CN101857908B - Slow-release type leather fragrance finishing agent and preparation method thereof - Google Patents
Slow-release type leather fragrance finishing agent and preparation method thereof Download PDFInfo
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- CN101857908B CN101857908B CN 201010202855 CN201010202855A CN101857908B CN 101857908 B CN101857908 B CN 101857908B CN 201010202855 CN201010202855 CN 201010202855 CN 201010202855 A CN201010202855 A CN 201010202855A CN 101857908 B CN101857908 B CN 101857908B
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Abstract
The invention discloses a slow-release type leather fragrance finishing agent which is a powdery solid prepared from beta-cyclodextrin and essences positioned in a cavity of the beta-cyclodextrin, wherein the particle size of the powdery solid is 5-30 mu m, and the outer surface of the powdery solid has a color endowed by a reactive dye or a direct dye. The invention also discloses a preparation method of the slow-release type leather fragrance finishing agent, comprising the following steps of: on the basis of introducing the essences to the cavity of the beta-cyclodextrin to form an inclusion complex, dying the complex by skillfully utilizing the characteristic that the reactive dye or the direct dye can form a covalent bond or a hydrogen bond with hydroxyl outside the cavity, and then introducing the beta-cyclodextrin and essence complex with a specific color to leather by using the processes of coating the grain side and dipping the flesh side of the leather. Because the embedded essences are relatively isolated from the external environment and the complex is endowed with a surface color, the slow-release type leather fragrance finishing agent can not only realize the durable preservation of leather fragrance, but also solve the problem that the beta-cyclodextrin and essence complex generates white dots in colored leather application.
Description
Technical field
The invention belongs to the Leather Chemicals technical field, be specifically related to a kind of slow-release type leather fragrance finishing agent and preparation method thereof.
Background technology
Along with progress and the growth in the living standard of material progress, the human consumer is more and more dense to the leatherware interest with permanent fragrant and specific function.And use essence that leather is carried out rear arrangement processing, except desirable its fragrance, also can play a role as sanitas, sterilant, deodorizing agent etc. simultaneously, this not only can improve the added value of leatherware greatly, improve the style of leatherware, but broadened application field also.
But when essence is directly put on leather surface and carries out spice finish, the volatility of each component molecule of essence is often higher, cause the fragrance remaining time of aqueous essence on leather fiber can not be lasting, people begin to seek a kind of rate of volatilization that can effectively control the essence molecule for this reason, make it can keep the way of relative permanent fragrant on leather fiber.
At present, the method for disclosed leather fragrance finishing mainly contains: 1. fragrant fatliquoring agent method (Wang Kunyu, Sun Bing, Zhou Hualong, but defend China, leaf is brave. the development [J] of the development of odor type oxidated and sulfited rape oil fatting agent and application (II)-odor type fat liquoring complex agent. and Chinese leather, 2004,17).The method is to utilize odor type combined oxidation sulphiting leather fat that leather is carried out stuffing.Because essence and stablizer all are contained in the fatting agent, thereby their can be along with fatting agent be penetrated into leather inside, thereby makes leather have fragrance.But the method lays particular emphasis on the synchronous infiltration of essence and fatting agent, do not consider the combination of essence and leather fiber, so that fragrance is still volatile, fragrance remaining time is relatively short, and because the stability of fatting agent self also can propose high requirement to the temperature condition that this product is preserved.2. membrane process (flavouring method of leather, Chinese invention patent, publication number CN 1303094A).The method is to cover air-locked film at the leather of crossing through the essence solution soaking, to reach the purpose of the permanent lasting of leather.Although yet this operation can solve the problem of lasting fragrance, the film of enclosing simultaneously also can reduce the water-permeable and air permeable of leather, and the use properties of leather is descended.3. polyurethane microcapsule method (with the leather that fragrant microcapsule is covered with paint, lacquer, colour wash, etc., U.S.'s patent of invention, publication number US2006216509A1).The method is utilized microcapsulary, and essence is encapsulated in the polyurethane microcapsule, then by covering with paint, lacquer, colour wash, etc. technique leather is carried out spice finish.But the weak point of the method is the microcapsule complex manufacturing technology, and is wayward, and cost is higher.
In recent years, as a kind of green non-poisonous odor additive, beta-cyclodextrin essence inclusion compound has caused widely to be paid close attention to.Because essence is behind beta-cyclodextrin inclusion compound, can control the fragrance rate of release, thereby beta-cyclodextrin essence inclusion compound is compared with general essence, the fragrance time length is longer, now be widely applied to the industries such as weaving, food, tobacco, makeup (Liu Liya, Wang Chaoxia, remaining water woods. develop fragrant healthy textile [J] with beta-cyclodextrin. fabrics for industrial use, 2002, (12): 35-38; Vertical big, seedling banyan Zan, Yuan Wenliang. the application [J] of cyclodextrin inclusion compound in foodstuffs industry. food engineering, 2009, (9): 13-14; Lee's Fan, Liu Zhihua reaches man of virtue and ability's life etc. the microencapsulation of several essence spice for cigarette and the applied research in tobacco [J] thereof. and Kunming University's journal, 2009,31 (3): 34-36; Strict and impartial strong, Luo Shuguang. the application [J] of beta-cyclodextrin in makeup. fragrance flavor and cosmetic, 1997, (3): 27-28.).Yet, still find no the report that beta-cyclodextrin essence inclusion compound is used for leather fragrance finishing at present.In addition, the inventor finds under study for action, if beta-cyclodextrin essence inclusion compound is directly used in leather fragrance finishing, because the intrinsic white of inclusion compound itself causes white point occurring at leather surface easily, it is restricted at coloured application.
Summary of the invention
Purpose of the present invention is exactly for the deficiencies in the prior art, at first provides a kind of and has the long period aroma retaining effect and can be applied to slow-release type leather fragrance finishing agent in the leather of all kinds.
Another object of the present invention provides the method for the above-mentioned slow-release type leather fragrance finishing agent of preparation.
In order to reach the object of the invention, the inventor is on the basis of published preparation beta-cyclodextrin essence clathrate means, furtherd investigate the dyeing behavior of inclusion compound, find owing to contain reactive group in the reactive dyestuff molecule, the formation covalent bonds can react with the hydroxyl of beta-cyclodextrin, and in the direct dye molecule also because having amino, hydroxyl, amide group etc., can form hydrogen bond with the hydroxyl of beta-cyclodextrin, so these two kinds of dyestuffs have been introduced respectively existing beta-cyclodextrin essence inclusion compound, thereby make the powdery solid of slow-release type leather fragrance finishing agent for being consisted of by beta-cyclodextrin and the essence that is positioned at its hole that provides, particle diameter is 5～30 μ m, and its outside surface has the color of being given by reactive dyestuffs or direct dyestuff.
The method of the above-mentioned slow-release type leather fragrance finishing agent of preparation provided by the invention, processing step and the condition of the method are as follows:
(1) in 60～80 ℃ water-bath, beta-cyclodextrin is dissolved in the water fully takes out after making saturated aqueous solution, be cooled to 35～50 ℃ and constant temperature, then slowly adding with the beta-cyclodextrin weight ratio under the magnetic agitation speed of 200～600r/min is 1: 4～10 essence, this essence is to dissolve in the alcoholic solvent by weight 1～5: 1 to drip behind the formation essence alcoholic solution, drips rear stirring 2～4 hours;
(2) in the solution that step (1) obtains, add dyeing accelerant by 20～40g/L first, after it dissolves fully, count 0.5～6% by the weight percent of water again and add reactive dyestuffs, and with 0.8～1.2 ℃/minute temperature rise rate temperature is risen to 55～65 ℃, constant temperature 0.5～1 hour added 10～20g/L alkaline agent fixation 0.5～1 hour at last, or
In the solution that step (1) obtains, add simultaneously by the weight percent of water and count 0.3～8% direct dyestuff and by the alkaline agent of 1～3g/L, and with 0.8～1.2 ℃/minute temperature rise rate with temperature to 60～80 ℃, constant temperature 20～35 minutes, add dyeing accelerant by 1～20g/L again, reacted 0.5～1 hour;
(3) step (2) solution that obtains is let cool to room temperature, and then in depositing below 4 ℃ more than 12 hours, filter, be drying to obtain slow-release type leather fragrance finishing agent.
Used essence is common daily use chemicals class essence in the above method, preferred cream jasmin france, rose compound, lavender oil, lemon flavour, osmanthus flower fragrance; The used alcoholic solvent of dilution essence is Virahol, propyl carbinol, ethanol and methyl alcohol, preferred alcohol.
The essence that adds in the above method and beta-cyclodextrin weight ratio preferred 1: 5～7.
Be preferably 25～35g/L with the used dyeing accelerant of reactive dyeing step in the above method; When the essence inclusion compound was used for the arrangement of light color leather, it was preferred 0.5～1.5% to add the weight percent of dyestuff, when being used for dark leather spice finish, adds the weight percent preferred 4～5% of dyestuff.
In the above method during with the dyeing of direct dyeing step, when the essence inclusion compound was used for the arrangement of light color leather, it was preferred 0.3～2% to add the weight percent of dyestuff, when being used for dark leather spice finish, adds the weight percent preferred 5～7% of dyestuff.
Used dyeing accelerant is sodium-chlor or anhydrous sodium sulphate in the above method; Alkaline agent is sodium hydroxide, yellow soda ash, tertiary sodium phosphate or sodium bicarbonate.
In addition, it should be noted that the added amount of dyeing accelerant and alkaline agent is take the volume of water as benchmark.
The present invention is by molecule embedding principle, utilize the outside hydrophilic constructional feature of beta-cyclodextrin hollow and inner hydrophobic, first hydrophobicity essence is introduced the beta-cyclodextrin hole and form Inclusion Complexes, then utilize dexterously reactive dyestuffs and direct dyestuff mostly to be greatly polar molecule, be difficult for entering and destroy the essence inclusion compound in the nonpolar cavity of cyclodextrin, but can with the hole outside hydroxyl form the characteristics of covalent linkage or hydrogen bond, inclusion compound is dyeed (as shown in drawings), make specific color on the inclusion compound band, to satisfy the different colours leather to the demand of spice finish.At last, cover with paint, lacquer, colour wash, etc. and the flesh noodles impregnation technology by grain side of leather, the beta-cyclodextrin essence inclusion compound with particular color is introduced in the leather.Because with can be relative with external environment isolated behind the essence embedding, reduced the volatilization loss of essence, and its release rate is slowed down, play the effect of slowly-releasing, greatly prolong the remaining time of fragrance in leather, given again beta-cyclodextrin essence inclusion compound appearance corresponding color in addition, thereby both can realize the lasting retention of leather fragrance, also solve the problem of beta-cyclodextrin essence inclusion compound whiting point in coloured leather is used, thereby enlarged its range of application.
Because slow-release type leather fragrance finishing agent provided by the invention and coating material for leather have good consistency, thereby can satisfy the requirement of leather finish operation.
Because the color of slow-release type leather fragrance finishing agent provided by the invention can adjust according to the needs of using, thereby applicable to the spice finish without the color leather.
Because the present invention dyestuff and the inclusion compound dyeing selected are suitable, thereby make inclusion compound have higher dye uptake and even dyeing effect preferably, for its introducing leather finish is had laid a good foundation.
Since after slow-release type leather fragrance finishing agent provided by the invention is introduced leather finish, high (the xerotripsis staining fastness: 4～5 grades of the color fastness to rubbing of coating; Thereby be difficult for fading wet rubbing staining fastness: 〉=3 grades).
Preparation method provided by the invention is simple to operate, is easy to control, and technical maturity can fairly largely be implemented.
Description of drawings
Fig. 1 is the molecule connection diagram of beta-cyclodextrin essence inclusion compound and reactive dyestuffs, and S-D-B-Re represents the chemical structure of general formula of reactive dyestuffs among the figure, and in the formula: S is water soluble group; D is the dyestuff color bodies; B connects base; Re is active group.
Fig. 2 is the molecule connection diagram of beta-cyclodextrin essence inclusion compound and direct dyestuff, S-D-NH among the figure
2Represent the chemical structural formula of direct dyestuff with S-D-OH, S is water soluble group in the formula; D is the dyestuff color bodies.
Embodiment
The below provides embodiment so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field still belongs to protection scope of the present invention according to the invention described above content to some nonessential improvement and the adjustment that the present invention makes.
In addition, material umber that what deserves to be explained is following each embodiment is weight part.
Embodiment 1
In 7.5 parts of beta-cyclodextrins, add 100 parts of distilled water, and be heated to 60 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 35 ℃ and constant temperature, then under the magnetic agitation speed of 200r/min, slowly drip by 1.8 parts of cream jasmin frances and 1.8 parts of mixing solutionss that methyl alcohol forms, drip rear stirring 3h; Adding is with the sodium-chlor of the volumeter 20g/L of water, adds 2.0 parts of reactive yellow X-RG after it is dissolved fully again, and with 1 ℃ of/minute temperature rise rate temperature risen to 55 ℃, behind the isothermal reaction 1h, adds the sodium bicarbonate with the volumeter 20g/L of water, fixation 1h; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
This slow-release type leather finishing composition is covered with paint, lacquer, colour wash, etc. after technique is used for Soft Cattle Upper Leather and covers with paint, lacquer, colour wash, etc. routinely, and by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time prolongs at least 90 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 2
In 5.0 parts of beta-cyclodextrins, add 50 parts of distilled water, and be heated to 65 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 40 ℃ and constant temperature, then under the magnetic agitation speed of 300r/min, slowly drip by 1.0 parts of rose compounds and 0.5 part of mixing solutions that ethanol forms, drip rear stirring 2.0h; Adding is with the anhydrous sodium sulphate of the volumeter 20g/L of water, add again 3.0 parts of brown JM-4R of activity after it is dissolved fully, and with 0.8 ℃ of/minute temperature rise rate temperature is risen to 60 ℃, behind the isothermal reaction 40min, adding is with the yellow soda ash of the volumeter 12g/L of water, fixation 30min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
This slow-release type leather finishing composition is covered with paint, lacquer, colour wash, etc. after technique is used for cowhide mat leather top finishing routinely, and by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time prolongs at least 90 days; The color staining fastness of anti-xerotripsis of coating is 5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 3
In 8.5 parts of beta-cyclodextrins, add 70 parts of distilled water, and be heated to 70 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 45 ℃ and constant temperature, then under the magnetic agitation speed of 350r/min, slowly drip by 1.06 parts of lavender oils and 0.35 part of mixing solutions that Virahol forms, drip rear stirring 2.5h; Adding is with the anhydrous sodium sulphate of the volumeter 25g/L of water, add again 2.8 parts of reactive black KN-B after it is dissolved fully, and with 1.2 ℃ of/minute temperature rise rates temperature is risen to 62 ℃, behind the isothermal reaction 50min, adding is with the sodium hydroxide of the volumeter 10g/L of water, fixation 43min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
This slow-release type leather finishing composition is used for that the sheepskin clothes grain is covered with paint, lacquer, colour wash, etc. and the flesh noodles dipping after, by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time prolongs at least 120 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 4
In 11.84 parts of beta-cyclodextrins, add 80 parts of distilled water, and be heated to 75 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 50 ℃ and constant temperature, then under the magnetic agitation speed of 300r/min, slowly drip by 1.69 parts of lemon flavours and 1.69 parts of mixing solutionss that propyl carbinol forms, drip rear stirring 4h; Adding is with the anhydrous sodium sulphate of the volumeter 40g/L of water, add again 0.4 part of brown JM-4R of activity after it is dissolved fully, and with 1 ℃ of/minute temperature rise rate temperature is risen to 65 ℃, behind the isothermal reaction 35min, adding is with the tertiary sodium phosphate of the volumeter 15g/L of water, fixation 50min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
After this slow-release type leather finishing composition was used for ox Sofa cushion leather and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time had prolonged at least 90 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 5
In 7.84 parts of beta-cyclodextrins, add 40 parts of distilled water, and be heated to 80 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 40 ℃ and constant temperature, then under the magnetic agitation speed of 400r/min, slowly drip by 0.87 part of osmanthus flower fragrance and 0.22 part of mixing solutions that methyl alcohol forms, drip rear stirring 3.5h; Adding is with the sodium-chlor of the volumeter 35g/L of water, add again 1.2 parts of reactive red K-2G after it is dissolved fully, and with 0.9 ℃ of/minute temperature rise rate temperature is risen to 55 ℃, behind the isothermal reaction 30min, adding is with the yellow soda ash of the volumeter 20g/L of water, fixation 40min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
This slow-release type leather finishing composition is used for that pigskin case and bag grain is covered with paint, lacquer, colour wash, etc. and the flesh noodles spraying after, compare by carrying out the leather that perfuming processes with direct adding essence, fragrance remaining time has prolonged at least 120 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 6
In 3.75 parts of beta-cyclodextrins, add 50 parts of distilled water, and be heated to 60 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 45 ℃ and constant temperature, then under the magnetic agitation speed of 450r/min, slowly drip by 0.62 part of cream jasmin france and 0.124 part of mixing solutions that ethanol forms, drip rear stirring 3.5h; Adding is with the sodium-chlor of the volumeter 25g/L of water, add again 2.5 parts of reddish brown K-2BP of activity after it is dissolved fully, and with 1.1 ℃ of/minute temperature rise rates temperature is risen to 60 ℃, behind the isothermal reaction 35min, adding is with the sodium bicarbonate of the volumeter 18g/L of water, fixation 45min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
After this slow-release type leather finishing composition was used for pig leather for making garment and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time prolonged at least 90 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 7
In 9.16 parts of beta-cyclodextrins, add 90 parts of distilled water, and be heated to 68 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 50 ℃ and constant temperature, then under the magnetic agitation speed of 600r/min, slowly drip by 1.83 parts of lemon flavours and 0.61 part of mixing solutions that ethanol forms, drip rear stirring 3h; Adding is with the sodium-chlor of the volumeter 28g/L of water, adds 0.9 part of Reactive blue K-3R after it is dissolved fully again, and with 1 ℃ of/minute temperature rise rate temperature risen to 65 ℃, behind the isothermal reaction 40min, adds the yellow soda ash with the volumeter 17g/L of water, fixation 35min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
For behind the cattle hide coating finish for shoe upper leather, by carrying out the leather comparison that perfuming is processed with direct adding essence, fragrance remaining time prolongs at least 90 days with this slow-release type leather finishing composition; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 8
In 7.5 parts of beta-cyclodextrins, add 100 parts of distilled water, and be heated to 63 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 50 ℃ and constant temperature, then under the magnetic agitation speed of 500r/min, slowly drip by 0.75 part of rose compound and 0.75 part of mixing solutions that ethanol forms, drip rear stirring 4h; Adding is with the sodium-chlor of the volumeter 40g/L of water, adds 0.8 part of reactive yellow brown K-GR after it is dissolved fully again, and with 1 ℃ of/minute temperature rise rate temperature risen to 55 ℃, behind the isothermal reaction 1h, adds the yellow soda ash with the volumeter 13g/L of water, fixation 58min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
After this slow-release type leather finishing composition is used for sheepskin garment leather and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming processes relatively, fragrance remaining time at least 90 days with direct adding essence; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 9
In 9 parts of beta-cyclodextrins, add 120 parts of distilled water, and be heated to 60 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 45 ℃ and constant temperature, then under the magnetic agitation speed of 5500r/min, slowly drip by 1.5 parts of lavender oils and 1.5 parts of mixing solutionss that ethanol forms, drip rear stirring 3h; Adding is with the sodium-chlor of the volumeter 25g/L of water, add again 1.8 parts of reactive red K-2G after it is dissolved fully, and with 1.2 ℃ of/minute temperature rise rates temperature is risen to 60 ℃, behind the isothermal reaction 45min, adding is with the yellow soda ash of the volumeter 15g/L of water, fixation 50min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
This slow-release type leather finishing composition is used for that pigskin case and bag grain is covered with paint, lacquer, colour wash, etc. and the flesh noodles spraying after, by carrying out leather that perfuming processes relatively, fragrance remaining time prolongation at least 120 days with direct adding essence; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 10
In 10.17 parts of beta-cyclodextrins, add 100 parts of distilled water, and be heated to 65 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 50 ℃ and constant temperature, then under the magnetic agitation speed of 500r/min, slowly drip by 1.45 parts of flower of Capa Jasmine essence and 1.45 parts of mixing solutionss that ethanol forms, drip rear stirring 3.5h; Adding is with the sodium-chlor of the volumeter 30g/L of water, adds 4.5 parts of reactive black KN-B after it is dissolved fully again, and with 1 ℃ of/minute temperature rise rate temperature risen to 55 ℃, behind the isothermal reaction 55min, adds the yellow soda ash with the volumeter 10g/L of water, fixation 40min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
This slow-release type leather finishing composition is used for that the sheepskin clothes grain is covered with paint, lacquer, colour wash, etc. and the flesh noodles spraying after, by carrying out leather that perfuming processes relatively, fragrance remaining time prolongation at least 120 days with direct adding essence; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 11
In 10.18 parts of beta-cyclodextrins, add 100 parts of distilled water, and be heated to 65 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 40 ℃ and constant temperature, then under the magnetic agitation speed of 250r/min, slowly drip by 2.54 parts of cream jasmin frances and 2.54 parts of mixing solutionss that methyl alcohol forms, drip rear stirring 3h; Add simultaneously 6 parts of direct fast blacks and with the volumeter 3g/L sodium bicarbonate of water, and with 1 ℃ of/minute temperature rise rate temperature is risen to 60 ℃, behind the constant temperature dyeing 35min, add the sodium-chlor with the volumeter 1g/L of water, continue dyeing 40min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
After this slow-release type leather finishing composition was used for Soft Cattle Upper Leather and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time prolonged at least 90 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 12
In 9 parts of beta-cyclodextrins, add 120 parts of distilled water, and be heated to 60 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 35 ℃ and constant temperature, then under the magnetic agitation speed of 200r/min, slowly drip by 1.8 parts of rose compounds and 0.9 part of mixing solutions that ethanol forms, drip rear stirring 4h; Add simultaneously 6 parts of direct dark brown ME and with the volumeter 2g/L yellow soda ash of water, and with 1 ℃ of/minute temperature rise rate temperature is risen to 65 ℃, behind the constant temperature dyeing 30min, add the anhydrous sodium sulphate with the volumeter 5g/L of water, continue dyeing 30min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
After this slow-release type leather finishing composition was used for cowhide mat leather top finishing, by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time prolonged at least 90 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 13
In 9.62 parts of beta-cyclodextrins, add 80 parts of distilled water, and be heated to 68 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 50 ℃ and constant temperature, then under the magnetic agitation speed of 300r/min, slowly drip by 1.2 parts of lavender oils and 0.4 part of mixing solutions that Virahol forms, drip rear stirring 2.5h; Add simultaneously 0.24 part of direct sky blue 5B and with the volumeter 1g/L yellow soda ash of water, and with 0.8 ℃ of/minute temperature rise rate temperature is risen to 70 ℃, behind the constant temperature dyeing 25min, add the anhydrous sodium sulphate with the volumeter 10g/L of water, continue dyeing 35min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
This slow-release type leather finishing composition is used for that the sheepskin clothes grain is covered with paint, lacquer, colour wash, etc. and the flesh noodles dipping after, by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time prolongs at least 120 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 14
In 11.79 parts of beta-cyclodextrins, add 60 parts of distilled water, and be heated to 80 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 45 ℃ and constant temperature, then under the magnetic agitation speed of 350r/min, slowly drip by 1.68 parts of lemon flavours and 1.68 parts of mixing solutionss that propyl carbinol forms, drip rear stirring 2h; Add simultaneously 2.4 parts of chrysophenines and with the volumeter 1g/L sodium hydroxide of water, and with 1.2 ℃ of/minute temperature rise rates temperature is risen to 65 ℃, behind the constant temperature dyeing 25min, add the sodium-chlor with the volumeter 15g/L of water, continue dyeing 45min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
This slow-release type leather finishing composition is used for that the sheepskin clothes grain is covered with paint, lacquer, colour wash, etc. and the flesh noodles dipping after, by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time prolongs at least 120 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 15
In 7.4 parts of beta-cyclodextrins, add 50 parts of distilled water, and be heated to 75 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 45 ℃ and constant temperature, then under the magnetic agitation speed of 400r/min, slowly drip by 0.82 part of osmanthus flower fragrance and 0.2 part of mixing solutions that methyl alcohol forms, drip rear stirring 3.5h; Add simultaneously 1.5 parts of direct yellowish-brown 3G and with the volumeter 2g/L tertiary sodium phosphate of water, and with 1 ℃ of/minute temperature rise rate temperature is risen to 75 ℃, behind the constant temperature dyeing 30min, add the sodium-chlor with the volumeter 20g/L of water, continue dyeing 50min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
After this slow-release type leather finishing composition was used for ox Sofa cushion leather and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time prolonged at least 120 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4.5 grades.
Embodiment 16
In 6.74 parts of beta-cyclodextrins, add 90 parts of distilled water, and be heated to 60 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 40 ℃ and constant temperature, then under the magnetic agitation speed of 500r/min, slowly drip by 1.20 parts of cream jasmin frances and 0.24 part of mixing solutions that ethanol forms, drip rear stirring 4h; Add simultaneously 0.9 part of direct fast yellow G and with the volumeter 2.5g/L yellow soda ash of water, and with 1.1 ℃ of/minute temperature rise rates temperature is risen to 70 ℃, behind the constant temperature dyeing 20min, add the sodium-chlor with the volumeter 8g/L of water, continue dyeing 52min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
After this slow-release type leather finishing composition was used for pigskin case and bag grain and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time had prolonged at least 90 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 17
In 7.12 parts of beta-cyclodextrins, add 70 parts of distilled water, and be heated to 65 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 50 ℃ and constant temperature, then under the magnetic agitation speed of 450r/min, slowly drip by 1.42 parts of lemon flavours and 0.48 part of mixing solutions that ethanol forms, drip rear stirring 3.5h; Add simultaneously 0.35 part of direct fast red 4B and with the volumeter 1.5g/L yellow soda ash of water, and with 1 ℃ of/minute temperature rise rate temperature is risen to 80 ℃, behind the constant temperature dyeing 20min, add the sodium-chlor with the volumeter 12g/L of water, continue dyeing 30min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
For behind the cattle hide coating finish for shoe upper leather, by carrying out the leather comparison that perfuming is processed with direct adding essence, fragrance remaining time prolongs at least 90 days with this slow-release type leather finishing composition; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 18
In 12.03 parts of beta-cyclodextrins, add 100 parts of distilled water, and be heated to 70 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 50 ℃ and constant temperature, then under the magnetic agitation speed of 600r/min, slowly drip by 1.2 parts of rose compounds and 1.2 parts of mixing solutionss that ethanol forms, drip rear stirring 3.8h; Add simultaneously 8.0 parts of direct fast blacks and with the volumeter 2.5g/L yellow soda ash of water, and with 0.8 ℃ of/minute temperature rise rate temperature is risen to 60 ℃, behind the constant temperature dyeing 30min, add the sodium-chlor with the volumeter 14g/L of water, continue dyeing 1h; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
After this slow-release type leather finishing composition was used for ox automobile sofa leather and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time prolonged at least 90 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Embodiment 19
In 8.24 parts of beta-cyclodextrins, add 110 parts of distilled water, and be heated to 60 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 45 ℃ and constant temperature, then under the magnetic agitation speed of 550r/min, slowly drip by 1.37 parts of flower of Capa Jasmine essence and 0.685 part of mixing solutions that ethanol forms, drip rear stirring 3h; Add simultaneously 2.2 parts of direct yellowish-brown 3G and with the volumeter 1g/L yellow soda ash of water, and with 1 ℃ of/minute temperature rise rate temperature is risen to 65 ℃, behind the constant temperature dyeing 25min, add the sodium-chlor with the volumeter 10g/L of water, continue dyeing 55min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
After this slow-release type leather finishing composition was used for ox Sofa cushion leather and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time prolonged at least 120 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4.5 grades.
Embodiment 20
In 7.5 parts of beta-cyclodextrins, add 100 parts of distilled water, and be heated to 62 ℃ in water-bath and take out after beta-cyclodextrin is dissolved fully, be cooled to 50 ℃ and constant temperature, then under the magnetic agitation speed of 500r/min, slowly drip by 1.07 parts of lavender oils and 0.214 part of mixing solutions that methyl alcohol forms, drip rear stirring 3h; Add simultaneously 7 parts of direct fast blacks and with the volumeter 2g/L yellow soda ash of water, and with 0.9 ℃ of/minute temperature rise rate temperature is risen to 60 ℃, behind the constant temperature dyeing 28min, add the sodium-chlor with the volumeter 15g/L of water, continue dyeing 40min; This solution is let cool to room temperature, then put in the refrigerator below 4 ℃ and deposit more than the 12h, take out and filter, be drying to obtain slow-release type leather fragrance finishing agent.
After this slow-release type leather finishing composition was used for Soft Cattle Upper Leather and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming processes relatively with direct adding essence, fragrance remaining time prolonged at least 90 days; The color staining fastness of anti-xerotripsis of coating is 4.5 grades, and the wet rubbing staining fastness is 4 grades.
Claims (7)
1. the preparation method of a slow-release type leather fragrance finishing agent, processing step and the condition of the method are as follows:
(1) in 60～80 ℃ water-bath, beta-cyclodextrin is dissolved in the water fully takes out after making saturated aqueous solution, be cooled to 35～50 ℃ and constant temperature, then slowly adding with the beta-cyclodextrin weight ratio under the magnetic agitation speed of 200～600r/min is 1: 4～10 essence, this essence is to dissolve in the alcoholic solvent by weight 1～5: 1 to drip behind the formation essence alcoholic solution, drips rear stirring 2～4 hours;
(2) in the solution that step (1) obtains, add dyeing accelerant by 20～40g/L first, after it dissolves fully, count 0.5～6% by the weight percent of water again and add reactive dyestuffs, and with 0.8～1.2 ℃/minute temperature rise rate temperature is risen to 55～65 ℃, constant temperature 0.5～1 hour added 10～20g/L alkaline agent fixation 0.5～1 hour at last, or
In the solution that step (1) obtains, add simultaneously by the weight percent of water and count 0.3～8% direct dyestuff and by the alkaline agent of 1～3g/L, and with 0.8～1.2 ℃/minute temperature rise rate with temperature to 60～80 ℃, constant temperature 20～35 minutes, add dyeing accelerant by 1～20g/L again, reacted 0.5～1 hour;
(3) step (2) solution that obtains is let cool to room temperature, and then in depositing below 4 ℃ more than 12 hours, filter, be drying to obtain slow-release type leather fragrance finishing agent.
2. the preparation method of slow-release type leather fragrance finishing agent according to claim 1, the essence that adds in the method and beta-cyclodextrin weight ratio are 1: 5～7.
3. the preparation method of slow-release type leather fragrance finishing agent according to claim 1 and 2 is 25～35g/L with the used dyeing accelerant of reactive dyeing step in the method; The reactive dyestuffs weight percent that adds is 0.5～1.5% or 4～5%.
4. the preparation method of slow-release type leather fragrance finishing agent according to claim 1 and 2 is 0.3～2% or 5～7% with the used direct dyestuff weight percent of direct dyeing step in the method.
5. the preparation method of slow-release type leather fragrance finishing agent according to claim 1 and 2, used dyeing accelerant is sodium-chlor or anhydrous sodium sulphate in the method; Alkaline agent is sodium hydroxide, yellow soda ash, tertiary sodium phosphate or sodium bicarbonate.
6. the preparation method of slow-release type leather fragrance finishing agent according to claim 3, used dyeing accelerant is sodium-chlor or anhydrous sodium sulphate in the method; Alkaline agent is sodium hydroxide, yellow soda ash, tertiary sodium phosphate or sodium bicarbonate.
7. the preparation method of slow-release type leather fragrance finishing agent according to claim 4, used dyeing accelerant is sodium-chlor or anhydrous sodium sulphate in the method; Alkaline agent is sodium hydroxide, yellow soda ash, tertiary sodium phosphate or sodium bicarbonate.
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| CN103114459B (en) * | 2013-03-11 | 2015-03-18 | 广西鑫深科技有限公司 | Fragrant artificial leather and preparation method thereof |
| CN103463655A (en) * | 2013-09-06 | 2013-12-25 | 上海应用技术学院 | Natural lavender incense piece and preparation method thereof |
| CN112724504A (en) * | 2020-12-10 | 2021-04-30 | 成都金发科技新材料有限公司 | Polypropylene composite material with long-acting fragrance and preparation method and application thereof |
| CN113737562B (en) * | 2021-08-23 | 2022-09-06 | 东莞市尚臻工艺品有限公司 | Color fixing and fragrance fixing method for dyeing soaked essence volatilization stick |
| CN114410851A (en) * | 2022-01-23 | 2022-04-29 | 浙江奥康鞋业股份有限公司 | Novel fragrant cow leather material and preparation process thereof |
| IT202200000938A1 (en) | 2022-03-24 | 2023-09-24 | Bi Qem Specialties S P A | Leather tanning or retanning compound with cyclodextrin-based inclusion compound |
| CN116162747A (en) * | 2023-04-18 | 2023-05-26 | 广州市鸿峥实业有限公司 | Perfuming type sheepskin handfeel agent |
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