CN100412261C - Modified silane sol with amino silicone oil emulsion and its preparation process and usage - Google Patents
Modified silane sol with amino silicone oil emulsion and its preparation process and usage Download PDFInfo
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- CN100412261C CN100412261C CNB200610028409XA CN200610028409A CN100412261C CN 100412261 C CN100412261 C CN 100412261C CN B200610028409X A CNB200610028409X A CN B200610028409XA CN 200610028409 A CN200610028409 A CN 200610028409A CN 100412261 C CN100412261 C CN 100412261C
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Abstract
The present invention relates to modified silane sol with amino silicone oil emulsion and a preparation method and purposes thereof. Stable transparent modified sol finishing agent is prepared by that amino silicone oil emulsion and gamma-(2, 3-epoxypropoxy) trimethoxysilane sol are mixed. The product can be used for soft anti-felting finishing of wool fabrics. The present invention is combined with the operation process of rolling, drying and baking and reduces solidification temperature of film forming, and thus, the wool fabrics can have favorable hand feeling and excellent wash-wear and anti-felting effects.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind ofly can handle the blending wool fabric that contains the wool composition and the anti-felting finish agent of all-wool cloth.
Background technology
Present industrialization felt proofing technology method commonly used mainly contains two kinds: a kind of is traditional chloridizing (claiming the oxychloride method again) preventing felting and shrinking of wood fabric processing technology, there are shortcomings such as the easy yellowing of wool and elasticity is impaired in the process of processing, particularly in discharge of wastewater, produce organochlorine (AOX) pollution, thereby limited the utilization of this technology.Second kind is the high polymer method that adopts non-chlorine, and to wool anti-felting finishing, this method shortcoming is that the wool fabric feel is hardened as polyurethane coating.Utilize the colloidal sol of organically-modified metal alkoxide preparation, under certain condition through condensation can form gel, drying forms firm transparent porous oxide film at wool surface at last again, thereby reach good anti-felting effect, but the wool fabric feel after the colloidal sol of this metal alkoxide preparation is handled is still harder, and, cause certain damage of wool fabric and yellowing because baking temperature is too high.
For this reason, in the sol-gal process wool anti-felting finishing process, in the anti-felting effect that guarantees durability, how to solve the harder problem of feel and seem particularly important.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of modified silane sol with amino silicone oil emulsion and its production and use, to solve defectives such as the easy yellowing of wool fabric in the prior art, Boardy Feeling.
The present invention is according to the preventing felting and shrinking of wood fabric principle, utilize amino silicon oil emulsion and homemade γ-(2, the 3-glycidoxy) propyl trimethoxy silicane colloidal sol blending and modifying obtains corresponding stable transparent colloidal sol, thereby wool fabric is carried out good soft durable feld proofing processing.
One of purpose of the present invention is to provide a kind of modified silane sol with amino silicone oil emulsion, contains amido silicon oil and γ-(2, the 3-glycidoxy) propyl trimethoxy silicane colloidal sol in this colloidal sol.Wherein the mass ratio of γ-(2, the 3-glycidoxy) propyl trimethoxy silicane colloidal sol and amido silicon oil is 10: 1～2: 1.
Another object of the present invention is to provide the preparation method of above-mentioned modified silane sol with amino silicone oil emulsion, this method comprises the steps:
1. prepare γ-(2, the 3-glycidoxy) propyl trimethoxy silicane colloidal sol: with mass ratio 12: 8: 5-18: 2: 5 γ-(2, the 3-glycidoxy) propyl trimethoxy silicane, alcohol and water mix, and adjust pH value to 3～4 of solution; Wherein said alcohol is C
1-4Organic alcohol;
2. the preparation of amino silicon oil emulsion: with water, emulsifying agent and buffer solution mixing, splash into amido silicon oil then, adjust pH value to 4～5.Wherein the mass ratio of amido silicon oil, emulsifying agent, buffer solution and water is: 10～30: 5～10: 1～2: 60～80; Described buffer solution is a glacial acetic acid; Described emulsifying agent is polyoxyethylene nonylphenol ether or SAS (dodecyl sodium sulfate);
3. will be 1. and the product of 2. preparation according to 10: 1～2: 1 ratio mixing, adjust pH value to 3～4, get final product.
The present invention also provides the purposes of above-mentioned modified silane sol with amino silicone oil emulsion as the soft anti-felting finish agent of wool fabric, and wherein the working concentration of modified silane sol with amino silicone oil emulsion is the aqueous solution of 50-100% (mass percent).
Its concrete method is: wool fabric is soaked two roll, dry, bake, neutralize washing and dry steps through two in this finishing agent, wherein liquid carrying rate is 70-90%, and bake out temperature is 60-100 ℃; Bake 120-180 ℃.
To technical scheme involved in the present invention be described in detail below.
The present invention is by preparation γ-(2, the 3-glycidoxy) propyl trimethoxy silicane colloidal sol, and amido silicon oil is carried out emulsification obtain stable emulsion, prepare the very high blending and modifying colloidal sol that can dilute arbitrarily of stability, and, make it produce excellent durable soft anti-felting effect by feld proofing to wool fabric, handle the hard deficiency of wool fabric feel plate thereby reduce colloidal sol, bake the film-forming temperature by reduction simultaneously, reduced the machining damage of wool fabric.
The present invention is amino silicon oil emulsion modification γ-(2, the 3-glycidoxy) propyl trimethoxy silicane colloidal sol, its amido silicon oil that contains is Dow corning 8600, another composition is γ-(2, the 3-glycidoxy) (trade mark is Z-6040 to propyl trimethoxy silicane colloidal sol (GPTMS), producer is Dowcorning Corporation), GPTMS contains following structural formula:
The method for preparing modified silane sol with amino silicone oil emulsion is as described below:
1. prepare γ-(2, the 3-glycidoxy) propyl trimethoxy silicane colloidal sols (can stablize and deposit more than half a year): at normal temperatures, take by weighing γ-(2, the 3-glycidoxy) propyl trimethoxy silicane (GPTMS), alcohol, water; Join successively in the beaker then, utilize pH value to 3～4 of the watery hydrochloric acid adjustment solution of 0.1mol/L; Powerful evenly stirring 2～10 hours is left standstill then and just can be used in 1～5 hour.Described γ-(2, the 3-glycidoxy) propyl trimethoxy silicane (GPTMS) is 12: 8 with the mass ratio of alcohol, water: 5-18: 2: 5.
The end of GPTMS is the silicon hydroxyl, but the dehydration of condensation at a certain temperature forms network structure and gives preventing felting and shrinking of wood fabric; And the other end has epoxy radicals, can with carboxyl, hydroxyl and the sulfydryl generation covalent bonds on the wool, add the effect of intermolecular hydrogen bonding, Van der Waals force, thereby the durability of textile finishing effect be improved.
Above-mentioned γ-(2, the 3-glycidoxy) propyl trimethoxy silicane (GPTMS) is 100% pure raw material; Described alcohol is C
1-4Organic alcohol, ethanol preferably.
2. the preparation of amino silicon oil emulsion (can stablize and deposit more than half a year): water, emulsifying agent and buffer solution are added by a certain percentage successively, the back intensification stirs, after stirring certain hour fast then, splash into amido silicon oil, the control rate of addition, adjust pH value to 4～5 after continuing to stir a period of time, after the cooling, placement a period of time is stand-by naturally.Wherein the mass ratio of amido silicon oil, emulsifying agent, buffer solution and water is: 10～30: 5～10: 1～2: between 60～80.Described buffer solution is an organic acid, and as glacial acetic acid etc., emulsifying agent is a nonionic and anionic surfactant is composite forms, as polyoxyethylene nonylphenol ether (n=50), SAS etc.
3. will be 1. and the product of 2. preparation by 10: 1～2: 1 mass ratio blend, evenly stir certain hour after, adjust pH value to 3～4, seal set aside for use.
Two kinds of products all contain the certain activity group, wherein but the silicon hydroxyl in 1. is except that self condensation dehydration, its epoxy radicals can also and 2. in the amino generation addition ring-opening reaction of product, the cross-linked network of Xing Chenging can give fabric good felt proofing performance under certain condition, and because the existence of amino in the cross-linked network, can pass through its protonated generation electric charge, and interact with wool, formation by strong electrostatic interaction and hydrogen bond, make it that better directionality be arranged and better distribution on fiber, by evenly being covered in wool surface, reached excellent lubrication, soft effect.
Amino silicon oil emulsion modification γ of the present invention-(2, the 3-glycidoxy) propyl trimethoxy siloxanes colloidal sol is a kind of soft anti-felting finish agent to wool fabric.This product is water-soluble finishing agent, and by dilution, (50-100%) uses in the finite concentration scope, can obtain the soft anti-felting effect of good wool, and its technology is: two soak two rolls (liquid carrying rate 70-90%) → dry → bake → dry naturally.Wherein oven dry is lax oven dry in pin pincers chain type heat setting machine, and bake out temperature is at 60-100 ℃,, bake 120-180 ℃, wash then, neutralize, drying.
The present invention has following advantage:
(1) utilize amino silicon oil emulsion modification γ-(2, the 3-glycidoxy) propyl trimethoxy silicane colloidal sol to prepare a kind of novel soft anti-felting finish agent.
(2) improved the too high problem of sol-gal process wool anti-felting finishing baking temperature.
(3) contain the siloxanes of being with amino side chain in amino silicon oil emulsion modification γ-(2, the 3-glycidoxy) propyl trimethoxy silicane collosol structure, thereby reduced the hard coarse shortcoming of fabric feel plate after baking, improved the flexibility of fabric.
(4) the big intermolecular covalent cross-linking of modification sol and wool fibre and in the reticulated film that fiber surface forms improves washability and the felt proofing performance of handling the back wool fabric.
Description of drawings
Fig. 1: modification sol (embodiment 3 prescriptions) infrared spectrogram
Fig. 2: modification sol (embodiment 4 prescriptions) infrared spectrogram
Fig. 3: the wool Electronic Speculum that is untreated figure
Fig. 4: the wool after the processing (embodiment 3 prescriptions) Electronic Speculum figure
Fig. 5: the wool after the processing (embodiment 4 prescriptions) Electronic Speculum figure
The specific embodiment
Embodiment 1
Preparation γ-(2, the 3-glycidoxy) propyl trimethoxy silicane colloidal sol.
At normal temperatures, take by weighing γ-(2, the 3-glycidoxy) propyl trimethoxy silicane (GPTMS) 56.2 grams, industrial alcohol 180 grams, water 45 grams; Add successively in the beaker then, utilize pH value to 3～4 of the watery hydrochloric acid adjustment solution of 0.1mol/L; Powerful evenly stirred 5 hours, leave standstill then 2 hours standby.
Embodiment 2
The preparation of amido silicon oil (Dow corning 8600) emulsion.
Water 140 gram, SAS16 gram and glacial acetic acid 4 grams are added successively, are warming up to 40 ℃ after stirring, stir 20 minutes fast then after, splash into 40 gram amido silicon oils, continue to stir after 15 minutes, adjust pH value to 4～5, reduce to room temperature, stand-by after placement a period of time.
Embodiment 3
Amino silicon oil emulsion among the 50 gram embodiment 2 is splashed into 100 γ-(2 that restrain among the embodiment 1, the 3-glycidoxy) at the bottom of the propyl trimethoxy silicane colloidal sol in the liquid, in the dropping process, keep end liquid normal temperature at the uniform velocity to stir, in 20 minutes, dropwise, continue to stir 1 hour, adjustment pH is 3-4, places ageing after several hours, obtain the modification sol of transparent and stable, sealing then, secluding air store stand-by.
Embodiment 4
The amino silicon oil emulsion of 65 gram the foregoing descriptions 2 is splashed into the γ-(2 of 65 grams, the 3-glycidoxy) at the bottom of the propyl trimethoxy silicane colloidal sol in the liquid, in normal temperature dropping process, it is at the uniform velocity even to keep end liquid to stir, and after dropwising in 25 minutes, continues to stir 1.5 hours, after adjustment pH is 3-4, place ageing several hours, obtain the modification sol of transparent and stable, sealing then, secluding air store stand-by.
Embodiment 5
(1) feld proofing
To be unstained but 100% wool gabardine (211g/m of process crabbing
2), two soak two and roll liquid carrying rate 70-80% in the foregoing description 3,4 colloidal sol dressing liquids, then at pin pincers chain type heat setting machine (M-TENDER NO.8078 type Rapid heat setting machine, Taiwan Labor Tex Co.LTD) dried 3 minutes for 80 ℃ in, 160 ℃ baked 3 minutes, and dried naturally.
(2) anti-felting effect test
With reference to Woolmark TM 31 testing standards and method, utilize standard washer (model is Wascator FQM71CLS, EIECTROLUx, program 3*5A wash cycles) to wash after, the area felting rate of test is in 3%.
(3) test and appraisal of physical property
Comprise ultimate strength (ASTM D 1424-96)., tearing brute force (ASTM 5034-95), creasy recovery angle (AATCC Technical Manual, vol.64.1989), the test of whiteness (WSB-II d/o type whiteness instrument), bending stiffness, test condition: relative humidity 65 ± 2%, 21 ± 1 ℃.
(5) test and appraisal of soft effect
Based on subjective assessment, the cloth cover soft effect has some improvement.
Effect after with embodiment 3 and 4 two prescriptions wool fabric being handled is seen Fig. 1, Fig. 4 and Fig. 2, Fig. 5 respectively.
Claims (5)
1. modified silane sol with amino silicone oil emulsion, it is characterized in that containing γ-(2, the 3-glycidoxy) propyl trimethoxy silicane colloidal sol and amido silicon oil, wherein the mass ratio of γ-(2, the 3-glycidoxy) propyl trimethoxy silicane colloidal sol and amido silicon oil is 10: 1～2: 1.
2. a method for preparing the described modified silane sol with amino silicone oil emulsion of claim 1 is characterized in that this method comprises the steps:
1. prepare γ-(2, the 3-glycidoxy) propyl trimethoxy silicane colloidal sol: with mass ratio 12: 8: 5-18: 2: 5 γ-(2, the 3-glycidoxy) propyl trimethoxy silicane, alcohol and water mix, and adjust pH value to 3～4 of solution; Wherein said alcohol is C
1-4Organic alcohol;
2. the preparation of amino silicon oil emulsion: with water, emulsifying agent and buffer solution mixing, splash into amido silicon oil then, adjust pH value to 4～5;
Wherein the mass ratio of amido silicon oil, emulsifying agent, buffer solution and water is: 10～30: 5～10: 1～2: between 60～80, described buffer solution is a glacial acetic acid; Described emulsifying agent is polyoxyethylene nonylphenol ether or SAS;
3. will be 1. and the product of 2. preparation according to 10: 1～2: 1 mass ratio mixing, adjust pH value to 3～4, get final product.
3. the described modified silane sol with amino silicone oil emulsion of claim 1 is as the purposes of the soft anti-felting finish agent of wool fabric.
4. purposes according to claim 3, with the modified silane sol with amino silicone oil emulsion dilute with water, the concentration of modified silane sol with amino silicone oil emulsion is 50-100%.
5. purposes according to claim 3, its concrete method is: wool fabric is soaked two steps of rolling, dry, bake, drying naturally through two in this finishing agent, wherein liquid carrying rate is 70-90%, and bake out temperature is 60-100 ℃, bakes 120-180 ℃.
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| CNB200610028409XA CN100412261C (en) | 2006-06-30 | 2006-06-30 | Modified silane sol with amino silicone oil emulsion and its preparation process and usage |
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| CN102493197B (en) * | 2011-12-12 | 2013-06-12 | 吴江万盛油脂有限公司 | Emulsion |
| CN114015055B (en) * | 2021-11-17 | 2023-04-14 | 江西晨光新材料股份有限公司 | Synthesis method and application of functional silane terminated polysiloxane |
| CN114622410A (en) * | 2022-03-04 | 2022-06-14 | 安徽德和织造有限公司 | Antibacterial, mothproof and anti-felting finishing method for cashmere fabric |
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Assignee: Zhangjiagang Jinling Textile Co., Ltd. Assignor: Donghua University Contract fulfillment period: 2008.8.18 to 2013.12.31 contract change Contract record no.: 2009320000817 Denomination of invention: Modified silane sol with amino silicone oil emulsion and its preparation process and usage Granted publication date: 20080820 License type: Exclusive license Record date: 2009.5.11 |
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