TWI606084B - Polyimide compound and application thereof - Google Patents

Description

Polyimine compound and its application

The present invention relates to a polyimine compound and its use, and in particular to a polyimine compound having good transparency and better mechanical properties and use thereof.

Polyimine compounds have the advantages of heat oxidation resistance, heat resistance, radioactivity resistance and chemical resistance. Therefore, polyimine compounds are often used in automotive materials, aerospace materials, insulating materials, and liquid crystal alignment films. However, the structure of the general polyimine compound is mostly composed of aromatic, and the color of the polymer film formed by the polyimide is easily brown or yellow, and the transparency of the polymer film is lowered, so that it cannot be applied to the high. The field of penetration.

In order to solve the defects of the above polyimine compound, a fluorine-containing group is generally introduced into an acid anhydride monomer and/or a diamine monomer of a polyamidene compound to polymerize to form a polyfluorene group having a fluorine-containing group. An amine compound can reduce the transparency of the formed polymer film. However, the fluorine-containing group tends to lower the mechanical properties of the polyimine compound, and cannot be used as a protective material, thereby limiting its application range.

In addition, in order to solve the aforementioned defects of transparency, another method is to form a polyimine compound by polymerizing a specific dimer diamine compound and an acid anhydride compound, but the obtained polyimine compound has Good transparency, but its mechanical properties are still poor. Furthermore, the synthesis step of the dimer diamine compound is complicated and difficult to prepare, and increases the manufacturing cost of the polyimine compound.

In view of this, it is not necessary to provide a polyimine compound and its use to improve the drawbacks of conventional polyimide compounds and their applications.

Accordingly, one aspect of the present invention provides a polyimine compound which forms a polyimine compound having good transparency and mechanical properties by a specific structure of a dianhydride compound and a diamine compound.

Another aspect of the present invention provides a polyimine-based polymer material which is formed by a polymerization reaction using the above-described polyimine compound.

Still another aspect of the present invention provides a polymer film formed by the above-described polyiminoimide polymer material.

According to still another aspect of the present invention, a patterned polymer film is provided which is formed by subjecting the polyimine-based polymer material to a lithography process.

According to one aspect of the invention, a polyamidene compound is proposed. This polyimine compound has a structure represented by the following formula (I):

In the formula (I), X represents a structure represented by the following formula (II), R ₁ represents an aliphatic group having a carbon number of 6 to 13, and n represents an integer of at least 11, wherein such R ₁ is two The ends are each bonded to a nitrogen atom:

In the formula (II), R ₁ represents an aliphatic group having a carbon number of 6 to 13, and R ₂ represents .

According to an embodiment of the present invention, the aforementioned R ₁ represents a linear alkyl group of 6 to 12.

According to an embodiment of the invention, the aforementioned R ₁ is dicyclohexylmethane.

According to another embodiment of the invention, the aforementioned n represents an integer from 11 to 50.

According to still another embodiment of the present invention, the polyamidene compound may have a molecular weight of from 80,000 to 300,000.

According to another aspect of the present invention, a polyimine-based polymer material is proposed. Here, the polyimine-based polymer material has a structure represented by the following formula (III):

In the formula (III), X represents a structure represented by the following formula (II), R ₁ represents an aliphatic group having a carbon number of 6 to 13, and R ₃ represents R ₄ represents a single bond, n represents an integer of at least 11, and m represents an integer from 0 to 15, wherein the two ends of these R ₁ are each bonded to a nitrogen atom:

In the formula (II), R ₁ represents an aliphatic group having a carbon number of 6 to 13, and R ₂ represents .

According to still another aspect of the present invention, a polymer film is proposed. The polymer film is formed of the above-mentioned polyimide-based polymer material, wherein the polymer film has a transmittance of not less than 50% for light having a wavelength of from 330 nm to 480 nm.

According to an embodiment of the present invention, the yellowing b value of the polymer film is from 5 to 15.9.

According to another embodiment of the present invention, the modulus of the polymer film is not less than 1660 MPa.

According to still another aspect of the present invention, a patterned polymer film is proposed. The patterned polymer film is formed by subjecting the aforementioned polyimine compound to a lithography process. The patterned polymer film has a transmittance of not less than 50% for light having a wavelength of 330 nm to 480 nm.

The polyimine compound of the present invention and the use thereof are obtained by polymerizing a monomer compound having a specific structure to form a polyimine compound having good transparency and preferable mechanical properties, and by using a polyimine compound A polymer film or a lithography process is carried out to obtain an unpatterned or patterned polymer film.

101/102/103/104/105‧‧‧ Curve

For a more complete understanding of the embodiments of the invention and the advantages thereof, reference should be made to the description below and the accompanying drawings. It must be emphasized that the various features are not drawn to scale and are for illustrative purposes only. The related drawings are described as follows: [Fig. 1] shows the wavelength of the transmitted light of the polymer film produced by the application examples 1 to 3 and the comparative application example 1 to the comparative application example 2 according to the present invention. A plot of penetration.

The making and using of the embodiments of the invention are discussed in detail below. However, it will be appreciated that the embodiments provide many applicable inventive concepts that can be implemented in a wide variety of specific content. The specific embodiments discussed are illustrative only and are not intended to limit the scope of the invention.

The present invention provides a polyimine compound. The polyimine compound is first polymerized to form an intermediate polymer by a specific fluorine-containing dianhydride compound and a diamine compound. Then, the polyimine compound having a double maleate terminal group of the present invention can be obtained by subjecting maleic anhydride to a capping reaction with the intermediate polymer.

The above-mentioned fluorine-containing dianhydride compound has a structure represented by the following formula (IV):

In the formula (IV), R ₂ represents .

When the polyimine compound of the present invention is formed by the reaction of the above-mentioned fluorine-containing dianhydride compound, the obtained polyimide component has good light transmittance due to the influence of the fluorine-containing R ₂ group. As a protective layer for optical components.

The specific diamine compound of the present invention may have a structure represented by the following formula (V): NH ₂ -R ₁ -NH ₂ formula (V)

In the formula (V), R ₁ represents an aliphatic group having a carbon number of 6 to 13.

The aforementioned aliphatic groups may include, but are not limited to, linear alkyl groups, branched alkyl groups, cycloalkyl groups, other suitable aliphatic groups, or any combination of the above.

Preferably, the aforementioned R ₁ may be a linear alkyl group having a carbon number of 6 to 12.

Preferably, the aforementioned R ₁ is dicyclohexylmethane.

The diamine compound may be used in an amount of from 101 mole percent to 120 mole percent, preferably from 102 mole percent to 110 mole percent, and more preferably from 100 mole percent based on the fluorine-containing dianhydride compound. 104 mole percentage to 106 mole percentage.

If the amount of the diamine compound used is less than 101 mol%, the terminal group of the formed intermediate polymer cannot be further subjected to a capping reaction with maleic anhydride, and cannot be reacted to form the polyimine compound of the present invention.

If the amount of the diamine compound used is more than 120 mole percent, the excess diamine compound merely increases the raw material cost of the reaction and does not contribute to the efficacy of the formed polyimine.

The amount of the maleic anhydride used may be from 2 mole percent to 20 mole percent, preferably from 5 mole percent to 15 mole percent, and more preferably, based on the amount of the fluorine-containing dianhydride compound used. It ranges from 8 moles to 12 moles.

If the amount of maleic anhydride used is less than 2 mole percent, too little maleic anhydride cannot completely block the intermediate polymer, so that the formed polyamidimide compound does not have a double male end group, and thus cannot be borrowed. The polyimine-based polymer material is formed by a polymerization reaction described later and another polyimide reaction.

If the amount of maleic anhydride used is greater than 20 mole percent, excess maleic anhydride increases the cost of the raw materials of the reaction and does not contribute to the efficacy of the formed polyimine.

The polyimine compound having a double maleate terminal group prepared by the present invention has a structure represented by the following formula (I):

In the formula (I), X represents a structure represented by the following formula (II), R ₁ is as defined above, and n represents an integer of at least 11, wherein the two ends of these R ₁ are bonded to a nitrogen atom, respectively. Conclusion:

In formula (II), R ₁ is as defined above, and R ₂ represents .

If n of the polyimine compound is less than 11, the subsequent production of the polyimine-based polymer material is inferior in mechanical properties, and the effect as a protective layer cannot be achieved. Secondly, when n is less than 11, the polyimine compound is less likely to form a polymer film.

The aforementioned n may preferably be an integer of from 11 to 50, and more preferably may be an integer of from 20 to 40.

The polyamidene compound of the present invention may have a molecular weight of from 80,000 to 300,000, preferably from 100,000 to 250,000, and more preferably from 108,000 to 210,000, corresponding to the aforementioned value of n.

In one embodiment, the polyimine compound produced by the present invention may have a viscosity of from 50 cP to 800 cP, preferably from 80 cP to 700 cP, and more preferably from 100 cP to 650 cP.

Further, a polyimine-based polymer material can be obtained by subjecting the polyimine compound to a polymerization reaction, wherein the polymerization reaction can be photopolymerization, thermal polymerization, other suitable polymerization or the above. Any combination of reactions.

The polyimine-based polymer material has a structure represented by the following formula (III):

In the formula (III), X, R ₁ and n are as defined above, and R ₃ represents R ₄ represents a single bond, and m represents an integer of 0 to 15, wherein the two ends of these R ₁ are each bonded to a nitrogen atom.

The m value in the above formula (III) preferably represents an integer of 2 to 12, and more preferably may be an integer of 5 to 10.

In the polyimine-based polymer material represented by the above formula (III), when n is at least an integer of 11, the polyimine-based polymer material may have preferable mechanical properties and may serve as a protective layer. .

In one embodiment, the polyimine-based polymer material formed by the polyimine compound may be a linear polymer material or a network polymer material by adjusting the reaction parameters of the polymerization reaction.

According to different polymerization mechanisms and/or different application requirements, the above polymerization reaction can induce a polymerization reaction of the polyamidene compound by using a polymerization initiator to form a polyimine-based polymer material.

The foregoing polymerization initiator may include, but is not limited to, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoylhydrazide), 1-[9-B Keto-6-(2-methylbenzoyl)-9H-indazol-3-yl]ethanone 1-(O-acetyl oxime), other suitable polymerization initiators or any mixture of the above materials.

The polymerization initiator may be used in an amount of from 0.5 mole percent to 30 mole percent, preferably from 1 mole percent to 20 mole percent, and more preferably, based on the amount of the polyimine compound used. It ranges from 5 moles to 10 moles.

In an application example, the polyimide-based polymer material of the present invention can further form a polymer film. In this application example, the aforementioned polyamidene compound is first dissolved in a solvent to form a polyimine solution. Then, the polyimine solution is coated on a substrate to form a polyimide film. Next, the polyimide film is baked at a high temperature to remove the solvent in the polyimide film.

Thereafter, the above-mentioned polymerization reaction is carried out on the solvent-removed polyimine film to react the polyamidene compounds in the polyimide film to form the above-mentioned polyimine-based polymer material. Polymer film.

The obtained polymer film has a transmittance of not less than 50% for light having a wavelength of from 330 nm to 480 nm, and the yellowing b value of the polymer film is from 5 to 15.9. In other words, the polymer film has good transparency. In one embodiment, the polymer film has a transmittance of not less than 50% for light having a wavelength of from 330 nm to 400 nm.

Further, when the n value of the polyimine compound represented by the above formula (I) is at least an integer of 11, the modulus of the polymer obtained is not less than 1660 MPa, and the tensile strength is not less than 69 MPa. Therefore, the obtained polymer film has good mechanical properties.

Among them, based on the demand as a protective layer, when the value of n is larger, the mechanical properties of the polymer film produced are better.

In another application example, the polyimide-based polymer material of the present invention can further form a patterned polymer film. The method for producing the patterned polymer film is the polymer film described above, the difference between the two is that the polyimide solution contains a photoresist, and after removing the solvent in the formed polyimide film, the polysiloxane The amine film is subjected to a lithography process to pattern the polyimide film and polymerize the polyimine compounds in the patterned polyimide film to form the above-mentioned polyimine polymer material. Further, a patterned polymer film can be obtained.

In this application example, in order to improve the handling convenience of the lithography process and the developing effect of the developer, the n value of the polyimine compound having the structure represented by the formula (I) may preferably be from 11 to 50. An integer, and more preferably an integer from 20 to 40.

Similarly, the prepared patterned polymer film has a transmittance of not less than 50% for light having a wavelength of 330 nm to 480 nm, and the yellowed b value of the patterned polymer film is 5 to 15.9. In one embodiment, the patterned polymer film has a transmittance of not less than 50% for light having a wavelength of from 330 nm to 400 nm.

Accordingly, the polyimine compound of the present invention can form a polyimine-based polymer material having good transparency and preferable mechanical properties after the above polymerization reaction.

Secondly, the polyimine compound of the present invention can also form an unpatterned or patterned polymer film by a polymerization reaction or a lithography process.

The following examples are used to illustrate the application of the present invention, and are not intended to limit the present invention, and various modifications and refinements can be made without departing from the spirit and scope of the invention.

Preparation of polyimine compounds Example 1

14.26 g (0.071 mol) of 1,12-dodecylamine and 150 g (1.513 mol) of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were added to the reaction flask under a water bath at room temperature. in. After completely dissolved, 30.04 g (0.067 mol) of 4,4'-hexafluorodianhydride (hereinafter abbreviated as 6FDA) was added to the NMP solution under a water bath at room temperature to carry out the reaction.

After the reaction for 16 hours, 0.69 g (0.008 mol) of maleic anhydride (hereinafter abbreviated as MA) was added to carry out a blocking reaction. Reaction 24 hours Thereafter, 80 ml of anhydrous toluene was added, and a water removal apparatus (Dean-Stark Trap) was placed on the reaction flask.

Then, the water removal step is carried out at 140 ° C, and when the amount of dehydration reaches the theoretical water content generated by the reaction, heating is continued to remove toluene, and the polyimine compound of Example 1 can be obtained. The obtained polyimine compound was evaluated in the following evaluation manner, and the results are shown in Table 1, in which the measurement methods of the viscosity and the molecular weight are described later.

Example 2

9.54 g (0.082 mol) of 1,6-hexanediox and 150 g (1.513 mol) of NMP were added to the reaction flask under a water bath at room temperature. After complete dissolution, 34.65 g (0.078 mol) of 6FDA was added to the NMP solution in a water bath at room temperature to carry out the reaction.

After 16 hours of reaction, 0.80 g (0.008 mol) of MA was added to carry out a capping reaction. After 24 hours of reaction, 80 ml of anhydrous toluene was added, and a water removal apparatus (Dean-Stark Trap) was placed on the reaction flask.

Then, the water removal step is carried out at 140 ° C, and when the amount of dehydration reaches the theoretical water content generated by the reaction, heating is continued to remove toluene, and the polyimine compound of Example 2 can be obtained. The obtained polyimine compound was evaluated in the following evaluation manner, and the results are shown in Table 1, in which the measurement methods of the viscosity and the molecular weight are described later.

Example 3

14.74 g (0.070 mol) of 4,4'-diaminodicyclohexylmethane and 150 g (1.513 mol) of NMP in a water bath at room temperature Add to the reaction flask. After complete dissolution, 29.57 g (0.067 mol) of 6FDA was added to the NMP solution in a water bath at room temperature to carry out the reaction.

After 16 hours of reaction, 0.68 g (0.006 mol) of MA was added to carry out a capping reaction. After 24 hours of reaction, 80 ml of anhydrous toluene was added, and a water removal apparatus (Dean-Stark Trap) was placed on the reaction flask.

Then, the water removal step is carried out at 140 ° C, and when the amount of dehydration reaches the theoretical water content generated by the reaction, heating is continued to remove toluene, and the polyimine compound of Example 3 can be obtained. The obtained polyimine compound was evaluated in the following evaluation manner, and the results are shown in Table 1, in which the measurement methods of viscosity and molecular weight are described later:

Preparation of polymer film Application example 1

First, 0.3% of Dicumyl Peroxide (DCP) was added to 100% by weight of the polyimine compound of Example 1, and the polyimine compound was coated on a copper foil to form Polyimine film. Then, the polyimide film was placed on a heating plate at 140 °C. After the solvent was removed, the polyimide film was placed in an oven at 200 ° C to carry out a polymerization reaction.

After 30 minutes, the polymer film formed on the copper foil was taken out from the oven and cooled to room temperature. Next, an etching process was performed to remove the copper foil, and the polymer film of Application Example 1 was obtained. The obtained polymer film was evaluated by the following evaluation method, and the results are shown in Table 2, and the detection methods of the chromaticity value and the mechanical property are described later.

Application Example 2 and Application Example 3

Application Example 2 and Application Example 3 are the same as the production method of the polymer film of Application Example 1, except that Application Example 2 and Application Example 3 were prepared using Example 2 and Example 3, respectively. The evaluation results of the polyimine compound are shown in Table 2, respectively, and are not described herein.

Comparative application example 1

First, the polyimine compound of Example 1 was coated on a copper foil to form a polyimide film. Then, the polyimide film was placed on a heating plate at 140 °C. After the solvent was removed, the polyimide film was cooled to room temperature. Next, an etching process was performed to remove the copper foil, and the polymer film of Comparative Application Example 1 was obtained. The evaluation results of the obtained polymer film are shown in Table 2, and will not be further described herein.

Comparative application example 2

First, a commercially available polyimine compound (product of Desinger Molecules Co., Ltd., model BMI-3005) was coated on the copper foil to form a polyimide film. . Then, the polyimide film was placed on a heating plate at 140 °C. After the solvent was removed, the solvent-removed polyimine film was irradiated with 1500 mJ of ultraviolet light to carry out a polymerization reaction.

Next, an etching process was performed to remove the copper foil, and the polymer film of Comparative Application Example 2 was obtained. The evaluation results of the obtained polymer film are shown in Table 2, and will not be further described herein.

Evaluation project Viscosity and molecular weight

The viscosity and molecular weight of the polyimine compound obtained in the foregoing Examples 1 to 3 were respectively manufactured by a viscosity meter (BROOKFIELD Co., Ltd., model number DV2T) and a polymer chromatography system (WATERS), and The measuring instrument is model acquity APC).

2. Chromaticity value

The polymer films of Application Examples 1 to 3 and Comparative Application Example 1 and Comparative Application Example 2 were cut into sample films each having a length and a width of 5 cm. Then, the sample film was placed in a colorimeter (manufactured by KONICA MINOLTA Co., Ltd., and its model number was KONICA spectrotophotometer CM-2300D), and the chromaticity value of the polymer film [lightness (L value), a value, Yellowing b value and yellowness (YI)].

Among them, those skilled in the art of the present invention can clearly understand that the greater the L value, the higher the brightness of the polymer film (ie, the more white the polymer film); the larger the value of a, the more reddish the polymer film. On the contrary, the greener the polymer film is, the more the b value is, the more yellow the polymer film is. On the contrary, the more the polymer film is blue, and the YI value is closer to 0, the more the polymer film is colorless and transparent.

3. Mechanical properties

The polymer films of the above-mentioned Application Example 1 to Application Example 3 and Comparative Application Example 1 and Comparative Application Example 2 were measured by a standard test method of American Society for Testing and Materials (ASTM) D 882. Tensile strength, elongation and modulus of the film.

Referring to Table 2, after the polymerization reaction, the polymer film formed by the polyimine compound of the present invention is close to a colorless and transparent polymer film, and has better mechanical properties.

Next, according to the evaluation results of Application Example 1 and Comparative Application Example 1, it is understood that the polymer mold obtained has a better mechanical property when the polyimide film is subjected to polymerization. Among them, although the chromaticity value of the polymer film of Application Example 1 was slightly increased, the increase was not large, so the polymer film obtained in Application Example 1 still had good transparency. Accordingly, the polyimine compound of the present invention has good transparency and mechanical properties.

The polymer film produced by the comparison application example 2, regardless of the polymer film formed by the polymerization reaction (Application Example 1 to Application Example 3) or the polymer film formed by the non-polymerization reaction (Comparative Application Example 1) The polymer film prepared by using the polyimine compound of the present invention has better transparency and mechanical properties.

Please refer to FIG. 1 , which is a graph showing the wavelength of the transmitted light of the polymer film produced by the application example 1 to the application example 3 and the comparative application example 1 to the comparative application example 2 according to the present invention. Figure. The graph of FIG. 1 is the application example 1 to the application example 3 and the comparison application example 1 and the comparison application example 2 The obtained polymer film was placed in an ultraviolet light absorber (manufactured by Hitachi Co., Ltd., model number U-4100), and the results were measured.

In Fig. 1, a curve 101 represents a measurement curve of the polymer film of Application Example 1; a curve 102 represents a measurement curve of the polymer film of Application Example 2; and a curve 103 represents a measurement curve of the polymer film of Application Example 3; Curve 104 represents a measurement curve of the polymer film of Comparative Application Example 1; and curve 104 represents a measurement curve of the polymer film of Comparative Application Example 2.

According to the curve 101 to the curve 103, the polymer film obtained by the polyimine compound of the present invention has a transmittance of not less than 50% for light having a wavelength of from 330 nm to 480 nm.

Under the influence of the different structures of the selected diamine compound, the stacking probability of the resonance region in the structure of the polyimine compound is different, and the probability of the red shift of the breakthrough curve is also different. Wherein, in the curve 101, since the carbon chain of the aliphatic group is long, the probability of stacking the resonance region of the molecular structure is lowered, thereby suppressing the degree of red shift of the curve; in the curve 103, due to the ring in the aliphatic group The alkyl group is easy to stack to generate resonance, and the degree of red shift of the curve is increased, so the transmittance of the curve 103 at the short wavelength is lower than the transmittance of the curve 101.

Further, in the region of the wavelength of 300 nm to 500 nm, the transmittance of the curve 101 to the curve 103 (Application Example 1 to Application Example 3) is lower than that of the curve 104 (Comparative Application Example 1), but according to the foregoing As is apparent from the description of Table 2, the polymer film produced by Application Examples 1 to 3 of the present invention still has good transparency and has preferable mechanical properties.

In the curve 105, the polymer film obtained in Comparative Example 2 was compared to light having a wavelength of 400 nm or more and the transmittance was more than 50%.

Accordingly, the polyimine compound of the present invention can produce a polymer film having good transparency and better mechanical properties.

The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.

Claims (8)

A polyimine compound having a structure represented by the following formula (I): In the formula (I), the X represents a structure represented by the following formula (II), the R ₁ is dicyclohexylmethane, and the n represents an integer of at least 11, wherein the two ends of the R ₁ are respectively a nitrogen Atomic bond: In formula (II), R ₁ is dicyclohexylmethane, and R ₂ represents . The polyimine compound as set forth in claim 1 wherein n represents an integer from 11 to 50. The polyimine compound as set forth in claim 1, wherein one of the polyimine compounds has a molecular weight of from 80,000 to 300,000. A polyimine-based polymer material having a structure represented by the following formula (III): In the formula (III), the X represents a structure represented by the following formula (II), and these R ₁ represent an aliphatic group having a carbon number of 6 to 13, and these R ₃ represent And R ₄ represents a single bond, the n represents an integer of at least 11, and the m represents an integer of 0 to 15, wherein the two ends of the R ₁ are respectively bonded to a nitrogen atom: In the formula (II), R ₁ represents an aliphatic group having a carbon number of 6 to 13, and the R ₂ represents . A polymer film formed by the polyimide-based polymer material according to claim 4, wherein the polymer film has a transmittance of not less than 50 for one wavelength of light of 330 nm to 480 nm. %. The polymer film as set forth in claim 5, wherein one of the polymer films has a yellowing b value of 5 to 15.9. The polymer film as set forth in claim 5, wherein one of the polymer films has a modulus of not less than 1660 MPa. A patterned polymer film formed by subjecting a polyimine compound according to any one of claims 1 to 3 to a lithography process, wherein the patterned polymer film is at a wavelength The transmittance of one of the light of 330 nm to 480 nm is not less than 50%.