TWI439508B - Polyamide acid composition, polyimide and polyimide film, and the like - Google Patents

Description

Polylysine composition, polyimine and polyimine film, and manufacturing method thereof

The present invention relates to a polyaminic acid composition using a specific ratio of a specific diamine component and a specific tetracarboxylic acid component; the present invention also relates to a polyimine which is obtained by hardening the polyaminic acid composition. .

The polyimine composition obtained by condensation copolymerization and hardening of an aromatic tetracarboxylic dianhydride and an aromatic diamine, wherein the polyimine film is excellent in electrical insulating properties and heat resistance, etc. It is applied to the use of electronic substrate materials such as flexible printed circuits (hereinafter referred to as FPC). The FPC is manufactured by laminating a polyimide film and a copper foil with an adhesive (such as an epoxy resin) to form a copper clad laminate (hereinafter referred to as CCL), and then providing a circuit on the copper foil. to make. Recently, due to the development of thinning, miniaturization, miniaturization, and assembly of electronic devices, the demand for high processability and high precision of substrate materials has increased, and the properties of polyimine films have also required high flexibility. Rate, high dimensional stability, low thermal expansion and low water absorption. Various proposals have been made so far to improve the properties of polyimine, including controlling the composition of the polyimine monomers and their arrangement (random, block, etc.).

The FPC is produced by laminating a polyimide film and a copper foil with an adhesive (for example, an epoxy resin) to form a CCL, and etching the copper foil to form an electronic circuit. Further, recently, due to the demand for finer pitch of electronic circuits, a chip-on-film (hereinafter referred to as COF) method has been widely used, and an IC chip or the like is directly assembled to an FPC via gold bumps or the like. The COF method includes a high temperature processing step of directly pressing a CCL or the like at a high temperature when assembling an IC wafer. When the thermal expansion rate of the polyimide film in a high temperature environment is different from that of the copper foil, problems such as wrinkles or curling on the CCL may occur. Further, when the glass transition temperature (Tg) of the polyimide film is low, there is a problem that the polyimide film is softened at the time of assembly, and the circuit and the IC wafer are buried. Therefore, in the COF application accompanying IC wafer assembly, the characteristics of the polyimide film are: even in a high temperature environment, the thermal expansion rate is the same as that of the copper foil, and has a high Tg, which can be prevented when the high temperature is crimped. soften. For the existing polyimine film, especially pyromellitic dianhydride (hereinafter referred to as pyromellitic acid or its anhydride is abbreviated as PMDA) and 4,4'-diaminodiphenyl ether (hereinafter referred to as ODA) And a combination of 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter referred to as PDA or its anhydride is abbreviated as BPDA) and p-phenylenediamine (hereinafter abbreviated as PDA) In the composition system, the problem is that the thermal expansion rate in a high temperature environment is much larger or much smaller than that of the copper foil. On the other hand, the multi-component system (three-component system or four-component system) composed of the above combination can control the coefficient of thermal expansion by adjusting the monomer ratio, but when the skeleton of BPDA-ODA (softer block) exists, This causes a problem that the Tg of the polyimide film is lowered.

For example, Japanese Laid-Open Patent Publication No. 59-164328 (hereinafter referred to as "Patent Document 1") discloses a varnish for producing an enameled wire, which comprises a block copolymerization portion of ODA-BPDA and a block copolymerization portion of ODA-PMDA. Polylysine composition.

Japanese Patent Publication No. Sho 61-111359 (hereinafter referred to as "Patent Document 2") discloses a polylysine composition having a combination of monomer components and a method for producing the same. PMDA, ODA, BPDA and PDA are combined and polymerized.

JP-A-63-314242 (hereinafter referred to as "Patent Document 3") discloses a polyimine copolymer film from a block copolymerized portion containing ODA-PMDA and ODA-dimethylbenzidine. The polyglycine copolymer solution of the block copolymerization portion was obtained.

In the document of Japanese Laid-Open Patent Publication No. Hei 6-313055 (hereinafter referred to as "Patent Document 4"), a mixture of polyamic acid of PDA-BPDA and polyamine of ODA-PMDA is obtained, and polyimine is produced by heating. The gist of the matter.

Japanese Patent No. 3,684,044 (hereinafter referred to as "Patent Document 5") discloses a polymerization of a polyglycolic acid having a block copolymerization portion of PDA-PMDA and a block copolymerization portion having ODA-BPDA. Polyamine composition polymerized by proline.

In the document of Japanese Laid-Open Patent Publication No. 2007-162005 (hereinafter referred to as "Patent Document 6"), a polyglycolic acid having a block copolymerization portion of PDA-PMDA and a block having ODA-BPDA are copolymerized. A polyamic acid mixture in which a part of the polyamic acid composition is polymerized to obtain a polyimide film.

Polyamino acids having a block copolymerization portion of PDA-BPDA are not described in Patent Documents 1, 2, 3, and 5. Further, the composition of polylysine having a block copolymerization portion of PDA-PMDA may cause the formed polyamine to have a low Tg and poor heat resistance.

In Patent Document 2, since PDA, ODA, BPDA, and PMDA are mixed and polymerized, heat resistance is lowered and the molecular weight is not high.

Patent Document 4 describes a mixture of polyamic acid of PDA-BPDA and polyamine of ODA-PMDA, but there is no description of the copolymer. In addition, only the example in which the monomer of each component is a molar is described, and the surface of the obtained polyimine film is formed into a fine concave structure, and characteristics such as heat resistance are unknown. The polyamic acid of PDA-BPDA and polyamino acid of ODA-PMDA are mixed for several days at room temperature, so uniform mixing is difficult, and even if it is mixable, there is a problem that the molecular weight is lowered.

In Patent Document 6, although polylysine having a block copolymerization portion of PDA-BPDA is obtained, the relationship between the combination ratio of each component and the modulus of elasticity still needs to be improved.

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamido acid composition which can improve the disadvantages of the prior art and obtain a polyimine film having excellent characteristics therefrom. The polyimide film obtained by using the polyaminic acid composition of the present invention has thermal expansion characteristics equivalent to those of copper foil even in a high temperature environment, and has high heat resistance.

The present invention develops a polyamic acid composition obtained by copolymerizing a block component composed of ODA and PMDA and a block component composed of PDA and BPDA in a specific ratio, and a polyimine obtained by hardening it. As a means of solving the above problems.

According to an embodiment, the present invention provides a polyaminic acid composition comprising the following components: a diamine component consisting of: greater than 50 mol% to 90 mol% of p-phenylenediamine, and 10 mol 4% to less than 50 mol% of 4,4'-diaminodiphenyl ether; and a tetracarboxylic acid component consisting of: 45 to 87 mol% of 3,3',4,4'-biphenyl a tetracarboxylic dianhydride, and 55 to 13 mol% of pyromellitic dianhydride; wherein the polyamic acid composition comprises the aforementioned p-phenylenediamine and the aforementioned 3,3',4,4'-biphenyltetra a block component composed of a copolymer of carboxylic acid dianhydride and a block component composed of a copolymer of the above-mentioned 4,4'-diaminodiphenyl ether and the above-mentioned pyromellitic dianhydride.

Further, the present invention provides a polyimine film which is formed by hardening the above polyamic acid composition.

According to an embodiment, the polyimine film described above has a coefficient of thermal expansion of -18 to -25 ppm/° C. during cooling from 400 ° C to 50 ° C, and a glass transition temperature of 350 ° C or higher.

According to an embodiment, the polyamidene film has a tensile modulus of 5.8 GPa or less.

Further, the elongation of the above polyimide film is 50% or more.

According to an embodiment, the ratio (TD/MD) of the transverse direction (TD) to the elongation in the longitudinal direction (MD) of the polyimide film is 0.95 to 1.05.

In addition, the present invention also provides a method for producing the above polylysine composition, characterized in that 3,3',4,4'-biphenyltetracarboxylic dianhydride and p-phenylene are used in a solvent. The amine is mixed and reacted to obtain a block copolymerization portion of the p-phenylenediamine and the 3,3',4,4'-biphenyltetracarboxylic dianhydride, wherein 3,3', 4,4'-linked The ratio of benzenetetracarboxylic dianhydride to p-phenylenediamine is from 90 to 100 mol% to 100 mol%; then, 4,4'-diaminodiphenyl ether is added, followed by the addition of pyromellitic dianhydride. The reaction is carried out to obtain a block copolymerization portion of the 4,4'-diaminodiphenyl ether and the pyromellitic dianhydride.

According to another embodiment, the present invention also provides a method for producing a polyimine which is obtained by hardening a polyamic acid composition prepared as described above to obtain a polyimine.

Further, the present invention provides a method for producing a polyimide film, which comprises applying the above polyamic acid composition onto a substrate, drying it to obtain a gel film, and heating the gel film to obtain a polyfluorene. Imine film.

The polyaminic acid composition of the present invention can improve the problems of the prior art and obtain a polylysine composition having a polyimine film having excellent characteristics. The polyimide film obtained by using the polyaminic acid composition of the present invention has thermal expansion characteristics similar to those of a copper foil even in a high temperature environment, and has high heat resistance. And it has the excellent characteristics of the elastic modulus ratio.

The present invention develops a polylysine composition which is composed of a block component composed of ODA and PMDA and a block component composed of PDA and BPDA, and a polyimine composition obtained by hardening it. As a means of solving the above problems.

The polyaminic acid composition of the present invention comprises a block component composed of a copolymer of p-phenylenediamine (PDA) and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and A block component composed of a copolymer of 4,4'-diaminodiphenyl ether (ODA) and pyromellitic dianhydride (PMDA). In all the components of the aromatic diamine, the PDA component ratio is more than 50 mol% to 90 mol%, the ODA is 10 mol% or more to less than 50 mol%; among all the components of the aromatic tetracarboxylic acid, the PMDA is 13 To 55 mol%, BPDA is 45 to 87 mol%.

The polyglycine composition of the present invention in an organic solvent is contained in the composition of the present invention even if it is partially imidized.

In the aromatic diamine component, when the ratio of PDA is lower than the above range and the ratio of ODA is too high, the elastic modulus of the obtained polyimide composition is too low or the coefficient of thermal expansion is too high, which is not preferable. Once the modulus of elasticity is too high, the polyimide film is prone to breakage or cracking during the manufacturing process and after a long period of use, especially in COF applications requiring a certain degree of softness. Further, the modulus of elasticity is too low, and the film is rationally deteriorated in the manufacturing step and the processing step.

Considering both the modulus of elasticity and the coefficient of thermal expansion, in a preferred embodiment, the PDA is 51 to 90 mol% and the ODA is 10 to 49 mol%. In a more preferred embodiment, the PDA is 70 to 90 mol% and the ODA is 10 to 30 mol%.

Further, when the ratio of the PDA is higher than the above range and the ratio of ODA is too low, the water absorption of the obtained polyimine is increased, the coefficient of thermal expansion is too low, or the modulus of elasticity is too high to impair the formability, which is not preferable.

In the aromatic tetracarboxylic acid component, when the ratio of BPDA is lower than the above range and the ratio of PMDA is too high, the elastic modulus of the obtained polyimine decreases, and the water absorption rate increases, which is not preferable. Further, when the ratio of BPDA is higher than the above range and the ratio of PMDA is too low, the gas permeability of the obtained polyimine is lowered, and bubbles are generated on the surface during heat hardening, or the adhesion is lowered, which is not preferable. In a preferred embodiment, the BPDA is 50 to 87 mol%, and the PMDA is 13 to 50 mol% or less.

The polyimine obtained by hardening the polyamic acid composition of the present invention preferably has the following characteristics: in the process of cooling from 400 ° C to 50 ° C, the coefficient of thermal expansion is -18 to -25 ppm / ° C, glass The conversion temperature is 350 ° C or higher, and the tensile modulus is 5.8 GPa or less.

More preferably, in the process of lowering from 400 ° C to 50 ° C, the coefficient of thermal expansion is -18 to -24 ppm / ° C, the glass transition temperature is 350 ° C to 400 ° C, and the tensile modulus is 5 to 5.8 GPa or less.

The stretch ratio of the polyimide film in which the polyimine is formed into a film is preferably 50% or more. The stretch ratio is preferably 50 to 100%.

The PMDA and BPDA forming the polyaminic acid composition may contain other aromatic tetracarboxylic acid components within a range not inhibiting the object of the present invention, and specific examples are, for example, 2,3',3,4'-biphenyltetra Carboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,3,6,7-naphthalenedicarboxylate Acid, 2,2-bis(3,4-dicarboxyphenyl)ether, pyridine-2,3,5,6-tetracarboxylic acid, and such guanamine-forming derivatives. When the polyamic acid composition is produced, it is also possible to add a small amount of the anhydride of the aromatic tetracarboxylic acid.

The p-phenylenediamine and the 4,4'-diaminodiphenyl ether which form the polyaminic acid composition may contain other aromatic diamine components in the range which does not inhibit the object of this invention, and a specific example is, for example. M-phenylenediamine, benzidine, p-xylylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenylanthracene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 3,3'-dimethoxybenzidine, 1, 4-bis(3methyl-5-aminophenyl)benzene, and such guanamine-forming derivatives. It is also possible to add a small amount of these aromatic diamines in the production of the polyaminic acid composition.

The method for producing the poly-proline composition of the present invention is a solvent in which BPDA is mixed with a PDA at a ratio of 90 to 100 mol%, and then ODA is added, and the aromatic tetracarboxylic acid component and the aromatic second are continuously added. The amine component is obtained by mixing and reacting PMDA in an amount equivalent to a molar amount.

The aromatic tetracarboxylic acid component and the aromatic diamine component constituting the polyamic acid are polymerized in a ratio substantially equal to the molar number. When BPDA is used in a ratio of 90 to 100 mol% to PDA, it has the advantage of controlling the degree of polymerization. It is better to use BPDA for a ratio of 95 to 100 mol% for PDA.

The polymerization reaction is preferably stirred and/or mixed in an organic solvent, and is carried out at a temperature ranging from 0 to 80 ° C for 10 minutes to 30 hours, as long as the polymerization reaction is carried out or the temperature is raised or lowered as needed within the above-mentioned sequence. No problem. Vacuum defoaming in a polymerization reaction is an effective method for producing an organic solvent solution of a good quality polyglycine composition.

The solvent used in the above production method, such as N,N-dimethylacetamide (hereinafter abbreviated as DMAc), dimethyl hydrazine, N-methyl-2-pyrrolidone, N,N-diethyl acetamide , N,N-dimethylformamide, N,N-diethylformamide, dimethylhydrazine, etc., may be used singly or in combination.

The polyamic acid composition obtained by the above production method is preferably prepared in a ratio of 10 to 30% by weight in the above solvent.

When the copolymerized polyaminic acid composition obtained by the above production method is cyclized to form a copolymerized polyimine, a chemical ring closure method in which a dehydrating agent and a catalyst are dehydrated or a thermal closed-loop method of thermal dehydration may be used. However, from the viewpoint of enhancing the strength of the polyimide film and improving productivity, it is preferable to carry out the chemical ring closure method. The dehydrating agent used in the chemical ring closure method, such as an aliphatic acid anhydride (e.g., acetic anhydride or the like), an aromatic acid anhydride (e.g., phthalic anhydride, etc.), may be used singly or in combination. In addition, the catalyst used is, for example, a complex cyclic tertiary amine (such as pyridine, picoline, quinoline, etc.), an aliphatic tertiary amine (such as triethylamine, etc.), an aromatic triamine (such as N). , N-dimethylaniline, etc.), etc., may be used singly or in combination.

In the method for producing a polyimide film, in the film stretching operation, first, a polyamine composition obtained by a series of reactions is chemically cyclized with a cyclization catalyst and a dehydrating agent, or heated by heating. The treatment is thermally cyclized, and the end portion of the obtained gel film of the polyimide is fixed, and the ratio of the transverse direction (TD) to the elongation in the longitudinal direction (MD) (TD/MD) is adjusted to be biaxially stretched. 0.95~1.05. When such a two-axis stretching operation is performed, the mechanical properties of the obtained polyimide film are improved, and the isotropy is further improved.

Among the mechanical properties of the polyimide film, it is preferred to adjust the tensile modulus to 5.8 GPa or less and the elongation to 50% or more. When the mechanical properties exceed the above range, the polyimide film is likely to be cracked or cracked during the production step and after a long period of use. In addition, when applied to COF, the polyimide film is too hard and is difficult to handle in use.

[Examples]

In the following, the present invention will be specifically described by way of examples and comparative examples, but the following examples are merely illustrative and not intended to limit the invention.

The characteristics of the examples and comparative examples were evaluated in the following manner.

(1) Thermal expansion rate (thermal expansion rate during cooling)

Machine: TMA-50 manufactured by Shimadzu Corporation

Measuring temperature range: 400 ° C ~ 50 ° C

Heating rate: -10 °C / min

(2) Tensile modulus and elongation

According to JIS K7113, a stress-deformation curve was obtained under the following conditions using the following apparatus, and the tensile modulus was determined from the slope of the initial rising portion.

Machine: AGS-J manufactured by Shimadzu Corporation

Stretching speed: 51mm/min

Load range: 400MPa

(3) Glass transition temperature

Machine: TA Instruments (INSTRUMENT) system DMAQ800

Heating rate: 3 ° C / min

Temperature range 50~450°C

Frequency: 1Hz

(Example 1)

255.0 g of DMAc was poured into a 500 ml separable flask, and 10.95 g (0.10 mol) of PDA and 28.12 g (0.096 mol) of BPDA were added thereto, and reacted at normal temperature and normal pressure for 1 hour. Next, 2.25 g (0.011 mol) of ODA was added, and after stirring uniformly, 3.68 g (0.017 mol) of PMDA was added, and the reaction was carried out for 1 hour to obtain a polyaminic acid solution. Further, 15 g of the polyamic acid solution was taken out, coated on a glass plate using an applicator, and dried by heating at 100 ° C for 20 minutes, and then the gel film was peeled off from the glass plate. The end of the gel film was fixed with a fixing rod, and the two axes were extended in the MD direction and the TD direction by the extension ratio shown in Table 1. Thereafter, the film was dried by heating at 200 ° C for 20 minutes, and then dried by heating at 300 ° C for 20 minutes. After heating and drying at 400 ° C for 20 minutes, the fixing rod was removed to obtain a polyimide film having a thickness of about 30 μm. Evaluation of each characteristic of the film was carried out, and the results are shown in Table 1.

(Example 2)

Polymerization of polyamic acid and preparation of polyfluorene by the same procedure as in Example 1 except that the molar ratio of the aromatic diamine component and the aromatic tetracarboxylic acid component shown in Table 1 and the order of addition and the elongation ratio were used. The imine film was evaluated for each characteristic, and the results are shown in Table 1. Further, the molar ratio of each component is a molar ratio in the wholly aromatic diamine component and the wholly aromatic tetracarboxylic acid component.

(Comparative examples 1 to 3)

Polymerization of polyamic acid and preparation of polyfluorene by the same procedure as in Example 1 except that the molar ratio of the aromatic diamine component and the aromatic tetracarboxylic acid component shown in Table 1 and the order of addition and the elongation ratio were used. The imine film was evaluated for each characteristic, and the results are shown in Table 1. Further, the molar ratio of each component is a molar ratio in the wholly aromatic diamine component and the wholly aromatic tetracarboxylic acid component.

(Comparative Example 4)

Using 239.1 g of DMAc, 1.870 g (0.0173 mol) of PDA and 3.659 g (0.0168 mol) of PMDA were added, and reacted at normal temperature and normal pressure for 1 hour, followed by addition of 25.398 g (0.1268 mol) of ODA, and stirring. After homogenization, 8.481 g (0.0288 mol) of BPDA was added and reacted for 1 hour. Next, 21.491 g (0.0985 mTorr) of PMDA was added, and the reaction was further carried out for 1 hour to obtain a polyaminic acid solution. Further, the molar ratio of each raw material to the polymerization was carried out at a ratio shown in Table 2, and a polyimide film having a thickness of about 25 μm was obtained from the polyamic acid solution. Evaluation of each characteristic of the film was carried out and shown in Table 2.

(Comparative Example 5)

The same starting materials as in Example 1 were used, except that 3.27 g (30.2 mmol) of PDA was added to 223.58 g of N-dimethylacetamide, and 6.54 g (30.0 mmol) of PMDA was added in fractions of nitrogen. The mixture was stirred at room temperature for 1 hour under an atmosphere. Next, 24.25 g (121.1 mmol) of ODA was added, and after stirring for 30 minutes, 1.34 g (4.5 mmol) of BPDA was added in portions, and after further stirring for 30 minutes, 24.51 g (112.4 mmol) of PMDA was added in portions. After stirring for 1 hour, 12.68 g of PMDA in N,N'-dimethylacetamide solution (6% by weight) was added dropwise over 30 minutes, and further stirred for 1 hour. The polyamic acid composition obtained was prepared in the same manner as in Example 1 except that the stretching was carried out (average film thickness: 30 μm).

(Comparative Example 6)

The same as in Example 1, as shown in Table 1.

The procedure was the same as in Comparative Example 5, except that the monomeric molar ratio of the polymeric polyamine composition shown in Table 2 was used. The obtained polyaminic acid composition was prepared into a polyimide film (average film thickness: 30 μm) in the same manner as in Comparative Example 5.

The Young's ratio, the coefficient of linear expansion, and the glass transition temperature of the obtained polyimide film were measured, and the results are shown in Table 2.

As described above, the polyimide film of the present invention has elasticity and flexibility suitable for COF application, and has excellent physical properties such as thermal expansion similar to that of copper foil even in a high temperature environment. Furthermore, since the BPDA-ODA block component having a low Tg is small, the polyimine film of the present invention has a Tg of 350 ° C or more, and film softening due to high-temperature heat treatment can be avoided.

Claims (9)

A polyaminic acid composition comprising more than 50 mol% to 90 mol% or less of p-phenylenediamine and 10 mol% or more to less than 50 mol% of 4,4'-diaminodiphenyl ether. a diamine component, and a tetracarboxylic acid component composed of 45 to 87 mol% of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 55 to 13 mol% of pyromellitic dianhydride Wherein the polyamic acid composition comprises a block component composed of a copolymer of the p-phenylenediamine and the 3,3',4,4'-biphenyltetracarboxylic dianhydride, and the 4,4' a block component composed of a copolymer of diaminodiphenyl ether and the pyromellitic dianhydride. A polyimine film formed by curing a polyamic acid composition according to claim 1 of the patent application. The polyimine film according to claim 2, wherein the thermal expansion rate in the process of lowering from 400 ° C to 50 ° C is -18 to -25 ppm / ° C, and the glass transition temperature is above 350 ° C. . The polyimine film according to claim 2, which has a tensile modulus of 5.8 GPa or less. The polyimine film described in claim 2, wherein the elongation is 50% or more. The ratio of the transverse direction (TD) to the elongation in the longitudinal direction (MD) (TD/MD) of the polyimide film according to the second aspect of the invention is 0.95 to 1.05. A method for producing a polylysine composition according to claim 1, wherein the ratio of 3,3',4,4'-biphenyltetracarboxylic dianhydride to p-phenylenediamine is 90 to 100 mol% to 100 mol%, which is mixed and reacted in a solvent to obtain a block copolymerization portion of the p-phenylenediamine and the 3,3',4,4'-biphenyltetracarboxylic dianhydride Thereafter, 4,4'-diaminodiphenyl ether is added, followed by addition of pyromellitic dianhydride to obtain the 4,4'-diaminodiphenyl ether and the pyromellitic acid The block copolymerization portion of the anhydride. A method for producing a polyimine which is obtained by hardening a polyaminic acid composition produced by the method described in claim 7 to obtain a polyimine. A method for producing a polyimide film, which comprises applying a polylysine composition produced by the method according to claim 7 of the patent application to a substrate, drying the film to obtain a gel film, and heating the gel film. The polyimine film was obtained.