JPH0328266A - Polyimide composition - Google Patents

Abstract

PURPOSE:To obtain a polyimide composition improved in heat deterioration resistance by incorporating an aromatic polyphosphate into a polyimide resin. CONSTITUTION:A polyimide resin, preferably a polyimide of formula I (wherein R01 is a tetravalent organic group: R02 is a divalent organic group), is mixed with an aromatic polyphosphate, preferably a compound of formula II (wherein R1 to R6 are each H or lower alkyl; (n) is a positive integer). The amount of the aromatic polyphosphate is preferably 0.01-10 pts.wt. based on 100 pts.wt. polyimide resin. A polyimide composition greatly improved in heat deterioration resistance both in molding and under high temperature conditions can be thus obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to polyimide useful as a heat-resistant resin. More specifically, it relates to a polyimide composition with improved heat deterioration resistance. [Prior art and issues] Polyimide has long been known to have excellent properties such as heat resistance, chemical resistance, electrical insulation, and mechanical strength, and is used as an electrical insulation material, heat insulation material, and spacecraft material. It is widely used as a material. Furthermore, in recent years, with the development of the electrical and electronic industry, polyimide resins have come to be required to be even more reliable. In particular, it has become necessary to further improve the thermal deterioration stability of mechanical properties such as electrical insulation and breaking strength. Among attempts to improve the thermal deterioration stability of Boli2D, US Patent No. 3.714. One of the methods disclosed in No. 116 is a method of adding an organic phosphorus compound to polyide ξ resin. However, the organic phosphorus compounds shown here are low molecular weight compounds or organic phosphorus compounds having aliphatic bonds in their molecular skeletons, and both have low thermal decomposition temperatures. Therefore, although the polyimide composition obtained by the above-mentioned modification method has excellent short-term heat stability at relatively low temperatures of about 200'C or less, it has poor thermal stability when subjected to high-temperature and long-term conditions. In this case, the organic phosphorus compound in the system was decomposed and scattered, and the improvement effect could not be realized. Furthermore, aromatic polyimides useful as highly heat-resistant electrical insulating materials are usually molded at high temperatures of 350'C or higher. Therefore, when an additive made of the above-mentioned organic phosphorus compound is applied to such an aromatic bolide, the organic phosphorus compound will volatilize and scatter during certain mold processing, or decompose and scatter, and will be released into the system. Therefore, the effect could not be expressed. [A Thousand Steps to Solving the Problems] In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that the intended purpose can be achieved by incorporating aromatic borifosphates. Heading, this invention has been completed. That is, the present invention includes a polyimide composition characterized by containing an aromatic polyphosphate. The aromatic polyphosphates used in the present invention are, for example, those of the general formula (I)? R,, R■R,R. , l? s and R4 each represent a hydrogen atom or a lower alkyl group, and n represents a positive integer. ) and similar compounds, such as cresyl resorcin polyphosphate, phenyl cresyl resorcin polyphosphate, xylyl resorcin polyphosphate, phenyl isopropylphenyl resorcin. Examples include polyphosphate, cresyl xylyl resorcinol polyphosphate, phenyl isobrobylphenyl diisopropylphenyl resorcinol, derivatives of these, and those into which substituents have been introduced. It is important that these compounds have boiling points and decomposition temperatures higher than those of their monomers, phenyl phosphates. The amount of these aromatic polyphosphates added is 0.00 parts by weight per 100 parts by weight of the polyimide resin. It is preferable to use 10 parts by weight. If the amount is less than 0.01% by weight, a sufficient effect cannot be obtained. Moreover, if it exceeds 10%, there is a tendency for the mechanical strength and other properties of the molded body made of the raw polyimide composite to be impaired.

An example of a method for obtaining the aromatic solidified composition of the present invention, that is, a method for mixing an aromatic polyphosphate with a polyimide resin, will be explained. (A) When the polyide ξ resin is insoluble and infusible, an aromatic polyphosphate is mixed with a polyamic acid solution, which is a precursor of polyimide, and then,
The polyamide ξ-ide composition of the present invention is obtained by thermally or chemically dehydrating and ring-closing ξ-ide.

(B) When the polyimide resin is solvent soluble: After mixing the aromatic polyphosphate into the polyimide solution, the solvent is removed to obtain the polyimide composition of the present invention. (C) When the polyimide resin is thermoplastic Aromatic polyphosphor 11 is mixed with the molten polyimide resin and then cooled to obtain the polyimide composite of the present invention.

(D) When the polyimide resin is a cured product of an imide oligomer, the aromatic polyphosphates are mixed into the imide oligomer, and then reacted and cured by a process such as heat or light. Obtain prestige.

Next, the polyimide resin used in the present invention will be explained. The present invention can be applied to so-called polyimide resins, thermoplastic resins such as polyetherimide, reactive ξ-dooligomers, etc. In particular, its characteristics are fully utilized when applied to polyimide resins that have a high mold temperature or are used in a high temperature range. In particular, it is suitably applied to those having a structure represented by the general formula (It)OO (Ra+ represents a tetravalent organic group, and ROf represents a divalent organic group).

Further, in the above general formula (II), Rot is a tetravalent aromatic group and Iloz is a divalent organic group, which is particularly suitable for polyimides. Polyimide resins are usually obtained by reacting diamines and diacid anhydrides in an organic polar solvent. Listing some of the diamines that make up the polyimide used in the present invention, aromatic diamines include, for example, paraphenyl diamine, 3.3'dimethoxy-44'-diaξnobiphenyl, 3. 3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 4,4'-diaminoparaterphenyl,
4.4'-bis(4-aξnophenoxy)bifpenyl,
4 4'-Diatanodiphenylsulfone, 3.3'-
Diadanodiphenylsulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3
-aminophenoxy)phenyl]sulfone, bis(1
-(2-aminophenoxy)phenyl]sulfone, 1
．． 4bis(4-aminophenoquine)Hensen, 1,3-
Bis(4-aminophenoxy)benzene, l,3-bis(3-aminophenoxy)benzene, l,4-bis(4
-aminophenoquine)benzene, bis(1-(4-aminophenoxy)phenyl]ether, 4,4'-diaξ
Nodiphenylmethane, bis(3-ethyl-4-aminophenyl)methane, bis(3-methyl-4-aminophenyl)methane, bis(3-chloro4-aminophenyl)
Methane, 3,3'-diaminodiphenylsulfone, 4
4'-diaminodiphenylsulfone, 2 2'5,5
4,4'-diaminobiphenyl, 4
4'-Diakinodiphenyl sulfide, 4.4'-
diagonodiphenyl ether, 3,3'-diaminodiphenyl ether, 3.4 diaminodiphenyl ether,
4.4'-diaminodiphenylmethane, 4.4'-diaminobiphenyl, 44'-diaminoctafluorobiphenyl, 2.4'-diaminotoluene, metaphenylenedia ξane, 2.2-bis(4-(4 -aminophenoxy)phenyl]propane, 2.2bis(4-(4-aξ
nophenoxy)phenyl]hexafluoropropane, 2
, 2-bis(4-yaminophenyl)propane, 2.2-
bis(4-aminophenyl)hexafluoropropane,
2.2-bis(3-hydroxy-4-aminophenyl)
Propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 99-bis(4-
Examples include (ξnophenyl)-10-hydroane 1.hracene, orthotolidine sulfone, and the like. These compounds may be used alone or in combination of two or more. Furthermore, 3,3'. It is also possible to use some polyvalent amine compounds such as 4.4'-biphenyltetraamine and 3.3'4.4'-tetraaminodiphenyl ether.
In addition, examples of the other component, diacid anhydride, are listed as follows:
Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3.3'. 4.4'-biphenyltetracarboxylic dianhydride, 3.3'. 4.4'-benzophenonetetracarboxylic dianhydride, naphthalene-1.
Examples include 2,5,6-tetracarboxylic dianhydride. Although an example of the structure of aromatic polyimide has been described here, the present invention can also be applied to aliphatic polyimide and the like. Examples of imide oligomers used in the present invention include bismaleide and nadic acid-terminated oligomers,
Examples include acetylene-terminated oligomers. Also, polyimide&ll$. Examples of forms obtained by molding objects include ordinary molded objects, sheets, films, and laminates, but in order to utilize the effects of the present invention most effectively, film-like forms are preferable. The reason for this is that film-like materials generally have a large specific surface area and are susceptible to thermal deterioration in the air. In this case, the presence of minute defects tends to lead to a decrease in breaking strength, which often becomes a serious problem.

[Effect]

In the past, organic phosphorus compounds have been used as additives to stabilize polyimide resins against heat deterioration, but as mentioned above, the thermal decomposition temperature or boiling point of these additives themselves is low, and as a result, they have been used as additives to stabilize polyimide resins. or when a certain mold is exposed to high temperature, the additive scatters out of the system and cannot be left in the system, so its effect cannot be fully utilized. I couldn't do it. In contrast, the present invention succeeded in improving the thermal stability of the additive itself by increasing the molecular weight of the additive made of such an organic phosphorus compound and further introducing an aromatic skeleton. As a result, the stabilizer remains in the system for a long time and maintains its effect during the resin molding process and even when the molded body is exposed to high temperatures for a long time. In this way, high-temperature molding polyethylene 4
This not only makes it possible to significantly improve the heat resistance and deterioration stability of polyimide resins, but also makes it possible to improve the heat deterioration stability of polyimide resins under harsh conditions of high temperatures and long periods of time. It is. [Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited in any way by these. Comparative Example 1 4.4′-diaξnodiphenylmethane and 3.3′. in dimethylacetamide solvent. 4.4"-benzophenonetetracarboxylic dianhydride was reacted in a conventional manner to obtain a 15% dimethylacetate solution of poly(ξ)doic acid. Acetic anhydride was added as a dehydrating agent and β as a dehydrating catalyst. - Added picoline, casted onto a support, and heated and dried in a hot air oven at about 100°C for about 5 minutes to obtain a self-supporting film. This was peeled off from the support and fixed to a support frame. After that, it was gradually heated and dried in a high-temperature hot air oven to 280°C. After being left to cool in the air, it was removed from the support frame.
A polyamide film with a thickness of approximately 50 μm was obtained. This film was aged in a hot air dryer at 250°C for 1000 hours. The dielectric breakdown voltage and tensile elongation at break before and after aging were measured, and the retention rate was calculated. The results are shown in Table I. Comparative Example 2 Polyimide resin 100 containing TPA (low molecular weight aromatic phosphates) along with a dehydrating agent and a dehydrating catalyst
0.0% by weight. Comparative Example 1 except that 5 parts by weight was added
Films were prepared and measured and evaluated using the same method. The results are shown in Table 1. Examples 1 to 9 Films were prepared and measured and evaluated in the same manner as in Comparative Example 1, except that a predetermined amount of aromatic polyphosphate If was added together with a dehydrating agent and a dehydrating catalyst. The results are shown in Table 1. Comparative Example 3 4,4'-diaminodiphenyl ether and pyromellitic dianhydride were reacted in a dimethylformamide solvent by a conventional method to obtain a 15% dimethylformamide solution of polyamic acid.

Acetic anhydride was added as a dehydrating agent and β-picoline was added as a dehydrating catalyst, and the mixture was cast onto a support and dried by heating in a hot air oven at about 100°C for about 5 minutes to obtain a self-supporting film. After peeling it off from the support and fixing it on the support frame, it was gradually heated and dried in a high-temperature hot air oven up to 450°C, then left to cool in the air, and then removed from the support frame to a thickness of about 50 μm. A polyimide film was obtained.

The film was aged in a hot air dryer at 300°C for 1000 hours. The dielectric breakdown voltage and tensile elongation at break before and after aging were measured, and the retention rate was calculated. The results are shown in Table 2.

Comparative Example 4 Polyimide resin 100 containing TPA (low molecular weight aromatic phosphates) along with a dehydrating agent and a dehydrating catalyst
A film was prepared and measured and evaluated in the same manner as in Comparative Example 1, except that 0.5 part by weight was added. The results are shown in Table 2.

Examples 10-19 A film was prepared and measured and evaluated in the same manner as in Comparative Example 3, except that a predetermined amount of a predetermined aromatic polyphosphate was added together with a dehydrating agent and a dehydrating catalyst. The results are shown in Table 2. (Explanation of abbreviations of additives in the table) PFR: Phenyl resorcinol polyphosphite CRP: Cresyl resorcinol polyphosphate PCRP: Phenyl cresyl resorcinol polyphosphate XRP: Xylyl resorcinol polyphosphate Phate PIRP: Phenyl, isopropylphenyl, resorcin, polyphosphate CXRP: Cresyl, xylyl, resorcin, polyphosphate PDRP: Phenyl, isobrobylphenyl, diisobropylphenyl, resorcin, polyphosphate TPP: }Riphenyl Phosphate (Low Molecular Weight Organic Phosphorus Compound) [Effects of the Invention] According to the present invention, a polyimide composition is provided which has dramatically improved thermal deterioration properties during molding and under high temperature conditions. Ru.

Claims (1)

[Scope of Claims] 1. A polyimide composition containing an aromatic polyphosphate. 2. The polyimide composition according to claim 1, wherein the content of the aromatic polyphosphate is 0.01 to 10 parts by weight based on 100 parts by weight of the polyimide resin. 3. Aromatic polyphosphates have the general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (R_1, R_2, R_3, R_4, R_5, R_6 each represent a hydrogen atom or a lower alkyl group, n 2. The polyimide composition according to claim 1, which is a composition comprising a compound having a structure represented by the formula (indicates a positive integer). 4. The polyimide composition according to claim 3, wherein in the general formula (I), n is an integer of 1 to 3. 5. Claim 1 in which the polyimide has a structure represented by general formula (II) ▲Mathematical formula, chemical formula, table, etc.▼ (R_0_1 represents a tetravalent organic group, R_0_2 represents a divalent organic group) The polyimide composition described. 6. The polyimide composition according to claim 5, wherein in general formula (II), R_0_1 is a tetravalent aromatic group and R_0_2 is a divalent aromatic group. 7. The polyimide composition according to claim 1, wherein the polyimide is a polyimide film. 8. The polyimide composition according to claim 1, wherein the polyimide is a cured product of an imide oligomer having a terminal functional group.