric analysis of a blank sample and example 1;
FIG. 8 is a DSC analysis of a blank sample versus example 1.
Detailed Description
The application is further illustrated and described below with reference to the drawings and examples.
Sodium Dodecyl Sulfate (SDS), sodium Dodecyl Benzene Sulfonate (SDBS), allyl Glycidyl Ether (AGE) and glacial acetic acid are all available from Alfa Aesar (Alfa Aesar) Inc. of Shanghai China and SDS and SDBS require recrystallization from ethanol prior to use. Hexamethylcyclotrisiloxane (D) 3 ) N-butyllithium (C) 4 H 9 Li) and chlorodimethylsilane (C) 2 H 7 ClSi) was purchased from Sigma Aldrich. Benzene and Tetrahydrofuran (THF) were purchased from chinese pharmaceutical groups company (beijing). Chloroplatinic acid formula H 14 Cl 6 O 6 Pt, molecular weight 517.9096, dark yellow transparent liquid, available from atanan platinum source chemical limited. SPG porous glass membranes with pore size of 0.5 μm were purchased from China medical group company. Pigskin A gelatin is purchased from China medical group company, and is used after dialysis.
Molecular weight of gelatin (M) as determined by gel permeation chromatography w ) About 1.40×10 5 g mol -1 ，M w /M n 1.43. The primary amino group content of gelatin was measured by Van-Slike method at 50℃and found to be 4.95X10 -4 g mol -1 . Van-Slike method is a specialized method for determining the amino content of amino acids or protein molecules. The method is to determine the primary amino content in amino acid or protein by reacting nitrous acid with the primary amino in amino acid or protein. The error in primary amino content in gelatin measured using this method is less than 1%.
The physical size of the emulsion droplets and the Polymer Dispersion Index (PDI) were measured with a laser particle size analyzer (Zetasizer 2000, malvern instruments, uk). The instrument converts the diffraction spectrum into a particle size distribution curve based on Mie scattering theory. First, the emulsion was carefully placed into a color matching tube. The tube was then placed in a ZetaSizer 2000 laser particle meter to measure PDI or electrophoretic mobility.
The viscosity of the sample in the reaction liquid at different time is measured by using a black-bone viscometer, the constant temperature tank is adjusted to 50 ℃, the black-bone viscometer is vertically placed in the constant temperature tank, 15mL of the sample to be measured is taken and added into the viscometer, the two pipes except the capillary are sealed, the liquid level is pumped to the upper scale mark of the glass ball at the upper end of the capillary by using an air pumping device, meanwhile, the air pumping device is removed, and the time required for the liquid level to flow down from the upper scale mark to the lower scale mark is recorded, so that the viscosity is calculated.
Raman spectra of reaction samples in the reaction solutions at different times were recorded with a raman spectrometer, raman spectral data were measured using an inVia type (Renishaw, uk) laser confocal raman spectrometer, first focused on the capillary surface using an optical microscope mode, stage focused on the particle surface was adjusted, and raman spectral data were obtained using a 633nm laser source.
The Zeta potential of the reaction sample in the reaction liquid at different times is measured by a Zetasizer Nano ZS type (Malvern, UK) laser particle sizer, the sample is sucked by a syringe and slowly injected into a cuvette with the Zeta potential, and a specific Zeta potential value can be measured by putting the cuvette into a sample tank of the instrument without bubbles. The experimental results were repeated 3 times.
The morphology of PDMS-E latex particles was characterized by Transmission Electron Microscopy (TEM). First, a TEM sample was prepared. The mixture of gelatin and emulsion was diluted about 20-fold at 50 ℃. The drop-like mixture was dropped onto the copper mesh. The excess liquid was absorbed by filter paper and dried with nitrogen at room temperature. TEM images were measured with JEM-2100.
The consumption of epoxy groups is detected by Raman spectroscopy, 858cm -1 The peak represents an epoxy group.
The synthetic method of the epoxy polysiloxane (PDMS-E) used in the embodiment of the application is as follows:
(1) Synthesis of Mono Si-H terminated polysiloxane (PDMS-H):
first 10mL of benzene was added to the flask, followed by 24mL of C 4 H 9 After 3 to 5 times of vacuum pumping and argon gas charging operations, 45.99 g of D3 is dissolved in 40mL of benzene and added dropwise into a flask. After 30min of reaction, 50mL of Tetrahydrofuran (THF) was added and the reaction was continued for 8h. Subsequently, 11mL of C 2 H 7 ClSi was injected into the flask to terminate the reaction. The obtained product PDMS-H is purified by filtration, reduced pressure distillation and the like, and 45.44g of the product is obtained, and the yield is 56.11%. D (D) 3 /C 4 H 9 Li/C 2 H 7 The molar ratio of ClSi is about 2:4:1.
(2) Preparation of epoxy polysiloxane (PDMS-E): 8.51g of AGE was charged into the flask, and after 30 minutes, 40. Mu.L of chloroplatinic acid (mass of chloroplatinic acid: 0.097 g) was added thereto. And under the condition of keeping argon gas, the reaction temperature is increased to 80 ℃, PDMS-H with the molar ratio of 1.6:1 to AGE is added at the speed of 1-2 d/s, after the dropwise addition is finished, the reaction temperature is continuously increased to 110 ℃, the reaction is continued for 6 hours, and then the reaction is finished. The product epoxy polysiloxane (PDMS-E) is obtained through purification by means of reduced pressure distillation and the like, and the yield is 84.32%.
Example 1
A modified gelatin for papermaking reinforcing agent, which is prepared by the following steps:
(1) Preparation of monodisperse PDMS-E emulsion particles:
PDMS-E was used as the dispersed phase, and was passed through SPG membrane pores (average pore diameter of SPG membrane 0.5 μm) under nitrogen pressure, added to deionized water (glacial acetic acid concentration 2 mol/L) containing SDS, SDBS and glacial acetic acid, and stirred at a rotation speed of 1300rpm to form PDMS-E oil-in-water emulsion (PDMS-E mass percentage in oil-in-water emulsion 1%). The SDS/SDBS ratio (w/w) was 0.54 and the total concentration of surfactant in deionized water was 0.4wt%.
(2) The monodisperse PDMS-E emulsion particles react with gelatin to modify the gelatin:
the stock solution was prepared by dissolving gelatin in distilled water (5 wt%) and after 3 hours the gelatin solution was heated to 50 ℃ to ensure complete dissolution of gelatin. Subsequently, the pH of the gelatin solution was adjusted to 10.0.+ -. 0.2 using sodium hydroxide solution (NaOH, 2.0 mol/L). Then, the PDMS-E emulsion particles prepared above were added to the gelatin solution at a rate of 20mL/min and stirred at 50℃for 5 hours. Mass ratio of PDMS-E to gelatin 0.757:1. to obtain the monodisperse PDMS-E latex particle modified gelatin with the viscosity of 1.10 mPas.
The average particle diameter of the epoxy polysiloxane obtained in example 1 is 678+ -65 nm (shown in fig. 1), and it can be seen from TEM image that the structure of the modified gelatin has a core-shell structure (shown in fig. 6), the core-shell structure is regularly distributed uniformly, and the shell layer is convenient to be adsorbed on the textile material.
The conversion of primary amino groups in gelatin was 12.5% (mole percent) and the epoxy group consumption in PDMS-E was 23.24% (mole percent).
The particle size of the modified gelatin under the optical microscope and the particle size of the modified gelatin under the TEM are somewhat different because: the latex particles under the optical microscope are detected in the latex, the particle size is consistent with the actual particle size result, and the modified gelatin particles in the TEM image can collapse and shrink to a certain extent after being subjected to treatments such as dripping on a copper mesh (carbon support film) and the like and treatments such as moisture drying and the like during testing. The size of the modified gelatin in the TEM image is smaller than the particle size of the latex particles, and the reason why some of the latex particles in the TEM image are not significantly spherical is that the TEM image is merely for observing the microstructure, and is not for reflecting the size of the modified gelatin particle size in the actual application state.
Example 2
A modified gelatin for papermaking reinforcing agent, which is prepared by the following steps:
(1) Preparation of monodisperse PDMS-E emulsion particles:
PDMS-E was used as the dispersed phase, and was passed through SPG membrane pores (average pore diameter of SPG membrane 0.5 μm) under nitrogen pressure, added to deionized water (acetic acid concentration 2 mol/L) containing SDS, SDBS and glacial acetic acid, and stirred at a rotation speed of 1300rpm to form PDMS-E oil-in-water emulsion (mass percentage of PDMS-E in oil-in-water emulsion 1%). The SDS/SDBS ratio (w/w) was 0.43 and the total concentration of surfactant in deionized water was 0.4wt%.
(2) The monodisperse PDMS-E emulsion particles react with gelatin to modify the gelatin:
the stock solution was prepared by dissolving gelatin in distilled water (5 wt%) and after 3 hours the gelatin solution was heated to 50 ℃ to ensure complete dissolution of gelatin. Subsequently, the pH of each prepared gelatin solution was adjusted to 10.0.+ -. 0.2 using sodium hydroxide solution (NaOH, 2.0 mol/L). Then, the PDMS-E emulsion prepared above was added to the gelatin solution at a rate of 20mL/min and stirred at 50℃for 5 hours. The mass ratio of PDMS-E to gelatin in the PDMS-E emulsion is 0.757:1. to obtain the monodisperse PDMS-E latex particle modified gelatin with the viscosity of 1.12 mPas.
The monodisperse epoxy polysiloxane obtained in example 2 has an average particle size of 571.+ -. 70nm, a core-shell structure also appears in the modified gelatin particle structure, the conversion of primary amino groups in the gelatin is 11.25% (mole%) and the epoxy group consumption in PDMS-E is 22.12% (mole%).
Comparative example 1
A modified gelatin is prepared by the following steps:
otherwise, the same as in example 1 was conducted except that the SPG film had an average pore diameter of 0.5. Mu.m; the SDS, SDBS=0.25 and the total concentration of the surfactant is 0.3 percent, and the monodisperse PDMS-E latex particle modified gelatin with the average particle diameter of 366+/-70 nm is obtained. The TEM morphology of the modified gelatin was aggregated small particles (fig. 7), with a primary amino conversion of 7.5% (mole percent) in the gelatin.
Comparative example 2
Otherwise, the same as in example 1 was conducted except that the SPG film had an average pore diameter of 0.7. Mu.m; sdbs=0.67, the total concentration of surfactant in deionized water was 0.5wt%. To obtain the monodisperse PDMS-E latex particle modified gelatin with the average particle diameter of 955+/-70 nm. The viscosity of the modified gelatin was 1.057 mPas, the conversion of primary amino groups in the gelatin was 13.73% (mole percent), and the epoxy group consumption in PDMS-E was 27.27% (mole percent).
1. Particle size distribution of monodisperse PDME-S emulsion particles obtained in examples 1 to 2 and comparative examples 1 to 2
The size of the prepared emulsion particles is described by the average particle size and the dispersion index (PDI), and the result shows that the PDI of the emulsion particles obtained by the embodiment of the application is less than 0.1, which indicates that the emulsion particles are uniformly distributed in the solution. Particle size variation Coefficient (CV) of less than 21% also indicates a sufficiently narrow particle size distribution. The monodisperse PDME-S latex particles obtained by the application are suitable for modifying gelatin to obtain modified gelatin with stable performance.
2. Microcosmic profile of modified gelatins of examples and comparative examples
The reaction of gelatin with PDMS-E latex particles is affected by a number of factors, the morphology of which is also very complex. Aggregation of the latex particle-modified gelatin fraction at small particle size scales of less than 400nm was visually observed by TEM images (FIGS. 5, 6). Whereas monodisperse regular core-shell structures are found in modified gelatin emulsions of medium particle size (500-750 nm). The larger size monodisperse emulsion particle modified gelatin helps reduce viscosity. This is probably due to the fact that when gelatin undergoes nucleophilic attack on the surface of latex particles, ordered colloidal aggregates can be obtained; while for smaller droplets, collapse of the droplet, nucleophilic attack and complex formation occur simultaneously. Resulting in different particle size monodisperse emulsion particles having different effects on the properties of the gelatin modification.
3. Secondary structure content of modified gelatins of examples and comparative examples
TABLE 1
Beta-sheet is a regular secondary structure, which is favorable for the extension of polypeptide molecular chains, so that the exposure of primary amino groups is promoted, and the formation of the beta-sheet structure enables the primary amino groups of gelatin to be fully exposed on the surface of latex particles. Gelatin spreads uniformly in latex particles to promote chemical grafting reaction of the latex particles and the gelatin, so that the viscosity of the emulsion can be reduced due to the increase of the beta-sheet structure. The modified gelatin with latex particles of different particle sizes has different secondary structures and different influences on the performance.
4. Application of modified gelatin as adhesive in printing and dyeing field
The following processes and additives are conventional means in the art or are commercially available products unless specifically stated otherwise. Performance test according to GB/T3921-2008 "textile color fastness to washing and rubbing color fastness", common standard for rubbing color fastness test: GB/T3920, and a textile perspiration resistance color fastness test method (GB/T3922-1995).
The application method comprises the following steps:
the modified gelatins prepared in examples 1 and 2 and comparative examples 1 and 2 were applied as binders to textiles. In order to illustrate the influence of the coating of the modified gelatin on the performance of the textile material, the modified gelatin and the coating are uniformly coated on the surface of the textile, and the whole or part of the surface of the textile is coated according to the requirement in actual use. The coating amount of the modified gelatin on the surface of the textile is 0.03-0.035 g/cm 2 。
Example 3
A modified printing and dyeing paint and a use method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1:1.5. The fabric is white pure cotton fabric. The modified gelatin is the gelatin obtained in example 1.
The coating comprises:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose;
and (3) pigment: 8304 dark blue 0.4g/L,8601 green 0.3g/L;
auxiliary agent: and 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on the surface of white blank pure cotton fabric, and drying at 120 ℃ with the coating amount of 0.03g/cm 2 。
Example 4
A modified printing and dyeing paint and a use method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1:2. The fabric is white pure cotton fabric. The modified gelatin is the gelatin obtained in example 1.
The coating comprises:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose;
and (3) pigment: 8304 dark blue 0.4g/L,8601 green 0.3g/L;
auxiliary agent: and 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on the surface of white blank pure cotton fabric with the coating amount of 0.03g/cm 2 。
Example 5
A modified printing and dyeing paint and a use method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1:1.5. The fabric is white pure cotton fabric. The modified gelatin is the gelatin obtained in example 2.
The coating comprises:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose;
and (3) pigment: 8304 dark blue 0.4g/L,8601 green 0.3g/L;
auxiliary agent: and 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on the surface of white blank pure cotton fabric with the coating amount of 0.035g/cm 2 。
Comparative example 3
A modified printing and dyeing paint and a use method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1:1. The fabric is white pure cotton fabric. The modified gelatin is the gelatin obtained in example 1.
The coating comprises:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose; .
And (3) pigment: 8304 dark blue 0.4g/L,8601 green 0.3g/L;
auxiliary agent: and 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on the surface of white blank pure cotton fabric with the coating amount of 0.03g/cm 2 。
Comparative example 4
A modified printing and dyeing paint and a use method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1:2.5. The fabric is white pure cotton fabric. The modified gelatin is the gelatin obtained in example 1.
The coating comprises:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose;
and (3) pigment: 8304 dark blue 0.4g/L,8601 green 0.3g/L;
auxiliary agent: and 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on the surface of white blank pure cotton fabric with the coating amount of 0.03g/cm 2 。
Comparative example 5
A modified printing and dyeing paint and a use method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1:1.5. The fabric is white pure cotton fabric. The modified gelatin is the gelatin obtained in comparative example 1.
The coating comprises:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose;
and (3) pigment: 8304 dark blue 0.4g/L,8601 green 0.3g/L;
auxiliary agent: and 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on white blank pure cotton fabricThe coating amount of the surface of the object is 0.03g/cm 2 。
Comparative example 6
A modified printing and dyeing paint and a use method thereof comprise the following steps: the mass ratio of the modified gelatin to the coating in the modified printing and dyeing coating is 1:1.5. The fabric is white pure cotton fabric. The modified gelatin is the gelatin obtained in comparative example 2.
The coating comprises:
10g/L of hydroxyethyl acrylate and 4.1g/L of sodium hydroxymethyl cellulose;
and (3) pigment: 8304 dark blue 0.4g/L,8601 green 0.3g/L;
auxiliary agent: and 0.2g/L of defoaming agent.
Coating the modified printing and dyeing paint on the surface of white blank pure cotton fabric with the coating amount of 0.03g/cm 2 。
Table 3 shows the effect of different modified gelatins as binders:
TABLE 3 Table 3
| Sample of | Color fastness to washing | Fastness to wet-hot color | Perspiration resistance color fastness |
| Example 3 | 5 | 4 | 4 |
| Example 4 | 4-5 | 4 | 4 |
| Example 5 | 4 | 4 | 4 |
| Comparative example 3 | 3 | 3 | 2 |
| Comparative example 4 | 3 | 2 | 2 |
| Comparative example 5 | 2 | 2 | 2 |
| Comparative example 6 | 3 | 4 | 3 |
| Blank sample (gelatin only) | 1-2 | 1-2 | 1-2 |
The dyed textile has good color fastness after using the modified gelatin adhesive, and has obviously improved color fastness to washing, wet scalding and perspiration compared with a blank sample. When the modified gelatin and the printing and dyeing paint are in a certain mass ratio, the color fastness is good.
FIG. 7 shows the results of thermogravimetric analysis of a blank sample (a) for a textile sample using gelatin alone as a coating, and a sample (b) for a textile sample using the modified gelatin of example 1 as a coating; the fabric selected for the sample was white plain cotton fabric.
TG results indicate that the blank samples showed two weight loss at 46.5 ℃ and 264.5 ℃ and the coating modified material showed only one weight loss at 273.8 ℃, which indicates improved thermal stability of the material after emulsion coating modification.
DSC analysis of blank samples (a) and (b) in fig. 8. As a result, the Tg of the blank sample was 215.7deg.C, and the Tg of the modified sample was two, 129 deg.C and 187.6deg.C, indicating microphase separated structure in the emulsion coated sample, and the Tg after modification was significantly reduced, indicating increased relative movement ability of the polymer molecular chains at low temperature, meaning increased flexibility of the modified material to some extent.
Claims (10)
1. The printing and dyeing coating containing the modified gelatin is characterized by comprising the modified gelatin and the coating, wherein the mass ratio of the modified gelatin to the coating is 1:1.5-2;
the modified gelatin is as follows: the method comprises the steps of modifying gelatin by using monodisperse epoxy polysiloxane (PDMS-E) emulsion drops, wherein the average particle size of the epoxy polysiloxane emulsion drops is 500-750 nm, and the mass ratio of the gelatin to the PDMS-E is 1:0.75 to 0.80; the viscosity of the modified gelatin is 1.10-1.12mPa.s, the primary amino conversion rate of the gelatin is 11-13 mol percent, and the epoxy group consumption in PDMS-E is 22-24 mol percent; the paint is a textile field conventional dyeing paint, wherein the textile field conventional dyeing paint comprises one or more of hydroxyethyl acrylate, sodium hydroxymethyl cellulose, polymethyl vinyl ether and acrylonitrile, and the paint also comprises pigment and an auxiliary agent;
preparation of monodisperse PDMS-E emulsion droplets:
PDMS-E is taken as a disperse phase, passes through the membrane pores of an SPG membrane emulsifier under the pressure of nitrogen, and is added into deionized water containing Sodium Dodecyl Sulfate (SDS), sodium Dodecyl Benzene Sulfonate (SDBS) and glacial acetic acid to form PDMS-E oil-in-water emulsion; the ratio (w/w) of SDS/SDBS is 0.43-0.54, the total concentration of the surfactant in the deionized water is 0.35-0.40 wt%, and the average pore diameter of the SPG film is 0.5+/-0.1 mu m;
the method for modifying gelatin by monodisperse PDMS-E emulsion droplets comprises the following steps:
dissolving gelatin in distilled water to prepare gelatin solution, and heating the gelatin solution to 49-51 ℃ after 2.5-3.5 h so as to ensure that gelatin is completely dissolved; subsequently, the pH of the gelatin solution was adjusted to 10.0.+ -. 0.2 using sodium hydroxide solution; then, the prepared PDMS-E emulsion is treated with 19-21 mL/min -1 Is added into the gelatin solution, and is stirred at 49-51 ℃ for 5-6 hours.
2. The printing and dyeing coating according to claim 1, wherein the modified gelatin has a secondary structure content of: the beta-sheet is 30-31%; the random curl is 26.2-27.5%; the alpha-helical structure is 21.4-23.5%; the beta-rotation angle is 19.8-20.2%.
3. The printing and dyeing paint of claim 1 wherein the glacial acetic acid concentration in the deionized water is 2-3 mol/L.
4. The printing and dyeing coating according to claim 1, wherein the mass fraction of PDMS-E in the oil-in-water emulsion is 0.95-1.05%.
5. The printing and dyeing paint of claim 1 wherein the sodium hydroxide solution has a concentration of 1.8 to 2.2mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The mass percentage of gelatin in the gelatin solution is 4.95-5.05wt%.
6. The method of using the printing and dyeing paint according to any one of claims 1 to 5, wherein the printing and dyeing paint is 0.03 to 0.035g/cm 2 Is applied to the textile.
7. The method of claim 6, wherein the textile substrate is white-base cotton fabric.
8. A textile fabric having excellent color fastness, characterized by comprising 0.03 to 0.035g/cm 2 A printing coating according to any one of claims 1 to 7; the glass transition temperatures Tg are 129℃and 187.6 ℃.
9. The textile of claim 8 wherein the substrate of the textile is a white-base purified cotton fabric.
10. The textile fabric according to claim 9, wherein the textile fabric has a color fastness to rubbing according to the commonly used standard GB/T3920 of the rubbing color fastness test of 4 to 5, a wet fastness to hot stamping according to the test of GB/T3921-2008 "textile color fastness to soaping" of 4, and a perspiration color fastness according to the test method of textile perspiration color fastness (GB/T3922-1995) of 4.
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| CN101928367A (en) * | 2010-08-24 | 2010-12-29 | 华南理工大学 | Environmentally-friendly acrylic ester coating printing adhesive emulsion and preparation method |
| CN106192473A (en) * | 2016-08-16 | 2016-12-07 | 朱玲 | A kind of gelatin-compounded pigment dyeing binding agent of polylysine |
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| CN103087631B (en) * | 2013-01-14 | 2014-01-01 | 山东轻工业学院 | Polysiloxane-modified gelatin leather finishing agent and preparation method thereof |
| CN103103765B (en) * | 2013-01-14 | 2013-10-09 | 山东轻工业学院 | Self-emulsifying wet rubbing resistant leather top layer coating agent and preparation method thereof |
| CN105399973B (en) * | 2015-12-22 | 2019-02-15 | 齐鲁工业大学 | Freeze-drying prepares monocycle oxygen terminated polysiloxane modified gelatin Gradient Film |
| CN105566661B (en) * | 2015-12-22 | 2019-03-22 | 齐鲁工业大学 | A kind of pH adjusting method preparation monocycle oxygen terminated polysiloxane modified gelatin Gradient Film |
| CN105419350B (en) * | 2015-12-22 | 2018-06-08 | 齐鲁工业大学 | Substrate adjusts method and prepares monocyclic oxygen terminated polysiloxane modified gelatin Gradient Film |
| CN105567081B (en) * | 2015-12-22 | 2018-08-17 | 齐鲁工业大学 | Mixing glycidol prepares modified gelatin Gradient Film with monocycle oxygen terminated polysiloxane |
| CN105542204B (en) * | 2015-12-22 | 2019-03-22 | 齐鲁工业大学 | A kind of preparation method of monocycle oxygen terminated polysiloxane modified gelatin parents' film |
| CN105384944B (en) * | 2015-12-22 | 2019-07-09 | 齐鲁工业大学 | Solvent precipitation prepares monocycle oxygen terminated polysiloxane modified gelatin parents' film |
| CN108219162A (en) * | 2018-03-05 | 2018-06-29 | 齐鲁工业大学 | A kind of retanning agent for significantly improving leather tearing toughness and preparation method thereof |
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| CN106192473A (en) * | 2016-08-16 | 2016-12-07 | 朱玲 | A kind of gelatin-compounded pigment dyeing binding agent of polylysine |
| CN108314755A (en) * | 2018-03-06 | 2018-07-24 | 中山大学 | A kind of environment-protection coating printing adhesive lotion and its preparation method and application |
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