JP7251749B2 - Polyguanamine, polyguanamine film, and method for producing polyguanamine - Google Patents

Description

The present invention relates to polyguanamine, polyguanamine films, and methods for producing polyguanamine.

In recent years, as mobile phones, digital cameras, displays, and other electronic devices have become more sophisticated, they have become smaller, lighter, and more flexible. Expectations for resin films are increasing.

In the process of forming desired functional elements on a transparent resin film, the transparent resin film is often exposed to high temperatures. For example, formation of functional elements such as polysilicon and oxide semiconductors requires a process in a temperature range of about 200.degree. C. to 600.degree. In the production of a hydrogenated amorphous silicon thin film, a temperature of about 200-300° C. may be applied to the film. heating may be required. Therefore, the transparent resin film is required to have heat resistance, but as a matter of fact, the number of transparent resin films that can withstand practical use in such a high temperature range is limited.

On the other hand, polyguanamine is attracting attention as a functional polymer material because it contains a triazine ring in its main chain and has good thermal and mechanical properties. In particular, ring-containing polyguanamines having a cyclic guanamine skeleton in the main chain are much more effective than straight-chain polyguanamines without a cyclic guanamine skeleton due to their aggregation properties due to intermolecular multiple hydrogen bonds resulting from the introduction of the cyclic guanamine skeleton. It is known to have high heat resistance, and a film made of polyguanamine is expected as a resin film that can withstand practical use in the above-mentioned high temperature range (see, for example, Non-Patent Documents 1 and 2). .

Haruki Sasaki, Tomohiro Kotaki, Yuji Shibasaki, Yoshiyuki Oishi, "Synthesis and Properties of Polyguanamines Containing Cyclic Guanamines", The Society of Polymer Science, 2018, vol. 67, No. 1, 3Pc003 Haruki Sasaki, Tomohiro Kotaki, Yuji Shibasaki, Yoshiyuki Oishi, "Elucidation of packing of polyguanamine containing high strength and high heat resistance cyclic guanamine", The Society of Polymer Science, 2018, vol. 67, No. 2, 2 Pe003

However, although the films made of ring-containing polyguanamine that have been reported so far have heat resistance that can withstand practical use in a high temperature range, they are insufficient in colorless transparency. However, it has not been used in place of glass substrates in the applications of display devices and other various electronic devices.

The present invention has been made in view of the above-described problems, and an object thereof is to provide a polyguanamine from which a polyguanamine film having both colorless transparency and heat resistance can be obtained. Another object of the present invention is to provide a polyguanamine film having both colorless transparency and heat resistance. Another object of the present invention is to provide a method for producing the polyguanamine.

As a result of intensive research on polyguanamine, the present inventors have found a polyguanamine capable of obtaining a polyguanamine film having both colorless transparency and heat resistance, and a method for producing the polyguanamine. The present invention has been completed.

That is, the polyguanamine according to the present invention is
A repeating unit represented by the following formula (1) (wherein A is a divalent organic group having an aromatic ring structure and/or an alicyclic structure),
It has a glass transition temperature of 350° C. or higher, a total light transmittance of 85% or higher, and a yellow index of 10 or lower when measured as a film having a thickness of 5 μm.

According to the configuration, since the glass transition temperature is 350° C. or higher, the polyguanamine film obtained using the polyguanamine has excellent heat resistance. Moreover, since the total light transmittance is 85% or more, the polyguanamine film obtained using the polyguanamine has high transparency. Moreover, since the yellow index is 10 or less, it can be said that the polyguanamine film obtained by using the polyguanamine is colorless.
That is, according to the polyguanamine according to the above configuration, the glass transition temperature is 350° C. or higher, the total light transmittance is 85% or higher, and the yellow index is 10 or lower. It is possible to obtain a polyguanamine film that also has excellent properties.

In the above structure, it is preferable that the coefficient of linear thermal expansion between 100 and 300°C is 50 ppm/°C or less.

When the linear thermal expansion coefficient is 50 ppm/°C or less, the polyguanamine film obtained using the polyguanamine is said to be more excellent in shape stability at high temperatures.

In the above constitution, the weight average molecular weight is preferably 170,000 or more.

When the weight average molecular weight is 170,000 or more, it can be said that the polyguanamine film obtained using the polyguanamine has high transparency and is colorless.

Moreover, the polyguanamine film according to the present invention is characterized by containing the polyguanamine.

According to the polyguanamine film of the above configuration, since it contains the polyguanamine, it has both colorless transparency and heat resistance.

Further, the method for producing polyguanamine according to the present invention includes:
5,17-dichlorotetraazacalix[2]arene[2]triazine and a diamine having an aromatic ring structure and/or an alicyclic structure are polymerized in an organic solvent to obtain polyguanamine,
A method for producing polyguanamine, wherein the step A is carried out under the following reaction conditions.
<Reaction conditions>
Under an inert gas atmosphere Moisture content of the organic solvent: 500 ppm or less Reaction temperature: 300°C or less Reaction time: 60 hours or less.

The present inventors have made intensive studies on a method for producing polyguanamine, and found that it is possible to improve colorless transparency by suppressing the generation of a component that colors polyguanamine (coloring component). rice field.
The present inventors presume that the coloring component is obtained by oxidizing raw materials, solvents, and decomposition products thereof for producing polyguanamine. Specifically, as the coloring component, (a) a decomposition product of 5,17-dichlorotetraazacalix[2]arene[2]triazine, which is a monomer raw material for producing polyguanamine (for example, m-phenylenediamine ( oxidized m-PDA)), (b) oxidized diamines, which are monomer raw materials for producing polyguanamine, (c) organic solvents for producing polyguanamine, and decomposition thereof I'm guessing that things are oxidized, etc.
The present inventors have found that it is possible to improve the colorless transparency by suppressing the decomposition of the raw material and the solvent, and by suppressing the oxidation of the raw material, the solvent, and decomposition products thereof. Found it.
As a result of intensive studies by the present inventors, 5,17-dichlorotetraazacalix[2]arene[2]triazine and diamines having an aromatic ring structure and/or an alicyclic structure were dissolved in an organic solvent. The present inventors have found that it is possible to improve the colorless transparency by adopting the reaction conditions described above in the step A of obtaining polyguanamine by polymerization in the medium, and have completed the present invention.
According to the method for producing polyguanamine according to the present invention, in the step A, since the reaction conditions are adopted, the decomposition of the raw material and the solvent is suppressed, and the raw material, the solvent, and the Oxidation of decomposition products can be suppressed, and polyguanamine having colorless transparency can be obtained.
Moreover, according to the method for producing polyguanamine according to the present invention, 5,17-dichlorotetraazacalix[2]arene[2]triazine is used as the monomer, so that polyguanamine having excellent heat resistance can be obtained. is possible.

According to the present invention, it is possible to provide a polyguanamine from which a polyguanamine film having both colorless transparency and heat resistance can be obtained. Also, it is possible to provide a polyguanamine film having both colorless transparency and heat resistance. Also, a method for producing the polyguanamine can be provided.

Embodiments of the present invention will be described below.

[Polyguanamine]
The polyguanamine according to this embodiment is
A repeating unit represented by the following formula (1) (wherein A is a divalent organic group having an aromatic ring structure and/or an alicyclic structure),
It has a glass transition temperature of 350° C. or higher, a total light transmittance of 85% or higher, and a yellow index of 10 or lower when measured as a film having a thickness of 5 μm.

As used herein, "polyguanamine" includes impurities that may be mixed during production (during synthesis) unless otherwise specified. That is, the term "polyguanamine" as used herein refers to a composition containing pure polyguanamine containing no impurities and impurities that may be mixed during production (pure polyguanamine containing no impurities and It means a composition (high-purity polyguanamine) containing and not containing impurities.
The glass transition temperature, the total light transmittance, and the yellow index of the polyguanamine should satisfy the numerical ranges described above, and it does not matter whether the impurities (for example, coloring components) are included.

A is a divalent organic group having an aromatic ring structure and/or an alicyclic structure. The above A has a structure in which two amino groups (NH ₂ groups) are binding terminals (two amino This is a structure in which this portion serves as a bond instead of a group).

The polyguanamine has a glass transition temperature of 350° C. or higher, preferably 400° C. or higher, more preferably 450° C. or higher, when measured as a film having a thickness of 5 μm. Further, the glass transition temperature is preferably as high as possible, and is, for example, 600° C. or lower, 575° C. or lower, or 550° C. or lower. Since the glass transition temperature is 350° C. or higher, the polyguanamine film obtained using the polyguanamine has excellent heat resistance. The glass transition temperature can be increased by containing the repeating unit represented by the above formula (1). The glass transition temperature can also be controlled, for example, by selecting the type of diamines used as monomers for producing the polyguanamine. The method for measuring the glass transition temperature is according to the method described in Examples.
The method for producing a film having a thickness of 5 μm for measuring the glass transition temperature is the method described in Example 5 or Example 6. When at least one of the films produced by the methods described in Examples 5 and 6 satisfies the numerical range of the glass transition temperature, the polyguanamine satisfies the numerical range of the glass transition temperature.

The polyguanamine has a total light transmittance of 85% or more, preferably 87% or more, and more preferably 89% or more when measured as a film having a thickness of 5 μm. Further, the total light transmittance is preferably as high as possible, but is, for example, 99% or less, 98% or less, or 97% or less. Since the total light transmittance is 85% or more, the polyguanamine film obtained using the polyguanamine has high transparency. The total light transmittance can be controlled by the conditions for producing the polyguanamine (for example, the reaction conditions for polymerization). The method for measuring the total light transmittance is according to the method described in Examples.
The method for producing a film having a thickness of 5 μm for measuring the total light transmittance is the method described in Example 5 or Example 6. When at least one of the films produced by the method described in Example 5 and Example 6 satisfies the numerical range of the total light transmittance, the polyguanamine satisfies the numerical range of the total light transmittance. do.

The polyguanamine has a yellow index (yellowness) of 10 or less, preferably 8 or less, and more preferably 6 or less when measured as a film having a thickness of 5 μm. The yellow index is preferably as small as possible, but is, for example, 0.1 or more, 0.2 or more, or 0.3 or more. Since the yellow index is 10 or less, it can be said that the polyguanamine film obtained using the polyguanamine is colorless. The yellow index can be controlled by the conditions for producing the polyguanamine (for example, the reaction conditions for polymerization). The method for measuring the yellow index is according to the method described in Examples.
The method for producing a film having a thickness of 5 μm for measuring the yellow index is the method described in Example 5 or Example 6. When at least one of the films produced by the methods described in Examples 5 and 6 satisfies the numerical range of the yellow index, the polyguanamine satisfies the numerical range of the yellow index.

The polyguanamine preferably has a linear thermal expansion coefficient of 50 ppm/° C. or less between 100 and 300° C., more preferably 40 ppm/° C. or less, still more preferably 30 ppm/° C. or less, and particularly preferably 20 ppm/°C or less. The coefficient of linear thermal expansion is preferably as small as possible, and is, for example, −20 ppm/° C. or more, −10 ppm/° C. or more, or −5 ppm/° C. or more. When the linear thermal expansion coefficient is 50 ppm/°C or less, the polyguanamine film obtained using the polyguanamine is said to be more excellent in shape stability at high temperatures. The coefficient of linear thermal expansion can be reduced by including the repeating unit represented by the above formula (1). Moreover, the linear thermal expansion coefficient can also be controlled, for example, by selecting the type of diamines as monomers for producing the polyguanamine. Specifically, the linear thermal expansion coefficient can be reduced by selecting diamines having a linear molecular structure or diamines having a fixed conformation. It can be significantly reduced by selecting diamines that are morphological. Examples of diamines having a linear molecular structure include 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl and 4-amino-N-(4-aminophenyl)benzamide. Examples of conformationally fixed diamines include 4,4′-[9H-fluorene-9,9-diyl]bisaniline. The method for measuring the coefficient of linear thermal expansion is according to the method described in Examples.

The polyguanamine preferably has a weight average molecular weight of 170,000 or more, more preferably 190,000 or more, and still more preferably 210,000 or more. Also, the weight average molecular weight is preferably 2,000,000 or less, more preferably 1,500,000 or less, and still more preferably 1,000,000 or less. When the weight average molecular weight is 170,000 or more, the polyguanamine film obtained using the polyguanamine has high transparency, colorlessness, and toughness. The weight average molecular weight can be controlled by the reaction conditions during polymerization. The method for measuring the weight average molecular weight is according to the method described in Examples.

[Polyguanamine film]
The polyguanamine film according to this embodiment contains the polyguanamine. Since the polyguanamine film according to the present embodiment contains the polyguanamine, it has both colorless transparency and heat resistance.

The content of the polyguanamine contained in the polyguanamine film is preferably 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more when the entire polyguanamine film is taken as 100% by mass. Moreover, it is also preferable that the content of the polyguanamine is 100% by mass. When the content of the polyguanamine is 50% by mass or more, higher colorless transparency and heat resistance can be obtained.

Compositions other than the polyguanamine contained in the polyguanamine film include, for example, fine particles described later in the section [Method for producing polyguanamine film] (listed as examples), and other transparent heat-resistant polymers (transparent polyimide, transparent polyamide , transparent polyamideimide, etc.).

The polyguanamine film has a glass transition temperature of 350° C. or higher, preferably 400° C. or higher, more preferably 450° C. or higher, when measured with a film thickness of 5 μm. Further, the glass transition temperature is preferably as high as possible, and is, for example, 600° C. or less, 575° C. or less, or 550° C. or less. When the glass transition temperature is 350°C or higher, the heat resistance is excellent.
Even when the thickness of the polyguanamine film is not 5 μm, the glass transition temperature is the same as when the thickness is 5 μm.

The polyguanamine film has a total light transmittance of 85% or more, preferably 87% or more, more preferably 89% or more, when measured with a film thickness of 5 μm. Further, the total light transmittance is preferably as high as possible, but is, for example, 99% or less, 98% or less, or 97% or less. Transparency is high in the said total light transmittance being 85 % or more.
When the thickness of the polyguanamine film is not 5 μm, whether or not the total light transmittance of the polyguanamine film satisfies the numerical range is determined as follows.
(1) Films with a thickness greater than 5 μm are measured as they are. If the measurement result of a film having a thickness of more than 5 μm satisfies the numerical range, the film having a thickness of 5 μm also satisfies the numerical range.
(2) For films with a thickness of less than 5 µm, if the film is soluble in an organic solvent, the film is re-dissolved in the organic solvent, coated and dried to form a film with a thickness of 5 µm and measured. The solvent water content, resin concentration, and drying conditions of the resin solution at this time are the same as in Example 6.

The polyguanamine film has a yellow index (yellowness) of 10 or less, preferably 8 or less, and more preferably 6 or less when measured with a film thickness of 5 μm. The yellow index is preferably as small as possible, but is, for example, 0.1 or more, 0.2 or more, or 0.3 or more. Since the yellow index is 10 or less, it can be said to be colorless.
When the thickness of the polyguanamine film is not 5 μm, whether or not the yellow index of the polyguanamine film satisfies the numerical range is determined as follows.
(1) Films with a thickness greater than 5 μm are measured as they are. If the measurement result of a film having a thickness of more than 5 μm satisfies the numerical range, the film having a thickness of 5 μm also satisfies the numerical range.
(2) For films with a thickness of less than 5 µm, if the film is soluble in an organic solvent, the film is re-dissolved in the organic solvent, coated and dried to form a film with a thickness of 5 µm and measured. The solvent water content, resin concentration, and drying conditions of the resin solution at this time are the same as in Example 6.

Although the thickness of the polyguanamine film is not particularly limited, it is preferably 3 μm or more, more preferably 11 μm or more, still more preferably 24 μm or more, and still more preferably 45 μm or more. Also, the thickness of the polyguanamine film is preferably 250 μm or less, more preferably 150 μm or less, and still more preferably 90 μm or less. When the thickness of the polyguanamine film is 250 µm or less, it can be suitably used particularly for flexible electronic devices.

[Method for producing polyguanamine]
The method for producing polyguanamine according to this embodiment includes:
5,17-dichlorotetraazacalix[2]arene[2]triazine and a diamine having an aromatic ring structure and/or an alicyclic structure are polymerized in an organic solvent to obtain polyguanamine,
The step A is carried out under the following reaction conditions.
<Reaction conditions>
Under an inert gas atmosphere Moisture content of the organic solvent: 500 ppm or less Reaction temperature: 300°C or less Reaction time: 60 hours or less.

5,17-dichlorotetraazacalix[2]arene[2]triazine is represented by the following formula (2).

5,17-Dichlorotetraazacalix[2]arene[2]triazine can be obtained by a known technique (for example, MX Wang, HB Yang, Journal of the American Chemical Society, 126, 15412-15422, ( 2004)).

Diamines having an aromatic ring structure and/or an alicyclic structure include, for example, 2,2′-dimethyl-4,4′-diaminobiphenyl, 1,4-bis[2-(4-aminophenyl)-2- propyl]benzene, 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-bis( 4-aminophenoxy)biphenyl, 4,4′-bis(3-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis [4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1, 1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 4-amino-N-(4- aminophenyl)benzamide, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2'-trifluoromethyl-4,4'-diaminodiphenyl ether, 3,3' -diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone , 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]methane, 1,1-bis[4-(4- aminophenoxy)phenyl]ethane, 1,2-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane, 1,2-bis[4 -(4-aminophenoxy)phenyl]propane, 1,3-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1 -bis[4-(4-aminophenoxy)phenyl]butane, 1,3-bis[4-(4-aminophenoxy)phenyl]butane, 1,4-bis[4-(4-aminophenoxy)phenyl]butane , 2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2,3-bis[4-(4-aminophenoxy)phenyl]butane, 2-[4-(4-aminophenoxy)phenyl] -2-[4-(4-aminophenoxy)-3-methylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, 2-[4-(4- aminophenoxy)phenyl]-2-[4-(4-aminophenoxy)-3,5-dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]propane , 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 1,3 -bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ketone , bis[4-(4-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfoxide, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3- aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, 1,3-bis[4-(4-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(3- aminophenoxy)benzoyl]benzene, 1,4-bis[4-(3-aminophenoxy)benzoyl]benzene, 4,4'-bis[(3-aminophenoxy)benzoyl]benzene, 1,1-bis[4- (3-aminophenoxy)phenyl]propane, 1,3-bis[4-(3-aminophenoxy)phenyl]propane, 3,4′-diaminodiphenyl sulfide, 2,2-bis[3-(3-aminophenoxy) ) phenyl]-1,1,1,3,3,3-hexafluoropropane, bis[4-(3-aminophenoxy)phenyl]methane, 1,1-bis[4-(3-aminophenoxy)phenyl] Ethane, 1,2-bis[4-(3-aminophenoxy)phenyl]ethane, bis[4-(3-aminophenoxy)phenyl]sulfoxide, 4,4′-bis[3-(4-aminophenoxy)benzoyl ] Diphenyl ether, 4,4′-bis[3-(3-aminophenoxy)benzoyl]diphenyl ether, 4,4′-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4 '-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfone, bis[4-{4-(4-aminophenoxy)phenoxy}phenyl]sulfone, 1,4-bis[4- (4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4- (4-amino-6-trifluoromethylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-fluorophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-methylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-cyanophenoxy)-α,α -dimethylbenzyl]benzene, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'-diphenoxybenzophenone, 3,4'-diamino-4,5'- Diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'- Phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone , 3,3′-diamino-4-biphenoxybenzophenone, 4,4′-diamino-5-biphenoxybenzophenone, 3,4′-diamino-4-biphenoxybenzophenone, 3,4′-diamino-5′- Biphenoxybenzophenone, 1,3-bis(3-amino-4-phenoxybenzoyl)benzene, 1,4-bis(3-amino-4-phenoxybenzoyl)benzene, 1,3-bis(4-amino-5- phenoxybenzoyl)benzene, 1,4-bis(4-amino-5-phenoxybenzoyl)benzene, 1,3-bis(3-amino-4-biphenoxybenzoyl)benzene, 1,4-bis(3-amino- 4-biphenoxybenzoyl)benzene, 1,3-bis(4-amino-5-biphenoxybenzoyl)benzene, 1,4-bis(4-amino-5-biphenoxybenzoyl)benzene, 2,6-bis[ 4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzonitrile, 4,4′-[9H-fluorene-9,9-diyl]bisaniline (also known as “9,9-bis(4-aminophenyl) fluorene”), spiro(xanthene-9,9′-fluorene)-2,6-diylbis(oxycarbonyl)]bisaniline, 4,4′-[spiro(xanthene-9,9′-fluorene)-2,6- diylbis(oxycarbonyl)]bisaniline, 4,4′-[spiro(xanthene-9,9′-fluorene)-3,6-diylbis(oxycarbonyl)]bisaniline, 5-amino-2-(p-aminophenyl) benzoxazole, 6-amino-2-(p-aminophenyl)benzoxazole, 5-amino-2-(m-aminophenyl)benzoxazole, 6-amino-2-(m-aminophenyl)benzoxazole, 2, 2′-p-phenylenebis(5-aminobenzoxazole), 2,2′-p-phenylenebis(6-aminobenzoxazole), 1-(5-aminobenzoxazolo)-4-(6-aminobenzo oxazolo)benzene, 2,6-(4,4'-diaminodiphenyl)benzo[1,2-d:5,4-d']bisoxazole, 2,6-(4,4'-diaminodiphenyl)benzo [1,2-d:4,5-d′]bisoxazole, 2,6-(3,4′-diaminodiphenyl)benzo[1,2-d:5,4-d′]bisoxazole, 2, 6-(3,4′-diaminodiphenyl)benzo[1,2-d:4,5-d′]bisoxazole, 2,6-(3,3′-diaminodiphenyl)benzo[1,2-d: 5,4-d']bisoxazole, 2,6-(3,3'-diaminodiphenyl)benzo[1,2-d:4,5-d']bisoxazole, 1,4-diaminocyclohexane, 1, 4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino- 2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 4,4'-methylenebis (2,6-dimethylcyclohexylamine), cyclohexane-1,4-diyldimethanamine, bicyclo[2,2,1]heptane-2,5-diamine, and aromatic rings and/or alicyclic rings of the above diamines part or all of the hydrogen atoms above are replaced with halogen atoms, alkyl or alkoxyl groups having 1 to 3 carbon atoms, cyano groups, or part or all of the hydrogen atoms of alkyl or alkoxyl groups are substituted with halogen atoms Examples thereof include diamines substituted with a halogenated alkyl group or alkoxyl group having 1 to 3 carbon atoms. Among these, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, m-phenylenediamine, p-phenylenediamine, 4-amino-N-(4-aminophenyl)benzamide, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 3,4 '-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4,4'-[9H-fluorene-9,9-diyl]bisaniline, 1,4-diaminocyclohexane, 1, 4-diamino-2-methylcyclohexane is preferred, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 4-amino-N-(4-aminophenyl)benzamide, 3,4′- More preferred are diaminodiphenyl ether, 3,4′-diaminodiphenyl sulfone, 4,4′-[9H-fluorene-9,9-diyl]bisaniline, 1,4-diaminocyclohexane, and 2,2′-bis(trifluoromethyl )-4,4′-diaminobiphenyl, 4-amino-N-(4-aminophenyl)benzamide, and 4,4′-[9H-fluorene-9,9-diyl]bisaniline are more preferred. Incidentally, the diamines having an aromatic structure and/or an alicyclic structure may be used singly or in combination.

The mixing ratio (molar ratio) of the raw material monomers is expressed by [5,17-dichlorotetraazacalix[2]arene[2]triazine]/[diamine], preferably 0.800 to 1.200/ 1.200 to 0.800, more preferably 0.900 to 1.100/1.100 to 0.900, still more preferably 0.950 to 1.050/1.050 to 0.950. By mixing the raw material monomers at the above mixing ratio, a high-molecular-weight polyguanamine can be obtained, and the polyguanamine film obtained using the polyguanamine has high transparency and is colorless. It can be said that it is strong.

The step A is carried out under the following reaction conditions. Step A (polymerization step) may be carried out continuously, or may be carried out by dividing the polymerization reaction as necessary. In addition, the reaction temperature may be increased or decreased within the following reaction conditions.
<Reaction conditions>
Under an inert gas atmosphere Moisture content of the organic solvent: 500 ppm or less Reaction temperature: 300°C or less Reaction time: 60 hours or less.

The inert gas is not particularly limited as long as it cannot react with either the raw material monomer or the product polyguanamine, but examples include nitrogen gas and rare gases (e.g., helium gas, neon gas, argon gas). etc. Mixing of oxygen can be suppressed by performing the step A in an inert gas atmosphere. Therefore, it is possible to suppress the oxidation of raw materials, organic solvents, and decomposition products thereof, and to reduce the amount of by-products. As a result, the heat resistance and colorless transparency of the finally obtained polyguanamine can be enhanced.

The inert gas atmosphere in the reaction conditions of the step A preferably has an oxygen concentration of less than 2.0%. The content is preferably 1.5% or less, more preferably 1.0% or less, even more preferably 1.0% or less, because the colorless transparency of polyguanamine can be improved. Since a lower oxygen concentration is preferable, the lower limit is not particularly limited.

The organic solvent is not particularly limited as long as it can dissolve both the raw material monomer and the product polyguanamine. Examples include N-methyl-2-pyrrolidone, N-acetyl-2- Examples include pyrrolidone, N,N-dimethylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, etc. These solvents can be used alone or in combination.

The moisture content of the organic solvent is preferably 500 ppm or less, more preferably 400 ppm or less, still more preferably 300 ppm or less, even more preferably 200 ppm or less, and even more preferably 100 ppm or less. Although the moisture content is preferably as small as possible, it is, for example, 1 ppm or more, 2 ppm or more, or 3 ppm or more. By setting the moisture content to 500 ppm or less, decomposition of raw materials and organic solvents can be suppressed, and the amount of by-products can be reduced. As a result, the heat resistance and colorless transparency of the finally obtained polyguanamine can be enhanced. The means for reducing the moisture content to 500 ppm or less is not particularly limited, but examples thereof include a method of dehydration with a dehydrating agent and a method of distillation.

The organic solvent is preferably subjected to bubbling treatment with the inert gas for preferably 10 minutes or longer, more preferably 20 minutes or longer, and still more preferably 30 minutes or longer. By performing the bubbling treatment for 10 minutes or more, oxygen in the organic solvent can be removed, and coloring in the polymerization step can be suppressed.

The reaction temperature is preferably 300° C. or lower, more preferably 250° C. or lower, and even more preferably 200° C. or lower. By setting the reaction temperature to 300° C. or lower, decomposition of the raw materials and the organic solvent can be suppressed, and the amount of by-products can be reduced. As a result, the heat resistance and colorless transparency of the finally obtained polyguanamine can be enhanced. The reaction temperature can be 50° C. or higher, 75° C. or higher, 100° C. or higher, or the like, from the viewpoint of yield improvement.

The reaction time is preferably within 60 hours, more preferably within 30 hours, still more preferably within 10 hours, and even more preferably within 5 hours. By setting the reaction temperature within 60 hours, decomposition of raw materials and organic solvents can be suppressed, and the amount of by-products can be reduced. As a result, the heat resistance and colorless transparency of the finally obtained polyguanamine can be enhanced. From the viewpoint of improving the yield, the reaction temperature can be set to 0.1 hours or more, 0.5 hours or more, or 1.0 hours or more.

In the step A, additives may be added. Examples of the additive include those that suppress aggregation between polyguanamine molecular chains, and those that capture and/or neutralize hydrogen chloride liberated during the reaction. The agent for suppressing aggregation between polyguanamine molecular chains is not particularly limited as long as the object can be achieved, and examples thereof include lithium chloride and sodium chloride. The substance that captures and/or neutralizes the hydrogen chloride liberated during the reaction is not particularly limited as long as the object can be achieved, but examples include cesium fluoride, potassium fluoride, cesium carbonate, Examples include potassium carbonate and sodium carbonate.

In step A, the pH of the reaction solution at the initial stage of the reaction is preferably in the range of 4.0 to 8.0, more preferably in the range of 4.5 to 7.5, and more preferably in the range of 5.0 to 7.5. It is more preferably within the range of 0. The pH of the reaction solution at the initial stage of the reaction is adjusted after charging 5,17-dichlorotetraazacalix[2]arene[2]triazine, diamines having an aromatic ring structure and/or an alicyclic structure, an organic solvent, etc., and stirring. A suitable amount of the reaction solution was sampled 10 minutes after the start of , and 20% by mass of deionized water was added to the sample solution, which was then measured using pH test paper. When the pH of the reaction solution at the initial stage of the reaction is within the range of 4.0 to 8.0, it is possible to prevent the polyguanamine from being strongly colored during the polymerization.

The terminal amino group of the polyguanamine is preferably 50 eq/t or less, more preferably 10 eq/t or less, in order to obtain a polyguanamine film excellent in colorless transparency.

Methods for reducing the terminal amino groups of the polyguanamine include a method of increasing the molecular weight, a method of using an excessive amount of dicarboxylic acid anhydride, and a method of terminal blocking with a monofunctional monomer. A polymer with more than 100-mer is preferable in order to obtain a polyguanamine film excellent in colorless transparency.

As the blocking agent for blocking the terminal amino group of the polyguanamine, for example, dicarboxylic acid anhydrides and acid chlorides are used. Those having groups are not preferable because they tend to be colored during heat treatment. Preferred dicarboxylic anhydrides include alicyclic dicarboxylic anhydrides such as cyclohexane-1,2-dicarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride and cyclohexane-1,3-dicarboxylic anhydride. and preferred acid chlorides include, but are not limited to, alicyclic acid chlorides such as cyclohexanecarbonyl chloride. These can also be used individually or in combination of 2 or more types.

In the first step A, the surrounding atmosphere when weighing and adding the raw material monomers and the like is not particularly limited, but the atmosphere is preferably replaced with the inert gas. In addition, there is a method of measuring the oxygen concentration of the atmosphere as an index for judging the degree of substitution with the inert gas. The oxygen concentration is preferably 1.5% or less, more preferably 1.0% or less, and 0.5. % or less is more preferable. By substituting with the inert gas until the oxygen concentration becomes 1.5% or less, it is possible to suppress the mixing of oxygen and water into the polymerization system during weighing and addition, and suppress coloring in the polymerization process. be able to.

In step A, the order of addition of the raw material monomers and the like is not particularly limited, but it is preferable to add 5,17-dichlorotetraazacalix[2]arene[2]triazine to the solution of aromatic diamines. However, when using a terminal blocking agent, it is preferable to add the terminal blocking agent after the synthesis of polyguanamine is completed.

The amount of the organic solvent used may be an amount sufficient to dissolve the raw material monomers, etc., and is usually an amount such that the solid content is 1 to 50% by mass, preferably the solid content is 5 to 35 mass%. %.

After step A, the polyguanamine obtained by the reaction may be reprecipitated from the reaction solution using a suitable poor solvent. Examples of the poor solvent include acetone, methanol, ethanol, and water, but are not particularly limited to these as long as they can efficiently reprecipitate. Also, the solvent for removing the residual reaction solvent after reprecipitation is not particularly limited, but it is preferable to use the solvent used for reprecipitation.

Polyguanamine can be obtained by drying after reprecipitation.

The polyguanamine obtained by the above production method can be used in the form of a solution containing polyguanamine as it is in the reaction solution after step A. Further, after the step A, the polyguanamine reprecipitated from the reaction solution by the above method can be dissolved again in the solvent to be available in the form of a solution containing polyguanamine. In the latter case, it is not particularly limited as long as it efficiently dissolves polyguanamine. Examples include o-cresol, m-cresol, p-cresol, N-methyl-2-pyrrolidone, N- Organic solvents such as acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, sulfolane, and halogenated phenols can be mentioned.

The means for mixing the polyguanamine and the solvent is not particularly limited, but for example, a method of mixing and stirring using a normal stirring blade, a stirring blade for high viscosity, a multi-screw extruder, or a static mixer is used. Further, mixing and stirring using a method using a high-viscosity mixing and dispersing machine such as a roll mill can be mentioned.

The content of polyguanamine in the polyguanamine solution obtained by the production method is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. In this case, the viscosity of the polyguanamine solution is preferably 0.1 to 2000 Pa·s, more preferably 1 to 1000 Pa·s, as measured by a Brookfield viscometer, in that stable liquid transfer is possible. .

[Method for producing polyguanamine film]
The method for producing a polyguanamine film according to this embodiment includes:
Step A-1 of preparing a guanamine solution;
A step B of applying a guanamine solution onto a substrate;
C. drying the guanamine solution coated on the substrate to remove the solvent.

As the guanamine solution prepared in step A-1, the guanamine solution described in step A can be used. When adding an additive other than guanamine and a solvent to the guanamine solution, step A-1 is obtained by adding a step of adding an additive (for example, fine particles) in step A. good.

As described above, in step A-1, fine particles may be added to the guanamine solution for the purpose of improving performance.

Examples of the timing of adding the fine particles include a method of adding and dispersing the fine particles in an organic solvent before synthesizing polyguanamine, followed by polymerization, a method of adding during the polymerization, a method of adding after the completion of polymerization, and the like. mentioned. From the viewpoint of making the fine particles less likely to agglomerate and dispersing them uniformly and efficiently, it is preferable to add the fine particles to an organic solvent before synthesizing the polyguanamine, disperse them, and then polymerize them.

The fine particles may be inorganic fine particles or organic fine particles, but preferably have an average particle diameter of 0.05 μm or more and 1 μm or less, more preferably 0.1 μm or more and 0.5 μm or less. By setting the average particle size to 0.05 μm or more, the resulting film can be imparted with sufficient slipperiness. In addition, formation of coarse particles due to secondary aggregation can be suppressed. Further, by setting the average particle size to 1 μm or less, deterioration of optical properties can be suppressed.

The inorganic fine particles are not particularly limited, and a material usually used as a filler may be used. Examples include silicon nitride, silicon oxide, titanium oxide, aluminum oxide, magnesium oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate. Moreover, these may be used in combination.

The organic fine particles are not particularly limited as long as they can be made into fine particles, but those with high heat resistance are preferred. Examples thereof include polyamide-based resins, polyimide-based resins, benzoguanamine-based resins, and melamine-based resins. Moreover, these may be used in combination.

The shape of the fine particles is preferably substantially spherical. “Substantially spherical” means that the shape of the fine particles projected onto a plane (for example, an image observed with a microscope) has an average sphericity of 0.7 or more, preferably 0.8 or more. The degree of sphericity is the ratio of the minor axis to the major axis of the circumscribed ellipse in the projection view, and if the sphericity is 1.0, it is a true sphere. The sphericity can be easily obtained by image processing of an enlarged image of particles. Average sphericity is the average of 20 randomly selected particles.

The absolute value of the difference between the refractive index of the fine particles and the refractive index of polyguanamine is preferably 0.1 or less. It should also be insoluble in all chemicals with which it comes into contact during the polyguanamine film manufacturing process.

The content of the fine particles is preferably 100 ppm or more and 2.0 mass % or less, more preferably 500 ppm or more and 0.5 mass % or less, relative to the resulting polyguanamine film. By containing the fine particles within the above range, it is possible to impart sufficient lubricity to the film. As a result, the transportability can be improved, and the occurrence of defects such as wrinkles and scratches on the film and the deterioration of the wound shape of the film when wound on a roll can be suppressed.
Moreover, by containing the fine particles within the above range, lubricity can be imparted to the film without deteriorating the optical properties of the film.

Further, in the step A-1, the guanamine solution contains surfactants such as fluorine-based and polysiloxane-based surfactants, antioxidants such as phenol-based, sulfur-based, phosphoric acid-based, and phosphorous-based antioxidants, carbon nanotubes, and nanometal Various functions may be added by adding conductive materials such as materials, ferroelectric materials such as barium titanate, phosphorus-based, halogen-based flame retardants, and other materials such as phosphors and ultraviolet absorbers. .

In step B, the method of applying the polyguanamine solution onto the substrate is not particularly limited, but examples include a method of spin coating such as spin coating, a method using a squeegee such as a doctor blade, an applicator, or a comma coater, and a screen printing method. etc.

The substrate is not particularly limited, but examples thereof include inorganic substrates such as silicon wafers, glass substrates and copper foils, and organic substrates such as polyethylene terephthalate films and polyimide films. The base material is preferably a base material that constitutes an electrical/electronic component, a wiring board, or the like.

In step C, the drying temperature condition for removing the solvent from the polyguanamine solution coated on the substrate is preferably 60° C. or higher, more preferably 120° C. or higher, and still more preferably 180° C. or higher. By setting the drying temperature to 60° C. or higher, the drying time can be shortened and sufficient drying can be performed. Moreover, the drying temperature condition is preferably 500° C. or lower, more preferably 450° C. or lower, and still more preferably 4000° C. or lower. By setting the drying temperature condition to 500° C. or lower, it is possible to prevent loss of the colorless transparency of the film due to heat deterioration. In addition, adverse effects such as deterioration of film physical properties can be prevented.

In step C, the oxygen concentration in the oven during drying is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less.

The above step C may be carried out continuously, or may be carried out dividedly as necessary. Moreover, the drying temperature may be increased or decreased within the above drying temperature conditions. As an example of performing the step C separately, "pre-baking" to make the residual amount of organic solvent in the polyguanamine film 1% or more and 50% or less, and "main drying" drying at a drying temperature higher than the temperature conditions of pre-baking drying” and “annealing” in which drying is performed at a higher temperature than the main drying. By annealing after the main drying, it is possible to make the polyguanamine molecular chains in the polyguanamine film more dense, and as a result, the heat resistance, dimensional stability, and mechanical properties of the polyguanamine film are further improved. be able to.

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Methods for evaluating physical properties in the following examples are as follows.

1. Moisture content of solvent Weigh 0.5 g of the solvent, use a Karl Fischer moisture content meter (manufactured by Hiranuma Sangyo Co., Ltd., AQ-300 type) as the device, use Aqualite RS (Kanto Chemical Co., Ltd.) as the generating liquid, and Aqua as the counter electrode liquid. Solvent water content was measured using Light CN (Kanto Kagaku Co., Ltd.).

2. Number average molecular weight (Mn) and weight average molecular weight (Mw) of polyguanamine
8 mg of polyguanamine was weighed, immersed in 8 mL of an eluent, heated and stirred at 145° C. for 10 hours, filtered through a 0.2 μm membrane filter, and the resulting solution was subjected to GPC analysis under the following conditions. was used to calculate the number average molecular weight and weight average molecular weight.
Device name: TOSOH HLC-8420GPC
Column: TSKgel SuperAWM-H×2 Eluent: DMAc/LiBr 30 mM + H ₃ PO ₄ 60 mM
Flow rate: 0.3mL/min
Concentration: 0.1%
Detector: RI detector Column temperature: 40°C
Injection volume: 10 μL
Molecular weight standard: standard polystyrene

3. Thickness of polyguanamine film The thickness of the polyguanamine film was measured using a micrometer (Millitron 1254D, Finereuf Co., Ltd.).

4. Glass transition temperature (Tg) and coefficient of linear thermal expansion (CTE) of polyguanamine film
The expansion ratio of the polyguanamine film was measured under the following conditions, and the temperature at the inflection point was defined as the glass transition temperature (Tg). A coefficient of linear thermal expansion (CTE) was calculated from the value.
Device name: TMA4000S manufactured by MAC Science
Sample length; 20mm
Sample width; 2mm
Heating start temperature; 25°C
Heating end temperature; 500°C
Temperature rise rate; 5°C/min
atmosphere; argon

5. Total light transmittance (TT) of polyguanamine film
The total light transmittance (TT) of the polyguanamine film was measured using Hazemeter (NDH5000, manufactured by Nippon Denshoku Co., Ltd.). A D65 lamp was used as the light source. In addition, the same measurement was performed 3 times and the arithmetic mean value was adopted.

6. Yellow index (YI) of polyguanamine film
Using a color meter (ZE6000, manufactured by Nippon Denshoku Co., Ltd.) and a C2 light source, the tristimulus values XYZ values of the polyguanamine film were measured according to ASTM D1925, and the yellowness index (YI) was calculated according to the following formula. In addition, the same measurement was performed 3 times and the arithmetic mean value was adopted.
YI=100×(1.28X−1.06Z)/Y

7. Tensile Breaking Strength and Tensile Breaking Elongation of Polyguanamine Film The polyguanamine film was cut into strips with a length of 100 mm and a width of 10 mm to form a test piece, and a tensile tester (manufactured by Shimadzu Corporation Autograph (trade name) model name AG-5000A) was used. ) at a tensile speed of 50 mm/min and a distance between chucks of 40 mm to determine the tensile strength at break and tensile elongation at break.

<Preparation of polyguanamine>
(Example 1)
945.00 g of low moisture content N-methyl-2-pyrrolidone (NMP) (moisture content: 50 ppm) was introduced into a 2 L reaction vessel in a glove box that was replaced with nitrogen until the oxygen concentration was 0.1% or less. and dry nitrogen was blown for about 15 minutes at a flow rate of 1.0 L/min. The moisture content of NMP after nitrogen blowing was 85 ppm. A reaction vessel was then charged with 131.70 g (0.300 mol) of 5,17-dichlorotetraazacalix[2]arene[2]triazine (TACLATA), 104.53 g (0.300 mol) of 9,9-bis(4 -Aminophenyl)fluorene (BAFL), 47.25 g of lithium chloride (LiCl) were introduced, and a nitrogen inlet tube, a reflux tube, a stirring seal, and a stirring bar were attached. Next, the reaction vessel was taken out from the glove box, and under a stream of dry nitrogen (flow rate 1.0 L/min, oxygen concentration in the reaction vessel 0.1% or less), a pale yellow reaction solution was obtained by stirring at a temperature of 150° C. for 3 hours. got Next, the reaction solution is air-cooled and reprecipitated by putting it into 30 L of a 1 wt% ammonia/methanol solution, and the obtained solid is stirred under reflux of 20 L of methanol for 3 hours, and then vacuum-dried at 180° C. for 12 hours. Polyguanamine A was thus obtained. Table 1 shows the appearance, number-average molecular weight, and weight-average molecular weight of the obtained polyguanamine A.
5,17-dichlorotetraazacalix[2]arene[2]triazine (TACLATA), 9,9-bis(4-aminophenyl)fluorene (BAFL), and lithium chloride (LiCl) were introduced into the reaction vessel. After 10 minutes from the start of stirring, a suitable amount of the reaction solution was sampled, 20% by mass of deionized water was added to the sample solution, and the pH was measured using pH test paper. The obtained pH value was defined as "the pH of the reaction solution at the beginning of the reaction". Table 1 shows the pH of the reaction solution at the initial stage of the reaction. In the following examples and comparative examples, the pH of the reaction solution at the initial stage of the reaction was similarly measured. Table 1 shows the results.

(Example 2)
945.00 g of low moisture content N-methyl-2-pyrrolidone (NMP) (moisture content: 50 ppm) was introduced into a 2 L reaction vessel in a glove box that was replaced with nitrogen until the oxygen concentration was 0.1% or less. and dry nitrogen was blown for about 15 minutes at a flow rate of 1.0 L/min. The moisture content of NMP after nitrogen blowing was 84 ppm. A reaction vessel was then charged with 131.70 g (0.300 mol) of 5,17-dichlorotetraazacalix[2]arene[2]triazine (TACLATA), 104.53 g (0.300 mol) of 9,9-bis(4 -Aminophenyl)fluorene (BAFL), 47.25 g of lithium chloride (LiCl) were introduced, and a nitrogen inlet tube, a reflux tube, a stirring seal, and a stirring bar were attached. Next, the reaction vessel was taken out from the glove box, and under a stream of dry nitrogen (flow rate 1.0 L/min, oxygen concentration in the reaction vessel 0.1% or less), a light yellow reaction solution was obtained by stirring at a temperature of 150° C. for 6 hours. got Next, the reaction solution is air-cooled and reprecipitated by putting it into 30 L of a 1 wt% ammonia/methanol solution, and the obtained solid is stirred under reflux of 20 L of methanol for 3 hours, and then vacuum-dried at 180° C. for 12 hours. Polyguanamine B was thus obtained. Table 1 shows the appearance, number average molecular weight and weight average molecular weight of Polyguanamine B thus obtained.

(Example 3)
945.00 g of low moisture content N-methyl-2-pyrrolidone (NMP) (moisture content: 50 ppm) was introduced into a 2 L reaction vessel in a glove box that was replaced with nitrogen until the oxygen concentration was 0.1% or less. and dry nitrogen was blown for about 15 minutes at a flow rate of 1.0 L/min. The moisture content of NMP after nitrogen blowing was 82 ppm. A reaction vessel was then charged with 131.70 g (0.300 mol) of 5,17-dichlorotetraazacalix[2]arene[2]triazine (TACLATA), 96.07 g (0.300 mol) of 2,2′-bis( Trifluoromethyl)-4,4′-diaminobiphenyl (TFMB) and 47.25 g of lithium chloride (LiCl) were introduced, and a nitrogen inlet tube, a reflux tube, a stirring seal and a stirring bar were attached. Next, the reaction vessel was taken out from the glove box, and under a stream of dry nitrogen (flow rate 1.0 L/min, oxygen concentration in the reaction vessel 0.1% or less), a pale yellow reaction solution was obtained by stirring at a temperature of 150° C. for 3 hours. got Next, the reaction solution is air-cooled and reprecipitated by putting it into 30 L of a 1 wt% ammonia/methanol solution, and the obtained solid is stirred under reflux of 20 L of methanol for 3 hours, and then vacuum-dried at 180°C for 12 hours. Polyguanamine C was thus obtained. Table 1 shows the appearance, number average molecular weight and weight average molecular weight of Polyguanamine C thus obtained.

(Example 4)
945.00 g of low moisture content N-methyl-2-pyrrolidone (NMP) (moisture content: 50 ppm) was introduced into a 2 L reaction vessel in a glove box that was replaced with nitrogen until the oxygen concentration was 0.1% or less. and dry nitrogen was blown for about 15 minutes at a flow rate of 1.0 L/min. The moisture content of NMP after nitrogen blowing was 80 ppm. A reaction vessel was then charged with 131.70 g (0.300 mol) of 5,17-dichlorotetraazacalix[2]arene[2]triazine (TACLATA), 68.18 g (0.300 mol) of 4-amino-N-( 4-Aminophenyl)benzamide (DABAN), 47.25 g of lithium chloride (LiCl) were introduced, and a nitrogen inlet tube, a reflux tube, a stirring seal, and a stirring bar were attached. Next, the reaction vessel was taken out from the glove box, and under a stream of dry nitrogen (flow rate 1.0 L/min, oxygen concentration in the reaction vessel 0.1% or less), a pale yellow reaction solution was obtained by stirring at a temperature of 150° C. for 3 hours. got Next, the reaction solution is air-cooled and reprecipitated by putting it into 30 L of a 1 wt% ammonia/methanol solution, and the obtained solid is stirred under reflux of 20 L of methanol for 3 hours, and then vacuum-dried at 180°C for 12 hours. Polyguanamine D was thereby obtained. Table 1 shows the appearance, number average molecular weight and weight average molecular weight of Polyguanamine D thus obtained.

(Comparative example 1)
945.00 g of N-methyl-2-pyrrolidone (NMP) (moisture content: 300 ppm), 131.70 g (0 5,17-dichlorotetraazacalix[2]arene[2]triazine (TACLATA), 104.53 g (0.300 mol) of 9,9-bis(4-aminophenyl)fluorene (BAFL), 47 0.25 g of lithium chloride (LiCl) was introduced, and a nitrogen inlet tube, a reflux tube, a stir seal, and a stir bar were attached. Next, the reaction vessel was removed from the glove box and stirred at a temperature of 150° C. for 3 hours under a stream of dry nitrogen (flow rate 0.1 L/min, oxygen concentration in the reaction vessel 5.0%) to obtain a brown reaction solution. rice field. Next, the reaction solution is air-cooled and reprecipitated by putting it into 30 L of a 1 wt% ammonia/methanol solution, and the obtained solid is stirred under reflux of 20 L of methanol for 3 hours, and then vacuum-dried at 180°C for 12 hours. Polyguanamine E was thereby obtained. Table 1 shows the appearance, number average molecular weight, and weight average molecular weight of Polyguanamine E obtained.

(Comparative example 2)
945.00 g of N-methyl-2-pyrrolidone (NMP) (moisture content: 250 ppm), 131.70 g (0 5,17-dichlorotetraazacalix[2]arene[2]triazine (TACLATA), 104.53 g (0.300 mol) of 9,9-bis(4-aminophenyl)fluorene (BAFL), 47 0.25 g of lithium chloride (LiCl) was introduced, and a nitrogen inlet tube, a reflux tube, a stir seal, and a stir bar were attached. Next, the reaction vessel was removed from the glove box and stirred at a temperature of 180° C. for 3 hours under a stream of dry nitrogen (flow rate 0.3 L/min, oxygen concentration in the reaction vessel 2.0%) to obtain a brown reaction solution. rice field. Next, the reaction solution is air-cooled and reprecipitated by putting it into 30 L of a 1 wt% ammonia/methanol solution, and the obtained solid is stirred under reflux of 20 L of methanol for 3 hours, and then vacuum-dried at 180°C for 12 hours. Polyguanamine F was thus obtained. Table 1 shows the appearance, number average molecular weight and weight average molecular weight of Polyguanamine F thus obtained.

<Preparation of polyguanamine film>
(Example 5)
150 g of polyguanamine A and 850 g of low-moisture content N,N'-dimethylacetamide (DMAc) (moisture content: 45 ppm) were introduced into a 2 L reaction vessel, equipped with a nitrogen introduction tube, a stirring seal, and a stirring bar, and dried. A polyguanamine resin solution was obtained by stirring at room temperature for 1 hour under a nitrogen stream. Next, the polyguanamine resin solution was applied onto a polyester film having a thickness of 188 μm, placed in an inert oven, and heat-treated at 80° C. for 30 minutes under a stream of dry nitrogen to obtain a semi-dried film (green film). Next, the green film was peeled off from the PET film, fixed to a metal frame, placed in an inert oven, and replaced with nitrogen at room temperature for 1.5 hours to reduce the oxygen concentration in the inert oven to 0.9% or less. , the temperature was raised to 150° C. over 10 minutes, and heat treatment was performed at 150° C. for 2 hours to obtain a colorless and transparent polyguanamine film having a thickness of 5 μm. Table 2 shows the physical properties of the obtained polyguanamine film.

(Example 6)
150 g of polyguanamine A and 850 g of low-moisture content N,N'-dimethylacetamide (DMAc) (moisture content: 48 ppm) were introduced into a 2 L reaction vessel, equipped with a nitrogen introduction tube, a stirring seal, and a stirring bar, and dried. A polyguanamine resin solution was obtained by stirring at room temperature for 1 hour under a nitrogen stream. Next, the polyguanamine resin solution was applied onto a polyester film having a thickness of 188 μm, placed in an inert oven, and heat-treated at 80° C. for 30 minutes under a stream of dry nitrogen to obtain a semi-dried film (green film). Next, the green film was peeled off from the PET film, fixed to a metal frame, placed in an inert oven, and replaced with nitrogen at room temperature for 1.5 hours to reduce the oxygen concentration in the inert oven to 0.9% or less. , heated to 150° C. over 10 minutes, heat-treated at 150° C. for 2 hours, further heated to 250° C. over 10 minutes, and heated at 250° C. for 3 hours to obtain a colorless and transparent film having a thickness of 5 μm. A polyguanamine film was obtained. Table 2 shows the physical properties of the obtained polyguanamine film.

(Example 7)
150 g of polyguanamine B and 850 g of low-moisture content N,N'-dimethylacetamide (DMAc) (moisture content: 45 ppm) were introduced into a 2 L reaction vessel, equipped with a nitrogen introduction tube, a stirring seal, and a stirring bar, and dried. A polyguanamine resin solution was obtained by stirring at room temperature for 1 hour under a nitrogen stream. Next, the polyguanamine resin solution was applied onto a polyester film having a thickness of 188 μm, placed in an inert oven, and heat-treated at 80° C. for 30 minutes under a stream of dry nitrogen to obtain a semi-dried film (green film). Next, the green film was peeled off from the PET film, fixed to a metal frame, placed in an inert oven, and replaced with nitrogen at room temperature for 1.5 hours to reduce the oxygen concentration in the inert oven to 0.9% or less. , heated to 150° C. over 10 minutes, heat-treated at 150° C. for 2 hours, further heated to 250° C. over 10 minutes, and heated at 250° C. for 3 hours to obtain a colorless and transparent film having a thickness of 5 μm. A polyguanamine film was obtained. Table 2 shows the physical properties of the obtained polyguanamine film.

(Example 8)
150 g of polyguanamine C and 850 g of low-moisture content N,N'-dimethylacetamide (DMAc) (moisture content: 47 ppm) were introduced into a 2 L reaction vessel, equipped with a nitrogen introduction tube, a stirring seal, and a stirring bar, and dried. A polyguanamine resin solution was obtained by stirring at room temperature for 1 hour under a nitrogen stream. Next, the polyguanamine resin solution was applied onto a polyester film having a thickness of 188 μm, placed in an inert oven, and heat-treated at 80° C. for 30 minutes under a stream of dry nitrogen to obtain a semi-dried film (green film). Next, the green film was peeled off from the PET film, fixed to a metal frame, placed in an inert oven, and replaced with nitrogen at room temperature for 1.5 hours to reduce the oxygen concentration in the inert oven to 0.9% or less. , heated to 150° C. over 10 minutes, heat-treated at 150° C. for 2 hours, further heated to 250° C. over 10 minutes, and heated at 250° C. for 3 hours to obtain a colorless and transparent film having a thickness of 5 μm. A polyguanamine film was obtained. Table 2 shows the physical properties of the obtained polyguanamine film.

(Example 9)
150 g of polyguanamine D and 850 g of low-moisture content N,N'-dimethylacetamide (DMAc) (moisture content: 42 ppm) were introduced into a 2 L reaction vessel, equipped with a nitrogen inlet tube, a stirring seal, and a stirring bar, and dried. A polyguanamine resin solution was obtained by stirring at room temperature for 1 hour under a nitrogen stream. Next, the polyguanamine resin solution was applied onto a polyester film having a thickness of 188 μm, placed in an inert oven, and heat-treated at 80° C. for 30 minutes under a stream of dry nitrogen to obtain a semi-dried film (green film). Next, the green film was peeled off from the PET film, fixed to a metal frame, placed in an inert oven, and replaced with nitrogen at room temperature for 1.5 hours to reduce the oxygen concentration in the inert oven to 0.9% or less. , heated to 150° C. over 10 minutes, heat-treated at 150° C. for 2 hours, further heated to 250° C. over 10 minutes, and heated at 250° C. for 3 hours to obtain a colorless and transparent film having a thickness of 5 μm. A polyguanamine film was obtained. Table 2 shows the physical properties of the obtained polyguanamine film.

(Comparative Example 3)
150 g of polyguanamine E and 850 g of low-moisture content N,N'-dimethylacetamide (DMAc) (moisture content: 43 ppm) were introduced into a 2 L reaction vessel, equipped with a nitrogen introduction tube, a stirring seal, and a stirring bar, and dried. A polyguanamine resin solution was obtained by stirring at room temperature for 1 hour under a nitrogen stream. Next, the polyguanamine resin solution was applied onto a polyester film having a thickness of 188 μm, placed in an inert oven, and heat-treated at 80° C. for 30 minutes under a stream of dry nitrogen to obtain a semi-dried film (green film). Next, the green film was peeled off from the PET film, fixed to a metal frame, placed in an inert oven, and nitrogen was substituted at room temperature for 1.5 hours to set the oxygen concentration in the inert oven to 8.0%. The temperature was raised to 150° C. over 10 minutes, heat-treated at 150° C. for 2 hours, further heated to 250° C. over 10 minutes, and heated at 250° C. for 3 hours to obtain a yellow polyguanamine having a thickness of 5 μm. got the film. Table 3 shows the physical properties of the obtained polyguanamine film.

(Comparative Example 4)
150 g of polyguanamine E and 850 g of low-moisture content N,N'-dimethylacetamide (DMAc) (moisture content: 46 ppm) were introduced into a 2 L reaction vessel, equipped with a nitrogen introduction tube, a stirring seal, and a stirring bar, and dried. A polyguanamine resin solution was obtained by stirring at room temperature for 1 hour under a nitrogen stream. Next, the polyguanamine resin solution was applied onto a polyester film having a thickness of 188 μm, placed in an inert oven, and heat-treated at 80° C. for 30 minutes under a stream of dry nitrogen to obtain a semi-dried film (green film). Next, the green film was peeled off from the PET film, fixed to a metal frame, placed in an inert oven, and replaced with nitrogen at room temperature for 1.5 hours to reduce the oxygen concentration in the inert oven to 0.9% or less. , heated to 150° C. over 10 minutes, heat-treated at 150° C. for 2 hours, further heated to 250° C. over 10 minutes, and heated at 250° C. for 3 hours to obtain a yellow polymer having a thickness of 5 μm. A guanamine film was obtained. Table 3 shows the physical properties of the obtained polyguanamine film.

(Comparative Example 5)
150 g of polyguanamine F and 850 g of low-moisture content N,N'-dimethylacetamide (DMAc) (moisture content: 46 ppm) were introduced into a 2 L reaction vessel, fitted with a nitrogen introduction tube, a stirring seal, and a stirring bar, and dried. A polyguanamine resin solution was obtained by stirring at room temperature for 1 hour under a nitrogen stream. Next, the polyguanamine resin solution was applied onto a polyester film having a thickness of 188 μm, placed in an inert oven, and heat-treated at 80° C. for 30 minutes under a stream of dry nitrogen to obtain a semi-dried film (green film). Next, the green film was peeled off from the PET film, fixed to a metal frame, placed in an inert oven, and replaced with nitrogen at room temperature for 1.5 hours to reduce the oxygen concentration in the inert oven to 0.9% or less. , heated to 150° C. over 10 minutes, heat-treated at 150° C. for 2 hours, further heated to 250° C. over 10 minutes, and heated at 250° C. for 3 hours to obtain a yellow polymer having a thickness of 5 μm. A guanamine film was obtained. Table 3 shows the physical properties of the obtained polyguanamine film.

The polyguanamines (polyguanamines A to D) of Examples 1 to 4 were synthesized under the following reaction conditions. Therefore, by forming a film under appropriate conditions, both colorless transparency and heat resistance can be achieved. Aligned polyguanamine films could be obtained (Examples 5-9).
On the other hand, the polyguanamines of Comparative Examples 1 and 2 (polyguanamines E and F) were synthesized under reaction conditions other than the following reaction conditions. A film could not be obtained (Comparative Examples 3-5).
<Reaction conditions>
Under an inert gas atmosphere Moisture content of the organic solvent: 500 ppm or less Reaction temperature: 300°C or less Reaction time: 60 hours or less.

Here, when the thickness of the polyguanamine film is greater than 5 μm, the film is measured as it is, and the measurement result is “a glass transition temperature of 350° C. or higher, a total light transmittance of 85% or higher, and a yellow index of The following reference examples 1 to 5 will be used to explain that if the condition "10 or less" is satisfied, the numerical range is always satisfied even when the thickness is 5 μm.

(Reference example 1)
A polyguanamine film according to Reference Example 1 was obtained in the same manner as in Example 6, except that the thickness was changed to 10 μm. Table 4 shows the physical properties of the obtained polyguanamine film.

(Reference example 2)
A polyguanamine film according to Reference Example 2 was obtained in the same manner as in Example 6, except that the thickness was changed to 15 μm. Table 4 shows the physical properties of the obtained polyguanamine film.

(Reference example 3)
A polyguanamine film according to Reference Example 3 was obtained in the same manner as in Example 6, except that the thickness was changed to 25 μm. Table 4 shows the physical properties of the obtained polyguanamine film.

(Reference example 4)
A polyguanamine film according to Reference Example 4 was obtained in the same manner as in Example 6, except that the thickness was changed to 50 μm. Table 4 shows the physical properties of the obtained polyguanamine film.

(Reference example 5)
A polyguanamine film according to Reference Example 5 was obtained in the same manner as in Example 8, except that the thickness was changed to 15 μm. Table 4 shows the physical properties of the obtained polyguanamine film.

Reference Examples 1 to 4 are examples in which the same polyguanamine A as in Example 6 is used and the thickness is made larger than 5 μm. As can be seen from the measurement results of Reference Examples 1 to 4, when measured with a thickness greater than 5 μm, "the glass transition temperature is 350 ° C. or higher, the total light transmittance is 85% or higher, and the yellow index is 10 or less”, it can be seen that when measured with a thickness of 5 μm, it always satisfies “a glass transition temperature of 350° C. or more, a total light transmittance of 85% or more, and a yellow index of 10 or less”. .
Similarly, Reference Example 5 is an example in which the same polyguanamine C as in Example 8 is used and the thickness is made larger than 5 μm. As can be seen from the measurement results of Reference Example 5, when measured with a thickness greater than 5 µm, "the glass transition temperature is 350 ° C. or higher, the total light transmittance is 85% or higher, and the yellow index is 10 or lower. , the glass transition temperature is 350° C. or higher, the total light transmittance is 85% or higher, and the yellow index is 10 or lower.

Claims (5)

Consisting only of repeating units represented by the following formula (1) (wherein A is a divalent organic group having an aromatic ring structure and/or an alicyclic structure),
A polyguanamine having a glass transition temperature of 350° C. or higher, a total light transmittance of 85% or higher, and a yellow index of 10 or lower when measured as a film having a thickness of 5 μm.

2. The polyguanamine according to claim 1, which has a coefficient of linear thermal expansion of 50 ppm/°C or less between 100 and 300°C. 3. The polyguanamine according to claim 1, which has a weight average molecular weight of 170,000 or more. A polyguanamine film comprising the polyguanamine according to any one of claims 1 to 3. 5,17-dichlorotetraazacalix[2]arene[2]triazine and a diamine having an aromatic ring structure and/or an alicyclic structure are polymerized in an organic solvent to obtain polyguanamine,
A method for producing polyguanamine, wherein the step A is carried out under the following reaction conditions.
<Reaction conditions>
Under an inert gas atmosphere Moisture content of the organic solvent: 500 ppm or less Reaction temperature: 300°C or less Reaction time: 60 hours or less.