JPH0651803B2 - Polyimide polymer molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a metal oxide-containing polyimide polymer molded product in which a metal oxide is uniformly blended.

[Prior Art] Polyimide-based polymers have excellent mechanical properties in a wide temperature range, and also have good electrical characteristics and chemical resistance, and therefore electrical / electronic parts, automobile parts, hygiene / food equipment Used for parts and medical equipment parts. Particularly in the field of electric / electronic parts mentioned above, the polyimide-based polymer film is an electric insulator or a semiconductor integrated circuit used for flexible printed boards, various electric motors, transformers, generators, etc. due to its excellent heat resistance. It has been put to practical use as a film carrier tape for mounting.

However, in general, organic polymers have a drawback that they have a higher coefficient of thermal expansion than inorganic substances, and polyimide polymers are no exception. Therefore, for example, in the case of application to a flexible printed circuit board, when bonding a metal foil to a polyimide film, in order to prevent curling that occurs due to the difference in the coefficient of thermal expansion, another material is used between the polyimide film and the metal foil. It is also necessary to provide an adhesive layer that Therefore, the material used for such an adhesive layer is generally inferior in heat resistance and there is a problem that the heat resistance of the polyimide film cannot be fully utilized.

Therefore, many attempts have been made to improve the coefficient of thermal expansion of polyimide polymers, and polyimides having various structures have been proposed. For example, Japanese Patent Laid-Open No. 60-250031 discloses that the material has low expansion property. A polyimide using a diamine component selected from is disclosed. Another example is an attempt to improve dimensional stability by using a compound having a special structure as an acid dianhydride or a diamine component which is a constituent of polyimide. However, use of a compound having a special structure as described above leaves problems such as difficulty in obtaining raw materials and toxicity.

[Problems to be Solved by the Invention] The present invention has been made in view of the above problems, and provides a diamine and an acid anhydride which are easily available as a polyimide-forming material in the presence of a silane coupling agent. The composition containing a metal alkoxide capable of becoming a metal oxide under a heat treatment temperature below the decomposition temperature of the polyimide-based polymer or the polyimide-based polymer obtained by reacting the polyimide-based polymer or its precursor Molded products obtained by molding at the processing temperature of 10% have significantly improved dispersibility of metal oxides compared with molded products prepared by simply mixing powders of metal oxides, and also have high heat resistance and mechanical strength. The present inventors have completed the present invention by finding the fact that they have excellent characteristics such as dimensional stability.

Therefore, the present invention newly provides a polyimide-based polymer molded product having characteristics that it can be suitably used as various parts or structural materials including electric / electronic parts in terms of application and use.

[Means for Solving Problems] That is, the present invention provides a polyimide-based polymer obtained by reacting a polyimide-forming material in the presence of a silane coupling agent or a polyamic acid-based polymer which is a precursor thereof, A metal oxide-containing polyimide-based polymer obtained by molding a composition containing a metal alkoxide that can become a metal oxide at a heat treatment temperature below the decomposition temperature of a polyimide polymer at a heat treatment temperature at which a metal alkoxide becomes a metal oxide. It is a united molded article.

In the present invention, the polyimide-forming material comprises a diamine and an acid anhydride that are easily available as described above, and as a polymer obtained by reacting in the presence of a silane coupling,
The following general formula [I] R is an alkyl group having 1 to 3 carbon atoms, an alkoxy group, or halogen; X is a single bond, -O-, -S-, -SO
_2- , An alkylene group having 1 to 6 carbon atoms and a perfluoroalkylene group are shown; m and n each represent an integer of 0 to 2. It is preferable that the polyimide-based polymer has a repeating unit represented by the formula (1) or its precursor.

The above polyimide polymer or polyamic acid polymer is obtained by the reaction of an acid anhydride and a diamine by a known method in the presence of a silane coupling agent, and the degree of polymerization as a polymer is N, N-dimethylacetamide. Medium, 30
The logarithmic viscosity η inh at 0 ° C. is preferably 0.3 to 4. The polyimide-based or polyamic acid-based polymer may be a combination of two or more kinds.

Polyimide-based polymer, the silane coupling agent contained in the precursor polyamic acid-based polymer is a metal alkoxide compounded in the polymer, dispersibility of other substances, is useful to improve the miscibility Therefore, the dimensional stability based on the properties such as coefficient of thermal expansion is remarkably improved in the molded product from the composition, as compared with the molded product not containing it. As the silane coupling agent, various known silane coupling agents may be used, but those having an appropriate functional group as well as a function as a dispersion improving agent and a dispersion stabilizer for improving the dispersibility and mixing property. By selecting, it becomes possible to bond with the functional group of the polymer, and the physical properties of the resulting molded article can be further improved. Such silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, which has one or more amino groups, especially primary and / or secondary amino groups,
Preferable examples include γ-glycidoxypropyltrimethoxysilane having one or more glycidyl groups, and γ-mercaptopropyltriethoxysilane having one or more mercapto groups. In addition, phenyl-based silane coupling agents such as phenyltrimethoxysilane, halogen-based silane coupling agents such as trimethylchlorosilane, silylamine-based silane coupling agents such as dimethyltrimethylsilylamine,
An acyloxysilane-based silane coupling agent such as vinyltriacetoxysilane, an acetamidosilane-based silane coupling agent such as N-trimethylsilylacetamide, and the like can also be exemplified. Among these silane coupling agents, especially the functional groups of the polyimide-based polymer or its precursor polyamic acid-based polymer such as -COOH, -NH ₂ , The effect is remarkable when a silane coupling agent having reactivity with the above is used.

Further, in a composition comprising a polyimide-based polymer containing a silane coupling agent obtained by the reaction of a polyimide-forming material in the presence of a silane coupling agent or a polyamic acid-based polymer which is a precursor thereof and a metal alkoxide, a metal alkoxide Even if a titanium coupling agent, an aluminum coupling agent, or the like is used as the silane coupling agent depending on the type of the above, the same effect is recognized.

In the process of the reaction of the polyimide-forming material in the presence of the silane coupling agent, the silane coupling agent is incorporated into the molecule of the polyimide polymer. Thus, the amount of the silane coupling agent contained in the polyimide-based polymer or the polyamic acid-based polymer exerts an effect with an extremely small amount, but it is a composition comprising a metal alkoxide,
It is preferable that the content of 0.01 to 20% by weight is contained in the finally obtained metal oxide-containing polyimide-based polymer molded by heat treatment. If it is less than this, the above effect is difficult to be expressed,
Further, when the amount is large, the physical properties of the molded article are deteriorated, so the content is more preferably 0.1 to 10% by weight.

In a composition comprising a polyimide-based polymer or a polyamic acid-based polymer containing a silane coupling agent and a metal alkoxide, the metal alkoxide may become a metal oxide at a heat treatment temperature below the decomposition temperature of the polyimide-based polymer. is necessary.

Examples of the metal alkoxide in the present invention include, for example, silicon tetramethoxide, Si alkoxide compounds such as silicon tetraethoxide, zirconium tetrapropoxide, Zr alkoxide compounds such as zirconium tetrabutoxide, titanium tetralypropoxide, and titanium tetrabutoxide. And the like, Al alkoxide compounds such as aluminium tri-Sec-butoxy, Sn alkoxide compounds such as tin tetrabutoxide, and partial condensates obtained by pre-condensing them can be used. These metal alkoxides undergo a condensation reaction when the composition is heat-treated and molded into a molded product to become a metal oxide. Here, in order to allow the condensation reaction to proceed smoothly, water and a catalyst may be added to carry out hydrolysis of the metal alkoxide while further promoting the condensation by heat treatment.

In the metal oxide-containing polyimide polymer molding of the present invention, the amount of the metal oxide derived from the metal alkoxide contained is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the polyimide component. When the molded product formed by molding the composition is formed into a film, for example, the composition depends on the viscosity of the polymer, but the solid content concentration is 5 to 50% by weight.
Is preferred. Although the heat resistance and the dimensional stability are improved according to the amount of the metal oxide in the molded product, if the amount is too small, the effect is difficult to be exhibited, and if the amount is too large, it tends to become brittle. Therefore, it is preferably 10 to 100 parts by weight.

It is generally known to incorporate inorganic oxides to improve the dimensional stability of organic polymers. For example, in the case of a polyimide film, JP-A-60-228557 discloses the following formula There has been proposed a method for producing a film having excellent surface smoothness, which is obtained by blending an aromatic polyether imide represented by the formula (3) with an inorganic filler. However, the amount of the inorganic filler compounded in the polyetherimide film is 100%.
It is limited to 10 parts by weight or less with respect to parts by weight, and it is described that the amount is preferably 10 parts by weight or less for the surface smoothness of the film.

Therefore, in a film made of a polyimide-based polymer, practical dimensional stability is not sufficient when the amount of the inorganic filler compounded is 10% by weight or less. This is because when 10% by weight or more of an inorganic filler is blended, the powder that normally exists as secondary particles cannot be completely converted into primary particles, and as a result, the particles themselves become defect points of the film. Therefore, the strength of the film is lowered, or the film becomes brittle, which makes it difficult to form the film itself in an extreme case.

The present invention is a molding obtained by molding a composition comprising a polyimide-based polymer or polyamic acid-based polymer containing a silane coupling agent (substantially a silane-modified polyimide polymer or polyamic acid-based polymer) and a metal alkoxide. As described above, a large amount of metal oxide is blended, but such a molded product is not known.

In the present invention, the metal oxide is not blended as an inorganic filler, but is blended with a polymer containing a silane coupling agent in the form of a metal alkoxide or a precursor thereof to obtain a composition, which is completely and uniformly dispersed. It As a compounding method, a method of mixing a metal alkoxide with a liquid polymer containing a silane coupling agent is used as follows. That is, a mixture of a polymer suspension and a metal alkoxide or a partial condensate thereof.

Mixing polymer solution with metal alkoxide or its partial condensate.

In the above, since the polymer is usually present in the form of fine powder, a composition in which the metal alkoxide to be mixed or the mixed system with the partial condensate thereof may or may not dissolve the polymer is a uniformly mixed composition. The thing is obtained.

The method of mixing the metal alkoxide or the partial condensate thereof with the polymer solution (varnish) is preferable in that the most uniformly dispersed composition can be obtained.

The above method is also applicable to polyamic acids containing silane coupling agents.

The metal alkoxide used here or its partial condensate is used without any other treatment, but an appropriate solvent may be added for the purpose of improving the mixing property and the dispersibility. Further, it may be further condensed by adding water or a catalyst or by heat treatment. The amount of water added is not particularly limited, but is preferably 0.1 to 4 equivalents relative to 1 equivalent of the alkoxy of the metal alkoxide, and if it is more than this, the stability of the composition of the polyimide polymer or polyamic acid polymer is high. Is reduced. Examples of the catalyst include acids known as hydrolysis catalysts such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid and toluenesulfonic acid, inorganic bases such as sodium hydroxide, and organic bases such as alkylamines.

The molding method of the composition comprising a polyimide-based polymer or polyamic acid-based polymer containing a silane coupling agent and a metal alkoxide is not particularly limited, but the composition is
Since it is a polymer suspension or a polymer solution (varnish), a cast molding method such as casting on a flat glass surface is suitable. As a heat treatment condition in cast molding, it is desirable to heat at 50 ° C. to 500 ° C., and at this time, imidization and polycondensation of metal alkoxide are performed. If the heating temperature is too low, the contribution of heating to the above reaction is small, while if it is too high, thermal decomposition occurs, so that the temperature is preferably 100 ° C to 400 ° C. The physical properties of the molded product obtained by such a method can be further improved by performing post-treatments such as stretching and curing treatment.

As the molded article in the present invention, for example, the film has heat resistance and high strength, and is used as a printed wiring board by laminating with a metal foil, an insulating film for various motors, a transformer /
It can be suitably used as an electrically insulating film such as an insulating film for a generator. Further, the composition as a solution or suspension, glass cloth, carbon fiber,
Aramid cloth, glass paper, carbon paper,
A molded article can be obtained by impregnating aramid paper or the like or dispersing it in the composition and molding. Further, a flexible wiring substrate, a liquid crystal alignment film, L
It can be applied to a passivation film for SI, an α-ray shielding film, a multilayer wiring interlayer insulating film for silicon / gallium arsenide chips, and the like.

[Function] For example, a composition obtained by casting a composition comprising a polyimide-based polymer or polyamic acid-based polymer containing a silane coupling agent in the present invention and a metal alkoxide has high heat resistance, high strength, and dimensional stability. Although the mechanism of action relating to superiority is not always clear,
Since the metal alkoxide is mixed with the polyimide component in the monomer state or in the form of a partial condensate, the metal oxide produced by condensation by heat treatment during molding is dispersed in a very uniform state, and at this time, the silane coupling agent is used. From the inclusion, it is presumed that the metal oxide promotes some kind of interaction or chemical bond with the polyimide component.

[Examples] Next, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to these Examples.

Preparation Example 1 Preparation of metal alkoxide (1) In a reactor equipped with a stirrer and a dropping funnel, 80 g of N, N-dimethylacetamide and 69.4 g of silicon tetraethoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged and stirred vigorously. ρ
-A mixture of 0.69 g of toluenesulfonic acid and 24.0 g of water was added dropwise at room temperature over 30 minutes. Further, the mixture was continuously stirred all day and night to prepare a homogeneous transparent partial condensate of silicon tetraethoxide (SiO ₂ conversion concentration: 11.5%).

Preparation Example 2 Preparation of metal alkoxide (2) In the same reactor as in Preparation Example 1, N, N-dimethylacetamide was added.
Charge 56.0 g and titanium tetra-i-propoxide (product of Nippon Soda Co., Ltd.) 71.4 g, add 25.1 g of acetylacetone and 4.5 g of water at room temperature with vigorous stirring, and continue stirring for a whole day and night to obtain a homogeneous transparent solution. A partial condensate of titanium tetra-i-propoxide (concentration of TiO ₂ 12.8%) was prepared.

Preparation Example 3 Preparation of metal alkoxide (3) In the same reactor as in Preparation Example 1, N, N-dimethylacetamide was added.
Charge 67.6 g and zirconium tetra-n-butyroxide (Matsumoto Kosho Co., Ltd. product) 49.4 g, add 12.9 g of acetylacetone and 2.32 g of water at room temperature with vigorous stirring, and continue stirring for a whole day and night to give a homogeneous transparent solution. Zirconium tetra-n-butyroxide partial condensate (ZrO ₂ equivalent concentration 12.0
%) Was prepared.

Example 1 19.8 g of 4,4′-diaminodiphenyl ether, 0.44 g of γ-aminopropyltriethoxysilane and 213 g of N, N-dimethylacetamide were charged into a reactor equipped with a stirrer and a reflux condenser, and vigorously passed through nitrogen gas. While stirring
At 10.degree. C., 21.81 g of pyromellitic dianhydride was added over 2 hours. The mixture was continuously stirred at room temperature for 6 hours to give a logarithmic viscosity of 1.53 dl / g (0.5 g / N, N-dimethytylacetamide 10
A silane-modified polyamic acid solution (0 ml, measured at 30 ° C.) was obtained.

Silane-modified polyamic acid solution thus obtained
100 g of the metal alkoxide (1) prepared in Preparation Example 1 (partial condensate of silicon tetraethoxide) was charged into a reactor similar to the above, and the mixture was vigorously stirred with nitrogen gas.
32.8 g was added dropwise over 30 minutes, and a brown, viscous liquid was cast on a glass plate with a knife coater, and the temperature was maintained at 50 ° C and 100 ° C.
C., 170.degree. C., 320.degree. C., and heat treatment at each temperature for 1 hour. After cooling, peel the film-shaped molded product from the glass plate, and then fix it on an iron frame. A film having a thickness of 50 μm was obtained by heat treatment at 320 ° C.

With respect to the properties of the film thus obtained, the tensile strength as mechanical strength was measured by ASTM D882-64, the flex resistance (MTT) was measured by ASTM D2176-63 T, and the linear expansion coefficient was measured by TMA method. The results are shown in Table 1.

Example 2 In the same reactor as in Example 1, 20.02 g of 4,4′-diaminodiphenyl ether and 213 g of N, N-dimethylacetamide were charged, and pyromellitic dianhydride was stirred at 10 ° C. while vigorously stirring with nitrogen gas. 21.81 g was added over a 2 hour period. Subsequently, 1.42 g of γ-glycidoxypropyltrimethoxysilane was added at room temperature and stirred for 6 hours,
A silane-modified polyamic acid solution having a logarithmic viscosity of 1.81 dl / g was obtained.

A viscous liquid was prepared in the same manner as in Example 1 except that 100 g of this silane-modified polyamic acid solution was used, and the solution was cast on a glass plate and heat-treated to give a thickness of 50 μm.
I got a film of.

The characteristics of this film were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 3 In the same reactor as in Example 1, charged with 19.62 g of 4,4′-diaminodiphenyl ether and 213 g of N, N-dimethylacetamide, and pyromellitic dianhydride at 10 ° C. with vigorous stirring through nitrogen gas. 20.00 g was added over 2 hours and stirring was continued until it was completely dissolved. 1.20 g of γ-anilinopropyltrimethoxysilane was added and stirred for 2 hours. Pyromellitic dianhydride with further stirring
After adding 1.81 g, the mixture was reacted at room temperature for 6 hours to obtain a silane-modified polyamic acid solution having an inherent viscosity of 1.74 dl / g.

100 g of this silane-modified polyamic acid solution and 18.6 g of the metal alkoxide (1) (partial condensate of silicon tetraethoxide) prepared in Preparation Example 1 and the metal alkoxide (2) prepared in Preparation Example 2 (titanium etora- i-Propoxide partial condensate) A viscous liquid was prepared in the same manner as in Example 1 except that 39.0 g of a mixed solution was used, and the mixture was cast on a glass plate and heat-treated to give a thickness of 50 μm. I got a film of.

The characteristics of this film were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 4 The logarithmic viscosity was the same as in Example 2 except that γ-mercaptopropyltrimethoxysilane was used instead of γ-glycidoxypropyltrimethoxysilane in Example 2.
A 1.85 dl / g silane-modified polyamic acid solution was obtained.

100 g of this silane-modified polyamic acid solution and the metal alkoxide prepared in Preparation Example 1 (1) (Partial condensate of silicon tetraethoxide) 18.6 g and Preparation example (3) (Partial condensate of zirconium tetra-n-butyroxide) ) A viscous liquid was prepared in the same manner as in Example 1 except that 39.4 g of the mixed solution was used, and the film was cast on a glass plate and heat-treated to obtain a film having a thickness of 50 μm.

The characteristics of this film were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 A polyamic acid solution was prepared in the same manner as in the method of obtaining the silane-modified polyamic acid solution in Example 2, except that γ-glycidoxypropyltrimethoxysilane was not added.

A viscous liquid was prepared in the same manner as in Example 1 using this polyamic acid solution, and then cast on a glass plate and heat-treated to obtain a film having a thickness of 50 μm.

The characteristics of this film were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 By adding only this polyamic acid solution to the polyamic acid solution prepared in Comparative Example 1 without using a metal alkoxide, casting on a glass plate and performing heat treatment in the same manner as in Example 1 A film having a thickness of 50 μm was obtained.

The characteristics of this film were measured in the same manner as in Example 1. The results are shown in Table 1.

[Advantages of the Invention] The present invention provides a metal oxide-containing polyimide-based polymer obtained by molding a composition comprising a polyimide-based polymer containing a silane coupling agent or a polyamic acid-based polymer which is a precursor thereof and a metal alkoxide. A preferable feature of the coalesced molded product is that the molded product such as a film or sheet formed by cast molding contains the metal oxide uniformly and in a large amount. Thus, a molded product such as a film or a sheet is excellent not only in heat resistance but also in mechanical strength, and in particular, it is recognized that dimensional stability is significantly improved as compared with a molded product of a polyimide polymer alone. Such an effect is exhibited by including a silane coupling agent together with a metal oxide, and has been newly discovered.

Claims (2)

[Claims] 1. A polyimide polymer obtained by reacting a polyimide-forming material in the presence of a silane coupling agent, or a polyamic acid polymer which is a precursor thereof, and a heat treatment at a temperature not higher than the decomposition temperature of the polyimide polymer. A metal oxide-containing polyimide polymer molded product obtained by molding a composition containing a metal alkoxide capable of forming a metal oxide at a temperature under a heat treatment temperature at which a metal alkoxide becomes a metal oxide. 2. A composition containing a solution or dispersion of a polyamic acid polymer obtained in the presence of a silane coupling agent and a metal alkoxide, wherein the polyamic acid polymer is a polyimide polymer and the metal alkoxide is The polyimide-based polymer molded article according to claim 1, which is cast-molded at a heat treatment temperature to form a metal oxide.