JPS62187764A - Heat-resistant resin film - Google Patents

Abstract

PURPOSE:To provide a heat-resistant resin film having excellent resistance to heat and chemicals, mechanical characteristics, dielectric characteristics and low water absorptive power and suitable for use as an electrical insulating film, consisting of a cured article obtd. by curing a mixture of an arom. polythioether sulfone polymer and a curing agent. CONSTITUTION:This heat-resistant film is formed from a cured article obtd. by curing a mixture of an arom. polythioether sulfone polymer and a curing agent. Pref. this film is prepd. by molding a mixture of an arom. polythioether sulfone polymer and at least one curing agent selected from the group consisting of epoxy compds. having at least two epoxy groups per molecule, aminoplast resins and a metal acetylacetonate into a film and heat-treating the film. Preferred examples of the metal acetylacetonate are Cu(II), Mn(II), Fe(III), or Ni(II) acetylacetonate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The claimed invention relates to a heat-resistant resin film with excellent heat resistance used in the electronic field, electrical field, or other applications.

[Prior art] Polyimide film, polyetherimide film, aromatic polyamide paper, polyether sulfone film, etc. are known as electrical insulating films used in flexible printed wiring boards, various electric motors, transformers and generators, etc. It is being However, although polyimide films have excellent heat resistance, they have problems such as high water absorption and poor alkali resistance.

In addition, aromatic polyamide paper has a high water absorption rate, a
There are problems such as insufficient mechanical strength, and films made of polyetherimide and polyethersulfone have low heat resistance and insufficient solvent resistance. Furthermore, in addition to electrical insulation, we also use a mechanical parts, precision equipment parts, automobile parts, food sanitation equipment parts, and other #
There are synthetic resin films that require physical properties such as thermal properties.

For example, heat-resistant films are required for speaker diaphragm materials and thermal packaging films. However, the above-mentioned problems have been pointed out in films conventionally used for these purposes, and a solution to these problems has been desired.

[Problems to be Solved by the Invention] In order to solve the above-mentioned problems, an excellent heat-resistant resin film is required. This #thermal resin is not only relatively inexpensive and has excellent mechanical properties, but also has a dielectric constant low enough for electrical insulation. It is necessary to have A power loss. Moreover, it must have high #thermal properties,
It is desirable that other properties such as chemical resistance and low water absorption are also sufficiently high.

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventor conducted research and examination on various heat-resistant resins and found that a cured product of an aromatic polythioether sulfone polymer can be used for these purposes. The present invention, which has been discovered to be an extremely suitable heat-resistant resin, is a film suitable for electrical insulation and other uses using this heat-resistant resin. It is a heat-resistant resin film made of a cured product obtained by curing a mixture of

The aromatic polythioethersulfone-based polymer in the present invention refers to an aromatic polythioethersulfone rli homopolymer or an aromatic polythioethersulfone copolymer, and among these, a homopolymer (m is 0 in the following general formula) JP-A No. 11B 47-13347, JP-B No. 53-25879, JP-B No. 53-25880, etc., and is known as a thermoplastic resin with excellent mechanical properties at high temperatures. There is.

As the copolymer, various copolymers having a thioether sulfone residue and another difunctional residue having an aromatic nucleus can be used. 4. +1 is preferably a copolymer represented by the following general formula (where m is not 0), and this copolymer is disclosed in Japanese Patent Application Nos. 59-193968 and 59-196723, which were invented by the present inventors. , Oyobi special request 1986-8
This thermoplastic resin has excellent mechanical properties at high temperatures and can be obtained by the method described in No. 386.

The aromatic polythioether sulfone polymer in the present invention has a hydrocarbon group represented by the following general formulas 1 to 8, which may be the same or different from each other.
are integers of 0 to 3, which may be the same or different; R represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; ra,
n satisfies the range of 0≦m/m+n<1, and when IB=0, it is a polythioethersulfone homopolymer. ) Aromatic polythioether sulfone-based polymers represented by the following are particularly preferred. Among these copolymers, m is not 0. It is obtained by reacting halodiphenylsulfones, diphenols represented by lo-Ar-OH, and alkali metal sulfides. In this reaction, alkali metal hydroxides and carbonates are used as dehalogenating agents, but diphenols can also be used in advance in place of the corresponding alkali metal phenoxides. This reaction can of course be carried out in one stage, but also in a multistage method using a precursor.

In addition, the cured product of the aromatic polythioethersulfone-based polymer in the present invention is a three-dimensionally crosslinked cured product obtained by curing a mixture of the aromatic polythioethersulfone-based polymer and a curing agent as described above. It is. As a curing agent, an epoxy compound having at least two epoxy groups in one molecule (ie, a so-called epoxy resin) is used.

Aminoblast resin or metal acetylacetonate is preferred. A cured product is obtained by mixing this curing agent with an aromatic polythioether sulfone polymer and heat-treating the mixture.

As the above-mentioned epoxy compound, a liquid or solid one can be used, and a partial polymer (prepolymer) can also be used. Such epoxy compounds include 1, for example, bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, bisphenol S, bisphenol AF, 1,3.5-hydroxybenzene, trihydroxy-diphenyldimethylmethane, 4
．． 4'-dihydroxybiphenyl, 1,1,2.2-
Glycidyl ethers such as tetrakis(4-hydroxyphenyl)ethane and their halogenated glycidyl ethers; butanediol.

Glycidyl ethers such as glycidyl ethers such as glycerin, glycidyl esters such as phthalic acid glycidyl esters, aniline, diaminobenzene, benzidine, methylene dianiline, diaminocyprohexane, incyanuric acid, aminocyclohexane, diaminodiphenylsulfone, diaminonaphthalene, xylene Diamine, cyclohexane bismethylamine.

Glycidyl epoxy resins such as glycidylamine series such as melamine; epoxidized olefins.

Examples include linear non-glycidyl epoxy resins such as epoxidized soybean oil and cyclic non-glycidyl epoxy resins such as vinylcyclohexene dioxide and dicyclopentadiene dioxide; novolac type epoxy resins and halogenated products thereof.

Aminoblast resins are aldehyde condensates of melamine, urea, guanamine, their analogs, and aliphatic or aromatic polyamino compounds.

Here, examples of the aliphatic polyamino compound include ethylenediamine, trimethylenediamine, tetramethylenediamine, 1,2-diaminopropylenediamine, 1,4-diaminocyclohexane, and 1°4-diaminocyclohexylmethane.

In addition, examples of aromatic polyamino compounds include EVA, P-
Phenylenediamine, m-phenylenediamine, 0-phenylenediamine, 2.4-)lylenediamine, P-7
Minobenzylamine, P-xylylenediamine, m-xylylenediamine, benzidine, 4,4'-diaminodiphenylmethane.

Examples include 4.4'-diaminodiphenyl ether, 4.4'-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, benzaldehyde, furfural, etc. in addition to formaldehyde as the aldehyde used in this case.

The above amine-aldehyde condensation products may have alkylol groups such as methylol, and in many cases,
At least a part of it can be etherified by reaction with alcohol to obtain a resin soluble in organic solvents.

For this purpose methanol, ethanol, furopanol.

Butanol, pentanol, hexanol, other 1
Hydrolic alcohols, aromatic alcohols such as benzyl alcohol, alicyclic alcohols such as cyclohexanol, monoethers of glycols such as cellosolve, halogen-substituted alcohols such as 3-chlorpropanol, and other substituted alcohols of sheep. is used.

Among these ethers, it is preferable to use amine-aldehyde resins etherified with methanol or butanol.

The amount of the epoxy compound and aminoblast resin added is 100% of the aromatic polythioethersulfone polymer.
0.5 to 50 for part (ffiffi part, same below)
parts, preferably 1 to 20 parts.

If the amount is less than this, curing will be insufficient, and if the amount is more than this, unreacted epoxy compounds and aminoplast resins will remain and mechanical or thermal properties will deteriorate, which is undesirable.These epoxy compounds and aminoplast resins are suitable additions. Two or more types may be used together within the range of amounts.

When these curing agents are used, the curing temperature in the heat treatment is usually between 150 and 400°C, and is preferably at least Tg of the aromatic polythioethersulfone polymer to 3.
The temperature is preferably 50°C or lower.

If it is lower than this, the curing rate will be slow, and if it is higher than this, a decomposition reaction will occur, which is undesirable.The curing time varies depending on the temperature, but it can usually be cured in about 5 minutes to 10 hours.

In addition, the metal acetylacetonate in the present invention has a different mechanism of action from the curing agent having a crosslinking group as described above, and is radically decomposed by heating to generate active radicals, and these radicals are used to generate aromatic nuclei, etc. It is thought that this causes oxidative crosslinking. Metal acetylacetonate is
It is a metal chelate compound of acetylacetone, and such compounds include (1) Group 1A of the periodic table, (2)
) Group IA, (3) Group mB.

(4) Group 1 VB, (5) Group VB, (6) Group VIB.

(7) Group ■B, (8) Group ■, (9) Group 1B.

(10) Group IB, (11) Group mA, (12)
Preference is given to each acetylacetonate of the lanthanide group.

Here, each of the above acetylacetonates (hereinafter acac
(1) Group 1A acac is Cs (I) a
cac (2) Group IA acac is Mg(H)
.

Ca(II), Sr(II)acac(3)
As Group 1A acac, La (m) acac
(4) As Group 1A acac, [Ti (m)
acac12Tic16, Zr (ff) + Z
rO(II) acac (5) Group 1A acac is V(III) acac (6) Group 1A acac is Cr(m).

No (m)acac (7) Group 1A acac is In(II).

Mn (m), Re (m)acac(8)
The first acac is Fe(m).

Go(II), Go(m), Rh(
m).

Old (II) acac (8) Group 1B acac includes Cu (H) ac
ac(lO) Group 1A acac is Zn (■)
.

Cd (II) acac (11) As the 1st I A acac, AI(m).

In (II) TI (I) acac(12
) Ce'(m) as a lanthanide family acac.

Sea (m), Gd (Iff), Er (
m).

Examples include Ta(III), Lu(m)acac, and the like.

In such acac, Cu(II
), mouth (II), Nn (m), Fe (m).

Go (II), old (II), , AI (m3,
acac such as Zn(II).

The amount of metal acetylacetonate added to the aromatic polythioethersulfone polymer is 0.05 to 10% by weight, preferably 0.1 to 5f based on the total amount of the polymer.
The amount of fi is in the range of %, and it is effective in an extremely small amount. Further, the curing temperature in the heat treatment when using this curing agent is usually carried out at a temperature of 150 to 400°C, preferably at least Tg of the aromatic polythioethersulfone polymer to 3.
A temperature of 50°C or less is preferable. If the temperature is lower than this, the curing speed will be slow, and if it is higher than this, a decomposition reaction will occur, which is undesirable. The curing time varies depending on the temperature, but is usually 5 minutes to
It can be cured in about 10 hours.

The method for producing the film of the cured product is not particularly limited, but preferably, a solution of a mixture of an aromatic polythioethersulfone polymer and a curing agent is
It is obtained by stretching and forming into a film, and curing this film under the above-mentioned curing conditions. That is, an aromatic polythioether sulfone polymer and a curing agent are dissolved in an organic solvent to form a solution of the mixture thereof, and this solution is cast onto a supporting substrate to remove the organic solvent, thereby forming an uncured product. After peeling the film on or from the support substrate, it is heated and cured to obtain a cured film. When heat-curing this uncured film, the film may be heat-cured in a fixed state, such as by fixing the edges, to prevent deformation.

Any organic solvent can be used as long as it can dissolve the aromatic polythioethersulfone polymer and the curing agent. Examples of solvents that can be used include dichloromethane.

Chloroform, 1,2-dichloroethane, 1,1.2
-) dichloroethane, halogenated solvents such as 1,1,2,2-tetrachloroethane, m-cresol, 0-
Phenolic solvents such as chlorophenol, p-chlorophenol, N,N-dimethylformamide, N,
N-dimethylacetamide, dimethyl sulfoxide, N
Examples include polar solvents such as -methyl-2-pyrrolidone and sulfolane. Mixtures of these can of course also be used. The amount of these solvents to be used is not particularly limited, but it is preferable that the solid content concentration is about 1 to 60% by weight, and insoluble matter should be removed from the resulting solution by filtration or the like before casting. is preferred.

The support substrate for the casting may be made of glass, metal, plastic, or other materials.

The casting surface is preferably a smooth flat surface, but is not limited to this, and may be a non-smooth surface such as an embossed surface, or a supporting substrate with low heat resistance such as a plastic film. When used, it is desirable to peel and remove the uncured film after molding and heat only the uncured film during heat curing.As the supporting substrate, for example, a glass plate, a steel plate, a polyester film, etc. can be used. Methods for casting the solution onto the supporting substrate include, for example, using a scraping-type applicator such as a doctor blade or a rod coater, using an extrusion slit such as a T-die, and also using a spray neat method. sell.

The cured film of aromatic polythioethersulfone polymer obtained in this way has excellent heat resistance, mechanical properties, chemical resistance, and dielectric properties.

It has low water absorption and can be particularly suitably used as electrical insulating films such as printed wiring boards, insulating films for various motors, transformers, and generators.

EXAMPLES The present invention will be specifically illustrated below with reference to Examples, but the present invention is not limited by these in any way.

Example 1 4,4'-dichlorodiphenylsulfone and sodium sulfide were added to a precursor obtained by reacting 4.4'-dichlorodiphenylsulfone, bisphenol A, and calcium carbonate, and the reaction was performed using the following formula. The aromatic polythioether sulfone polymer shown below was obtained (for details, see the above-mentioned Japanese Patent Application No. 8386/1986).

m/n-10/1 tl 1nh-0,135:PhOH/1,1,2.2
- in tetrachloroethane 3/2 (weight ratio), 30°C, 0
．． Measured at 5 g/dl 10 g of this polymer and 0.5 g of hexamethoxymethylmelamine were dissolved in 70 g of 1.1,2.2-tetrachloroethane, and insoluble materials were removed by filtration. This solution was cast onto a glass substrate using a doctor blade, air-dried for 30 minutes, and then heated at 100°C for 1 hour.
After drying at 70° C. for 1 hour, the self-supporting film was peeled off from the glass substrate. The ends of this self-retaining film were fixed and heat treated at 320° C. for 30 minutes to obtain a film with a thickness of 50 μm and a smooth surface. Table 1 shows the physical properties of this film.

Example 2 N, N, N' instead of hexamethoxymethylmelamine
, thickness 50μ■ except that 0.5g of N'-tetraglycidyl-■-xylylenediamine was used.
obtained the film. Table 1 shows the physical properties of this film.

Example 3 In Example 1, instead of bisphenol A, 4.4'
-Dihydroxydiphenyl was used to produce the following copolymer in a similar manner.

(m/n=1/1, η1nhsO, 87) 10 g of this polymer, 0.58 hexamethoxymethylmelamine
was dissolved in 70 g of 1.1,2.2-tetrachloroethane, and insoluble materials were removed by filtration.

From this solution, a smooth film with a thickness of 50 μm was obtained in the same manner as in Example 1. Table 1 shows the physical properties of this film.

Example 4 Cu (acac
) was used in the same manner as in Example 3 except that 0.1 g of
Films of μ-intestine were obtained. Table 1 shows the physical properties of this film.

Comparative Example 1 The physical properties of a commercially available polyimide film (“°Kapton” manufactured by DuPont) having a thickness of 50 μm were measured. The results are shown in Table 1.

Comparative Example 2 Commercially available polyether sulfone (Victrex PE5
1.1,2 10g of pellets of 300P IC1)
．． After dissolving in 70 g of 2-tetrachloroethane and removing insoluble matter by filtration, a film was prepared in the same manner as in Example 1, but when heated at 320°C, the film softened and the smooth film was I couldn't get it. Therefore, heat treatment was performed at 320° C. for 30 minutes without peeling from the glass substrate, and after cooling, the film was peeled from the glass substrate to obtain a film with a thickness of 50 μm.

The physical properties of this film are shown in Table 1.

[Effects of the Invention] The cured film obtained from the aromatic polythioethersulfone polymer and curing agent of the present invention has excellent heat resistance,
It is a heat-resistant electrical insulating film that exhibits mechanical properties, chemical resistance, dielectric properties, and low water absorption, as well as sufficient flexibility.

Claims (1)

[Claims] 1. A heat-resistant resin film comprising a cured product obtained by curing a mixture of an aromatic polythioethersulfone polymer and a curing agent. 2. The film is made of an aromatic polythioethersulfone polymer and at least one curing agent selected from epoxy compounds having at least two epoxy groups in one molecule, aminoplast resins, and metal acetylacetonates. The film according to claim 1, which is obtained by molding a mixture into a film and heat-treating it.