CN102585253B - Preparation method of thermoplastic polyimide (TPI) particles for modifying surfaces of polyimide (PI) films - Google Patents
Preparation method of thermoplastic polyimide (TPI) particles for modifying surfaces of polyimide (PI) films Download PDFInfo
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- CN102585253B CN102585253B CN201110440277.2A CN201110440277A CN102585253B CN 102585253 B CN102585253 B CN 102585253B CN 201110440277 A CN201110440277 A CN 201110440277A CN 102585253 B CN102585253 B CN 102585253B
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Abstract
The invention discloses a preparation method of thermoplastic polyimide (TPI) particles for modifying the surfaces of polyimide (PI) films. Through the adoption of a technological process of dissolving TPI powder in an organic solvent and precipitating the TPI particles through a poor solvent and combining with parameter control of the concentration, the temperature and the spraying process, qualified particles are obtained. The technological process is simple, the production cost is low and the work efficiency is high; through regulating the parameters of the liquor concentration and a spraying device, the prepared TPI particles has controllable particle size and regular shapes and is suitable for being consolidated on the surfaces of the PI printing films, and the surfaces of the modified PI printing films are enabled to have a high roughness, high compatibility and high cohesiveness.
Description
Technical field
The present invention relates to a kind of film for board substrate, be specifically related to a kind of preparation method of the TPI particulate for the modification of PI film surface.
Background technology
Flexible circuit (FPC) claim again flexible circuit, is that the one of making as base material taking mylar or polyimide has height reliability, excellent flexible printed wiring.Be widely used in the fields such as aerospace, mobile phone, digital camera, notebook computer, liquid-crystal display, phonotape and videotape, automobile.Traditional flexible circuit manufacture craft process complexity not only produces a large amount of chemical waste fluids in making processes, causes the puzzlement of environmental pollution, and has caused the larger waste of copper resource.
Under environmental protection and the requirement that economizes on resources, printed circuit technique is developed faster; Directly printed wiring is exactly the method that forms conducting wire at the direct printing conductive slurry of flexible insulation substrate surface.With respect to FPC wet method processing procedure, directly printed circuit technology processing procedure is simpler, and not only wastewater discharge is few, more environmental protection, and the waste that can not produce copper resource.But with respect to traditional F PC wet processing, this printing process has proposed requirements at the higher level to the undertake the printing of multinomial performance of film of polyimide (PI), especially, on affecting the cohesiveness of undertaking the printing of between film and conducting metal slurry of product life, has relatively high expectations especially.
For the cohesiveness that ensures that conducting wire and polyimide (PI) are undertaken the printing of between film, need to increase the cohesiveness on the film surface of undertaking the printing of, thereby need, to its modifying surface processing, increase affinity.And the preferred mode of carrying out surface modification treatment is to increase roughness on surface, thermoplastic polyimide (TPI) particulate that adopts the curing mode increase of surface coated to have affinity is to increase surfaceness and close-burning better way.Due to the special property of printed wiring, the thermoplastic polyimide for to its surface modification (TPI) particulate is had relatively high expectations, comprise particle diameter and shape.
In prior art, be that powder is made in mechanical disintegration processing and chemical reaction makes for the comparatively direct mode of preparation of medlin particulate.In addition polyamic acid is dissolved in extremely optimum solvent, add again poor solvent to precipitate and obtain polyamic acid micropartical, the particulate obtaining adds hot-imide, in imidization, control size and the pattern of medlin particulate by suppressing side reaction, in the situation that keeping size and pattern constant, be transformed into medlin particulate.Above-mentioned particulate preparation method need use the solvent of strong polarity and obtain and imide particle particle diameter inhomogeneous, distribution range is wider, even not controlled, and, this particulate must not be used for polyimide (PI) the film modification of undertaking the printing of, and is used in polyimide (PI) the film modification of undertaking the printing of, and needs further screening to use yet, and screening process and making processes are comparatively complicated, increase cost.
Therefore, need a kind of preparation method of the TPI particulate for the modification of PI film surface, technological process is simple, there is lower production cost and higher production efficiency, thermoplastic polyimide (TPI) diameter of particle making is controlled, and there is more regular shape, be suitable for being consolidated in polyimide (PI) and undertake the printing of film surface to its modification, make polyimide (PI) after the modification film surface of undertaking the printing of there is good roughness, affinity and cohesiveness.
Summary of the invention
In view of this, object of the present invention provides a kind of preparation method of the TPI particulate for the modification of PI film surface, technological process is simple, there is lower production cost and higher production efficiency, thermoplastic polyimide (TPI) diameter of particle making is controlled, and there is more regular shape, be suitable for being consolidated in polyimide (PI) and undertake the printing of film surface to its modification, make polyimide (PI) after the modification film surface of undertaking the printing of there is good roughness, affinity and cohesiveness.
The preparation method of the TPI particulate for the modification of PI film surface of the present invention, comprises the following steps:
A. thermoplastic polyimide powder is dissolved in to the thermoplastic polyimide organic solution that in organic solvent, organizer volume concentrations is 2%～20%, described organic solvent temperature is 15 DEG C-50 DEG C;
B. thermoplastic polyimide organic solution being to vaporific sprays to being added with in the poor solvent of dispersion agent, the addition of dispersion agent is that every 100 milliliters of poor solvents add 0.5-5 gram, the temperature of poor solvent is 15 DEG C-50 DEG C, described thermoplastic polyimide organic solution forms vaporific sprinkling by flusher, the spray pressure of described flusher is 0.1MPa-0.5MPa, and nozzle bore is 1-10 micron; Then the mixture forming after spraying is further disperseed by ultrasonic wave; Obtaining particle diameter is the thermoplastic polyimide particulate of 0.1～5 μ m.
Further, described organic solvent is sulfur-bearing solvent or nitrogen-containing solvent, and sulfur-bearing solvent comprises one or more the mixture in acetone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) and tetramethylene sulfone; Nitrogen-containing solvent comprises one or more the mixture in N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide and hexanolactam; Described poor solvent comprises one or more the mixture in water, methyl alcohol, ethanol, propyl alcohol and tetramethylolmethane;
Further, in step a and step b, organic solvent temperature is 25 DEG C-30 DEG C, and the temperature of poor solvent is 25 DEG C-30 DEG C;
Further, described dispersion agent is polyvinylpyrrolidone, and addition is that every 100 milliliters of poor solvents add 3 grams;
Further, in step b, for thermoplastic polyimide organic solution is formed by flusher, vaporific to be sprayed into the ultrasonic frequency that mixture that poor solvent forms carries out dispersion treatment be 30KHz, and power is 300-800W.
Beneficial effect of the present invention: the preparation method of the TPI particulate for the modification of PI film surface of the present invention, adopt the technological process that thermoplastic polyimide powder is dissolved in to organic solvent and separates out by poor solvent, in conjunction with concentration, parameter control when temperature and sprinkling, obtain qualified particulate, and realize strong impact and cavitation by ultrasonic wave, further disperse and granulating, be beneficial to and ensure granulating shape, technological process is simple, there is lower production cost and higher production efficiency, parameter by strength of solution and flusher is reconciled, make thermoplastic polyimide (TPI) diameter of particle that makes controlled, and there is more regular shape, be suitable for being consolidated in polyimide (PI) and undertake the printing of film surface to its modification, make polyimide (PI) after the modification film surface of undertaking the printing of there is good roughness, affinity and cohesiveness.
Embodiment
The present invention is used for the preparation method's of the TPI particulate of PI film surface modification embodiment:
Embodiment mono-
The preparation method who is used for the TPI particulate of PI film surface modification, comprises the following steps:
A. thermoplastic polyimide powder is dissolved in to the thermoplastic polyimide organic solution that in organic solvent, organizer volume concentrations is 2%～20%, described organic solvent temperature is 25 DEG C-30 DEG C;
B. thermoplastic polyimide organic solution being to vaporific sprays to being added with in the poor solvent of dispersion agent, the addition of dispersion agent is that every 100 milliliters of poor solvents add 3 grams, the temperature of poor solvent is 25 DEG C-30 DEG C, described thermoplastic polyimide organic solution forms vaporific sprinkling by flusher, the spray pressure of described flusher is 0.1MPa-0.5MPa, and nozzle bore is 1-10 micron; Then the mixture forming after spraying is further disperseed by ultrasonic wave; Obtaining particle diameter is the thermoplastic polyimide particulate of 0.1～4.41 μ m.
In the present embodiment, described organic solvent is sulfur-bearing solvent acetone, in the present embodiment, organic solvent is replaced with to the mixture in other sulfur-bearing solvents tetrahydrofurane, dimethyl sulfoxide (DMSO), tetramethylene sulfone or acetone and tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) and tetramethylene sulfone by acetone, or with the akin material of above-mentioned sulfur-bearing solvent physical properties, the thermoplastic polyimide particulate obtaining has essentially identical character, there is no significant difference; Above-mentioned organic solvent is replaced with to nitrogen-containing solvent N-Methyl pyrrolidone, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, hexanolactam or N-Methyl pyrrolidone, N, dinethylformamide, N, the mixture of N-N,N-DIMETHYLACETAMIDE and hexanolactam, or with the akin material of above-mentioned nitrogen-containing solvent physical properties, the thermoplastic polyimide particulate obtaining has essentially identical character, there is no significant difference;
In the present embodiment, in step b, for thermoplastic polyimide organic solution is formed by flusher, vaporific to be sprayed into the ultrasonic frequency that mixture that poor solvent forms carries out dispersion treatment be 30KHz, and power is 300-800W, in the present embodiment, power is 300W.
In the present embodiment, by adjusting the thermoplastic polyimide organic solution of spray pressure, nozzle bore and different concns, obtain different thermoplastic polyimide diameter of particle, this particle diameter need be controlled at 0.1～4.41 μ m, can be found out by following table, the solution of same volume concentration, spray pressure is larger, nozzle bore is less, the diameter of particle obtaining is just less, scope width is narrower, therefore, can obtain required diameter of particle and scope by adjusting liquor capacity concentration, spray pressure and nozzle bore, specifically see the following form:
Table 1
Embodiment bis-
The preparation method who is used for the TPI particulate of PI film surface modification, comprises the following steps:
A. thermoplastic polyimide powder is dissolved in to the thermoplastic polyimide organic solution that in organic solvent, organizer volume concentrations is 2%～20%, described organic solvent temperature is 30 DEG C-50 DEG C;
B. thermoplastic polyimide organic solution being to vaporific sprays to being added with in the poor solvent of dispersion agent, the addition of dispersion agent is that every 100 milliliters of poor solvents add 0.5 gram, the temperature of poor solvent is 30 DEG C-50 DEG C, described thermoplastic polyimide organic solution forms vaporific sprinkling by flusher, the spray pressure of described flusher is 0.1MPa-0.5MPa, and nozzle bore is 1-10 micron; Then the mixture forming after spraying is further disperseed by ultrasonic wave; Obtaining particle diameter is the thermoplastic polyimide particulate of 0.1～5 μ m.
In the present embodiment, described organic solvent is sulfur-bearing solvent acetone, in the present embodiment, organic solvent is replaced with to the mixture in other sulfur-bearing solvents tetrahydrofurane, dimethyl sulfoxide (DMSO), tetramethylene sulfone or acetone and tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) and tetramethylene sulfone by acetone, or with the akin material of above-mentioned sulfur-bearing solvent physical properties, the thermoplastic polyimide particulate obtaining has essentially identical character, there is no significant difference; Above-mentioned organic solvent is replaced with to nitrogen-containing solvent N-Methyl pyrrolidone, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, hexanolactam or N-Methyl pyrrolidone, N, dinethylformamide, N, the mixture of N-N,N-DIMETHYLACETAMIDE and hexanolactam, or with the akin material of above-mentioned nitrogen-containing solvent physical properties, the thermoplastic polyimide particulate obtaining has essentially identical character, there is no significant difference;
In the present embodiment, in step b, for thermoplastic polyimide organic solution is formed by flusher, vaporific to be sprayed into the ultrasonic frequency that mixture that poor solvent forms carries out dispersion treatment be 30KHz, and power is 300-800W, in the present embodiment, power is 300W.
In the present embodiment, by adjusting spray pressure, the thermoplastic polyimide organic solution of nozzle bore and different concns, obtain different thermoplastic polyimide diameter of particle, this particle diameter need be controlled at 0.09～4.01 μ m, can be found out by following table, the solution of same volume concentration, spray pressure is larger, nozzle bore is less, the diameter of particle obtaining is just less, scope width is narrower, therefore, by adjusting liquor capacity concentration, spray pressure and nozzle bore can obtain required diameter of particle and scope, and the temperature of solution and poor solvent also has impact to particle diameter, be that the higher particle diameter of temperature is on average less, but and not obvious, specifically see the following form:
Table 1
Embodiment tri-
The preparation method who is used for the TPI particulate of PI film surface modification, comprises the following steps:
A. thermoplastic polyimide powder is dissolved in to the thermoplastic polyimide organic solution that in organic solvent, organizer volume concentrations is 2%～20%, described organic solvent temperature is 15 DEG C-30 DEG C;
B. thermoplastic polyimide organic solution being to vaporific sprays to being added with in the poor solvent of dispersion agent, the addition of dispersion agent is that every 100 milliliters of poor solvents add 0.5 gram, the temperature of poor solvent is 15 DEG C-30 DEG C, described thermoplastic polyimide organic solution forms vaporific sprinkling by flusher, the spray pressure of described flusher is 0.1MPa-0.5MPa, and nozzle bore is 1-10 micron; Then the mixture forming after spraying is further disperseed by ultrasonic wave; Obtaining particle diameter is the thermoplastic polyimide particulate of 0.1～5 μ m.
In the present embodiment, described organic solvent is sulfur-bearing solvent acetone, in the present embodiment, organic solvent is replaced with to the mixture in other sulfur-bearing solvents tetrahydrofurane, dimethyl sulfoxide (DMSO), tetramethylene sulfone or acetone and tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) and tetramethylene sulfone by acetone, or with the akin material of above-mentioned sulfur-bearing solvent physical properties, the thermoplastic polyimide particulate obtaining has essentially identical character, there is no significant difference; Above-mentioned organic solvent is replaced with to nitrogen-containing solvent N-Methyl pyrrolidone, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, hexanolactam or N-Methyl pyrrolidone, N, dinethylformamide, N, the mixture of N-N,N-DIMETHYLACETAMIDE and hexanolactam, or with the akin material of above-mentioned nitrogen-containing solvent physical properties, the thermoplastic polyimide particulate obtaining has essentially identical character, there is no significant difference;
In the present embodiment, in step b, for thermoplastic polyimide organic solution is formed by flusher, vaporific to be sprayed into the ultrasonic frequency that mixture that poor solvent forms carries out dispersion treatment be 30KHz, and power is 300-800W, in the present embodiment, power is 800W.
In the present embodiment, by adjusting spray pressure, the thermoplastic polyimide organic solution of nozzle bore and different concns, obtain different thermoplastic polyimide diameter of particle, this particle diameter need be controlled at 0.11～4.99 μ m, can be found out by following table, the solution of same volume concentration, spray pressure is larger, nozzle bore is less, the diameter of particle obtaining is just less, scope width is narrower, therefore, by adjusting liquor capacity concentration, spray pressure and nozzle bore can obtain required diameter of particle and scope, and the temperature of solution and poor solvent also has impact to particle diameter, be that the higher particle diameter of temperature is on average less, but and not obvious, and the present embodiment adopts the ul-trasonic irradiation that power is 800W, reduction that can equalising temp, specifically see the following form:
Table 1
As can be seen from the above-described embodiment, the TPI diameter of particle scope for the modification of flexible PCB PI film surface making by the present invention is narrower, and can obtain different particle size range by technique adjustment, thereby obtains required product.
Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (3)
1. for a preparation method for the TPI particulate of PI film surface modification, it is characterized in that: comprise the following steps:
A. thermoplastic polyimide powder is dissolved in to the thermoplastic polyimide organic solution that in organic solvent, organizer volume concentrations is 2%～20%, described organic solvent temperature is 15 DEG C-50 DEG C; Described organic solvent comprises one or more the mixture in acetone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) and tetramethylene sulfone, or comprise N-Methyl pyrrolidone, N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide and hexanolactam;
B. thermoplastic polyimide organic solution being to vaporific sprays to being added with in the poor solvent of dispersion agent, the addition of dispersion agent is that every 100 milliliters of poor solvents add 0.5-5 gram, the temperature of poor solvent is 15 DEG C-50 DEG C, described thermoplastic polyimide organic solution forms vaporific sprinkling by flusher, the spray pressure of described flusher is 0.1MPa-0.5MPa, and nozzle bore is 1-10 micron; Then the mixture forming after spraying is further disperseed by ultrasonic wave, the ultrasonic frequency of carrying out dispersion treatment is 30KHz, and power is 300-800W; Obtaining particle diameter is the thermoplastic polyimide particulate of 0.1～5 μ m; Described poor solvent comprises one or more the mixture in water, methyl alcohol, ethanol, propyl alcohol and tetramethylolmethane.
2. the preparation method of the TPI particulate for the modification of PI film surface according to claim 1, is characterized in that: in step a, organic solvent temperature is 25 DEG C-30 DEG C; In step b, the temperature of poor solvent is 25 DEG C-30 DEG C.
3. the preparation method of the TPI particulate for the modification of PI film surface according to claim 2, is characterized in that: described dispersion agent is polyvinylpyrrolidone, and addition is that every 100 milliliters of poor solvents add 3 grams.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1807510A (en) * | 2006-02-07 | 2006-07-26 | 南京工业大学 | Thermoplastic polyimide microporous material and its preparation process |
| CN101230136A (en) * | 2007-01-22 | 2008-07-30 | 东丽纤维研究所（中国）有限公司 | Polyimide microparticle and preparation method thereof |
| CN101463135A (en) * | 2009-01-13 | 2009-06-24 | 吉林大学 | Preparation of water-dispersion polyamic acid particle |
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| US20080269457A1 (en) * | 2006-04-11 | 2008-10-30 | Sony Chemical & Information Device Corporation | Process For Producing Polyimide Fine Particle |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807510A (en) * | 2006-02-07 | 2006-07-26 | 南京工业大学 | Thermoplastic polyimide microporous material and its preparation process |
| CN101230136A (en) * | 2007-01-22 | 2008-07-30 | 东丽纤维研究所（中国）有限公司 | Polyimide microparticle and preparation method thereof |
| CN101463135A (en) * | 2009-01-13 | 2009-06-24 | 吉林大学 | Preparation of water-dispersion polyamic acid particle |
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Effective date of registration: 20161024 Address after: 401220 Changshou District of Chongqing economic and Technological Development Zone United Road No. 22 Patentee after: Chongqing Yuntianhua hanen New Material Development Co Ltd Patentee after: Yutianhua Co., Ltd., Yunnan Address before: 657800 Zhaotong City, Yunnan province Shuifu county to jingjiaba Patentee before: Yutianhua Co., Ltd., Yunnan |