CN111113754A - Method for improving edge strength of polyamide acid film - Google Patents
Method for improving edge strength of polyamide acid film Download PDFInfo
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- CN111113754A CN111113754A CN201911154030.7A CN201911154030A CN111113754A CN 111113754 A CN111113754 A CN 111113754A CN 201911154030 A CN201911154030 A CN 201911154030A CN 111113754 A CN111113754 A CN 111113754A
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- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
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- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses a method for improving the edge strength of a polyamic acid film, which comprises the step of casting a defoamed polyamic acid resin solution to form the film, and the step is as follows: coating a coating liquid on a specific area of a support body, and then casting the defoamed polyamic acid resin solution onto the support body to form a film; wherein: the coating liquid comprises the following components in parts by weight: 70-90 parts of aprotic polar solvent, 0-30 parts of DMP-3010, 0.1-1 part of tri-primary amine crosslinking agent and 0.5-2 parts of triphenyl phosphite. The coating liquid is coated in a specific area by combining the coating liquid with a specific ratio, so that the imidization degree of the edge of the obtained polyamic acid gel film is effectively improved, the mechanical property of the edge is enhanced, the times of edge breaking and film breaking caused by edge abnormity in the processes of longitudinal stretching, transverse stretching, imidization and the like are effectively reduced, and the yield is improved.
Description
Technical Field
The invention relates to a polyimide film, in particular to a method for improving the edge strength of a polyamic acid film.
Background
When the biaxially oriented polyimide film for a Flexible Copper Clad Laminate (FCCL) is prepared, usually, a polyamic acid resin solution with a certain viscosity is extruded from a continuously running support (ring) through a die head to form a smooth liquid film, the smooth liquid film is heated, reacted and dried in a furnace body along with the support, and then peeled from the support to obtain a gel film (i.e., a polyamic acid film, also called a self-supporting film), the obtained gel film is conveyed to a metal roller for longitudinal stretching, then two transverse sides (two sides in the width direction of the gel film) of the gel film are fixed by pins or metal clips, and the like, the gel film is continuously conveyed into a heating furnace for transverse stretching and high-temperature imidization, the imidized film is shaped to eliminate stress, and finally the biaxially oriented polyimide film with high performance is obtained.
When the gel film is longitudinally stretched, transversely stretched, imidized or shaped, pins or metal clips or other devices are needed to fix two side edges of the gel film, so that the phenomenon that the width of the film is reduced due to shrinkage deformation towards the center is avoided, and transverse stretching is carried out at the same time. When the polyamide acid gel film is clamped at the transverse pulling inlet, the polyamide acid gel film is easy to be broken or cracked due to higher temperature, and the edge or the film is easy to be broken due to the defect of the clamping position during subsequent stretching, imidization and sizing, so that the production yield of the film is influenced. Even if the prior art reduces the temperature of the pin or the metal clip by additionally arranging the cold air device, the gel film is not completely imidized and is subsequently required to be stretched, imidized and shaped in a heating furnace at 100-500 ℃, so that the edge part of the gel film clamped by the pin or the metal clip is still easy to generate defects, and the edge breaking and the film breaking can not be avoided.
In the actual production process, the proper solvent content of the lateral edges is controlled by adjusting the thickness of the lateral edges of the gel film, so that the production continuity of the polyimide film can be effectively improved. However, the solvent content of the gel film is easily changed by the stability of the production equipment, thickness fluctuation and other factors during the production process, so that the production is unstable. When the resin is extruded from the die and falls on the support, the thickness of the part of the prepared gel film extending to the center of the gel film within a certain transverse distance (usually about 4 mm) from the boundary parallel to the length direction of the support is thicker due to contraction of the edge of the resin curtain, so that the edge of the gel film is crisp or the strength is insufficient during longitudinal stretching, and the film is torn, torn or broken, thereby affecting the production yield. In the invention of patent publication No. CN104479156A, 20-200 mm of the side portion of a polyamic acid film peeled from a steel strip is subjected to rapid local heating treatment at 150-200 ℃ by using an up-and-down heating tube before being transversely pulled, thereby reducing the solvent content, improving the edge strength and finally improving the film yield. However, the yield of the polyamic acid resin film with large molecular structure rigidity is not greatly improved because the temperature is 150-200 ℃ which is a temperature region with severe thermal degradation of the polyamic acid.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for improving the edge strength of a polyamic acid film by coating a coating liquid on a support to increase the imidization degree of two sides of the obtained gel film in the transverse direction.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for improving the edge strength of a polyamic acid film comprises the step of casting the defoamed polyamic acid resin solution to form the film, wherein the step of casting the defoamed polyamic acid resin solution to form the film comprises the following steps: coating a coating liquid on a support body, and then casting the defoamed polyamic acid resin solution onto the support body to form a film; wherein:
the coating liquid comprises the following components in parts by weight: 70-90 parts of aprotic polar solvent, 10-30 parts of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), 0.1-1 part of tri-primary amine crosslinking agent and 0.5-2 parts of triphenyl phosphite; the tri-primary amine cross-linking agent is one or the combination of more than two of 1,3, 5-tri (4-aminophenoxy) benzene and derivatives thereof;
the areas where the coating liquid was applied on the support were: taking the boundary of a liquid film formed by the defoamed polyamic acid resin solution which drools to the support body and is parallel to the length direction of the support body as a base line, taking a line segment obtained by offsetting the base line by 3-5 cm towards the longitudinal center line of the liquid film as a first line segment, taking a line segment obtained by offsetting the base line by 1-2 cm towards the direction far away from the liquid film as a second line segment, and mutually connecting end points of the two line segments positioned at the same side, so that the surrounded area is the area needing coating liquid.
According to the invention, the coating liquid with a specific ratio is coated on a specific area, so that the imidization degree of the edge of the obtained polyamic acid gel film is effectively improved, the mechanical property of the edge is enhanced, and the problem of low yield caused by edge abnormity in the processes of longitudinal stretching, transverse stretching, imidization and the like is solved. In the composition of the coating liquid with a specific ratio, 2,4, 6-tris (dimethylaminomethyl) phenol is selected as a catalyst, and the imidization ring-closing reaction of the polyamic acid resin can be effectively accelerated when the polyamic acid resin is heated, so that the imidization rate of the skeleton polyamic acid is improved, and the polyamic acid resin is not easy to degrade when being heated; secondly, the selected tri-primary amine cross-linking agent enables the polyamic acid polymer to generate cross-linking reaction with small molecules in the process of salivating to remove the solvent, thereby avoiding the problem of poor mechanical property caused by the rapid reduction of molecular weight when the polyamic acid resin is degraded by heating. Both play the effect that increases gel membrane limit intensity, make limit portion difficult for producing the defect in the twinkling of an eye receiving the centre gripping of hot chain pincers or even hot melt wear or the scheduling problem of season cracking, also improve limit portion gel membrane simultaneously and be unfavorable for the shortcoming of imidization because of the sheltering from of chain clamp in horizontal drawing drying tunnel, improved polyimide film production yield greatly.
In the method of the present invention, the derivative of 1,3, 5-tris (4-aminophenoxy) benzene may be specifically one or a combination of two selected from the following formulae (1) to (3):
in the method of the present invention, the composition of the coating liquid is preferably: 75-85 parts of aprotic polar solvent, 15-25 parts of 2,4, 6-tris (dimethylaminomethyl) phenol, 0.2-0.8 part of tri-primary amine crosslinking agent and 0.8-1.5 parts of triphenyl phosphite. The coating liquid should be uniformly brushed when coating, and the coating amount of the coating liquid is preferably 0.001-0.005 g/cm2。
In the method of the present invention, the aprotic polar solvent may be a conventional solvent in the prior art, and specifically 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.
In the method of the invention, the defoamed polyamic acid resin solution is obtained by defoaming the polyamic acid resin solution according to a conventional process. The polyamic acid resin solution is prepared by putting diamine and dianhydride into an aprotic polar solvent and performing polycondensation reaction, which is the same as the prior art. Wherein, the selection and the dosage of the diamine, the dianhydride and the aprotic polar solvent are the same as those of the prior art, and the temperature and the time of the polycondensation reaction are also the same as those of the prior art. The following are preferred:
the diamine may be one or a combination of two or more selected from 4,4 '-diaminodiphenyl ether (ODA), 3, 4' -diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, and biphenyldiamine. When the diamine is selected from the above two or more kinds, the ratio of the diamine to the diamine may be arbitrarily selected.
The 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), 2,3,3 ', 4' -diphenylethertetracarboxylic dianhydride, and 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride (BTDA). When the dianhydride is selected from a combination of two or more of the above, the ratio of the dianhydride to the dianhydride may be any ratio.
The choice of the aprotic polar solvent is the same as previously described.
The molar ratio of the total amount of diamine to dianhydride used is generally 1: 0.8 to 1.02, more preferably 1: 0.99 to 1.01; the reaction temperature can be 0-80 ℃, preferably 0-60 ℃, more preferably 0-50 ℃, and the reaction time is usually 5-40 h.
Compared with the prior art, the method is characterized in that: the coating liquid with a specific ratio is combined with a specific area to coat the coating liquid, so that the imidization degree of the edge of the obtained polyamic acid gel film is effectively improved, the mechanical property of the edge is enhanced, the times of edge breaking and film breaking caused by edge abnormity in the processes of longitudinal stretching, transverse stretching, imidization and the like are effectively reduced, and the yield is improved.
Drawings
Fig. 1 is a schematic view of a region where a coating liquid is required to be applied in the method of the present invention.
The reference numbers in the figures are:
1 polyamic acid gel film, 2 steel belt, 3 second line segment, 4 boundary (base line) parallel to the length direction of the steel belt of the liquid film formed on the steel belt after defoaming, 5 first line segment, x1 represents the distance of the base line towards the direction far away from the liquid film, and x2 represents the distance of the base line towards the longitudinal center line of the liquid film.
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.
The parts referred to in the following examples are parts by weight.
Example 1
1) Weighing the components according to the following weight ratio, and uniformly mixing and stirring to obtain a coating liquid;
80 parts of DMAC (dimethyl acetamide), 3020 parts of DMP-3020 parts of 1,3, 5-tris (4-aminophenoxy) benzene and 1 part of triphenyl phosphite;
2) adding 22kg of ODA, 11.3kg of PDA and 320kg of DMAC into a reaction kettle, dissolving, adding 46.5kg of PMDA (adding in 3 times), reacting for 5 hours at normal temperature to obtain a polyamic acid resin solution with the viscosity of 20 ten thousand centipoise, and conveying the polyamic acid resin solution to a defoaming kettle for defoaming to obtain the defoamed polyamic acid resin solution;
3) setting the temperature of a casting upper drying tunnel to be 180 ℃ and the temperature of a lower drying tunnel to be 190 ℃, firstly coating a coating liquid on a steel strip, casting the defoamed polyamic acid resin solution onto the steel strip (namely, in the whole casting process, before the resin solution falls onto the steel strip each time, coating of the coating liquid is finished in a corresponding area), and removing 72% of a solvent in a casting furnace to obtain a polyamic acid gel film; wherein:
the coating amount of the coating liquid was 0.002g/cm2The areas where the coating liquid is applied are: taking the boundary of a liquid film formed by casting the defoamed polyamic acid resin solution onto a steel belt, which is parallel to the length direction of the steel belt, as a base line, taking a line segment obtained by shifting the base line towards the longitudinal center line of the liquid film by 4cm (namely, the shifting distance of the base line towards the longitudinal center line of the liquid film is 4cm) as a first line segment, taking a line segment obtained by shifting the base line towards the direction away from the liquid film by 2cm (namely, the shifting distance of the base line towards the direction away from the liquid film is 2cm) as a second line segment, and mutually connecting end points of the two line segments positioned on the same side to obtain a third line segment and a fourth line segment, wherein a region surrounded by the first line segment, the second line segment, the third line segment and the fourth line segment is a region needing coating liquid, and is specifically shown as a; in fig. 1, 1 is a polyamic acid gel film, 2 is a steel belt, 3 is a second line segment, 4 is a boundary (i.e., a base line) parallel to the length direction of the steel belt of a liquid film formed by casting a defoamed polyamic acid resin solution onto the steel belt, 5 is a first line segment, x1 is a distance by which the base line is shifted toward a direction away from the liquid film, and x2 is a distance by which the base line is shifted toward the longitudinal centerline of the liquid film;
4) the polyamic acid gel film is peeled from the steel belt, longitudinally stretched at a stretch ratio of 5% (120 ℃) and then sent into an imine furnace, and then is preheated (150 ℃), transversely stretched (180 ℃) and 300 ℃) at a stretch ratio of 5%), imidized (400-550 ℃) and shaped (350 ℃) to obtain the polyimide film with the thickness of 13 mu m.
The imidization rate of the side portion (i.e., the portion coated with the coating liquid) of the polyamic acid gel film obtained in step 3) of this example, and the mechanical properties such as tensile strength and elongation at break were measured, and the results are shown in table 1 below.
The number of broken edges and total broken film, yield and yield in the case of continuous production for 10 days according to the method of this example were counted and shown in Table 1 below.
Comparative example 1
Example 1 was repeated except that:
step 1) is omitted, and in step 3), the coating liquid is not coated on the steel belt, but the defoamed polyamic acid resin solution is directly cast on the steel belt, and the rest is not changed.
The imidization rate of the side portion (i.e., the portion coated with the coating liquid) of the polyamic acid gel film obtained in this comparative example, and the mechanical properties such as tensile strength and elongation at break were measured, and the results are shown in table 1 below.
The number of broken edges and the total number of broken films, yields and yields in the case of continuous production for 10 days by the method described in this comparative example were counted, respectively, and the results are shown in Table 1 below.
Example 2
1) Weighing the components according to the following weight ratio, and uniformly mixing and stirring to obtain a coating liquid;
70 parts of DMF (dimethyl formamide), 3015 parts of DMP (dimethyl formamide), 1 part of a tri-primary amine crosslinking agent shown in a formula (1) and 0.5 part of triphenyl phosphite;
2) adding 21.5kg of p-phenylenediamine and 320kg of DMF (dimethyl formamide) into a reaction kettle, dissolving, adding 58.7kg of BPDA (added in 3 times), reacting for 8 hours at normal temperature to obtain a polyamic acid resin solution with the viscosity of 20 ten thousand centipoise, and conveying the polyamic acid resin solution to a defoaming kettle for defoaming to obtain a defoamed polyamic acid resin solution;
3) setting the temperature of a casting upper drying tunnel at 160 ℃ and the temperature of a lower drying tunnel at 170 ℃, firstly coating a coating liquid on a steel belt, casting the defoamed polyamic acid resin solution on the steel belt, and removing 69% of solvent in a casting furnace to obtain a polyamic acid gel film; wherein:
the coating amount of the coating liquid was 0.003g/cm2The areas where the coating liquid is applied are: taking the boundary of a liquid film formed by casting the defoamed polyamic acid resin solution onto a steel belt, which is parallel to the length direction of the steel belt, as a base line, taking a line segment obtained by offsetting the base line by 5cm towards the longitudinal center line of the liquid film as a first line segment, taking a line segment obtained by offsetting the base line by 1cm towards the direction far away from the liquid film as a second line segment, mutually connecting end points of the two line segments positioned at the same side to obtain a third line segment and a fourth line segment, wherein the area enclosed by the first line segment, the second line segment, the third line segment and the fourth line segment is the area needing coating liquid;
4) the same as in example 1.
The imidization rate of the side portion (i.e., the portion coated with the coating liquid) of the polyamic acid gel film obtained in step 3) of this example, and the mechanical properties such as tensile strength and elongation at break were measured, and the results are shown in table 1 below.
The number of broken edges and total broken film, yield and yield in the case of continuous production for 10 days according to the method of this example were counted and shown in Table 1 below.
Example 3
Example 1 was repeated except that: in the step 1), the dosage of the DMP-30 is changed to 10 parts.
The imidization rate of the side portion (i.e., the portion coated with the coating liquid) of the polyamic acid gel film obtained in step 3) of this example, and the mechanical properties such as tensile strength and elongation at break were measured, and the results are shown in table 1 below.
The number of broken edges and total broken film, yield and yield in the case of continuous production for 10 days according to the method of this example were counted and shown in Table 1 below.
Example 4
Example 1 was repeated except that: in the step 1), the dosage of DMP-30 is 30 parts, and the dosage of triphenyl phosphite is changed to 2 parts.
The imidization rate of the side portion (i.e., the portion coated with the coating liquid) of the polyamic acid gel film obtained in step 3) of this example, and the mechanical properties such as tensile strength and elongation at break were measured, and the results are shown in table 1 below.
The number of broken edges and total broken film, yield and yield in the case of continuous production for 10 days according to the method of this example were counted and shown in Table 1 below.
Example 5
Example 1 was repeated except that: in the step 1), the amount of 1,3, 5-tris (4-aminophenoxy) benzene was changed to 1 part, and the amount of triphenyl phosphite was changed to 2 parts.
The imidization rate of the side portion (i.e., the portion coated with the coating liquid) of the polyamic acid gel film obtained in step 3) of this example, and the mechanical properties such as tensile strength and elongation at break were measured, and the results are shown in table 1 below.
The number of broken edges and total broken film, yield and yield in the case of continuous production for 10 days according to the method of this example were counted and shown in Table 1 below.
Example 6
Example 1 was repeated except that: in the step 1), the dosage of 1,3, 5-tri (4-aminophenoxy) benzene is changed to 0.1 part; the areas where the coating liquid was applied were: taking the boundary of a liquid film formed on a steel belt by casting the defoamed polyamic acid resin solution to be parallel to the length direction of the steel belt as a base line, taking a line segment obtained by shifting the base line by 3cm towards the longitudinal center line of the liquid film (namely, the shifting distance of the base line towards the longitudinal center line of the liquid film is 3cm) as a first line segment, taking a line segment obtained by shifting the base line by 1.5cm towards the direction away from the liquid film (namely, the shifting distance of the base line towards the direction away from the liquid film is 1.5cm) as a second line segment, mutually connecting end points of the two line segments positioned on the same side to obtain a third line segment and a fourth line segment, and taking the area surrounded by the first line segment, the second line segment, the third line segment and the fourth line segment as an area needing coating liquid.
The imidization rate of the side portion (i.e., the portion coated with the coating liquid) of the polyamic acid gel film obtained in step 3) of this example, and the mechanical properties such as tensile strength and elongation at break were measured, and the results are shown in table 1 below.
The number of broken edges and total broken film, yield and yield in the case of continuous production for 10 days according to the method of this example were counted and shown in Table 1 below.
Example 7
Example 1 was repeated except that: in the step 1), the solvent is changed into NMP, and the dosage is changed into 90 parts.
The imidization rate of the side portion (i.e., the portion coated with the coating liquid) of the polyamic acid gel film obtained in step 3) of this example, and the mechanical properties such as tensile strength and elongation at break were measured, and the results are shown in table 1 below.
The number of broken edges and total broken film, yield and yield in the case of continuous production for 10 days according to the method of this example were counted and shown in Table 1 below.
Example 8
Example 1 was repeated except that: in the step 1), the crosslinking agent is changed into a tri-primary amine crosslinking agent shown in the formula (3) (the dosage is unchanged), and the coating amount is changed into 0.001g/cm2。
The imidization rate of the side portion (i.e., the portion coated with the coating liquid) of the polyamic acid gel film obtained in step 3) of this example, and the mechanical properties such as tensile strength and elongation at break were measured, and the results are shown in table 1 below.
The number of broken edges and total broken film, yield and yield in the case of continuous production for 10 days according to the method of this example were counted and shown in Table 1 below.
TABLE 1
As can be seen from table 1, the imidization degree and the mechanical strength of the polyamic acid film can be significantly improved by the method of the present invention, the number of broken edges during longitudinal stretching, transverse stretching and imidization can be reduced, and the yield of the polyimide film can be improved.
Claims (5)
1. A method for improving the edge strength of a polyamic acid film comprises the step of casting a defoamed polyamic acid resin solution to form the film, and is characterized in that: the step of casting the defoamed polyamic acid resin solution to form a membrane comprises the following steps: coating a coating liquid on a support body, and then casting the defoamed polyamic acid resin solution onto the support body to form a film; wherein:
the coating liquid comprises the following components in parts by weight: 70-90 parts of aprotic polar solvent, 10-30 parts of 2,4, 6-tris (dimethylaminomethyl) phenol, 0.1-1 part of tri-primary amine crosslinking agent and 0.5-2 parts of triphenyl phosphite; the tri-primary amine cross-linking agent is one or the combination of more than two of 1,3, 5-tri (4-aminophenoxy) benzene and derivatives thereof;
the areas where the coating liquid was applied on the support were: taking the boundary of a liquid film formed by the defoamed polyamic acid resin solution which drools to the support body and is parallel to the length direction of the support body as a base line, taking a line segment obtained by offsetting the base line by 3-5 cm towards the longitudinal center line of the liquid film as a first line segment, taking a line segment obtained by offsetting the base line by 1-2 cm towards the direction far away from the liquid film as a second line segment, and mutually connecting end points of the two line segments positioned at the same side, so that the surrounded area is the area needing coating liquid.
2. The method of claim 1, wherein: the derivative of the 1,3, 5-tri (4-aminophenoxy) benzene is one or a combination of two selected from the following formulas (1) to (3):
3. the method of claim 1, wherein: the coating liquid comprises the following components: 75-85 parts of aprotic polar solvent, 15-25 parts of 2,4, 6-tris (dimethylaminomethyl) phenol, 0.2-0.8 part of tri-primary amine crosslinking agent and 0.8-1.5 parts of triphenyl phosphite.
4. The method according to any one of claims 1 to 3, wherein: the coating amount of the coating liquid is 0.001 to 0.005g/cm2。
5. The method according to any one of claims 1 to 3, wherein: the aprotic polar solvent is one or the combination of more than two of N, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, N-diethylacetamide and N, N-diethylformamide.
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