CN101255654B - Grafting method for improving combining force between metallic sedimentary deposit and polyamide fibre surface - Google Patents
Grafting method for improving combining force between metallic sedimentary deposit and polyamide fibre surface Download PDFInfo
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- CN101255654B CN101255654B CN2008100603573A CN200810060357A CN101255654B CN 101255654 B CN101255654 B CN 101255654B CN 2008100603573 A CN2008100603573 A CN 2008100603573A CN 200810060357 A CN200810060357 A CN 200810060357A CN 101255654 B CN101255654 B CN 101255654B
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Abstract
The invention discloses a polyamide fiber surface grafting method which improves binding forces with the metal deposition layers. After the oil pollution and slurry on the surface of the polyamide fiber are full removed, sulfhydryl which can do complex with metal with is grafted on the fiber surface. The sulfhydryl can be led into the surfaces of aliphatic polyamide fibers, yarns and fabrics through the invention, through the strong chemical role between the sulfhydryl and the metal, strong and firm bonding forces between the fiber matrix and the metal deposition layers are obtained, and the bonding forces can be greatly improved compared to surface etching, coursing and the coupling role of a coupling agent, thereby the abrasion resistance, the scrubbing resistance, the bending resistance and the washing resistance of the metal fiber and the fabrics are improved.
Description
Technical field
The present invention relates to the functionalization textile material, especially relate to improve adhesion between silver metal sedimentary deposit and the polyamide fiber matrix a kind of and improve polyamide fiber surface grafting method with combining ability between metallic sedimentary deposit.
Background technology
By to after fibrous material surface physics or the chemical method plated metal, will give fibrous material electric conductivity, thermal conductivity, reflective and capability of electromagnetic shielding.Because the flexible characteristic of fiber and goods thereof, metalized fibers and textiles have the not available formability of traditional metal materials, pliability and gas permeability.
Fibre metalization metal deposition layer commonly used is the double-deck deposition successively of copper, nickel, corronil or copper/nickel.Because silver has very excellent electric conductivity, thermal conductivity and pliability, is the metallized preferable metal level alternative of fibrous material.Yet, because the difference of physicochemical property between fibrous matrix and the metal level, the adhesion between metal level and the fiber and always be the major issue that fibre metalization is paid close attention in conjunction with fastness.
Can be by the adhesion between method raising metal deposition layer physics, chemistry and that the two combines and the fiber.Physical method is to adopt the corrasion to fiber surface such as solvent, oxidant, obtains coarse fiber surface, thereby improves the adhesion between metal deposition layer and the fiber.This method all has certain effect to the matrix and the metal deposition layer of all kinds, but more effective to thicker metal deposition layer, and limited to thin sedimentary deposit effect.Chemical method then is by changing the surface chemistry state of matrix, is used for improving adhesion between matrix and the metal deposition layer by chemical bonding.This method all has good effect to the metal deposition layer of different-thickness, simultaneously, this method has selectivity, and promptly different types of matrix and different kinds of metals sedimentary deposit need select specific chemical bond to realize adhesion between matrix and the metal deposition layer.
The matrix of unlike material, different conditions need adopt different matrix surface processing methods with different metal levels.Surface metalation for Maranyl, Japan Patent JP63270475 adopts hydrochloric acid to carry out the etching alligatoring, Japan Patent JP60100678 adopts the alligatoring of chromic acid etching, and U.S. Pat 4362799 adopts multi-phenol swelling treatment, 4322516 using plasma etchings of German patent DE.For silver metallized deposition, China patent CN02112707.7 proposes to handle glass to improve the adhesion between deposited silver layer and the glass by hydrosulphonyl silane, and China patent CN200510111539.5 proposition use amino silicane coupling agent improves the adhesion between glass and nonmetal basal body and the silver metal sedimentary deposit.Japan Patent JP2002-047573 has proposed to adopt nitrogen heterocyclic ring class (imidazoles) epoxy silane of silver-colored coupling to improve adhesion between matrix and the deposited silver layer.
For polyamide fiber, because fibre fineness very thin (10-40 μ m) adopts etching processing the overetch alligatoring often to occur and causes fiber strength to descend greatly, perhaps etching alligatoring deficiency causes the adhesion raising effect between matrix and the metal level not obvious.In addition, the effect between coupling agent and the matrix is mainly by electrostatic force, so the use of coupling agent is limited to the adhesion effect that improves between matrix and the metal deposition layer.
Summary of the invention
The polyamide fiber surface grafting method that the purpose of this invention is to provide a kind of raising and combining ability between metallic sedimentary deposit, to improve the adhesion between fiber and the metal deposition layer, especially the adhesion between fiber and the silver metal sedimentary deposit lays the foundation for obtaining friction resistant, bend resistance, the good silver metallized fatty polyamide fiber of washing durability.
The technical solution adopted in the present invention is:
1) preliminary treatment, fiber is banked up through high temperature alkaline scouring or normal temperature alkali lye, with finish, slurry and the spot of removing fiber surface.
2) grafting is handled, and carries out surperficial sulfhydrylation grafting through pretreated fiber and handles.
Sulfhydrylation grafting processing scheme is as follows:
Described polyamide fiber preliminary treatment comprises through high temperature alkaline scouring or normal temperature alkali lye banks up:
High temperature alkaline scouring condition is: NaOH 1-10g/l, and sodium phosphate trimer 1-5g/l, OP-102-10ml/l, temperature 80-95 ℃, bath raio 1: 10-1: 20, time 30-60min;
The normal temperature alkali condition of banking up is: NaOH 40-100g/l, and sodium phosphate trimer 1-5g/l, OP-102-10ml/l, bath raio 1: 10-1: 20, time 12-24h;
High temperature alkaline scouring or the normal temperature alkali employing running water of banking up is handled washing the fibre surface, back, running water washing 3-5 road, last one deionized water washing;
Described sulfhydrylation grafting treatment conditions are:
1) 50% formic acid swelling treatment fiber is 2-6 hour, and bath raio is 1: 10;
2) concentration of methanol solution of paraformaldehyde is 10-30%, 60 ℃ of reaction temperatures, and reaction time 50-120min, bath raio is 1: 1.5-1: 3;
3) thiocarbamide is 10-30g/l, and concentration of hydrochloric acid is 36% concentrated hydrochloric acid 10-30ml/l, 30 ℃ of reaction temperatures, and reaction time 30-60min, bath raio is 1: 10;
4) KOH concentration is 0.5-2g/l, and bath raio is 1: 10.
5) clean, the fiber after the sulfhydrylation grafting is through the deionized water washing.
Described polyamide fiber is polyamide fibre 6 or 66 nylon fiber, and its fibre fineness is between 0.1-10dtex.Described polyamide fiber occurs with the form of staple fibre, long filament, yarn, knitted fabric, woven fabric or non-weaving cloth.
The beneficial effect that the present invention has is:
Mercapto groups can be incorporated into the surface of fatty polyamide fiber, yarn and fabric by the present invention, by the extensive chemical effect between sulfydryl and the metal, obtain adhesion firm between fibrous matrix and the metal deposition layer, compare with surface etch, alligatoring and coupling agent coupled action, the adhesion between fibrous matrix and the metal level be can improve greatly, thereby ABRASION RESISTANCE, rub resistance, anti-bending and the washing resistance of metalized fibers and fabric improved.
The specific embodiment
Embodiment 1:
Fibrous material: polyamide fibre 66 long filaments, specification are 70d/32f.
1, preliminary treatment
High temperature alkaline scouring condition is NaOH 1g/l, sodium phosphate trimer 5g/l, surfactant 10ml/l, 95 ℃ of temperature, bath raio 1: 10, time 60min.
Wash 4 roads after the preliminary treatment from the beginning, deionization is washed 1 road.
2, sulfhydrylation graft modification
The 20g fiber is swelling 2h in 200ml 50% formic acid solution under 25 ℃ of temperature at first.The 3g paraformaldehyde is joined the 30g methanol solution, under the solid NaOH of 1mg catalysis, be heated to 60 ℃, obtain adding 85% formic acid 2ml after the clear solutions, fully adding through pretreated fiber 20g reaction 120min under the stirring condition afterwards.Afterwards fiber is taken out, put into the middle stirring reaction 60min of aqueous hydrochloric acid solution 200ml (thiocarbamide 10g/l, 36% hydrochloric acid 10ml/l) of 25 ℃ of thiocarbamides of temperature.Afterwards fiber is taken out, 200ml concentration be in the KOH solution of 0.5g/l in and 20min.
3, clean
After the sulfhydrylation graft modification, fully wash 3 roads with deionized water, obtaining can the silver metallized standby fiber in surface.
Embodiment 2:
Fibrous material: polyamide fibre 66 staple fibres, fineness are 3D, and length is 38mm.
1, preliminary treatment
High temperature alkaline scouring condition is NaOH 4g/l, sodium phosphate trimer 4g/l, surfactant 2ml/l, 95 ℃ of temperature, bath raio 1: 20, time 45min.
Wash 4 roads after the preliminary treatment from the beginning, deionization is washed 1 road.
2, sulfhydrylation graft modification
The 20g fiber is swelling 2h in 200ml 50% formic acid solution under 25 ℃ of temperature at first.The 6g paraformaldehyde is joined the 30g methanol solution, under the solid NaOH of 2mg catalysis, be heated to 60 ℃, obtain adding 85% formic acid 2ml after the clear solutions, fully adding through pretreated fiber 20g reaction 80min under the stirring condition afterwards.Afterwards fiber is taken out, put into the middle stirring reaction 45min of aqueous hydrochloric acid solution (thiocarbamide 20g/l, 36% hydrochloric acid 20ml/1) of 25 ℃ of 200ml thiocarbamides of temperature.Afterwards fiber is taken out, 200ml concentration be in the KOH solution of 1g/l in and 10min.
3, clean
After the sulfhydrylation graft modification, fully wash 3 roads with deionized water, obtaining can the silver metallized standby fiber in surface.
Embodiment 3:
Fibrous material: polyamide fibre 6 staple fibres, fineness are 3D, and length is 38mm.
1, preliminary treatment
High temperature alkaline scouring condition is NaOH 10g/l, sodium phosphate trimer 1g/l, surfactant 2ml/l, 95 ℃ of temperature, bath raio 1: 20, time 60min.
Wash 4 roads after the preliminary treatment from the beginning, deionization is washed 1 road.
2, sulfhydrylation graft modification
The 20g fiber is swelling 2h in 200ml 50% formic acid solution under 25 ℃ of temperature at first.The 9g paraformaldehyde is joined the 30g methanol solution, under the solid NaOH of 2mg catalysis, be heated to 60 ℃, obtain adding 85% formic acid 2ml after the clear solutions, fully adding through pretreated fiber 20g reaction 50min under the stirring condition afterwards.Afterwards fiber is taken out, put into the middle stirring reaction 30min of aqueous hydrochloric acid solution (thiocarbamide 30g/l, 36% hydrochloric acid 30ml/l) of 25 ℃ of 200ml thiocarbamides of temperature.Afterwards fiber is taken out, 200ml concentration be in the KOH solution of 1g/l in and 10min.
3, clean
After the sulfhydrylation graft modification, fully wash 3 roads with deionized water, obtaining can the silver metallized standby fiber in surface.
Embodiment 4:
Textile material: 190T Nylon Taffeta chinlon 6 filament grid woven fabric, grid is of a size of 2mm * 2mm, and fabric specification is 70d/32f * 70d/32f, and Gram Mass is 75g/m
2
1, preliminary treatment
The normal temperature alkali condition NaOH 80g/l that banks up, sodium phosphate trimer 4g/l, surfactant 8ml/l, bath raio 1: 10, time 12h.
Pretreated fabric is through washing 4 roads from the beginning, and deionization is washed 1 road.
2, sulfhydrylation graft modification
0.5m
2Fabric is swelling 4h in 400ml 50% formic acid solution under 25 ℃ of temperature at first.The 15g paraformaldehyde is joined the 100g methanol solution, under the solid NaOH of 2mg catalysis, be heated to 60 ℃, obtain adding 85% formic acid 5ml after the clear solutions, under stirring condition, add afterwards through pretreated fabric 0.5m
2, reaction 50min.Afterwards fabric is taken out, put into the middle stirring reaction 30min of aqueous hydrochloric acid solution (thiocarbamide 30g/l, 36% hydrochloric acid 20ml/l) of 25 ℃ of 400ml thiocarbamides of temperature.Afterwards fabric is taken out, 400ml concentration be in the KOH solution of 1g/l in and 10min.
3, clean
After the sulfhydrylation graft modification, fully wash 3 roads with deionized water, obtaining can the silver metallized standby fabric in surface.
Embodiment 5:
Textile material: polyamide fibre 6 non-weaving cloths, fibre fineness are 1.5D, and length 38mm, Gram Mass are 50g/m
2
1, preliminary treatment
The normal temperature alkali condition NaOH 40g/l that banks up, sodium phosphate trimer 5g/l, surfactant 10ml/l, bath raio 1: 20, time 24h.
Pretreated fabric is through washing 4 roads from the beginning, and deionization is washed 1 road.
2, sulfhydrylation graft modification
0.5m
2Fabric is swelling 5h in 250ml 50% formic acid solution under 25 ℃ of temperature at first.The 10g paraformaldehyde is joined the 100g methanol solution, under the solid NaOH of trace catalysis, be heated to 60 ℃, obtain adding 85% formic acid 5ml after the clear solutions, under stirring condition, add afterwards through pretreated fabric 0.5m
2, reaction 80min.Afterwards fabric is taken out, put into the middle stirring reaction 30min of aqueous hydrochloric acid solution (thiocarbamide 10g/l, 36% hydrochloric acid 20ml/l) of 25 ℃ of 250ml thiocarbamides of temperature.Afterwards fabric is taken out, 250ml concentration be in the KOH solution of 0.5g/l in and 10min.
3, clean
After the sulfhydrylation graft modification, fully wash 3 roads with deionized water, obtaining can the silver metallized standby fabric in surface.
Embodiment 6:
Textile material: polyamide fibre 66 warp-knitted fabrics, used yarn specification is 70d/32f * 70d/32f, Gram Mass is 70g/m
2
1, preliminary treatment
The normal temperature alkali condition NaOH 100g/l that banks up, sodium phosphate trimer 1g/l, surfactant 2ml/l, bath raio 1: 20, time 12h.
Pretreated fabric is through washing 4 roads from the beginning, and deionization is washed 1 road.
2, sulfhydrylation graft modification
0.5m
2Fabric is swelling 6h in 350ml 50% formic acid solution under 25 ℃ of temperature at first.The 12g paraformaldehyde is joined the 100g methanol solution, under the solid NaOH of trace catalysis, be heated to 60 ℃, obtain adding 85% formic acid 5ml after the clear solutions, under stirring condition, add afterwards through pretreated fabric 0.5m
2, reaction 50min.Afterwards fabric is taken out, put into the middle stirring reaction 30min of aqueous hydrochloric acid solution (thiocarbamide 10g/l, 36% hydrochloric acid 30ml/l) of 25 ℃ of 350ml thiocarbamides of temperature.Afterwards fabric is taken out, 350ml concentration be in the KOH solution of 2g/l in and 10min.
3, clean
After the sulfhydrylation graft modification, fully wash 3 roads with deionized water, obtaining can the silver metallized standby fabric in surface.
Claims (3)
1. the polyamide fiber surface grafting method of raising and combining ability between metallic sedimentary deposit is characterized in that the step of this method is as follows:
1) preliminary treatment: with finish, slurry and the spot of removing the polyamide fiber surface;
Comprise through high temperature alkaline scouring or normal temperature alkali lye and banking up:
High temperature alkaline scouring condition is: NaOH 1-10g/l, and sodium phosphate trimer 1-5g/l, OP-102-10ml/l, temperature 80-95 ℃, bath raio 1: 10-1: 20, time 30-60min;
The normal temperature alkali condition of banking up is: NaOH 40-100g/l, and sodium phosphate trimer 1-5g/l, OP-102-10ml/l, bath raio 1: 10-1: 20, time 12-24h;
High temperature alkaline scouring or the normal temperature alkali employing running water of banking up is handled washing the fibre surface, back, running water washing 3-5 road, last one deionized water washing;
2) grafting is handled: carry out surperficial sulfhydrylation grafting through pretreated polyamide fiber and handle, sulfhydrylation grafting processing scheme is as follows:
Described sulfhydrylation grafting treatment conditions are:
1) 50% formic acid swelling treatment fiber is 2-6 hour, and bath raio is 1: 10;
2) concentration of methanol solution of paraformaldehyde is 10-30%, 60 ℃ of reaction temperatures, and reaction time 50-120min, bath raio is 1: 1.5-1: 3;
3) thiocarbamide is 10-30g/l, and concentration of hydrochloric acid is 36% concentrated hydrochloric acid 10-30ml/l, 30 ℃ of reaction temperatures, and reaction time 30-60min, bath raio is 1: 10;
4) KOH concentration is 0.5-2g/l, and bath raio is 1: 10;
5) clean, the fiber after the sulfhydrylation grafting is through the deionized water washing.
2. the polyamide fiber surface grafting method of a kind of raising according to claim 1 and combining ability between metallic sedimentary deposit, it is characterized in that: described polyamide fiber is polyamide fibre 6 or 66 nylon fiber, and its fibre fineness is between 0.1-10dtex.
3. the polyamide fiber surface grafting method of a kind of raising according to claim 1 and combining ability between metallic sedimentary deposit is characterized in that: described polyamide fiber occurs with the form of staple fibre, long filament, yarn, knitted fabric, woven fabric or non-weaving cloth.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100603573A CN101255654B (en) | 2008-04-08 | 2008-04-08 | Grafting method for improving combining force between metallic sedimentary deposit and polyamide fibre surface |
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|---|---|---|---|
| CN2008100603573A CN101255654B (en) | 2008-04-08 | 2008-04-08 | Grafting method for improving combining force between metallic sedimentary deposit and polyamide fibre surface |
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| CN101255654A CN101255654A (en) | 2008-09-03 |
| CN101255654B true CN101255654B (en) | 2010-04-14 |
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| CN103898747A (en) * | 2014-03-06 | 2014-07-02 | 北京化工大学 | Preparation method for durable and inflaming retarding after-finishing chinlon fabric |
| CN105839402A (en) * | 2016-03-30 | 2016-08-10 | 武汉理工大学 | Chemical modification method for surface of aramid fiber and application of same in preparation of silver-coated aramid composite fiber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075180A (en) * | 1993-02-27 | 1993-08-11 | 商成杰 | Antibacterial deodourizing fabric and preparation method thereof and prepared product |
| CN1546778A (en) * | 2003-12-02 | 2004-11-17 | 中国科学院东北地理与农业生态研究所 | Method for preparing mercapto cotton |
| EP0799928B1 (en) * | 1996-04-05 | 2004-12-15 | Mitsubishi Paper Mills, Ltd. | Antibacterial antifungal agent and fibrous material containing the same |
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2008
- 2008-04-08 CN CN2008100603573A patent/CN101255654B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075180A (en) * | 1993-02-27 | 1993-08-11 | 商成杰 | Antibacterial deodourizing fabric and preparation method thereof and prepared product |
| EP0799928B1 (en) * | 1996-04-05 | 2004-12-15 | Mitsubishi Paper Mills, Ltd. | Antibacterial antifungal agent and fibrous material containing the same |
| CN1546778A (en) * | 2003-12-02 | 2004-11-17 | 中国科学院东北地理与农业生态研究所 | Method for preparing mercapto cotton |
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