TW201809080A - Polyimide precursor composition and application thereof - Google Patents

Abstract

The present invention relates to a polyimide precursor composition and an application thereof. The polyimide precursor composition includes a polyamic acid and a monomer compound. The polyamic acid is obtained by reacting a monomer mixture, in which the monomer mixture includes a diamine compound and a dianhydride compound. The aforementioned monomer compound has two acid groups and two ester groups. The polyimide precursor composition can be futher reacted to obtain the polyimide with excellent mechanism properties and film properties.

Description

Polyimide precursor composition and application thereof

The present invention relates to a polyfluorene imide precursor composition and its application, and in particular, to a polyfluorene imide precursor composition capable of preparing a polyfluorene imine having good mechanical properties and film properties.

Polyimide has the advantages of thermal oxidation resistance, heat resistance, radiation resistance, and chemical resistance. Therefore, polyimide is often used in applications such as automotive materials, aviation materials, insulation materials, and liquid crystal alignment films. Polyfluorene imine is generally prepared by performing a cyclization reaction (ie, amidation reaction) on the polyphosphonium acid. Among them, polyamino acids are formed by the reaction of a dianhydride compound and a diamine compound.

However, based on the total usage of the diamine compound is 100 mol%, when the total usage of the dianhydride compound is not less than 98 mol%, the formed polyamic acid segment will extend indefinitely, increasing the production The molecular weight of polyamic acid is obtained, and its viscosity is greatly improved. Therefore, when the polyamidic acid is made into a polyimide by coating and forming a film, an excessively high viscosity will reduce the coating property of the polyamic acid, and it will be difficult to coat and form a film.

In order to solve the coating defects caused by the aforementioned excessive viscosity, by adjusting the reaction conditions of the aforementioned reaction, the molecular weight of polyamic acid can be reduced. It has a suitable viscosity and can be coated into a film, and then a polyfluorene imide film can be prepared through a cyclization reaction. However, when the molecular weight of the polyamidic acid is reduced, the mechanical properties of the polyimide film obtained are also reduced, which cannot meet the application requirements.

In addition, in the aforementioned reaction, in order to obtain an appropriate coating viscosity, it is necessary to obtain appropriate parameter conditions through complicated experiments, which requires a large amount of time and cost, and increases manufacturing costs. Moreover, the prepared polyamic acid is still unable to balance coating properties and mechanical properties.

In view of this, it is urgent to provide a polyimide precursor composition and its application to improve the drawbacks of the conventional polyimide precursor composition and its application.

Therefore, it is one aspect of the present invention to provide a polyimide precursor composition which reacts a monomer compound with polyamic acid to obtain a polyimide having good mechanical properties and film properties. amine.

Another aspect of the present invention is to provide a method for producing polyimide, which is formed by using the aforementioned polyimide precursor composition to react.

Another aspect of the present invention is to provide a polyimide, which is produced by the aforementioned manufacturing method.

Another aspect of the present invention is to provide a polyimide, which is prepared by the aforementioned manufacturing method and has specific repeating units.

According to one aspect of the present invention, a polyimide precursor composition is provided. The polyimide precursor composition includes polyamidic acid and a monomer compound, wherein the polyamidic acid is prepared from a monomer mixture through a first reaction, and the monomer mixture includes a diamine compound and a dianhydride compound. This monomer compound has two acid groups and two ester groups.

According to an embodiment of the present invention, the aforementioned monomer compound has a structure represented by the following formula (I):

In formula (I), R ₁ represents And R ₂ represents an alkyl group having 1 to 16 carbon atoms.

According to another embodiment of the present invention, based on the total amount of the diamine compound used is 100 mole percent, and the amount of the monomer compound used is 1 mole percent to 10 mole percent.

According to another aspect of the present invention, a method for manufacturing polyfluorene imine is proposed. In this method, a monomer mixture is first provided, and a first reaction is performed on the monomer mixture to obtain polyamic acid. The monomer mixture includes a diamine compound and a dianhydride compound.

Then, the monomer compound and the polyamidic acid are mixed to form a polyimide precursor, wherein the monomer compound has two acid groups and two ester groups. Next, a second reaction is performed on the polyimide precursor to obtain a polyimide.

According to an embodiment of the present invention, the aforementioned dianhydride compound includes pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'- Benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphosphophthalic dianhydride, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, ethylene glycol-bistrimellitic anhydride Or bisphenol A diether dianhydride.

According to another embodiment of the present invention, the aforementioned diamine compound includes p-phenylenediamine or 9,9'-bis (4-aminophenyl) fluorene.

According to another embodiment of the present invention, the aforementioned monomer compound has a structure represented by the following formula (I):

In formula (I), R ₁ represents And R ₂ represents an alkyl group having 1 to 16 carbon atoms.

According to another embodiment of the present invention, based on the total amount of the diamine compound used is 100 mole percent, the amount of dianhydride compound used is greater than Or equal to 90 mol% and less than 98 mol%, and the amount of the monomer compound used is 1 mol% to 10 mol%.

According to another aspect of the present invention, a polyfluorene imine is proposed. This polyimide is prepared by reacting a monomer mixture and a monomer compound by the aforementioned method. The monomer mixture includes a diamine compound and a dianhydride compound.

According to another aspect of the present invention, a polyfluorene imine is proposed. This polyimide has repeating units represented by the following formula (II-1) and formula (II-2):

In formula (II-1), Ar ₁ represents And A represents a divalent organic group derived from the diamine compound; in Formula (II-2), Ar ₂ represents a divalent organic group derived from the dianhydride compound, and A represents a divalent organic group derived from the diamine compound Valent organic radical.

The polyimide precursor composition of the present invention and the application thereof are made by reacting polyamic acid with a monomer compound to extend the molecular chain length of the polyimide obtained, so that it can be made Has good mechanical properties and film properties. Secondly, through the introduction of monomer compounds, the polymer The imine has an appropriate molecular weight, and can suppress the increase in viscosity caused by the extension of the molecular chain, thereby being easy to process.

100‧‧‧ Method

110‧‧‧Procedure for providing monomer mixture

120‧‧‧ the step of performing the first reaction on the monomer mixture to obtain polyamic acid

130‧‧‧ The step of mixing a monomer compound and a polyamic acid to form a polyimide precursor

140‧‧‧Step of performing second reaction on polyimide precursor

150‧‧‧ Steps to obtain polyimide

200‧‧‧Polyimide laminate

210‧‧‧The first copper foil

220‧‧‧The first thermoplastic polyimide layer

230‧‧‧Polyimide layer

240‧‧‧Second thermoplastic polyimide layer

250‧‧‧Second copper foil

210a / 220a / 230a / 240a‧‧‧Side

In order to have a more complete understanding of the embodiments of the present invention and its advantages, please refer to the following description and cooperate with the corresponding drawings. It must be emphasized that the various features are not drawn to scale and are for illustration purposes only. The contents of the related drawings are described as follows: [FIG. 1] A flowchart showing a method for manufacturing polyimide according to an embodiment of the present invention.

[Fig. 2] A side view showing a polyimide laminate according to an embodiment of the present invention.

The manufacture and use of the embodiments of the invention are discussed in detail below. It is understood, however, that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific content. The specific embodiments discussed are for illustration only and are not intended to limit the scope of the invention.

Please refer to FIG. 1, which is a flowchart illustrating a method for manufacturing polyimide according to an embodiment of the present invention. In an embodiment, the method 100 first provides a monomer mixture and performs a first reaction on the monomer mixture to obtain a polyamic acid, as shown in steps 110 and 120.

The aforementioned monomer mixture may include a diamine compound and a dianhydride compound. This diamine compound may include, but is not limited to, 3,4’-diaminodiphenyl ether (3,4'-diaminodiphenyl ether), 4,4'-diaminodiphenyl ether, p-phenylene diamine, m-phenylenediamine ), 3,5-diaminobenzoic acid, 2,2'-bis (4-aminophenyl) propane [2,2'-bis (4-aminophenyl) propane], 4, 4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl碸 (3,4'-diaminodiphenyl sulfone), 4,4'-diaminodiphenyl sulfide, 1,3-bis (4-aminophenoxy) benzene [1, 3-bis (4-aminophenoxy) benzene], 1,3-bis (3-aminophenoxy) benzene [1,3-bis (3-aminophenoxy) benzene], 1,4-bis (4-aminophenoxy) Phenyl] benzene [1,4-bis (4-amino phenoxy) benzene], 4,4-bis (4-aminophenoxy) -biphenyl [4,4-bis (3-aminophenoxy) biphenyl], 2, 2'-bis [4- (4-aminophenoxy) phenyl] propane {2,2'-bis [4- (4-aminophenoxy) phenyl] propane}, 2,2'-bis [4- (3 -Aminophenoxyphenyl) yl] propane {2,2'-bis [4- (3-aminophenoxy) pheny] propane}, 2,2'-di -4,4'-diaminobiphenyl (2,2'-dimethyl-4,4'-diamino biphenyl), 3,3'-dimethyl-4,4'-diaminobiphenyl (3,3 '-dimethyl-4,4'-diaminobiphenyl), 3,3'-dihydrocarbyl-4,4'-diaminobiphenyl (3,3'-dihydroxybiphenyl-4,4'-diamino), 9,9'- Bis (4-aminophenyl) fluorene [9,9'-bis (4-aminophenyl) fluorene], 2,2'-bis (4- [3-aminophenoxy] phenyl) fluorene [2,2 ' -bis (4- (3-aminophenoxy) phenyl) sulfon], 2,6-diaminopyridine, polyoxypropylenediamine, 4,4 '-(1,3-diisopropylalkylphenyl) diphenylamine [4,4' -(1,3-phenylenediisopropylidene) bisaniline; Bisaniline-M], 4,4 '-(1,4-diisopropylalkylbenzene) diphenylamine [4,4'-(1,4-phenylenediisopropylidene) bisaniline; Bisaniline- P], norbornane dimethylamine (NBDA), other appropriate diamine compounds or any combination of the above diamine compounds.

The dianhydride compound may include, but is not limited to, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (3,3', 4,4'-biphenyl tetracarboxylic dianhydride), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalate Anhydride (4,4'-oxydiphthalic dianhydride), 3,3 ', 4,4'-diphenylsulfonium tetracarboxylic dianhydride (3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride), ethylene glycol- Ethylene glycol-bis-trimellitate anhydride, bisphenol A diether dianhydride {2,2-Bis [4- (3,4-dicarboxyphenoxy) phenyl] propanedi anhydride}, other suitable dianhydride compounds or the above Any mixture of dianhydride compounds.

Based on the total used amount of the diamine compound is 100 mole percent, the used amount of the dianhydride compound may be greater than or equal to 90 mole percent and less than 98 mole percent, preferably greater than or equal to 94 mole percent and less than 98 Mole percentage, and more preferably 96 mole percentage and 97 mole percentage Fractional ratio (ie, greater than or equal to 96 mole percent and less than or equal to 97 mole percent).

If the dianhydride compound is used in an amount of not less than 98 mol%, the molecular chain length of the prepared polyamic acid is likely to increase, and its molecular weight is increased, which in turn increases the viscosity of the polyamic acid and easily forms a semi-solid It is gel-like and therefore cannot be applied as a film.

If the amount of dianhydride compound is less than 95 mole percent, although the terminal group of the obtained polyamic acid may be a diamine group, the molecular weight of the polyamino acid is relatively low. When the subsequent second reaction is performed, The formed polyimide has lower viscosity and poor processability, which makes it difficult to effectively meet the needs of the application.

When the use amount of the dianhydride compound is in the foregoing range, the prepared polyamic acid can have a proper molecular chain, a proper molecular weight, and a proper viscosity, so it is helpful for coating to form subsequent polymer醯 imine layer.

In one embodiment, the molecular weight of the obtained polyamidic acid can be 50,000 to 150,000. According to the requirements of the application, the molecular weight of the polyamidic acid can be adjusted appropriately, but the polyamidic acid must further perform a second reaction with the subsequent monomer compound to form a polyimide or polyimide layer.

After step 120 is performed, a monomer compound and the foregoing polyamidic acid are mixed to form a polyimide precursor of the present invention, as shown in step 130.

The aforementioned monomer compound has two acid groups and two ester groups. In one embodiment, the monomer compound may have a structure represented by the following formula (I):

In formula (I), R ₁ represents And R ₂ represents an alkyl group having 1 to 16 carbon atoms.

The aforementioned monomer compounds may be used alone or in combination.

The aforementioned R ₁ may preferably be or , And better yet . The aforementioned R ₂ may preferably be an alkyl group having 1 to 4 carbon atoms, and more preferably may be an alkyl group having 2 carbon atoms.

Please continue to refer to FIG. 1. After step 130 is performed, a second reaction is performed on the polyimide precursor to obtain the polyimide of the present invention, as shown in steps 140 and 150.

In steps 130 and 140, the monomer compound may be subjected to a second reaction between the acid group and the ester group and the terminal groups (ie, amine groups) of the two polyamino acid segments, respectively, so as to extend the prepared polymer. The molecular chain of fluorene imine causes polyamines having a lower molecular weight to react to form fluorenes having a higher molecular weight, thereby improving the mechanical properties of the polyfluorene.

According to this, by introducing the monomer compound, the present invention can effectively overcome the disadvantage that the conventional polyimide cannot take into account both mechanical properties and film properties.

Therefore, based on the total used amount of the aforementioned diamine compound being 100 mole percent, the used amount of the monomer compound may be 1 mole percent to 10 mole percent, preferably 1 mole percent to 5 mole percent, and more Preferably, it is from 2 mole percent to 3 mole percent.

If the amount of the monomer compound is less than 1 mole percent, too few monomer compounds limit the binding of the polyfluorene acid segments, and shorten the molecular chain length of the polyfluorene imine thus reducing its film-forming properties. Therefore, it has poor film properties.

In an embodiment, in steps 140 and 150, the polyimide prepared as described above may have a repeating unit represented by the following formula (II-1) and formula (II-2):

In Formula (II-1), Ar ₁ may represent a divalent organic group derived from a monomer compound having two acid groups and two ester groups, and A may represent a divalent organic group derived from the aforementioned diamine compound. ; And in the formula (II-2), Ar ₂ may represent a divalent organic group derived from the aforementioned dianhydride compound, and A may represent a divalent organic group derived from the aforementioned diamine compound.

In one embodiment, the aforementioned polyfluorene imide may be composed of repeating units represented by formula (II-1) and formula (II-2), wherein the polyfluorene imide may be a block copolymer or a block copolymer. Random copolymer.

Based on the aforementioned monomer compounds, Ar ₁ may have different structures.

In an embodiment, Ar ₁ may represent . When Ar ₁ represents the aforementioned group, since the structure of the aforementioned group is relatively rigid, the mechanical properties of the obtained polyimide can be further improved. It should be noted that, although its structure is relatively rigid, the polyimide laminates produced by compounding polyimide with copper foil (the manufacturing method of polyimide laminates are described below, which is not included here. (More details) can still have good flexibility (Flexural Endurance). The flexibility of this polyimide laminate can be greater than 10,000, and its flexibility is measured by the testing method of Japanese Industrial Standards (JIS) No. C-5016 8.7. During the bending test, the copper foil of this polyimide laminate must be etched to form a circuit layer that meets the requirements of the application.

In another embodiment, the aforementioned Ar ₁ may preferably be or , And better yet

Wherein, based on polyimide being 100%, the content of the repeating unit shown in formula (II-1) in the prepared polyimide may be 1% to 10%, preferably 1% to 5%. And more preferably, it is 2% to 3%.

In a specific example, the flexibility endurance of the polyimide laminate obtained by the present invention may be greater than 10,000.

Preparation method of polyimide laminated board

The method for preparing polyimide laminates is well known to those having ordinary knowledge in the technical field to which this application belongs. Therefore, the following is simply stated.

Please refer to FIG. 2, which is a side view of a polyimide laminate according to an embodiment of the present invention. The polyimide laminate 200 includes a first copper foil 210, a first thermoplastic polyimide layer 220 disposed on the first copper foil 210, and a polyimide disposed on the first thermoplastic polyimide layer 220. The amine layer 230, the second thermoplastic polyimide layer 240 provided on the polyimide layer 230, and the second copper foil 250 provided on the second thermoplastic polyimide layer 240.

Wherein, in the method for preparing the polyimide laminate 200, a thermoplastic polyimide solution is first coated on the side 210a of the first copper foil 210, and the solvent is removed at a temperature of 80 ° C to 190 ° C, and A first thermoplastic polyamic acid layer may be formed.

Then, the polyimide precursor composition prepared by the present invention is coated on the side surface 220a of the first thermoplastic polyamic acid layer. Heating to 80 ° C to 190 ° C to remove the solvent can form a polyamic acid layer.

Similarly, the second thermoplastic polyamino acid is coated on the side surface 230a of the polyamino acid layer and heated to remove the solvent to form a second thermoplastic polyamino acid layer.

Next, a cyclization reaction (i.e., amidation reaction) is performed on the laminated board laminated with the first copper foil, the first thermoplastic polyamic acid layer, the polyamic acid layer, and the second thermoplastic polyamino acid layer, namely A laminated board having a first thermoplastic polyimide layer 220, a polyimide layer 230, and a second thermoplastic polyimide layer 240 can be prepared.

After that, the second copper foil 250 is set on the side surface 240 a of the second thermoplastic polyimide layer 240 and a pressing process is performed to obtain the polyimide laminate 200 of the present invention. The temperature of the pressing process can be 320 ° C to 380 ° C, and the pressure can be 50kgf / cm ² to 100kgf / cm ² .

The following uses examples to illustrate the application of the present invention, but it is not intended to limit the present invention. Any person skilled in the art can make various changes and decorations without departing from the spirit and scope of the present invention.

Preparation of Polyamic Acid Synthesis Example 1

In a four-necked reactor of 1,000 ml with nitrogen, 19.630 grams (0.182 moles) of p-phenylenediamine and 2.639 grams (0.0075 moles) of 9,9'-bis (4-aminophenyl) 芴And 425 grams of N-methyl-2-pyridine Pyrrolidone, and mixed uniformly at 20 ° C to 30 ° C to form a diamine compound solution.

Then, 7.434 g (0.034 mole) of pyromellitic dianhydride is added to the diamine compound solution to perform a preliminary reaction, and a reacted solution can be formed. Next, 44.565 grams (0.151 mol) of 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride are divided into three equal parts, and added to the foregoing by batch addition. The solution was stirred with continuous stirring for the reaction.

After 4 hours, the polyamic acid of Synthesis Example 1 was obtained.

Synthesis Example 2

In a four-necked reactor of 1,000 ml with nitrogen, 26.112 grams (0.242 moles) of p-phenylenediamine and 3.511 grams (0.01 moles) of 9,9'-bis (4-aminophenyl) hydrazone were charged. And 400 grams of N-methyl-2-pyrrolidone, and mixed uniformly at 20 ° C to 30 ° C to form a diamine compound solution.

Then, 9.888 g (0.045 mole) of pyromellitic dianhydride is added to the diamine compound solution to perform a preliminary reaction, and a reacted solution can be formed. Next, divide 58.54 g (0.199 mol) of 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride into three equal parts, and add it to the aforementioned one by adding it in portions. The solution was stirred with continuous stirring for the reaction.

After 4 hours, the polyamic acid of Synthesis Example 2 was obtained.

Synthesis Example 3

In a four-necked reactor of 1,000 ml with nitrogen, 32.491 grams (0.3 moles) of p-phenylenediamine and 4.368 grams (0.013 moles) were charged. 9,9'-bis (4-aminophenyl) fluorene and 375 grams of N-methyl-2-pyrrolidone, and mixed uniformly at 20 ° C to 30 ° C to form a diamine compound solution.

Then, 12.304 g (0.056 mole) of pyromellitic dianhydride is added to the diamine compound solution to perform a preliminary reaction, and a reacted solution can be formed. Next, divide 70.995 g (0.241 mole) of 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride into three equal parts, and add it to the aforementioned one by adding it in portions. The solution was stirred with continuous stirring for the reaction.

After 4 hours, the polyamic acid of Synthesis Example 3 was obtained.

Preparation of polyimide precursor composition

The polyimide precursor compositions of Examples 1 to 3 and Comparative Examples 1 to 3 are prepared according to Table 1 below. Among them, for convenience of comparison, the usage amounts of the dianhydride compounds and diamine compounds in Synthesis Examples 1 to 3 corresponding to those used in Examples 1 to 3 are listed in Table 1 together.

Example 1

The polyfluorene imide precursor composition of Example 1 was added 0.731 g (about 0.002 mole) of 3,3 ', 4,4'-diphenyldicarboxylic acid diethyl ester to the polyfluorene of Synthesis Example 1. After mixing in the amino acid, the polyfluorene imide precursor composition of Example 1 can be obtained. Its viscosity is about 12000cps and its solid content is 15%. The obtained polyimide precursor composition was evaluated by the following evaluation methods of coating properties and film properties. The results obtained are shown in Table 1.

Example 2

The polyfluorene imide precursor composition of Example 2 was added 1.945 g (about 0.005 mole) of 3,3 ', 4,4'-diphenyldicarboxylic acid diethyl ester to the polyfluorene of Synthesis Example 2. After mixing in the amino acid, the polyfluorene imide precursor composition of Example 2 can be obtained. Its viscosity is about 12000cps and its solid content is 20%. The obtained polyimide precursor composition was evaluated by the following evaluation methods of coating properties and film properties. The results obtained are shown in Table 1.

Example 3

The polyfluorene imide precursor composition of Example 3 was added 4.841 g (about 0.013 mole) of 3,3 ', 4,4'-diphenyldicarboxylic acid diethyl ester to the polyfluorene of Synthesis Example 3. After mixing in the amino acid, the polyfluorene imide precursor composition of Example 3 can be obtained. Its viscosity is about 12000cps and its solid content is 25%. The obtained polyimide precursor composition was evaluated by the following evaluation methods of coating properties and film properties. The results obtained are shown in Table 1.

Comparative Example 1

In a four-necked reactor of 1,000 ml with nitrogen, 19.675 grams (0.182 moles) of p-phenylenediamine and 2.645 grams (0.008 moles) of 9,9'-bis (4-aminophenyl) 芴And 425 grams of N-methyl-2-pyrrolidone, and mixed uniformly at 20 ° C to 30 ° C to form a diamine compound solution.

Then, 7.451 g (0.034 mole) of pyromellitic dianhydride was added to the diamine compound solution to perform a preliminary reaction, and a reacted solution was formed. Next, 45.225 grams (0.154 moles) of 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride are divided into three equal parts, and added to the above by batch addition. The solution was stirred with continuous stirring for the reaction.

After 4 hours, the polyimide precursor composition of Comparative Example 1 was prepared, but the polyimide precursor composition (that is, polyamic acid) was a semi-solid gel. Its solid content is 15%. The prepared polyimide precursor composition could not be applied to form a film, so its applicability and film properties were not measured.

Comparative Example 2

In a four-necked reactor of 1,000 ml with nitrogen gas charged, 26.431 g (0.245 mole) of p-phenylenediamine and 3.554 g (0.01 mole) of 9,9'-bis (4-aminophenyl) 苯基And 400 grams of N-methyl-2-pyrrolidone, and mixed uniformly at 20 ° C to 30 ° C to form a diamine compound solution.

Then, 10.009 g (0.046 mole) of pyromellitic dianhydride is added to the diamine compound solution to perform a preliminary reaction, and a reacted solution can be formed. Next, divide 60.005 g (0.204 mole) of 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride into three equal parts, and add it to the foregoing by batch adding. The solution was stirred with continuous stirring for the reaction.

After 4 hours, the polyimide precursor composition of Comparative Example 2 can be prepared, but the polyimide precursor composition (that is, polyamic acid) is a semi-solid gel. Its solid content is 20%. The prepared polyimide precursor composition could not be applied to form a film, so its applicability and film properties were not measured.

Comparative Example 3

In a four-necked reactor of 1,000 ml with nitrogen gas charged, 19.824 g (0.183 mole) of p-phenylenediamine and 2.665 g (0.008 mole) of 9,9'-bis (4-aminophenyl) 芴And 425 grams of N-methyl-2-pyrrole Alkanone, and mixed uniformly at 20 ° C to 30 ° C to form a diamine compound solution.

Then, 7.507 g (0.034 mole) of pyromellitic dianhydride was added to the diamine compound solution to perform a preliminary reaction, and a reacted solution was formed. Next, 45.005 grams (0.153 moles) of 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride are all divided into three equal parts, and it is added to the foregoing by batch addition. The solution was stirred with continuous stirring for the reaction.

After 4 hours, the polyimide precursor composition of Comparative Example 3 (that is, the polyamidic acid referred to in the present invention) can be obtained. Its viscosity is about 12000cps and its solid content is 15%. The obtained polyimide precursor composition was evaluated by the following evaluation methods of coating properties and film properties. The results obtained are shown in Table 1.

Preparation of polyimide laminates

In the following, polyimide laminates of application examples 1 to 3 and comparative application example 1 were prepared according to Table 2.

Application example 1

The preparation method of the polyfluorene imide laminate of Application Example 1 is as described above, and is not repeated here. Among them, the polyimide precursor composition of Application Example 1 uses the composition of Example 1 described above. The obtained polyimide laminate was evaluated by the following evaluation methods of film properties and mechanical properties, and the results are shown in Table 2.

Application Example 2 and Comparative Application Example 1

Application Example 2 and Comparative Application Example 1 use the same preparation method as the polyfluorene imide laminate of Application Example 1, except that Application Example 2 uses the polyimide precursor composition of the foregoing Example 2, and Comparative Application Example 1 uses the polyfluorene imide precursor composition of Comparative Example 3, and its conditions and evaluation results are shown in Table 2, which will not be repeated here.

Evaluation method Coatability

The coating property of the polyimide layer is to apply the polyimide precursor composition of the foregoing Examples 1 to 3 and Comparative Examples 1 to 2 to 1/3 ounces (thickness of about 0.012 mm), respectively. ) On a copper foil, and further heated to carry out a cyclization reaction to form a polyfluorene imide layer, and determine its coatability based on whether the polyfluorene imide precursor composition can be coated into a film.

Film properties

Thermal properties

The thermal properties of the polyimide layer are measured by the instruments and methods well known to those having ordinary knowledge in the technical field to which the present invention pertains. Coefficient of Thermal Expansion (CTE), glass transition temperature (T _g ) of amine layer and thermal cracking temperature (T _d ) of 5% weight loss. The results are shown in Table 1 and will not be repeated here.

Dimensional stability

The dimensional stability of the polyimide layer was measured by methods well known to those having ordinary knowledge in the technical field to which the present invention belongs. The dimensional stability of the polyimide layers prepared in Example 3 and Comparative Examples 1 to 2 in the machine direction (MD) and the transverse direction (TD). The results are shown in Table 2 and will not be repeated here.

3. Mechanical properties

The mechanical properties of the polyimide layer are measured by the apparatus and methods well known to those having ordinary knowledge in the technical field to which the present invention pertains. The polyimides prepared in the foregoing Examples 1 to 3 and Comparative Examples 1 to 2 are measured. The amine layer has tensile strength, elongation, and flexibility. The results are shown in Table 2 and will not be repeated here.

Among them, the tensile strength is measured by using the test method of IPC-TM-650 No. 2.4.19 in the American Connecting Circuit Industries (Association Connecting Electronics Industries). The flexural fracture test is to visually observe the flexed surface of the polyimide layer and evaluate it based on the following criteria:

：: No cracks appear on the surface.

×: Cracks appear on the surface.

Please refer to Table 1. In polyphosphonic acid, based on the total amount of diamine compound used is 100 mole percent. When the total amount of dianhydride compound is not less than 98.0 mole percent (ie, Comparative Example 1 and Comparative Example 2), Polyamic acid is easy to form a semi-solid gel, and cannot be coated into a film, and polyimide cannot be obtained.

Please refer to Table 1 and Table 2 at the same time. Based on the total used amount of the diamine compound is 100 mole percent, and when the total used amount of the dianhydride compound is greater than or equal to 95 mole percent and less than 98 mole percent (ie, Examples 1 to 3), The polyamic acid has a suitable viscosity and can have good coating properties. Among them, in order to further improve the mechanical properties of the obtained polyimide, Examples 1 to 3 introduce a monomer compound of 1 mole percent to 5 mole percent, and use two acid groups of the monomer compound And the two ester groups react with polyamidic acid, which can extend the molecular chain of the polyamidoimide produced, thereby increasing its molecular weight and improving mechanical properties. Therefore, the application examples 1 and 2 can have better flexibility, and have good tensile strength and elongation strength.

In Comparative Application Example 1, the total amount of the diamine compound used in Comparative Example 3 was 100 mole percent, and the total amount of the dianhydride compound used was 97.9 mole percent, but the polyimide precursor composition of Comparative Example 3 No monomer compound was added. According to this, although the polyimide precursor composition (i.e., polyamic acid) of Comparative Example 3 can still be coated into a film, the obtained polyimide (i.e., Comparative Application Example 1) has poor flexibility. Flexibility.

According to this, when the total used amount of the diamine compound is 100 mol%, when the total used amount of the dianhydride compound is within the aforementioned range of the present invention, the prepared polyamic acid may have better coatability. Secondly, the polyimide precursor composition of the present invention can be formed by mixing polyamidic acid with a monomer compound, and a polyimide having good mechanical properties and film properties can be obtained.

Although the present invention has been disclosed as above in the embodiments, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field to which the present invention pertains can make various changes and modifications without departing from the spirit and scope of the present invention. Retouching, so the scope of protection of the present invention shall be determined by the scope of the attached patent application.

100‧‧‧ Method

110‧‧‧Procedure for providing monomer mixture

120‧‧‧ the step of performing the first reaction on the monomer mixture to obtain polyamic acid

130‧‧‧ The step of mixing a monomer compound and a polyamic acid to form a polyimide precursor

140‧‧‧Step of performing second reaction on polyimide precursor

150‧‧‧ Steps to obtain polyimide

Claims (10)

A polyimide precursor composition comprises polyamidic acid, which is prepared from a monomer mixture through a first reaction, wherein the monomer mixture includes a diamine compound and a dianhydride compound; and a monomer compound , With two acid groups and two ester groups. For example, the polyimide precursor composition described in item 1 of the patent application scope, wherein the monomer compound has a structure represented by the following formula (I): In formula (I), R ₁ represents And R ₂ represents an alkyl group having 1 to 16 carbon atoms. For example, the polyfluorene imide precursor composition described in item 1 of the scope of the patent application, wherein the total amount of the diamine compound used is 100 mole percent, and the amount of the monomer compound used is 1 mole percent to 10 moles. Ear percentage. A method for manufacturing polyimide, comprising: providing a monomer mixture, wherein the monomer mixture includes a diamine compound and a dianhydride compound; performing a first reaction on the monomer mixture to obtain polyamic acid; mixing A monomer compound and the polyimide acid to form a polyimide precursor, wherein the monomer compound has two acid groups and two ester groups; and performing a second step on the polyimide precursor Reaction to obtain the polyfluorene. For example, the method for producing polyfluorene imine as set forth in the scope of the patent application, wherein the dianhydride compound includes pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxodiphosphophthalic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic acid Acid dianhydride, ethylene glycol-bistrimellitic anhydride or bisphenol A type diether dianhydride. The method for manufacturing polyfluorene imine as set forth in the scope of application for patent 4, wherein the diamine compound comprises p-phenylenediamine or 9,9'-bis (4-aminophenyl) fluorene. For example, the manufacturing method of polyfluorene imine as set forth in the scope of application for patent 4, wherein the monomer compound has a structure represented by the following formula (I): In formula (I), R ₁ represents or And R ₂ represents an alkyl group having 1 to 16 carbon atoms. For example, the manufacturing method of polyimide as described in item 4 of the scope of the patent application, wherein based on the total usage of the diamine compound is 100 mole percent, and the usage amount of the dianhydride compound is 90 mole percent or more Less than 98 mole percent, and the monomer compound is used in an amount of 1 mole percent to 10 mole percent. A polyimide is prepared by reacting a monomer mixture and a monomer compound as described in any one of claims 4 to 8 of the patent application scope, wherein the monomer mixture comprises a diamine compound and A dianhydride compound. A polyimide, wherein the polyimide has a repeating unit represented by the following formula (II-1) and formula (II-2): In formula (II-1), Ar ₁ represents And A represents a divalent organic group derived from the diamine compound; in Formula (II-2), Ar ₂ represents a divalent organic group derived from the dianhydride compound, and A represents a divalent organic group derived from the diamine compound Divalent organic radical.