CN101857908A - 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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- CN101857908A CN101857908A CN 201010202855 CN201010202855A CN101857908A CN 101857908 A CN101857908 A CN 101857908A CN 201010202855 CN201010202855 CN 201010202855 CN 201010202855 A CN201010202855 A CN 201010202855A CN 101857908 A CN101857908 A CN 101857908A
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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 leather chemical industry material technology field, be specifically related to a kind of slow-release type leather fragrance finishing agent and preparation method thereof.
Background technology
Along with the progress and the growth in the living standard of material progress, the human consumer is more and more dense to the leatherware interest that has lasting fragrance and specific function.And use essence that leather is carried out back arrangement processing, except that 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 lasting relatively fragrance 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).This 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 this method lays particular emphasis on the synchronous infiltration of essence and fatting agent, do not consider combining of essence and leather fiber, make fragrance still volatile, fragrance remaining time is shorter relatively, 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).This method is to cover air-locked film on the leather of crossing through the essence solution soaking, to reach the purpose of the permanent lasting of leather.Though 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).This method is utilized microcapsulary, and essence is encapsulated in the polyurethane microcapsule, by covering with paint, lacquer, colour wash, etc. technology leather is carried out spice finish then.But the weak point of this 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 industries such as weaving, food, tobacco, makeup (Liu Liya, Wang Chaoxia, Chen Shuilin. develop fragrant health care textiles [J] with beta-cyclodextrin. fabrics for industrial use, 2002, (12): 35-38; Vertical big, seedling banyan Zan, Yuan Wenliang. cyclodextrin inclusion compound is at Application in Food Industry [J]. 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 inherent white of inclusion compound own causes white point occurring at leather surface easily, its application in coloured leather is restricted.
Summary of the invention
Purpose of the present invention is exactly at 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 disclosed 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 of 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 existing beta-cyclodextrin essence inclusion compound respectively, thereby make the powdery solid of slow-release type leather fragrance finishing agent that provides for constituting by beta-cyclodextrin and the essence that is positioned at its hole, 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, the processing step and the condition of this 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, slowly adding with the beta-cyclodextrin weight ratio under the magnetic agitation speed of 200～600r/min then 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 the back and stirs 2～4 hours;
(2) in the solution that step (1) is obtained, add dyeing accelerant by 20～40g/L earlier, after treating that it dissolves fully, count 0.5～6% by the weight percent of water again and add reactive dyestuffs, and temperature is risen to 55～65 ℃ with 0.8～1.2 ℃/minute temperature rise rate, 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) is obtained, 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 put be chilled to room temperature, and then, filter, be drying to obtain slow-release type leather fragrance finishing agent in depositing below 4 ℃ more than 12 hours.
Used essence is common daily use chemicals class essence in the above method, preferred cream jasmin france, rose compound, lavandula angustifolia essence, lemon flavour, osmanthus flower fragrance; The used alcoholic solvent of dilution essence is Virahol, propyl carbinol, ethanol and methyl alcohol, preferred alcohol.
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, added 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, added 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 that volume in water is a benchmark.
The present invention is by molecule embedding principle, utilize the outside hydrophilic constructional feature of beta-cyclodextrin hollow and inner hydrophobic, earlier hydrophobicity essence is introduced the beta-cyclodextrin hole and form the inclusion complex compound, utilize reactive dyestuffs and direct dyestuff mostly to be polar molecule greatly then dexterously, be difficult for entering and destroy the essence inclusion compound in the nonpolar cavity of cyclodextrin, but can form the characteristics of covalent linkage or hydrogen bond with the hydroxyl outside the hole, inclusion compound is dyeed (as shown in drawings), make color specific on the inclusion compound band, to satisfy the demand of different colours leather to spice finish.At last, cover with paint, lacquer, colour wash, etc. and the flesh noodles impregnation technology, the beta-cyclodextrin essence inclusion compound of band particular color is introduced in the leather by grain side of 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, prolong the remaining time of fragrance in leather greatly, given beta-cyclodextrin essence inclusion compound appearance corresponding color in addition again, 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 spice finish without the color leather.
Because the present invention dyestuff and the inclusion compound dyeing selected for use 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, color fastness to rubbing height (the xerotripsis staining fastness: 4～5 grades 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 a water soluble group; D is the dyestuff color bodies; B connects base; Re is an 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 a water soluble group in the formula; D is the dyestuff color bodies.
Embodiment
Provide embodiment below 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 in water-bath, be heated to 60 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 35 ℃ and constant temperature, under the magnetic agitation speed of 200r/min, slowly drip then, drip the back and stir 3h by 1.8 parts of cream jasmin frances and 1.8 parts of mixing solutionss that methyl alcohol is formed; Adding is with the sodium-chlor of the volumeter 20g/L of water, adds 2.0 parts of reactive yellow X-RG again after it is dissolved fully, 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 put be chilled to room temperature, put then 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 technology is used for the soft upper leather of ox and covers with paint, lacquer, colour wash, etc. routinely, and by carrying out leather that perfuming handles 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 in water-bath, be heated to 65 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 40 ℃ and constant temperature, under the magnetic agitation speed of 300r/min, slowly drip then, drip the back and stir 2.0h by 1.0 parts of rose compounds and 0.5 part of mixing solutions that ethanol is formed; Adding is with the anhydrous sodium sulphate of the volumeter 20g/L of water, add 3.0 parts of brown JM-4R of activity after it is dissolved fully again, and temperature is risen to 60 ℃, behind the isothermal reaction 40min with 0.8 ℃ of/minute temperature rise rate, adding is with the yellow soda ash of the volumeter 12g/L of water, fixation 30min; This solution put be chilled to room temperature, put then 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 technology is used for cowhide mat leather top finishing routinely, and by carrying out leather that perfuming handles 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 in water-bath, be heated to 70 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 45 ℃ and constant temperature, under the magnetic agitation speed of 350r/min, slowly drip then, drip the back and stir 2.5h by 1.06 parts of lavandula angustifolia essence and 0.35 part of mixing solutions that Virahol is formed; Adding is with the anhydrous sodium sulphate of the volumeter 25g/L of water, add 2.8 parts of reactive black KN-B after it is dissolved fully again, and temperature is risen to 62 ℃, behind the isothermal reaction 50min with 1.2 ℃ of/minute temperature rise rates, adding is with the sodium hydroxide of the volumeter 10g/L of water, fixation 43min; This solution put be chilled to room temperature, put then 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 handles 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 in water-bath, be heated to 75 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 50 ℃ and constant temperature, under the magnetic agitation speed of 300r/min, slowly drip then, drip the back and stir 4h by 1.69 parts of lemon flavours and 1.69 parts of mixing solutionss that propyl carbinol is formed; Adding is with the anhydrous sodium sulphate of the volumeter 40g/L of water, add 0.4 part of brown JM-4R of activity after it is dissolved fully again, and temperature is risen to 65 ℃, behind the isothermal reaction 35min with 1 ℃ of/minute temperature rise rate, adding is with the tertiary sodium phosphate of the volumeter 15g/L of water, fixation 50min; This solution put be chilled to room temperature, put then 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 handles 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 in water-bath, be heated to 80 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 40 ℃ and constant temperature, under the magnetic agitation speed of 400r/min, slowly drip then, drip the back and stir 3.5h by 0.87 part of osmanthus flower fragrance and 0.22 part of mixing solutions that methyl alcohol is formed; Adding is with the sodium-chlor of the volumeter 35g/L of water, add 1.2 parts of reactive red K-2G after it is dissolved fully again, and temperature is risen to 55 ℃, behind the isothermal reaction 30min with 0.9 ℃ of/minute temperature rise rate, adding is with the yellow soda ash of the volumeter 20g/L of water, fixation 40min; This solution put be chilled to room temperature, put then 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 the leather comparison that perfuming is handled 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 in water-bath, be heated to 60 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 45 ℃ and constant temperature, under the magnetic agitation speed of 450r/min, slowly drip then, drip the back and stir 3.5h by 0.62 part of cream jasmin france and 0.124 part of mixing solutions that ethanol is formed; Adding is with the sodium-chlor of the volumeter 25g/L of water, add 2.5 parts of reddish brown K-2BP of activity after it is dissolved fully again, and temperature is risen to 60 ℃, behind the isothermal reaction 35min with 1.1 ℃ of/minute temperature rise rates, adding is with the sodium bicarbonate of the volumeter 18g/L of water, fixation 45min; This solution put be chilled to room temperature, put then 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 handles 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 in water-bath, be heated to 68 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 50 ℃ and constant temperature, under the magnetic agitation speed of 600r/min, slowly drip then, drip the back and stir 3h by 1.83 parts of lemon flavours and 0.61 part of mixing solutions that ethanol is formed; Adding is with the sodium-chlor of the volumeter 28g/L of water, adds 0.9 part of Reactive blue K-3R again after it is dissolved fully, 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 put be chilled to room temperature, put then 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 the cattle hide upper leather and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming handles 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 8
In 7.5 parts of beta-cyclodextrins, add 100 parts of distilled water, and in water-bath, be heated to 63 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 50 ℃ and constant temperature, under the magnetic agitation speed of 500r/min, slowly drip then, drip the back and stir 4h by 0.75 part of rose compound and 0.75 part of mixing solutions that ethanol is formed; Adding is with the sodium-chlor of the volumeter 40g/L of water, adds 0.8 part of yellowish-brown K-GR of activity again after it is dissolved fully, 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 put be chilled to room temperature, put then 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 handles 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 in water-bath, be heated to 60 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 45 ℃ and constant temperature, under the magnetic agitation speed of 5500r/min, slowly drip then, drip the back and stir 3h by 1.5 parts of lavandula angustifolia essence and 1.5 parts of mixing solutionss that ethanol is formed; Adding is with the sodium-chlor of the volumeter 25g/L of water, add 1.8 parts of reactive red K-2G after it is dissolved fully again, and temperature is risen to 60 ℃, behind the isothermal reaction 45min with 1.2 ℃ of/minute temperature rise rates, adding is with the yellow soda ash of the volumeter 15g/L of water, fixation 50min; This solution put be chilled to room temperature, put then 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 handles 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 in water-bath, be heated to 65 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 50 ℃ and constant temperature, under the magnetic agitation speed of 500r/min, slowly drip then, drip the back and stir 3.5h by 1.45 parts of flower of Capa Jasmine essence and 1.45 parts of mixing solutionss that ethanol is formed; Adding is with the sodium-chlor of the volumeter 30g/L of water, adds 4.5 parts of reactive black KN-B again after it is dissolved fully, 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 put be chilled to room temperature, put then 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 handles 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 in water-bath, be heated to 65 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 40 ℃ and constant temperature, under the magnetic agitation speed of 250r/min, slowly drip then, drip the back and stir 3h by 2.54 parts of cream jasmin frances and 2.54 parts of mixing solutionss that methyl alcohol is formed; Add 6 parts of direct fast blacks simultaneously and with the volumeter 3g/L sodium bicarbonate of water, and temperature is risen to 60 ℃, behind the constant temperature dyeing 35min, add sodium-chlor, continue dyeing 40min with the volumeter 1g/L of water with 1 ℃ of/minute temperature rise rate; This solution put be chilled to room temperature, put then 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 the soft upper leather of ox and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming handles 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 in water-bath, be heated to 60 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 35 ℃ and constant temperature, under the magnetic agitation speed of 200r/min, slowly drip then, drip the back and stir 4h by 1.8 parts of rose compounds and 0.9 part of mixing solutions that ethanol is formed; Add 6 parts of direct dark brown ME simultaneously and with the volumeter 2g/L yellow soda ash of water, and temperature is risen to 65 ℃, behind the constant temperature dyeing 30min, add anhydrous sodium sulphate, continue dyeing 30min with the volumeter 5g/L of water with 1 ℃ of/minute temperature rise rate; This solution put be chilled to room temperature, put then 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 handles 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 in water-bath, be heated to 68 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 50 ℃ and constant temperature, under the magnetic agitation speed of 300r/min, slowly drip then, drip the back and stir 2.5h by 1.2 parts of lavandula angustifolia essence and 0.4 part of mixing solutions that Virahol is formed; Add 0.24 part of direct acid blue 5B simultaneously and with the volumeter 1g/L yellow soda ash of water, and temperature is risen to 70 ℃, behind the constant temperature dyeing 25min, add anhydrous sodium sulphate, continue dyeing 35min with the volumeter 10g/L of water with 0.8 ℃ of/minute temperature rise rate; This solution put be chilled to room temperature, put then 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 handles 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 in water-bath, be heated to 80 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 45 ℃ and constant temperature, under the magnetic agitation speed of 350r/min, slowly drip then, drip the back and stir 2h by 1.68 parts of lemon flavours and 1.68 parts of mixing solutionss that propyl carbinol is formed; Add 2.4 parts simultaneously and directly freeze Huang and, and temperature is risen to 65 ℃, behind the constant temperature dyeing 25min, add sodium-chlor, continue dyeing 45min with the volumeter 15g/L of water with 1.2 ℃ of/minute temperature rise rates with the volumeter 1g/L sodium hydroxide of water; This solution put be chilled to room temperature, put then 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 handles 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 in water-bath, be heated to 75 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 45 ℃ and constant temperature, under the magnetic agitation speed of 400r/min, slowly drip then, drip the back and stir 3.5h by 0.82 part of osmanthus flower fragrance and 0.2 part of mixing solutions that methyl alcohol is formed; Add 1.5 parts of direct yellowish-brown 3G simultaneously and with the volumeter 2g/L tertiary sodium phosphate of water, and temperature is risen to 75 ℃, behind the constant temperature dyeing 30min, add sodium-chlor, continue dyeing 50min with the volumeter 20g/L of water with 1 ℃ of/minute temperature rise rate; This solution put be chilled to room temperature, put then 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 handles 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 in water-bath, be heated to 60 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 40 ℃ and constant temperature, under the magnetic agitation speed of 500r/min, slowly drip then, drip the back and stir 4h by 1.20 parts of cream jasmin frances and 0.24 part of mixing solutions that ethanol is formed; Add 0.9 part of direct fast yellow G simultaneously and with the volumeter 2.5g/L yellow soda ash of water, and temperature is risen to 70 ℃, behind the constant temperature dyeing 20min, add sodium-chlor, continue dyeing 52min with the volumeter 8g/L of water with 1.1 ℃ of/minute temperature rise rates; This solution put be chilled to room temperature, put then 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 handles 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 in water-bath, be heated to 65 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 50 ℃ and constant temperature, under the magnetic agitation speed of 450r/min, slowly drip then, drip the back and stir 3.5h by 1.42 parts of lemon flavours and 0.48 part of mixing solutions that ethanol is formed; Add 0.35 part of direct fast red 4B simultaneously and with the volumeter 1.5g/L yellow soda ash of water, and temperature is risen to 80 ℃, behind the constant temperature dyeing 20min, add sodium-chlor, continue dyeing 30min with the volumeter 12g/L of water with 1 ℃ of/minute temperature rise rate; This solution put be chilled to room temperature, put then 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 the cattle hide upper leather and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming handles 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 18
In 12.03 parts of beta-cyclodextrins, add 100 parts of distilled water, and in water-bath, be heated to 70 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 50 ℃ and constant temperature, under the magnetic agitation speed of 600r/min, slowly drip then, drip the back and stir 3.8h by 1.2 parts of rose compounds and 1.2 parts of mixing solutionss that ethanol is formed; Add 8.0 parts of direct fast blacks simultaneously and with the volumeter 2.5g/L yellow soda ash of water, and temperature is risen to 60 ℃, behind the constant temperature dyeing 30min, add sodium-chlor, continue dyeing 1h with the volumeter 14g/L of water with 0.8 ℃ of/minute temperature rise rate; This solution put be chilled to room temperature, put then 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 artificial leather and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming handles 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 in water-bath, be heated to 60 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 45 ℃ and constant temperature, under the magnetic agitation speed of 550r/min, slowly drip then, drip the back and stir 3h by 1.37 parts of flower of Capa Jasmine essence and 0.685 part of mixing solutions that ethanol is formed; Add 2.2 parts of direct yellowish-brown 3G simultaneously and with the volumeter 1g/L yellow soda ash of water, and temperature is risen to 65 ℃, behind the constant temperature dyeing 25min, add sodium-chlor, continue dyeing 55min with the volumeter 10g/L of water with 1 ℃ of/minute temperature rise rate; This solution put be chilled to room temperature, put then 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 handles 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 in water-bath, be heated to 62 ℃ and make beta-cyclodextrin dissolve the back fully to take out, be cooled to 50 ℃ and constant temperature, under the magnetic agitation speed of 500r/min, slowly drip then, drip the back and stir 3h by 1.07 parts of lavandula angustifolia essence and 0.214 part of mixing solutions that methyl alcohol is formed; Add 7 parts of direct fast blacks simultaneously and with the volumeter 2g/L yellow soda ash of water, and temperature is risen to 60 ℃, behind the constant temperature dyeing 28min, add sodium-chlor, continue dyeing 40min with the volumeter 15g/L of water with 0.9 ℃ of/minute temperature rise rate; This solution put be chilled to room temperature, put then 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 the soft upper leather of ox and covers with paint, lacquer, colour wash, etc., by carrying out leather that perfuming handles 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. slow-release type leather fragrance finishing agent, this finishing composition are for by beta-cyclodextrin be positioned at the powdery solid that the essence in its hole constitutes, and particle diameter is 5～30 μ m, and its outside surface has the color of being given by reactive dyestuffs or direct dyestuff.
2. method for preparing the described slow-release type leather fragrance finishing agent of claim 1, the processing step and the condition of this 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, slowly adding with the beta-cyclodextrin weight ratio under the magnetic agitation speed of 200～600r/min then 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 the back and stirs 2～4 hours;
(2) in the solution that step (1) is obtained, add dyeing accelerant by 20～40g/L earlier, after treating that it dissolves fully, count 0.5～6% by the weight percent of water again and add reactive dyestuffs, and temperature is risen to 55～65 ℃ with 0.8～1.2 ℃/minute temperature rise rate, 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) is obtained, 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 put be chilled to room temperature, and then, filter, be drying to obtain slow-release type leather fragrance finishing agent in depositing below 4 ℃ more than 12 hours.
3. the method for preparing slow-release type leather fragrance finishing agent according to claim 2, essence that adds in this method and beta-cyclodextrin weight ratio are 1: 5～7.
4. according to claim 2 or the 3 described methods that prepare slow-release type leather fragrance finishing agent, be 25～35g/L with the used dyeing accelerant of reactive dyeing step in this method; The reactive dyestuffs weight percent that adds is 0.5～1.5% or 4～5%.
5. according to claim 2 or the 3 described methods that prepare slow-release type leather fragrance finishing agent, be 0.3～2% or 5～7% with the used direct dyestuff weight percent of direct dyeing step in this method.
6. according to claim 2 or the 3 described methods that prepare slow-release type leather fragrance finishing agent, used dyeing accelerant is sodium-chlor or anhydrous sodium sulphate in this method; Alkaline agent is sodium hydroxide, yellow soda ash, tertiary sodium phosphate or sodium bicarbonate.
7. the method for preparing slow-release type leather fragrance finishing agent according to claim 4, used dyeing accelerant is sodium-chlor or anhydrous sodium sulphate in this method.
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| CN103114459A (en) * | 2013-03-11 | 2013-05-22 | 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 |
| CN113737562A (en) * | 2021-08-23 | 2021-12-03 | 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 |
| CN116162747A (en) * | 2023-04-18 | 2023-05-26 | 广州市鸿峥实业有限公司 | Perfuming type sheepskin handfeel agent |
| IT202200000938A1 (en) | 2022-03-24 | 2023-09-24 | Bi Qem Specialties S P A | Leather tanning or retanning compound with cyclodextrin-based inclusion compound |
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| CN103114459A (en) * | 2013-03-11 | 2013-05-22 | 广西鑫深科技有限公司 | Fragrant artificial leather and preparation method thereof |
| 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 |
| CN113737562A (en) * | 2021-08-23 | 2021-12-03 | 东莞市尚臻工艺品有限公司 | Color fixing and fragrance fixing method for dyeing soaked essence volatilization stick |
| 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 |
| EP4249553A1 (en) | 2022-03-24 | 2023-09-27 | SPECIALTIES S.p.A. BI-QEM | Leather or retanning compound with cyclodextrin-based inclusion compound |
| WO2023180923A1 (en) | 2022-03-24 | 2023-09-28 | 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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