CN108117658B - Preparation method of anti-electrostatic adsorption imide film - Google Patents
Preparation method of anti-electrostatic adsorption imide film Download PDFInfo
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Abstract
The invention discloses a preparation method of an anti-static agglomeration-absorption imide film, which comprises the following steps: 1) preparing a polyamic acid film; 2) preparing a polyamic acid composite solution containing hydrophilic particles, which specifically comprises the following steps: uniformly dispersing hydrophilic particles in a polar aprotic solvent, and then adding diamine and dianhydride for reaction to obtain the polyimide resin; wherein the hydrophilic particles are silicon oxide and/or titanium oxide, and the addition amount of the hydrophilic particles is 0.1-10 w/w% of the solid content of the obtained composite solution; the dosage of the polar aprotic solvent is controlled so that the viscosity of the obtained composite solution is 10-10000 mPa & s; 3) and coating the obtained composite solution on the surface of a polyamic acid film, and then stretching and carrying out thermal imidization to obtain the polyimide film. The method can enlarge the adding amount of the hydrophilic particles to 10% of the solid content of the polyamic acid composite solution, and ensure that the surface static electricity of the prepared PI film is effectively reduced on the basis of keeping the original transparency and insulativity of the PI film.
Description
Technical Field
The invention relates to a polyimide film, in particular to a preparation method of an anti-static-adsorption polyimide film.
Background
The Polyimide (PI) film has excellent heat resistance, chemical resistance and mechanical strength, good insulating property, electric strength of about 300kV/mm, and volume resistivity of 1012～1016Omega. m, surface resistivity of 1015～1020Omega, is widely used as an electronic insulating film in the fields of microelectronics, liquid crystal display, medical treatment and the like. However, due to the high surface resistivity of the PI film, the PI film generates a large charge accumulation due to friction between the film and the film during the production and post-treatment processes, and is not easily dissipated, thereby generating static electricity, although the surface can be temporarily removed by an online static electricity eliminating deviceHowever, the surface charge also generates static electricity due to slight friction during transportation, storage, use and the like, and the PI film with the static electricity on the surface is easy to adsorb impurities such as dust in the air, and the poorer the air cleanness, the more the adsorbed impurities are, which not only affects the appearance quality and forms bumps, pits or indentations, but also greatly reduces the electrical strength of the PI film and affects the quality and the service life of products such as electronic components and the like. Therefore, how to solve the problem of static electricity of polyimide films is a common requirement of various manufacturers.
A great deal of literature data at home and abroad reports the technical research of the antistatic PI film, most of the literature patents can reduce the surface resistivity of the PI film to 10 by adding carbon fillers, such as graphite micro-sheets, graphene sheets, carbon fibers and the like, conductive metals or oxides and conductive high polymer materials8Omega, plays an antistatic role, but the volume resistivity of the obtained PI film is reduced to 1010Omega m, the insulativity of the PI film is greatly reduced. The polyimide film for electrical insulation of national standard GB/T13542.6-2006 requires the surface resistivity to be more than or equal to 1014～1015Omega, volume resistivity is more than or equal to 1010～1013Omega m, therefore, the prior antistatic PI film is difficult to meet the use requirement of electronic or electric insulation.
In the prior art, it has also been reported that the PI film is coated with a conductive material on its surface to make the obtained film have antistatic properties, for example, in patent publication No. CN104292488, a conductive solution composed of graphite oxide and carbon nanotubes is coated on the surface of the PI film by spin coating to make the film have antistatic properties. However, no report is known about that the obtained film has the function of preventing electrostatic adsorption by coating the polyamic acid composite solution containing hydrophilic inorganic particles on the surface of the PI film.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of an anti-static-adsorption imide film. The method can enlarge the adding amount of the hydrophilic particles to 10 percent of the solid content of the polyamic acid composite solution, and ensure that the prepared PI film keeps the original transparency and transparencyEffectively reducing surface static electricity on the basis of insulativity, wherein the surface resistivity of the obtained PI film is more than or equal to 1016Omega, volume resistivity is more than or equal to 1013Omega. m, hygroscopicity < 2%.
The preparation method of the anti-static-attraction agglomeration imide film comprises the following steps:
1) preparing a polyamic acid film;
2) preparing a polyamic acid composite solution containing hydrophilic particles, which specifically comprises the following steps: uniformly dispersing hydrophilic particles in a polar aprotic solvent, and then adding aromatic diamine and tetracarboxylic dianhydride to react to prepare a polyamic acid composite solution containing the hydrophilic particles; wherein the content of the first and second substances,
the hydrophilic particles are silicon oxide and/or titanium oxide, and the addition amount of the hydrophilic particles is 0.1-10 w/w% of the solid content of the obtained composite solution; the dosage of the polar aprotic solvent is controlled so that the viscosity of the obtained composite solution is 10-10000 mPa & s;
3) and coating the polyamide acid composite solution containing the hydrophilic particles on the surface of a polyamide acid film, and then stretching and carrying out thermal imidization to obtain the anti-electrostatic adsorption polyimide film.
The applicant finds in research that the addition amount of the hydrophilic particles can be increased to 10% of the solid content of the polyamic acid composite solution by adopting the method, the hydrophilic angle of the surface of the obtained PI film is reduced from 85 degrees to below 45 degrees, dust adsorption is effectively prevented, the insulativity of the original PI film is maintained, the electrical strength is more than or equal to 320kV/mm, and the surface resistivity is more than or equal to 1016Omega, volume resistivity is more than or equal to 1013Omega.m, the hygroscopicity is less than 2 percent, and the original transparency of the PI film is not changed.
In step 1) of the above preparation method, the polyamic acid film is prepared by using the conventional technique. Specifically, the aromatic diamine and the tetracarboxylic dianhydride are placed in a polar aprotic solvent to carry out polycondensation reaction to obtain a polyamic acid resin solution, and then defoaming, casting and heating curing are carried out to obtain the polyamic acid film. Wherein, the selection and the dosage of the aromatic diamine, the tetracarboxylic dianhydride and the polar aprotic solvent are the same as those in the prior art, and the temperature and the time of the polycondensation reaction are also the same as those in the prior art. The following are preferred:
the aromatic diamine may be one or a combination of two or more selected from 4,4 '-diaminodiphenyl ether (ODA), 3, 4' -diaminodiphenyl ether, 3 '-diaminodiphenyl ether, 1, 4-diaminobenzene (p-PDA), 1, 3-diaminobenzene (m-PDA), 1, 2-diaminobenzene (o-PDA), 4' -Diaminobiphenyl (DBZ), 4 '-diamino-3, 3' -dimethylbiphenyl (OTD), 4 '-diamino-2, 2' -dimethylbiphenyl (MTD). When the aromatic diamine is selected from the above two or more kinds of diamines, the ratio of the aromatic diamine to the aromatic diamine can be arbitrarily determined.
The tetracarboxylic dianhydride may be one or a combination of any two or more selected from pyromellitic dianhydride (PMDA), 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3 ', 4' -biphenyltetracarboxylic dianhydride (a-BPDA), 3,3 ', 4, 4' -diphenylethertetracarboxylic dianhydride (ODPA), 2,3,3 ', 4' -diphenylethertetracarboxylic dianhydride, 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride (BTDA), and 2,3,3 ', 4' -benzophenonetetracarboxylic dianhydride. When the tetracarboxylic dianhydride is selected from the above two or more kinds of combinations, the ratio of the tetracarboxylic dianhydride to the tetracarboxylic dianhydride can be any ratio.
The molar ratio of the aromatic diamine to the tetracarboxylic dianhydride may be 0.9 to 1.1: 1, preferably 0.95-1.05: 1, more preferably 0.99 to 1.01: 1; the temperature of the polycondensation reaction can be 0-80 ℃, preferably 0-60 ℃, more preferably 0-50 ℃, and the reaction time is usually 3-12 h. When the tetracarboxylic dianhydride and the aromatic diamine are added for reaction, the tetracarboxylic dianhydride is preferably added in batches, so that the reaction is more uniform and more complete.
The polar aprotic solvent may be one or a combination of any two or more selected from N, N-Dimethylacetamide (DMAC), N-Dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), N-diethylacetamide and N, N-diethylformamide; when the polar aprotic solvent is selected from the above-mentioned two or more kinds of combinations, the ratio therebetween may be any ratio. The amount of the polar aprotic solvent may be, specifically, 8 to 30 w/w%, preferably 10 to 25 w/w%, and more preferably 15 to 21 w/w% of the solid content in the polyamic acid resin solution when the aromatic diamine, the tetracarboxylic dianhydride, and the polar aprotic solvent react to form the polyamic acid resin solution.
In step 2) of the above preparation method, the hydrophilic particles may be dispersed in the polar aprotic solvent by using conventional methods and apparatuses, for example, by using a homogenizer, a grinder, a sand mill, an emulsifying machine, or an ultrasonic dispersing machine. The hydrophilic particles can be dispersed in part of the polar aprotic solvent, and then the rest of the polar aprotic solvent is added and uniformly mixed; the hydrophilic particles may also be dispersed in the entire amount of polar aprotic solvent at once.
In step 2) of the above preparation method, silicon oxide (SiO) is selected2) In the case of the hydrophilic particles, it is preferable to use silicon oxide having an average particle diameter of 10 to 500nm, more preferably silicon oxide having an average particle diameter of 100nm or less, and still more preferably silicon oxide having an average particle diameter of 50nm or less. In the selection of titanium oxide (TiO)2) In the case of the hydrophilic particles, titanium oxide having an average particle diameter of 10 to 500nm is preferably used, more preferably titanium oxide having an average particle diameter of 100nm or less, and still more preferably titanium oxide having an average particle diameter of 50nm or less. When the hydrophilic particles are selected from the combination of silicon oxide and titanium oxide, the proportion of the silicon oxide and the titanium oxide can be any proportion under the premise that the total addition amount accounts for 0.1-10 w/w% of the solid content of the obtained composite solution. The addition amount of the hydrophilic particles is preferably 0.2-3 w/w% of the solid content of the obtained composite solution, and is further preferably 0.3-2 w/w% of the solid content of the obtained composite solution.
In the step 2) of the preparation method, the stability of the composite solution can be effectively controlled by controlling the viscosity of the composite solution, the hydrophilic particles are uniformly dispersed in the composite solution, and the uniform coating thickness can be obtained when the composite solution is coated on the surface of the polyamic acid film, so that the consistency of various performances of the film and the appearance smoothness are ensured. The amount of the polar aprotic solvent is preferably controlled so that the viscosity of the obtained composite solution is 50 to 5000 mPas, and more preferably controlled so that the viscosity of the obtained composite solution is 100 to 1500 mPas.
In step 2) of the above preparation method, the selection of the aromatic diamine, the tetracarboxylic dianhydride and the polar aprotic solvent is the same as in step 1), and the amounts of the aromatic diamine and the tetracarboxylic dianhydride used are also the same as in step 1).
In step 3) of the above preparation method, the obtained polyamic acid composite solution containing hydrophilic particles is generally coated on the upper and lower surfaces of the polyamic acid film, and the coating thickness is preferably controlled to be 50 to 1000nm (coating amount is about 0.07 to 1.6 g/m)2) (ii) a Preferably, the coating thickness of the upper and lower surfaces of the polyamic acid film is the same, and the coating process is the same. The coating of the hydrophilic particle-containing polyamic acid composite solution may be performed by a conventional coating method, such as a known coating method, for example, a printing method, a spray coating method, a dipping method, a bar coating method, a roll coating method, or a blade coating method. The operations of stretching, thermal imidization, etc. after coating are the same as the prior art.
Compared with the prior art, the method has the advantages that the coating containing the hydrophilic inorganic particles is coated on the surface of the polyamic acid film, the adding amount of the hydrophilic particles can be increased to 10% of the solid content of the polyamic acid composite solution, the hydrophilic angle of the surface of the obtained PI film is reduced from 85 degrees to below 45 degrees, dust adsorption is effectively prevented, the insulativity of the original PI film is maintained, the electrical strength is more than or equal to 320kV/mm, and the surface resistivity is more than or equal to 10 DEG16Omega, volume resistivity is more than or equal to 1013Omega.m, the hygroscopicity is less than 2 percent, and the original transparency of the PI film is not changed.
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
Example 1
1) Adding 4kg of ODA into 47.3kg of DMAc, stirring until the ODA is completely dissolved, adding 2.5kg of PMDA, reacting for 1 hour, adding 1.5kg of PMDA, reacting for 1 hour, adding 0.34kg of PMDA, and reacting for 5 hours to obtain a polyamic acid resin solution; defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, and heating (155 ℃) to remove the solvent to obtain a polyamic acid (PAA) film;
2) dispersing 8.3g of silicon oxide (with the average particle size of 15nm) in 47.3kg of DMAc, dispersing into a suspension by using a homogenizer, then adding 4kg of ODA into the suspension, stirring until the silicon oxide is completely dissolved, adding 2.5kg of PMDA, reacting for 1 hour, adding 1.5kg of PMDA, reacting for 1 hour, adding 0.34kg of PMDA, reacting for 5 hours, diluting the obtained solution with DMAc, and uniformly stirring to obtain a polyamide acid composite solution containing hydrophilic particles and having the viscosity of 1000 mPas;
3) and (3) coating the obtained polyamide acid composite solution containing hydrophilic particles on a PAA film by adopting a roll coating method (the thickness of the coating is controlled to be 300nm), and then performing unidirectional stretching and thermal imidization at 400 ℃ to obtain the antistatic adsorption PI film with the thickness of the coating of 300 nm.
Example 2
Example 1 was repeated except that: the amount of silica added in step 2) was 41.5 g.
Example 3
Adding 4kg of ODA into 47.4kg of DMAc, stirring until the ODA is completely dissolved, adding 2.5kg of PMDA, reacting for 1 hour, adding 1.5kg of PMDA, reacting for 1 hour, adding 0.37kg of PMDA, and reacting for 5 hours to obtain a polyamic acid resin solution; defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, and heating (155 ℃) to remove the solvent to obtain a PAA film;
the remaining steps example 1 was repeated except that: the amount of silica added in step 2) was 83 g.
Example 4
Example 1 was repeated except that: the solvent in step 1) was DMF and the amount of silica added in step 2) was 249 g.
Example 5
1) Adding 4kg of ODA into 47.3kg of NMP, stirring until the ODA is completely dissolved, adding 2.5kg of PMDA, reacting for 1 hour, adding 1.5kg of PMDA, reacting for 1 hour, adding 0.34kg of PMDA, and reacting for 5 hours to obtain a polyamic acid resin solution; defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, and heating (155 ℃) to remove the solvent to obtain a PAA film;
2) dispersing 926g of silicon oxide (with the average particle size of 15nm) in 53kg of DMAc, dispersing into suspension by using a homogenizer, adding 4kg of ODA, stirring until the silicon oxide is completely dissolved, adding 3.1kg of ODPA, reacting for 1 hour, adding 2kg of PMDA, reacting for 1 hour, finally adding 0.16kg of PMDA, reacting for 5 hours, diluting the obtained solution with DMAc, and stirring uniformly to obtain a polyamic acid composite solution containing hydrophilic particles and having the viscosity of 10000 mPas;
3) and coating the obtained polyamide acid composite solution containing hydrophilic particles on a PAA film by adopting a blade coating method, and then performing unidirectional stretching and thermal imidization at 400 ℃ to obtain the anti-static adsorption PI film with the coating thickness of 300 nm.
Example 6
Example 1 was repeated except that: in step 2), the hydrophilic particles were a combination of silica and titania, wherein the amount of silica added was 30g and the amount of titania (average particle diameter of 20nm) added was 11.5 g.
Example 7
Example 2 was repeated except that: in step 2), the average particle diameter of the silica was 100 nm.
Example 8
Adding 4kg of ODA into 47.5kg of DMAc, stirring until the ODA is completely dissolved, adding 2.5kg of PMDA, reacting for 1 hour, adding 1.5kg of PMDA, reacting for 1 hour, adding 0.38kg of PMDA, and reacting for 5 hours to obtain a polyamic acid resin solution; defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, and heating (155 ℃) to remove the solvent to obtain a PAA film;
the remaining steps example 2 was repeated except that: in step 2), the average particle diameter of the silica was 500 nm.
Example 9
Example 2 was repeated except that:
in the step 2), the viscosity of the polyamic acid composite solution containing the hydrophilic particles is controlled to be 10mPa & s;
in the step 3), the coating method is a spraying method, and the coating thickness is 50 nm.
Example 10
Example 2 was repeated except that:
in the step 1), a solvent is DMAc + DMF;
in the step 2), the viscosity of the polyamic acid composite solution containing the hydrophilic particles is controlled to be 10mPa & s;
in the step 3), the coating method is a dip coating method, and the coating thickness is 1 um.
Example 11
Example 2 was repeated except that:
in the step 1), 96kg of DMAc + NMP is used as a solvent;
in the step 3), the coating method is a spraying method.
Example 12
Adding 4kg of ODA into 28.5kg of DMAc, stirring until the ODA is completely dissolved, adding 0.62kg of ODPA, reacting for 1 hour, adding 3kg of PMDA, reacting for 1 hour, finally adding 0.88kg of PMDA, and reacting for 5 hours to obtain a polyamic acid resin solution; defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, and heating (155 ℃) to remove the solvent to obtain a PAA film;
example 2 was repeated for the remaining steps.
Example 13
Adding 3.2kg of ODA and 0.68kg of DBZ into 47kg of DMAc, stirring for 1h, adding 2.5kg of PMDA, reacting for 1h, adding 1.5kg of PMDA, reacting for 1h, adding 0.34kg of PMDA, and reacting for 5h to obtain a polyamic acid resin solution; defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, and heating (155 ℃) to remove the solvent to obtain a PAA film;
example 2 was repeated for the remaining steps.
Example 14
Adding 3.6kg of ODA and 0.34kg of OTD into 47kg of DMAc, stirring for 1h, adding 2.5kg of PMDA, reacting for 1h, adding 1.5kg of PMDA, reacting for 1h, adding 0.34kg of PMDA, and reacting for 5h to obtain a polyamic acid resin solution; defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, and heating (155 ℃) to remove the solvent to obtain a PAA film;
example 2 was repeated for the remaining steps.
Example 15
Example 2 was repeated except that: in step 2), the hydrophilic particles were titanium oxide (average particle diameter 20nm) and added in an amount of 41.5 g.
Example 16
Example 15 was repeated except that: step 2) is prepared according to the following method:
40g of titanium oxide (average particle diameter of 30nm) was dispersed in 46kg of DMAc, and dispersed into a suspension by a homogenizer, 3.26kg of ODA and 0.2kg of PDA were added, and after stirring for 1 hour, 2.66kg of BPDA was added, reaction was carried out for 1 hour, 1.95kg of PMDA was added, reaction was carried out for 5 hours, the resulting solution was diluted with DMAc, and after stirring uniformly, a polyamic acid composite solution containing hydrophilic particles having a viscosity of 1000 mPas was obtained.
Example 17
Example 15 was repeated except that: the average particle diameter of the titanium oxide in the step 2) was 100 nm.
Example 18
Example 15 was repeated except that: the thickness of the coating in the step 3) is controlled to be 500 nm.
Example 19
Example 15 was repeated except that:
in the step 2), the adding amount of the titanium oxide is 166 g;
in step 3), the coating thickness was controlled to 200 nm.
Example 20
1) Adding 3.2kg of ODA and 0.68kg of MTD into 46kg of DMAc, stirring for 1h, adding 0.84kg of BTDA, reacting for 1h, adding 3kg of PMDA, reacting for 1h, adding 0.47kg of PMDA, and reacting for 5h to obtain a polyamic acid resin solution; defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, and heating (155 ℃) to remove the solvent to obtain a PAA film;
2) dispersing 664g of titanium oxide (with the average particle size of 20nm) in 47.3kg of DMAc, dispersing into a suspension by using a homogenizer, then adding 4kg of ODA into the suspension, stirring until the titanium oxide is completely dissolved, adding 2.5kg of PMDA, reacting for 1 hour, adding 1.5kg of PMDA, reacting for 1 hour, adding 0.34kg of PMDA, reacting for 5 hours, diluting the obtained solution with DMAc, and uniformly stirring to obtain a polyamide acid composite solution containing hydrophilic particles and having the viscosity of 1000 mPas;
3) and (3) coating the obtained polyamide acid composite solution containing hydrophilic particles on a PAA film by adopting a roll coating method (the thickness of the coating is controlled to be 200nm), and then performing unidirectional stretching and thermal imidization at 400 ℃ to obtain the antistatic adsorption PI film with the thickness of 200 nm.
Example 21
Adding 2.32kg of ODA and 0.84kg of PDA into 18.5kg of DMAc, stirring for 1h, adding 2.84kg of BPDA, reacting for 1h, adding 1.9kg of PMDA, and reacting for 5h to obtain a polyamic acid resin solution; defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, and heating (155 ℃) to remove the solvent to obtain a PAA film;
the remaining steps repeat example 15.
Comparative example 1
Example 1 was repeated except that the coating of the composite solution was not performed.
Comparative example 2
Example 1 was repeated except that the amount of silica added was 996 g.
Comparative example 3
Example 1 was repeated, except that the amount of silica added was 4.1 g.
Comparative example 4
Example 1 was repeated, except that the coating thickness was 40 nm.
Comparative example 5
Example 1 was repeated, except that the coating thickness was 1200 nm.
The compounding ratio data, coating method and coating thickness of the above examples and comparative examples are collated as shown in table 1 below.
Table 1:
the PI films obtained in the above examples and comparative examples were measured for properties such as hydrophilic angle, moisture absorption, electrical strength, surface resistivity, volume resistivity, and tensile strength, and the results are shown in table 2 below:
table 2:
Claims (6)
1. the preparation method of the anti-electrostatic adsorption imide film comprises the following steps:
1) preparing a polyamic acid film;
2) preparing a polyamic acid composite solution containing hydrophilic particles, which specifically comprises the following steps: uniformly dispersing hydrophilic particles in a polar aprotic solvent, and then adding aromatic diamine and tetracarboxylic dianhydride to react to prepare a polyamic acid composite solution containing the hydrophilic particles; wherein the content of the first and second substances,
the hydrophilic particles are silicon oxide and/or titanium oxide, and the addition amount of the hydrophilic particles is 0.1-10 w/w% of the solid content of the obtained composite solution; the dosage of the polar aprotic solvent is controlled so that the viscosity of the obtained composite solution is 10-10000 mPa & s;
3) and coating the polyamide acid composite solution containing the hydrophilic particles on the upper surface and the lower surface of the polyamide acid film, preferably controlling the thickness of the coating to be 50-1000 nm, and then stretching and thermally imidizing to obtain the anti-electrostatic adsorption polyimide film.
2. The method of claim 1, wherein: in the step 2), the adding amount of the hydrophilic particles is 0.2-3 w/w% of the solid content of the obtained composite solution.
3. The method of claim 1, wherein: in the step 2), the adding amount of the hydrophilic particles is 0.3-2 w/w% of the solid content of the obtained composite solution.
4. The method of claim 1, wherein: in the step 2), the dosage of the polar aprotic solvent is controlled so that the viscosity of the obtained composite solution is 50-5000 mPa & s.
5. The method of claim 1, wherein: in the step 2), the dosage of the polar aprotic solvent is controlled to control the viscosity of the obtained composite solution to be 100-1500 mPa & s.
6. The production method according to any one of claims 1 to 5, characterized in that: in the step 2), the polar aprotic solvent is one or a combination of any two or more selected from N, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, N-diethylacetamide and N, N-diethylformamide.
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