JPH0347641B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for curing aromatic polysulfone/polythioethersulfone copolymers. [Prior Art] Aromatic polysulfones are well known, for example, RN Johnson et al.; J. Polymer Sci., A-1 5.
2375 (1967). These aromatic polysulfones are used as thermoplastic resins that have excellent mechanical properties at high temperatures, as well as good chemical resistance and electrical properties, such as electrical/electronic parts, aircraft parts, etc.
Practical applications are progressing in some areas such as automobile parts, sanitary food equipment parts, and medical equipment parts. On the other hand, aromatic polythioether sulfone was developed by JP-A-Sho.
It is disclosed in Japanese Patent Publication No. 47-13347, Japanese Patent Publication No. 53-25879, Japanese Patent Publication No. 53-25880, and is known as a thermoplastic resin with excellent mechanical properties at high temperatures. In addition, the aromatic polysulfone/polythioethersulfone copolymer was disclosed in a patent application filed in 1983 by the present inventors.
−193968, Patent Application No. 1983-196723 and Patent Application No. 1983
It is a thermoplastic resin with excellent mechanical properties at high temperatures and can be obtained by the method proposed in No.-8386. [Problems to be Solved by the Invention] All of the above copolymers have excellent mechanical properties, but because they are thermoplastic resins, they deform at temperatures above the glass transition temperature (Tg). Sisters,
There is a problem in that it has poor heat resistance when used at high temperatures. Therefore, in application fields where use at high temperatures is unavoidable, resins such as polyetheretherketone or polyimide are used, but these resins are quite expensive and cannot be used as general-purpose resins. It's not appropriate. In view of the above-mentioned problems, the present inventors have conducted various studies and studies on curing methods for improving the heat resistance of aromatic polysulfone/polythioethersulfone copolymers. As a result, heat treatment in the presence of aminoplast resin is effective for improving the heat resistance of aromatic polysulfone/polythioethersulfone copolymers; The present invention was completed by discovering the fact that the effect is specifically observed only in copolymers. [Means for Solving the Problems] The present invention provides an aromatic polysulfone/polythioethersulfone copolymer characterized in that an aromatic polysulfone/polythioethersulfone copolymer and an aminoplast resin are mixed and heat treated. A method of curing coalescence is provided. The aromatic polysulfone/polythioethersulfone copolymer of the present invention has the following formula: (However, Ar in the formula is

【formula】

【formula】

[Formula], R ¹ to R ⁷ represent hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different from each other; a to e are 0 to 4;
f and g are integers of 0 to 3 and may be the same or different; Y is a single bond, -O-, -S-, -SO ₂ -

【formula】

selected from the formula; R represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; m, n are 0<m/m+n<1
satisfies the range of ). In the present invention, the aminoplast resin mixed with the aromatic polysulfone/polythioethersulfone copolymer is an aldehyde condensate of melamine, urea, guanamine, analogs thereof, and aliphatic or aromatic polyamino compounds. Here, examples of the aliphatic polyamino compound include ethylenediamine, trimethylenediamine, tetramethylenediamine, 1,2-diaminepropylenediamine, 1,4-diaminocyclohexane,
Examples include 1,4-diaminocyclohexylmethane. In addition, examples of aromatic polyamino compounds include P-phenylenediamine, m-phenylenediamine, 0-phenylenediamine, 2,4-tolylenediamine, p-aminobenzylamine, p-
xylylene diamine, m-xylylene diamine,
benzidine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,
Examples include 4'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfide. Among these, compounds obtained by reacting melamine, urea, or benzoguanamine with formaldehyde are the most well known and can be cited as the most preferably used. Similar condensation products can be obtained by using acetaldehyde, crotonaldehyde, acrolein, benzaudehyde, furfural, etc. as the aldehyde used in this case, in addition to formaldehyde. The amine and aldehyde condensation products mentioned above may have an alkylol group such as methylol, and in many cases, at least a portion thereof is etherified by reaction with an alcohol to form a resin soluble in organic solvents. can be obtained. For this purpose, methanol, ethanol, furopanol, butanol, pentanol, hexanol, and other monohydric alcohols, as well as aromatic alcohols such as benzyl alcohol, cycloaliphatic alcohols such as cyclohexanol, and glycols such as cellosolve are used for this purpose. Monoethers, halogen-substituted alcohols such as 3-chloropropanol, and other substituted alcohols are used. Among these ethers, it is preferable to use amine-aldehyde resins etherified with methanol or butanol. The amount of the aminoplast resin added above is 0.5 to 100 parts (parts by weight, same hereinafter) of the aromatic polysulfone/polythioethersulfone copolymer.
50 parts, preferably 1 to 20 parts. If the amount is less than this, curing will be insufficient, and if it is more than this, unreacted aminoplast resin will remain and mechanical or thermal properties will deteriorate, which is not preferable. Several of these aminoplast resins may be used in combination within a suitable addition amount. The curing temperature in the heat treatment is usually between 150 and 400°C, preferably aromatic polysulfone/
Tg of polythioethersulfone copolymer is 350 or more
℃ or higher is preferable. If it is lower than this, the curing rate will be slow, and if it is higher than this, a separation reaction will occur, which is not preferable. The curing time varies depending on the temperature, but it can usually be cured in about 5 minutes to 10 hours. The aromatic polysulfone/polythioethersulfone copolymer and the aminoplast resin can be mixed by any conventional means as long as they can be mixed uniformly. For example, a method in which both are mixed in a solvent that dissolves only the aminoplast resin, and then the solvent is removed;
Alternatively, a method may be used in which both are mixed in a solvent and then the solvent is removed. In the curing method of the present invention, a crosslinking reaction proceeds during the curing reaction by heat treatment, and as a result, the resulting cured product of the aromatic polysulfone/polythioethersulfone copolymer is an uncured product that does not undergo such a curing reaction. It shows superior heat resistance compared to
Moreover, since it has chemical resistance and water resistance, it can be used as laminates, films, and sheet parts for mechanical parts, automobile parts, electric/electronic parts, sanitary food machine parts, etc. [Example] Example 1 The following formula [However, m/n=1/1, ηinh=0.40 (phenol/1,1,2,2,-tetrachloroethane=
3/2 weight ratio, 30°C, concentration 0.5 g/dl)] 2.5 g of the copolymer shown in the following and 0.25 g of hexamethoxymethylmelamine were dissolved in 10 g of m-cresol, and then cast on a glass substrate. The solvent was removed by drying at 100°C for 1 hour and at 200°C for 1 hour.
Thereafter, a curing reaction was carried out at 240°C for 3 hours to obtain a cured film. This film was insoluble in polar solvents such as m-cresol and N-methyl-2-pyrrolidone and did not melt even at 300°C. Swelling degree (representing the degree of crosslinking) when this film was immersed in m-cresol for 15 minutes at room temperature
was 105%. Furthermore, the temperature (Th) at which no deformation occurred even when immersed in a solder bath for 30 seconds was 240°C. Examples 2 to 9 Cured in the same manner as in Example 1, except that the copolymer, aminoplast resin, and curing conditions in Example 1 were changed to the copolymer, aminoplast resin, and curing conditions shown in Table 1. The reaction was carried out to obtain a cured film. The properties of the obtained film were measured in the same manner as in Example 1. The results are shown in Table 1.

[Table] Comparative Examples 1 to 4 In Example 1, the aminoplast resin was not mixed, the copolymer was other copolymer or polymer as shown in Table 2, and the curing conditions were changed. A curing reaction was carried out in the same manner as in Example 1 to obtain a cured film. The properties of these films were measured in the same manner as in Example 1. The second result is
Shown in the table.

[Table] [Effects of the Invention] The present invention is a method for curing aromatic polysulfone/polythioethersulfone copolymer, and is characterized in that the copolymer and aminoplast resin are mixed and heat treated. This is because the cured product obtained by this method has excellent curing properties that dramatically improve heat resistance. Moreover, since the cured product has excellent solvent resistance and water resistance, it is recognized that the cured product can be used in a wide range of applications.

Claims (1)

[Claims] 1 Mixing aromatic polysulfone/polythioethersulfone copolymer and aminoplast resin,
A method for curing an aromatic polysulfone/polythioethersulfone copolymer, the method comprising heat treatment.