CN1431359A - Textile product with effects of bird's nest and its preparing method - Google Patents
Textile product with effects of bird's nest and its preparing method Download PDFInfo
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- CN1431359A CN1431359A CN 03114882 CN03114882A CN1431359A CN 1431359 A CN1431359 A CN 1431359A CN 03114882 CN03114882 CN 03114882 CN 03114882 A CN03114882 A CN 03114882A CN 1431359 A CN1431359 A CN 1431359A
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Abstract
A fabric with nest effect is prepared through fixing the dextrin with hole structure to the fabric by use of dihydroxydihydroxymethyl cycloethene urea (DMDUEU), butane tetracarboxylic acid (BTCA) and sol-gel technique, and storing the volatile substance (essence or refined oil) in the holes of dextrin.
Description
Technical field:
The present invention relates to textiles that has nest's effect and preparation method thereof, relate to or rather with three kinds of different preparation methods cyclodextrin is anchored on the textiles, will guest molecule essence or volatile materials be stored in its cavity and form inclusion compound adaptably with the cyclodextrin stereo molecule.The invention belongs to technical field of textile chemical engineering.
Background technology:
Textiles is just experiencing at present to multifunction direction development stages, and the fragrance textiles not only makes the people that the impression of back to nature is arranged, and has also increased aesthstic artistic effect for product.The key of fragrance textile production is the slow release long-acting problem, and it should have desirable influence power, the property retained, persistence and stability.Desirable influence power is meant that spices should have high aroma strength; Persistence is meant that spices has long effect in product; The property retained is meant that the spices dilution is dispersed in the ability that adheres to product in the water.Stability is meant that spices is not subject to the effect of air and oxidation deterioration in storage process.Studies show that both at home and abroad, essence microcapsuleization is that the effective way that addresses this problem is (as [1] A scent of theunusual.International Dyer.2000,56 (6): 26-26[2] New Finishes using Microencapsulation.High-tech Textile.1998,34 (4): 12-12).Microcapsules technology is that the natural or synthetic high polymer filmogen of a kind of usefulness coats the technology that forms fine particle that makes to dispersed solids or liquid.Its objective is core and external environment are kept apart, with protection and stable core, odor barrier and control release etc.It can protect essence to avoid the influence of external environment factor, and prolongs it and release the fragrant time limit.The preparation method who is usually used in the essence microcapsule of textiles has situ aggregation method and gelatin-Arabic gum complex coacervation.Situ aggregation method is to be the wall material with synthesized polymer materials such as melamine resins, and arrangement back textiles can remaining a certain amount of formaldehyde.When the gelatin-Arabic gum complex coacervation coated essence, water miscible one-tenth branch was ostracised and obtains a kind of essence of proportioning imbalance outside microcapsules.The combination of essence microcapsule and textiles is by adhesive, so the quality quality of adhesive becomes the key problem in technology that essence microcapsule is applied to textiles.Essence microcapsule has special requirement to adhesive, if the too high meeting of temperature causes the loss of essence.And the low-temperature adhesive technology is ripe not enough at present, especially formaldehydeless low-temperature adhesive.Another shortcoming of this technology is after the fragrance release of essence microcapsule finishes, and just no longer has the fragrance function.The present invention is exactly a technical problem of avoiding low-temperature adhesive, provides simultaneously constantly to load filling essence, provides the lasting textiles of longer time with this, and can take in the process at textiles according to the personal preference and change fragrance and have actual application value.
Cyclodextrin is that Villiers in 1891 is isolated from the starch digestion liquid of bacillus (Bacillus) amylobacter (Bacillusamylobacter) the earliest.Schardinger in 1903 has determined that it is a kind of chain starch presents the cylinder shape structure through the conversion of glucose degraded a material, and successfully isolate pure bacillus, be named as bacillus macerans (Bacillus macerans), it is still the normal bacterial classification that uses of research cyclodextrin so far.Two research groups of nineteen fifty-three French and Cramer have separated, have characterized the physicochemical properties of cyclodextrin.But because there is dispute in the judgement of toxicity, the developing research that relates to Application Areas is never carried out.Up to the seventies in 20th century, show the toxicologic study result of relevant cyclodextrin as legal qualification unit after, just given up people's misgivings.From then on the research work of cyclodextrin becomes increasingly active.Japanese scholar in 1975 the firm more grade that rises abruptly is isolated Alkaliphilic bacillus, has from then on begun the suitability for industrialized production of cyclodextrin.Szejtli has released a large amount of achievements in research in food, medicine and other fields, is described as " father of cyclodextrin ".After the seventies, cyclodextrin is fast-developing and become and construct supramolecular significant subject.The character that various supramolecular aggregations show is the basis of design molecular device and nano material.Cyclodextrin and copper, lithium, plumbous form highly structured, the cyclodextrin from collective and the modification of metal-complexing base all demonstrates special function uniformly.On the basis of effect that the cyclodextrin molecular hole is coated guest molecule and mechanism further investigation thereof, to have set up and developed an emerging subject-host-guest chemistry, it is to enliven the most in the current chemical research field and one of the field that deepens continuously.
Cyclodextrin is the cyclic oligomer sugar compounds that is linked with α-1,4 glucoside key by 6 to 12 glucopyranose units that is formed through the enzymolysis ring by amylase.What have use value is alpha-cyclodextrin, beta-schardinger dextrin-and the gamma-cyclodextrin that contains 6,7,8 glucopyranose units.In the basic unit of each glucopyranose, form the pyranoid ring of a main body, represent its space conformation usually with the chair form structure by 5 carbon atoms and 1 oxygen atom.The basic cellular construction of glucopyranose is
Beta-schardinger dextrin-is made up of 7 basic unit of glucopyranose, and has the stereochemical structure of certain altitude.Cavity upper and lower end bore difference, bore is bigger is called wide mouth end, and bore is less is called thin mouthful of end.Because each glucopyranose units of forming all is
4C
1Conformation, all secondary hydroxyls all come the Kuan Kou edge of ring molecule, and primary hydroxyl all comes thin mouthful of edge.Therefore, whole molecule becomes awl post or truncated cones shape garland.Cavity inside is being arranged and is being joined the glycosyloxy bridge atom, and the nonbonding duplet of oxygen atom points to the center, makes to have very high electron density in the cavity, shows the character of some lewis base.Glucopyranose ring C-3, C-5 hydrogen atom are positioned at cavity and have covered and join the glycosyloxy atom, make cavity inside become the hydrophobicity space.Natural cyclodextrin has three kinds of alpha-cyclodextrin, β ring before we notice it essence and gamma-cyclodextrins.Its main character is shown in Table 1.
The main character of table 1 cyclodextrin
| Cyclodextrin | Alpha-cyclodextrin | Beta-schardinger dextrin- | Gamma-cyclodextrin |
| The glucose unit number | ????6 | ????7 | ????8 |
| Molecular weight | ????972 | ????1135 | ????1297 |
| Crystal form (by water crystallization) | The hexagonal sheet | Monoclinic crystal | Side's sheet or rectangular post |
| Crystallization moisture (%) | ????10.2 | ????13.2-14.5 | ????8.13-17.7 |
| Water solubility (g/100ml, 25 ℃) | ????14.5 | ????1.85 | ????23.2 |
| Hole, cave internal diameter (A 0, dust) | ????5-6 | ????7-8 | ????9-10 |
| Cave height of holes (A 0, dust) | ????7.9±0.1 | ????7.9±0.1 | ????7.9±0.1 |
| Hole, cave volume (ml/mol) | ????104 | ????157 | ????256 |
| Hole, gram molecule cave volume (ml/g) | ????0.1 | ????0.14 | ????0.20 |
| Outside diameter (A 0, dust) | ????14.6±0.4 | ????15.4±0.4 | ????17.5±0.4 |
By table 1 as seen: alpha-cyclodextrin molecule hole crack is less, can only coat less guest molecule usually, such as: aliphatic hydrocarbon, CO
2And propane equimolecular; The gamma-cyclodextrin molecule is bigger, can coat bigger guest molecule, such as: organic macrocycle compounds etc., but because of its cost height, application is restricted.Beta-schardinger dextrin-molecule hole is of moderate size, and can better coat some vitamin and little aromatic molecules etc.Because beta-schardinger dextrin-solubility is low, crystallization easily, separation, purification, avirulence, easily biological-degradable and production cost are lower, so be widely used in every field such as chemical industry, medicine, food, dyestuff, photographic material, cosmetic.Cyclodextrin has many application (as [1] .Hans-Jurgen Buschmann et al at field of textiles, Cyclodextrins andDextrins as New Auxiliaries in Dyeing.Melliand Textilberichte, 1991 (12) [2] Hans-JurgenBuschmann et al.The Use of Cyclodextrins in Textile Processes.J, Text.Inst.1998 (89)).Cyclodextrin can be used as dyeing assistant in dyeing, it can form inclusion compound with dyestuff and be used for retarding agents.Also can reduce the surfactant that remains in the textile processing on the fabric face, they can influence coloration of textile materials performance, wettability, surperficial absorption property, hydrophilic finiss effect, coating result etc.Load the fragrance textile techniques but but cyclodextrin is applied to filling, do not appear in the newspapers both at home and abroad.
Sol-gel (sol-gel) is synthetic to be the new method that a kind of immediate development replaces high temperature solid-state synthetic reaction preparation pottery, glass and many solid materials.It can form one transparent and the good film of adherence is given fabric chemistry and physical modification by coating on different textiless.Sol-gel process owing to mix some micro-even doping that realize on molecular levels through the solution reaction step with being easy to equal and quantitative.The diffusion of component generally is in nanometer range in the collosol-gelatum system, and therefore reaction is carried out easily, and temperature is lower.
Summary of the invention:
The object of the present invention is to provide a kind of textiles and preparation method thereof with nest's effect.
Textiles with nest's effect provided by the invention is because be that a kind of cyclodextrin that has hole characteristics with molecular structure is anchored on the textiles, volatility such as the guest molecule-essential oil that will adapt with the cyclodextrin host molecule or essence is stored in its cavity again, its effect is similar to the nest of birds, so be referred to as the textiles of nest's effect.Thereby the compound that this structure forms prolongs fragrance remaining time with the vapour pressure that reduces volatile substance, improves by the heat-resistant stability of reserve substance.Simultaneously after the volatilization of guest molecule-essence or sesame oil uses up, can be according to user's demand, the essence or the sesame oil that refill other kind easily can constantly be reused.
Textiles with nest's effect provided by the invention is implemented by following 3 kinds of preparation technologies:
(1) textiles be impregnated in contains 2D resin (dihydroxy dihydroxymethyl cyclic ethylene urea, DMDUEU), magnesium chloride, the transparency finishing aqueous solution of beta-schardinger dextrin-, pad (taking liquid rate 85-100%) through padding machine, then 80 ℃ of following preliminary dryings 5 minutes, bake at 160-180 ℃ and cyclodextrin to be anchored on the textiles in 3-6 minute.Usefulness contains the aqueous solution or the ethanolic solution dipping of essence or is sprayed on the textiles again.Naturally dry the filling of finishing essence then.
Its transparency finishing solution specifically consists of:
2D resin 40-90g/l
Magnesium chloride 20-80g/l
Beta-schardinger dextrin-5-90g/l
(2) textiles be impregnated in contain fourth unit tetrabasic carboxylic acid (BTCA), inferior sodium phosphate, the transparency finishing aqueous solution of beta-schardinger dextrin-pads (taking liquid rate 85-100%) through padding machine, then 80 ℃ of following preliminary dryings 5 minutes, bake at 160-180 ℃ and cyclodextrin to be anchored on the textiles in 3-6 minute.Usefulness contains the aqueous solution or the ethanolic solution dipping of essence or is sprayed on the textiles again.Naturally dry the filling of finishing essence then.
The concrete prescription of described transparency finishing solution is:
BTCA BTCA 40-90g/l
Inferior sodium phosphate 20-80g/l
Beta-schardinger dextrin-5-90g/l
(3) textiles be impregnated in the solubilized stable glue that contains γ-glycidyl ether oxygen propyl dimethoxy silane, ethyl orthosilicate, cyclodextrin, absolute ethyl alcohol, hydrochloric acid and distilled water composition, under 100-130 ℃, heat-treat behind the impregnating textiles; The textiles that maybe will be adsorbed with cyclodextrin impregnated in wherein, heat-treats under 100-130 ℃ then; Or a certain amount of cyclodextrin added in the solubilized stable glue, and textiles be impregnated in wherein, under 100-130 ℃, heat-treat then, and then filling essence.
Described stable sol formula of liquid is:
γ-glycidyl ether oxygen propyl dimethoxy silane 75-152g/l
Ethyl orthosilicate 70-138g/l
Cyclodextrin 0.6-12g/l
Absolute ethyl alcohol 370-750
Hydrochloric acid (30%) 5-20ml/l
Distilled water 150-170ml/l
The first two plants nest's effect of implementing for 2D resin and BTCA BTCA among above-mentioned three kinds of preparation methods, and the third is nest's effect textiles of implementing with sol-gel technique.
Yet, the textiles no matter which kind of technology is made with nest's effect, as long as size match, essential oil or essence all can enter in the cavity by hydrophobic effect power.But the essence of filling has: cream jasmin france, and rosemary, essence, lavender essence, sandalwood fragrance, Forest Bath essence or flavoring rose essence etc., only can water-fastly to wash number of times be 5-12 time to the first two nest's effect of planting technology.The third can water-fastly wash number of times is 10-15 time, and the former each filling fragrance remaining time is 20-25 days, and the latter is about 30 days.
This shows that the advantage with textiles of nest's effect provided by the invention is:
1. be host molecule with the cyclodextrin, and volatile substances such as guest molecule-essence that adapts with it or essential oil store its cavity, form compound;
2. the present invention is by using 2D resin, BTCA BTCA or the above-mentioned compound of sol-gel technology preparing, needn't just can realizing the fragrance textiles by means of adhesive.
3. the textiles that has nest's effect can make the consumer in use, selects and filling different cultivars essence or essential oil by the personal preference.
Specific implementation method:
Below by embodiment, further illustrate substantive distinguishing features of the present invention and marked improvement.
Embodiment 1:
Adopt the textiles of the concrete nest of the enforcement effect of 2D resin and cyclodextrin.Solution composition:
2D resin 50g/l
Magnesium chloride 20g/l
Beta-schardinger dextrin-40g/l
Concrete preparation technology is: textiles be impregnated in contain the 2D resin, magnesium chloride, the transparency finishing solution of beta-schardinger dextrin-pads (taking liquid rate 85-100%) through padding machine, then 80 ℃ of following preliminary dryings 5 minutes, bake at 180 ℃ and cyclodextrin to be anchored on the textiles in 3 minutes.With the aqueous solution impregnating textiles that contains lavender essence 12 hours.Naturally dry then and get final product.
Embodiment 2:
Adopt the textiles with nest's effect of the enforcement of polybasic carboxylic acid BTCA and cyclodextrin.Solution composition:
Polybasic carboxylic acid formaldehydeless finishing agent BTCA 70g/l
Inferior sodium phosphate 60g/l
Beta-schardinger dextrin-40g/l
Concrete preparation technology is: textiles be impregnated in contain polybasic carboxylic acid BTCA, the transparency finishing solution of beta-schardinger dextrin-, pad (taking liquid rate 85-100%) through padding machine,, bake at 160 ℃ and cyclodextrin to be anchored on the textiles in 6 minutes then 80 ℃ of following preliminary dryings 5 minutes.Be sprayed on the textiles with the ethanolic solution that contains cream jasmin france.Naturally dry then and get final product.Embodiment 3:
The textiles that the enforcement of employing sol-gel technique and cyclodextrin has nest's effect.Solution composition:
γ-glycidyl ether oxygen propyl dimethoxy silane 140g/l
Ethyl orthosilicate 120g/l
Cyclodextrin 8g
Absolute ethyl alcohol 700ml/l
Hydrochloric acid (30%) 15ml/l
Distilled water 170ml/l
Concrete preparation technology is: textiles be impregnated in contain the solubilized stable glue that γ-glycidyl ether oxygen propyl dimethoxy silane, ethyl orthosilicate, cyclodextrin, absolute ethyl alcohol, hydrochloric acid and distilled water are formed, heat-treat under 120 ℃ behind the impregnating textiles.With the ethanolic solution impregnating textiles that contains rosemary, essence 12 hours.Naturally dry then and get final product.The result:
Claims (8)
1, a kind of textiles with nest's effect is characterized in that the cyclodextrin that has the hole characteristics with molecular structure is anchored on the textiles, and the guest molecule essential oil or the essence that adapt with the cyclodextrin host molecule are stored in its cavity, forms compound.
2, the textiles with nest's effect according to claim 1 is characterized in that described cyclodextrin is beta-schardinger dextrin-or gamma-cyclodextrin.
3, the textiles with nest's effect according to claim 1 is characterized in that described essence or essential oil are: cream jasmin france, rosemary, essence, lavender essence, sandalwood fragrance, Forest Bath essence or flavoring rose essence.
4, a kind of preparation method with textiles of nest's effect is characterized in that
(1) textiles be impregnated in to contain the 2D resin be dihydroxy dihydroxymethyl cyclic ethylene urea, the transparency finishing solution that magnesium chloride, beta-schardinger dextrin-are formed, pad through padding machine,, bake at 160-180 ℃ and cyclodextrin to be anchored on the textiles in 3-6 minute then 80 ℃ of following preliminary dryings 5 minutes; Usefulness contains the aqueous solution or the ethanolic solution dipping of essence or is sprayed on the textiles again.Naturally dry the filling of finishing essence then.
(2) described transparency finishing solution specifically consists of:
2D resin 40-90g/l
Magnesium chloride 20-80g/l
Beta-schardinger dextrin-5-90g/l
5, by the described manufacture method with textiles of nest's effect of claim 4, the solvent that it is characterized in that described transparency finishing solution is a water.
6, a kind of preparation method with textiles of nest's effect is characterized in that
(1) textiles be impregnated in contains BTCA, the transparency finishing solution of inferior sodium phosphate, beta-schardinger dextrin-, pad through padding machine, then 80 ℃ of following preliminary dryings 5 minutes, bake at 160-180 ℃ and cyclodextrin to be anchored on the textiles in 3-6 minute, again with the aqueous solution that contains essence or ethanolic solution dipping or be sprayed on the textiles.Naturally dry the filling of finishing essence then;
(2) the concrete prescription of described transparency finishing solution is:
Fourth unit tetrabasic carboxylic acid, BTCA 40-90g/l
Inferior sodium phosphate 20-80g/l
Beta-schardinger dextrin-5-90g/l
7,, it is characterized in that beta-schardinger dextrin-transparency finishing solution solvent is a water by the described preparation method of claim 6 with textiles of nest's effect.
8, a kind of preparation method with textiles of nest's effect is characterized in that
(1) textiles be impregnated in the solubilized stable glue that contains γ-glycidyl ether oxygen propyl dimethoxy silane, ethyl orthosilicate, cyclodextrin, absolute ethyl alcohol, hydrochloric acid and distilled water composition, under 100-130 ℃, heat-treat behind the impregnating textiles; The textiles that maybe will be adsorbed with cyclodextrin impregnated in wherein, heat-treats under 100-130 ℃ then; Or cyclodextrin added in the solubilized stable glue, and textiles be impregnated in wherein, under 100-130 ℃, heat-treat then, and then filling essence.
(2) described stable sol formula of liquid is:
γ-glycidyl ether oxygen propyl dimethoxy silane 75-152g/l
Ethyl orthosilicate 70-138g/l
Cyclodextrin 0.6-12g/l
Absolute ethyl alcohol 370-750g/l
Hydrochloric acid (30%) 5-20ml/l
Distilled water 150-170ml/l
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03114882 CN1208513C (en) | 2003-01-14 | 2003-01-14 | Textile product with effects of bird's nest and its preparing method |
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| CN 03114882 CN1208513C (en) | 2003-01-14 | 2003-01-14 | Textile product with effects of bird's nest and its preparing method |
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| CN1431359A true CN1431359A (en) | 2003-07-23 |
| CN1208513C CN1208513C (en) | 2005-06-29 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366816C (en) * | 2005-01-19 | 2008-02-06 | 财团法人工业技术研究院 | Surface modification method for slow-release type anti-insect and anti-microbe fabric |
| CN101781847B (en) * | 2010-02-03 | 2012-01-11 | 浙江三元电子科技有限公司 | Sol-gel technology based activation process before chemical plating on fabric |
| CN102517911A (en) * | 2011-12-16 | 2012-06-27 | 江南大学 | Method for fixing cyclodextrins on fabric through resin crosslinking initiated by ultraviolet |
-
2003
- 2003-01-14 CN CN 03114882 patent/CN1208513C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366816C (en) * | 2005-01-19 | 2008-02-06 | 财团法人工业技术研究院 | Surface modification method for slow-release type anti-insect and anti-microbe fabric |
| CN101781847B (en) * | 2010-02-03 | 2012-01-11 | 浙江三元电子科技有限公司 | Sol-gel technology based activation process before chemical plating on fabric |
| CN102517911A (en) * | 2011-12-16 | 2012-06-27 | 江南大学 | Method for fixing cyclodextrins on fabric through resin crosslinking initiated by ultraviolet |
| CN102517911B (en) * | 2011-12-16 | 2013-10-16 | 江南大学 | Method for fixing cyclodextrins on fabric through resin crosslinking initiated by ultraviolet |
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| Publication number | Publication date |
|---|---|
| CN1208513C (en) | 2005-06-29 |
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Assignee: Jiaxing Queping Textile Chemical Industry Co., Ltd. Assignor: Donghua University Contract fulfillment period: 2007.11.26 to 2015.11.25 contract change Contract record no.: 2008330000665 Denomination of invention: Textile product with effects of bird's nest and its preparing method Granted publication date: 20050629 License type: Exclusive license Record date: 2008.9.26 |
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