CN101168613B - Method for modifying ABS plastic - Google Patents
Method for modifying ABS plastic Download PDFInfo
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- CN101168613B CN101168613B CN2006100633090A CN200610063309A CN101168613B CN 101168613 B CN101168613 B CN 101168613B CN 2006100633090 A CN2006100633090 A CN 2006100633090A CN 200610063309 A CN200610063309 A CN 200610063309A CN 101168613 B CN101168613 B CN 101168613B
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Abstract
The invention provides a modified method of ABS plastic. ABS aggregate and modified powder body which is easy to be eroded are mixed to obtain modified ABS. After the modified ABS plastic obtained by adopting the method is coarsened, the surface area is increased greatly, the hydrophilicity of the surface is strengthened, and the adhesive force of a coating after being plated is increased. The modified ABS plastic only requires shorter acid corrosion and coursing time (the acid corrosion and the coursing in this time cannot erode PC), and the ideal coarsening effect can be achieved. Coupling agent is used, the compatibility between the modified powder body and the ABS can be enhanced, and the fine compound bounding surface can be obtained; solvent can improve the operation effect of the coupling agent; dispersant agent can lead the materials to be mixed to be evener, thus the modified quality is improved.
Description
[technical field]
The present invention relates to a kind of method of modifying of ABS plastic, especially a kind of easily by the method for modifying of the ABS plastic of alligatoring.
[background technology]
Parts such as mobile phone key are many to be raw material with ABS and PC, adopt double-shot moulding, the surface of product ABS part after electroplating is an electrolytic coating, the surface of PC part is not by plating and printing opacity, the surface has the metal-like of plated item to the pattern part of product (being the ABS part), and rest part (being the PC part) can printing opacity.This processing requirement is electroplated partly very clear, neat with the boundary of electroless plating part (being ABS part and PC part), to guarantee good visual effect.
In this technology, for reaching good electroplating effect, need before plating, carry out acid etching alligatoring (purpose is the surface of alligatoring ABS part) to product surface, the PC part surface of product also can stand the acid etching alligatoring.The required condition of acid etching roughening process that can make the surface of product A BS part reach desirable alligatoring effect at present is the time: 10～15min, coarsening solution temperature: 70 ℃～75 ℃, coarsening solution consist of: chromic acid 350g～450g/L and sulfuric acid 350～400g/L.Under such acid etching alligatoring condition, occurring PC easily also can be by alligatoring, and it is partly unintelligible with the boundary of PC part to electroplate back ABS, and the obscurity boundary of product surface pattern influences visual effect; If the shortening coarsening time, the surface of ABS part may be corroded again inadequately, and it is not strong to electroplate the back coating adhesion, influences electroplating effect.
[summary of the invention]
Technical problem to be solved by this invention provides a kind of easily by the method for modifying of the ABS plastic of alligatoring.
For solving the problems of the technologies described above, the invention provides a kind of method of modifying of ABS plastic, the ABS pellet is mixed obtaining modified ABS with the modified powder that easily is corroded, the weight ratio of ABS pellet and the two consumption of modified powder is 100:2～100:40.The modified ABS that employing the inventive method obtains is when alligatoring, and its modified powder easily is corroded (comparing with ABS plastic), thereby makes product surface just can reach ideal alligatoring effect through the alligatoring of short period.
As improvement of the present invention, coupling agent, modified powder and the mixing of ABS pellet can be obtained modified ABS.The use of coupling agent can improve the consistency between modified powder and the ABS, obtains good compound interface, thereby improves the mechanical property of product.
As improvement of the present invention, also dispersion agent, modified powder and the mixing of ABS pellet can be obtained modified ABS.It is more even that the adding dispersion agent can make mixing of materials get, and improves the quality of products.
As a further improvement on the present invention, can adopt following steps:
1) coupling agent and solvent obtain mixed solution;
2) mixed solution that modified powder and step 1) are obtained mixes;
3) with ABS pellet and step 2) mixture that obtains mixes.
The adding solvent can improve the compatible effect of modified powder and ABS pellet.
Further improve step 2 as the present invention) process be: after the mixed solution that modified powder and step 1) are obtained mixes, the gained mix products again with dispersant.
In technique scheme, the weight ratio of coupling agent and the two consumption of solvent is 1:5～1:20 in the step 1); Step 2) weight ratio of coupling agent and the two consumption of modified powder is 1:100～40:100 in; The weight ratio of dispersion agent and the two consumption of modified powder is 0.1:1～0.1:5; Coupling agent is one or more in titanate coupling agent, KH-550 type silane coupling agent, KH-560 type silane coupling agent, the KH-570 type silane coupling agent, and solvent is one or more in benzene,toluene,xylene, N-N dimethylformamide, ethanol, propyl alcohol, butanols, acetone, the butanone; Step 2) used dispersion agent can be among dispersion agent TAS-2A, dispersion agent TAS-3A, the dispersion agent TAF one or more.
In technique scheme, modified powder is one or more in anatase-type nanometer titanium dioxide, nano silicon, nano-sized magnesium hydroxide, super fine alumina, ultra-fine barium sulfate, super-fine talc, zirconium dioxide, nano-calcium carbonate, nano zine oxide, zeolite, the montmorillonite; The particle diameter of modified powder is 10nm～5000nm.
In technique scheme, the particle diameter of ABS pellet is: 50um～5000um.
Step 3) products therefrom melt pelletization can be convenient to mass transport and storage like this.
Step 2) and the mixing process in the step 3) can adopt high-speed mixer, mixing time all is 5～20min.
The present invention mixes ABS and modified powder, used modified powder is corroded than ABS is easier, modified powder is corroded and makes ABS plastic surface produce small hole during alligatoring, thereby the ABS plastic specific surface area is increased greatly, promote ABS plastic C-C key oxidative cleavage in the acid etching coarsening process simultaneously and form hydrophilic hydroxyl and carboxyl, reach the purpose that the sticking power of coating increases after making the ABS plastic surface hydrophilicity further strengthen, electroplate.ABS plastic after the modification only needs short acid etching coarsening time (the acid etching alligatoring of this time is not enough to corrode PC) just can reach ideal alligatoring effect.The use coupling agent can improve the consistency between modified powder and the ABS, obtains good compound interface; Solvent can improve the result of use of coupling agent; It is more even that dispersion agent can make mixing of materials get, and improves the modification quality.
[description of drawings]
For convenience of explanation, the present invention uses following preferred embodiment and accompanying drawing to do to describe in detail.
Fig. 1 is the stereoscan photograph of the unmodified ABS plastic of Comparative Examples of the present invention after corrosion.
Fig. 2 is the stereoscan photographs of the embodiment of the invention one gained modified ABS plastics after corrosion.
Fig. 3 is the stereoscan photographs of the embodiment of the invention two gained modified ABS plastics after corrosion
Fig. 4 is the stereoscan photographs of the embodiment of the invention three gained modified ABS plastics after corrosion
[embodiment]
Below in each embodiment and the Comparative Examples used ABS pellet be the ABS of Taiwan Qi Mei company limited, model is PA-727, particle diameter is 2～5mm; High-speed mixer originates from Yili Machinery Co., Ltd., Zhangjiagang City, model SHR-10A, and rotating speed is selected 1500rpm for use.
Embodiment one
As follows ABS plastic is carried out the application method of modification:
(1) according to the mixed solution of weight ratio 1:10 preparation titanate coupling agent and dehydrated alcohol;
(2) be that the nano-titania particle of 10～25nm and mixed solution that step (1) makes join in the high-speed mixer simultaneously with particle diameter, wherein the weight ratio of titanate coupling agent and titanium dioxide is 2:100, high-speed mixing stirred 10 minutes, make nano titanium oxide and titanate coupling agent thorough mixing, obtain mixed powder;
(3) mixed powder that ABS pellet and step (2) are made joins in the high-speed mixer by weight 100:4, high-speed mixing stirred 10 minutes, the mixed powder thorough mixing that ABS pellet and step (2) are made obtains the modified ABS pellet of coated with nanometre TiO 2 particles.
(4) be melt pelletization on 160/220/220/220/220/220/220/210 ℃ of (temperature from the machine barrel to the head) twin screw rotating speed dual-screw pelletizer that is 60rpm with the modified ABS pellet of step (3) gained in temperature schedule.
Embodiment two
As follows ABS plastic is carried out the application method of modification:
(1) according to the mixed solution of weight ratio 1:15 preparation silane resin acceptor kh-550 and acetone;
(2) be that the nano-sized magnesium hydroxide particle of 50～100nm and mixed solution that step (1) makes join in the high-speed mixer simultaneously with particle diameter, wherein the weight ratio of silane coupling agent and nano-sized magnesium hydroxide is 1:10, high-speed mixing stirred 10 minutes, make nano-sized magnesium hydroxide and silane coupling agent thorough mixing, obtain mixed powder;
(3) mixed powder high-speed mixing in high-speed mixer that dispersion agent TAS-2A and step (2) are made, wherein the weight ratio of nano-sized magnesium hydroxide particle is 1:1 in the mixed powder that makes of dispersion agent TAS-2A and step (2), makes new mixed powder after the mixing;
(4) ABS pellet and the prepared new mixed powder of step (3) are joined in the high-speed mixer by weight 20:100, high-speed mixing stirred 10 minutes, make new mixed powder and ABS pellet thorough mixing, obtain the modified ABS pellet of coated with nanometre magnesium hydroxide.
(5) be melt pelletization on 160/220/220/220/220/220/220/210 ℃ of (temperature from the machine barrel to the head) twin screw rotating speed dual-screw pelletizer that is 60rpm with the modified ABS pellet of step (4) gained in temperature schedule.
Embodiment three
As follows ABS plastic is carried out the application method of modification:
(1) according to the mixed solution of weight ratio 1:20 preparation silane coupling agent kh-570 and acetone;
(2) mixed solution that super fine alumina and step (1) are made joins high-speed mixer (Yili Machinery Co., Ltd., Zhangjiagang City simultaneously, model SHR-10A, rotating speed is selected 1500rpm for use, down together), wherein the weight ratio of silane coupling agent KH-570 and super fine alumina is 1:10, high-speed mixing stirred 10 minutes, made super fine alumina and silane coupling agent KH-570 thorough mixing, obtained mixed powder;
(3) high-speed mixing in high-speed mixer with dispersion agent TAS-3A and the prepared mixed powder of step (2), wherein the weight ratio of super fine alumina is 1:2 in the mixed powder that makes of dispersion agent TAS-3A and step (2), makes new mixed powder after the mixing;
(4) ABS pellet and the prepared new mixed powder of step (3) are joined in the high-speed mixer by weight 20:100, high-speed mixing stirred 10 minutes, make new mixed powder and ABS pellet thorough mixing, obtain the modified ABS pellet of surface coverage super fine alumina;
(5) be melt pelletization on 160/220/220/220/220/220/220/210 ℃ of (temperature from the machine barrel to the head) twin screw rotating speed dual-screw pelletizer that is 60rpm with the modified ABS pellet of step (4) gained in temperature schedule.
Comparative Examples: unmodified ABS pellet, Qi Mei company limited in Taiwan produces, and model is PA-727.
Performance comparison
(1) respectively modified ABS pellet after the melt pelletization among each embodiment and the injection moulding of comparative example A BS pellet are obtained sample, the Shooting Technique condition is 80 ℃ of drying temperatures; Time of drying 4h; 260 ℃ of melt temperatures; Injection temperature: 250 ℃ at nozzle; One section 260 ℃; Two sections 250 ℃; Three sections 240 ℃; 60 ℃ of die temperatures; Injection pressure: first class pressure 150MPa; Secondary pressure 75MPa; Three stage pressure 60MPa; Back pressure 3MPa; Screw speed 30rpm; Machine barrel shot weight 60%.
(2) with each sample alligatoring under the same conditions that obtains in (1), coarsening solution is by H
2SO
4(400g/L) and CrO
3(350g/L) form, coarsening time 5min with the degree of corrosion of each sample surfaces after the scanning electron microscope inspection alligatoring, sees Fig. 1-Fig. 4, and the magnification of each figure is 2000.Fig. 1-Fig. 4 is followed successively by Comparative Examples, embodiment one, embodiment two, embodiment three, embodiment four.
From Fig. 1-Fig. 4 as can be seen, through the corrosion after, few, the depth as shallow of unmodified ABS surface void quantity, alligatoring deficiency; (coarsening time of this series products is that 10～15min) corrosion have just formed a large amount of holes on the surface in the production practice and modified ABS only passes through 5min, and the hole area is big, hole depth is darker, extent of corrosion is obviously than unmodified ABS height, and its easy alligatoring has obtained very big improvement.
Claims (4)
1. the method for modifying of an ABS plastic is characterized in that: may further comprise the steps:
1) coupling agent and solvent obtain mixed solution;
2) mixed solution that modified powder and step 1) are obtained mixes; The gained mix products again with dispersant;
3) with ABS pellet and step 2) mixture that obtains mixes; The weight ratio of ABS pellet and the two consumption of modified powder is 100: 2～100: 40;
The weight ratio of coupling agent described in the step 1) and the two consumption of solvent is 1: 5～1: 20; The weight ratio of coupling agent step 2) and the two consumption of modified powder is 1: 100～40: 100; The weight ratio of described dispersion agent and the two consumption of modified powder is 0.1: 1～0.1: 5; Described coupling agent is one or more in titanate coupling agent, KH-550 type silane coupling agent, KH-560 type silane coupling agent, the KH-570 type silane coupling agent, and described solvent is one or more in benzene,toluene,xylene, N-N dimethylformamide, ethanol, propyl alcohol, butanols, acetone, the butanone; Step 2) used dispersion agent is one or more among dispersion agent TAS-2A, dispersion agent TAS-3A, the dispersion agent TAF;
Described modified powder is one or more in anatase-type nanometer titanium dioxide, nano silicon, nano-sized magnesium hydroxide, super fine alumina, ultra-fine barium sulfate, super-fine talc, zirconium dioxide, nano-calcium carbonate, nano zine oxide, zeolite, the montmorillonite; The particle diameter of described modified powder is 10nm～5000nm.
2. the method for modifying of ABS plastic according to claim 1, it is characterized in that: the particle diameter of described ABS pellet is 50um～5000um.
3. the method for modifying of ABS plastic according to claim 2 is characterized in that: with step 3) products therefrom melt pelletization.
4. the method for modifying of ABS plastic according to claim 3 is characterized in that: step 2) and step 3) in mixing process adopt stirring mixer, mixing time all is 5～20min, the rotating speed of stirring mixer is 300-3000rpm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100633090A CN101168613B (en) | 2006-10-25 | 2006-10-25 | Method for modifying ABS plastic |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100633090A CN101168613B (en) | 2006-10-25 | 2006-10-25 | Method for modifying ABS plastic |
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| CN101168613A CN101168613A (en) | 2008-04-30 |
| CN101168613B true CN101168613B (en) | 2011-01-12 |
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| CN2006100633090A Active CN101168613B (en) | 2006-10-25 | 2006-10-25 | Method for modifying ABS plastic |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260401A (en) * | 2011-07-20 | 2011-11-30 | 上海瑞尔实业有限公司 | Method for preparing toughened, reinforced and anti-aging acrylonitrile-butadiene-styrene (ABS) nano composite material |
| CN102604319A (en) * | 2012-04-10 | 2012-07-25 | 上海瑞尔实业有限公司 | Method for preparing nanometer PC (Poly Carbonate)/ABS (Acrylonitrile Butadiene Styrene) modified alloy |
| CN103214782B (en) * | 2013-04-28 | 2015-04-08 | 合肥工业大学 | ABS (Acrylonitrile Butadiene Styrene) heat-conduction and insulating composite with excellent processability |
| CN104277410B (en) * | 2013-07-03 | 2018-08-17 | 合肥杰事杰新材料股份有限公司 | A kind of preparation method of the fire-retardant plating ABS of electronic apparatus shell |
| CN103554824B (en) * | 2013-10-31 | 2016-07-27 | 朱勇 | Environment friendly flame-proof ABS material for electric energy meter of electric power system housing |
| CN105733169A (en) * | 2014-12-10 | 2016-07-06 | 黑龙江鑫达企业集团有限公司 | Preparation method of low-warpage ABS special-purposed 3D printing material |
| CN105713335A (en) * | 2015-09-18 | 2016-06-29 | 怀宁县明发塑业有限责任公司 | Nano modified high-impact-resistance ABS composite plastic |
| CN105237939A (en) * | 2015-11-18 | 2016-01-13 | 上海瀚氏模具成型有限公司 | Composite ABS plastic for automotive interior trims and preparation method of composite ABS plastic |
| CN105647101A (en) * | 2016-04-12 | 2016-06-08 | 苏州甫众塑胶有限公司 | Enhanced-type electric appliance shell plastic material and preparation method thereof |
| CN107474347A (en) * | 2017-08-23 | 2017-12-15 | 柳州市颖航汽配有限公司 | Rubber modification method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042167A (en) * | 1988-10-05 | 1990-05-16 | 聚塑料株式会社 | The electrostatic coating method and the coated plastic molding of crystalline thermoplastic resin mo(u)lded item |
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2006
- 2006-10-25 CN CN2006100633090A patent/CN101168613B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042167A (en) * | 1988-10-05 | 1990-05-16 | 聚塑料株式会社 | The electrostatic coating method and the coated plastic molding of crystalline thermoplastic resin mo(u)lded item |
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