JPS63193935A - Polyimide polymer molded article - Google Patents

Abstract

PURPOSE:To obtain the titled molded article having excellent mechanical strength, heat resistance and water and moisture resistance and suitable for electrical and electronic parts, by heat-treating a material comprising a metal alkoxide and a polymer containing biphenyltetracarboxylic acid dianhydride as essential component. CONSTITUTION:The objective molded article having improved dispersibility of metal oxide can be produced by heat-treating and molding a composition containing (A) 100pts.wt. of a polymer containing biphenyltetracarboxylic acid dianhydride as an essential component or a polyimide polymer composed of a polyamic acid polymer [e.g. a polymer composed of the unit of formula I and formula II (Ar<1> is group of formula III or IV; Ar' and Ar'' are group of formula V, VI, VII or VIII; R is 1-3C alkyl, alkoxy or halogen; X is -O-, -S-, -SO2, group of formula IX, 1-6C alkylene or perfluoroalkylene; n is 0-2)] and (B) 1-200pts.wt. of a metal alkoxide (e.g. silicon tetramethoxide) in terms of metal oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a molded polyimide polymer in which a metal oxide is uniformly dispersed.

[Prior Art] Polyimide polymers are known as resins that have excellent mechanical properties, especially at high temperatures, as well as good chemical resistance and electrical properties, and are used in electrical and electronic parts, aircraft parts, automobile parts, It is being used in a wide range of fields, including sanitary skewers, food equipment parts, and medical equipment parts.

In particular, in the practical application of the electric fist electronic components mentioned above, polyimide polymer films can be used as electrical insulators or semiconductor integrated circuits such as flexible printed circuit boards, various electric motors, transformers, and generators. It is applied to film carrier tapes for mounting.

However, organic polymers generally have a drawback of having a higher coefficient of thermal expansion than inorganic materials, and even polyimide polymers, which have excellent heat resistance, are no exception to this.

Under these current circumstances, when a polyimide polymer film is used, for example, as a flexible printed circuit board, it is important to avoid curling of the board due to the difference in thermal expansion coefficient between the polyimide film and the laminated metal foil. It became necessary to prevent this, and an adhesive layer was provided. However, since the materials used for such adhesive layers generally have inferior heat resistance than polyimide films, there has been a problem in that the inherent heat resistance of polyimide films cannot be fully demonstrated.

Therefore, many attempts have been made to improve the coefficient of thermal expansion of polyimide polymers, and polyimides with various structures have been proposed. A polyimide using a diamine component is disclosed. Many of these attempts attempt to improve the drawbacks by using compounds with special structures in the acid dianhydride or diamine components that are the constituent components of polyimide.
Because it is a special compound, raw materials are difficult to obtain, and toxicity remains a problem.

Furthermore, it has become clear that the widely used polyimide consisting of pyromery, tonic anhydride, and diaminodiphenyl ether has a high water absorption rate in addition to the above-mentioned drawbacks, and also has a problem in alkali resistance.

[Problems to be solved by the invention] The present inventors aim to improve the mechanical strength, heat resistance, water/moisture resistance, chemical resistance, etc. of molded products made of polyimide polymers, particularly films and sheets. various studies as
We have considered this.

As a result, metal alkoxides or their partial condensates and tetracarboxylic dianhydrides, which can become metal oxides during heat treatment below the decomposition temperature of polyimide polymers containing biphenyltetracarboxylic dianhydride as essential components, are used as essential components. A molded product obtained by heat-treating and molding a composition containing the obtained polyimide polymer or its precursor polyamic acid polymer is compared to a molded product simply blending metal oxide powder. The present invention was completed based on the finding that the dispersibility of the metal oxide is significantly improved and that the molded product can satisfactorily achieve the above object.

Therefore, in terms of application and use, the present invention provides a novel polyimide-based polymer molded product containing a fully bent oxide, which has properties that are practically satisfactory for use in the fields of electrical/electronic parts or structural materials. The purpose is to

[Means for Solving the Problems] That is, the present invention provides a polyimide-based polymer molded product containing a metal oxide, in which the polyimide-based polymer is a polymer obtained using biphenyltetracarboxylic dianhydride as an essential component. A composition comprising a metal alkoxide or a partial condensate thereof, which is composed of a polyamic acid polymer that is a polymer or a precursor thereof, and which can become a metal oxide under heat treatment at a temperature below the decomposition temperature of these polymers, and the aforementioned polymer. The object of the present invention is to provide a polyimide polymer molded product obtained by heat treating and molding a product.

The polyimide polymer in the present invention consists of the following formulas [1] and [II] as constituent elements.

R represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group, or a halogen group; represents an alkylene group, and n represents an integer from O to 2.) Here, the ratio of biphenyltetracarboxylic dianhydride and other acid anhydrides contained as essential components in the polymer is:
Weight ratio of 5:95 to 100:0, preferably 10:90
~100:0. If the amount of biphenyltetracarboxylic dianhydride is too small, no improvement will be observed in the water resistance, salt resistance, chemical resistance, and especially alkali resistance of the molded product.

In the present invention, the metal oxide contained in the molded polyimide polymer is converted into a metal oxide due to a condensation reaction of the metal alkoxide when the composition consisting of polyimide or polyamic acid and metal alkoxide is heat-treated. It is what it is. Examples of such metal alkoxides include Si compounds such as silicon tetramethoxide and silicon tetraethoxide, Zr compounds such as zirconium tetrapropoxide and zirconium tetrabutoxide, titanium tetra-i-propoxide, and titanium tetra-n.
- Ti compound aluminum such as butoxide - Tri5
Examples include AI compounds such as ec-butoxide.

In a composition containing a polyimide polymer or a polyamic acid polymer and a metal alkoxide, the metal alkoxide is preferably 1 to 200 parts by weight as a metal oxide per 100 parts by weight of the polyimide polymer.
Heat resistance and dimensional stability increase depending on the amount of metal oxide in the polymer. Heat resistance and dimensional stability improve depending on the amount of metal oxide, but if it is too small, it is difficult to achieve the effect, and if it is too large, it is difficult to express the effect. In some cases, there is a tendency to become brittle. Therefore, it is preferably 10 to 100 parts by weight. As the metal alkoxide, a partially condensed product in which condensation has proceeded in advance is also used, and this can be used alone or in combination with a metal alkoxide. (Hereinafter, metal alkoxy includes partial condensates unless specifically specified as partial condensates.) Conventionally, inorganic oxide fillers have been used as a means to improve the dimensional stability of molded products made of organic polymers. Addition is well known. Regarding films as molded products of polyimide polymers, for example, Japanese Patent Application Laid-Open No. 1110-228557 discloses a film with a smooth surface obtained by forming a film from a composition in which an inorganic filler is blended with polyetherimide represented by the following formula. A method for obtaining superior films is disclosed. In such a polyetherimide film, the inorganic filler added to the polymer is limited to 10 parts by weight or less per 100 parts by weight of the polymer, and in order to maintain the surface smoothness of the film, the amount must be 10 parts by weight or less. is said to be desirable. However, if the amount of inorganic filler is less than 10% by weight, the dimensional stability is not sufficient for practical use as a polyimide film.The present inventors also found that if the amount of inorganic filler is 10% by weight or more, 10% by weight or more is usually used. It is difficult to completely convert the powder that exists as secondary particles into primary particles, and as a result, the particles themselves become defective points, reducing the strength of the film or making it brittle, and in extreme cases. It has been confirmed that it is difficult to make into a film.

' In the present invention, the metal oxide is not blended as an inorganic filler, but is blended into the polymer in the form of a metal alkoxide to form a composition, and therefore the composition is completely homogeneous. .

Conventionally, metal oxide sol is mixed with resin, or metal oxide is generated by hydrolytic condensation of metal alkoxide, and this is applied to the surface of the substrate to form a coating layer. Techniques for improving physical properties are known in the technical field of surface treatment; for example,
It is disclosed in Japanese Patent Application Laid-Open No. 1-50945, Japanese Patent Application Laid-Open No. 154751-1982, and Japanese Patent Application Laid-open No. 294F39-1987. However, no metal oxide-containing polyimide polymer molded product is known, which is obtained by heat-treating a composition containing a metal alkoxide and a polyimide polymer or a polyamic acid polymer, and then molding the resulting product into, for example, a film or sheet. do not have. Therefore, the method for obtaining such a molded body is also unknown.

The composition containing a metal alkoxide and a polyimide polymer or a polyamic acid polymer in the present invention includes:
The metal alkoxide is condensed into a metal oxide by heat treatment when obtaining the molded body. The means for preparing a composition containing a metal alkoxide and a polyimide polymer or a polyamic acid polymer, that is, mixing, is carried out by any of the following three methods.

■ Direct mixing of polymer and metal alkoxide or its partial condensate.

■Mixing of polymer suspension and metal alkoxide or its partial condensate.

■Polymer solution (varnish) and metal alkoxide or
Mixing with its partial condensate.

Regarding (2) above, when the polymer is in a relatively large form such as a block or pellet, it is desirable to dissolve the polymer in a mixing system, and when the polymer is in the form of a fine powder, the polymer is preferably dissolved in a mixing system. Even if the composition is not necessarily dissolved in the system, a uniformly mixed composition can be obtained. In case (2), the polymer is usually present in the form of a fine powder, so whether the mixed system with the metal alkoxide or its partial condensate is able to dissolve the polymer or not, it is uniform as described in (2) above. A composition mixed with the following is obtained. (2) The method of mixing the metal alkoxide or its partial condensate with the varnish produces the most uniformly dispersed composition. The solvent used as the polymer solution does not dissolve the polymer. Although there are no particular limitations as long as it is non-woven, N,N-dimethylacetamide can be exemplified as a suitable example.

The metal alkoxide used in the present invention or
The partial condensate can be used without any other treatment, but for the purpose of improving miscibility and dispersibility with the polymer, it may be hydrated by adding an appropriate solvent or in the presence of water or a catalyst. The condensation of metal alkoxides during hydrolysis, which may be further condensed by decomposition or heat treatment, is presumed to proceed as follows.

M(OR)n+nH2O→ M(OH)n+nR(O
H)M(OH)n + NOn/2”/2H20 The amount of water used here is considered to follow the above formula as long as it is equal to or more than the number of equivalents of Alcolade, but if the amount of water used is equal to or more than the number of equivalents of Alcolade, The degree of condensation can be controlled by adjusting the amount.Also, in order to facilitate the progress of condensation, a catalyst such as an acid or a base can be used.Acids as such catalysts include hydrochloric acid, sulfuric acid, etc. , nitric acid, phosphoric acid, organic acids such as p-)luenesulfonic acid, and bases include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as alkylamines. Heating is effective in making the final stage proceed smoothly.

Furthermore, a silane coupling agent may be added to the composition in order to improve the miscibility. In this case, the silane coupling agent acts simply as a dispersion improver or dispersion stabilizer for the polymer and the dispersed substance. In addition, by selecting a material having an appropriate functional group, it becomes possible to bond it to the functional group of the polymer, thereby significantly improving the physical properties of the resulting molded product. Examples of the silane coupling agents that can be used include alkyl-based silane coupling agents such as methyltrimethoxysilane, halogen-based silane coupling agents such as γ-chloropropyltrimethoxysilane, and vinyl-based silane coupling agents such as vinyltriethoxysilane. Silane coupling agents, methacrylic silane coupling agents such as γ-methacryloxypropyltrimethoxysilane, epoxy silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, etc. Mercaptosilane coupling agents, hydroxy-based silane coupling agents such as γ-(jetanolamine)propyltriethoxysilane, incyanate-based silane coupling agents such as γ-incyanatopropyltrimethoxysilane, γ-7minopropylt' Examples include amine-based silane coupling agents such as rimethoxysilane or their salt types, and these silane coupling agents may be used alone or in combination of two or more. It is sufficient to simply add and mix at the time of film formation, but if the polymer has a functional group and some interaction or bond formation with the silane coupling agent can be expected, it may be necessary to mix it with the polymer in advance or add it by heating, etc. It is also effective to perform pretreatment. In addition, titanate coupling agents and aluminum coupling agents can also be used depending on the type of metal alkoxide. In addition, for the purpose of stabilizing metal alkoxides and compositions and adjusting reactions, chelating agents such as acetylacetone,
The use of complexing agents is also effective.

In the present invention, when forming a composition containing a metal alkoxide and a polyimide polymer or a polyamic ugly polymer into a film or sheet, if the composition is in a liquid state, heat treatment is performed together with casting film formation. In addition, if the metal alkoxide or its partial condensate is made of a composition that has been condensed by hydrolysis or heat treatment as described above, and if it is liquid, it can be heat treated and solidified at the same time as cast film formation. If the shape is a shape, it is made into a molded product by extrusion molding by heating and melting. The temperature range in the heat treatment is preferably 50°C to 500°C, but if the temperature is too low, the contribution of heating to condensation will be small, and if the temperature is too high, the polyimide polymer will thermally decompose.
This temperature range of 400 DEG C. also applies to the precondensation of the metal alkoxides mentioned above.

The molded product obtained by the above-mentioned molding method is subjected to post-treatments such as stretching and curing, so that the physical properties of the molded product can be further improved. The suspension can also be obtained as a molded article with excellent heat resistance by impregnating glass cloth, carbon fiber, glass paper, carbon paper, aramid paper, etc., or by dispersing a fibrous base material.

In the molded product of the present invention, for example, the film can be laminated with metal foil to form a printed wiring board having heat resistance and high strength.

In addition, it can be used as an electrical insulating film, such as insulating films for various motors and insulating films for transformers and generators. Furthermore, by applying the composition directly onto metal foil and heating it, the composition can be applied to flexible wiring boards, liquid crystal alignment films, passivation films for LSIs, alpha-ray shielding films for silicon, multilayer wiring interlayer insulation films for gallium-arsenic chips, etc. It can be used to obtain

[Function] In the present invention, the mechanism by which a molded product made of a polyimide polymer containing a metal oxide through condensation of a metal alkoxide has excellent high strength and dimensional stability is not necessarily clear, but is uniformly dispersed by blending it into the polymer in the form of an alkoxide,
Moreover, as the metal oxide is heated and hardened as it is molded, the condensation reaction progresses and the molded product is formed in a uniformly dispersed state. It is presumed that this is due to either the action or the formation of a chemical bond.

In particular, it can be assumed that the improved water resistance, moisture resistance, and chemical resistance of the molded article is due to the hydrophobicity of the biphenyltetracarboxylic acid component.

[Example] The present invention will be explained in more detail with reference to Examples.
It goes without saying that the present invention is not limited only to these examples.

Preparation Example 1 Preparation of metal alkoxide (1) In a reactor equipped with a stirrer and a dropping funnel, N, N-
80 g of dimethylacetamide and 69.4 g of silicone tetraethoxide (Tokyo Kasei Co., Ltd.) were charged, and while nitrogen gas was introduced and vigorously stirred, a mixture of 0.89 g of p-)luenesulfonic acid and 2a, og of water was heated to 30 g at room temperature. It took several minutes to drip. Furthermore, by continuing stirring day and night, a homogeneous transparent partial condensate of silicone tetraethoxide (Si
02 equivalent concentration 11.5%) was prepared.

Preparation Example 2 Preparation of Metal Alkoxide (2) In a reactor similar to Preparation Example 1, 56 g of N,N-dimethylacetamide and 71.4 g of titanium tetrabroboxide (Nippon Soda Co., Ltd.) were charged, and nitrogen gas was passed through the mixture and the mixture was vigorously stirred. At the same time, add 25.1 g of acetylacetone and 4 ml of water.
．． 5 g at room temperature, and continued stirring day and night.
Homogeneous transparent partial condensate of titanium-1-propoxide (T
(i02 equivalent concentration: 12.8%) was prepared.

Preparation Example 3 Preparation of Metal Alkoxide (3) In a reactor similar to Preparation Example 1, 87.6 g of N,N-dimethylacetamide and 49.4 g of zirconium tetra-n-butyroxide (Matsuki Koshosha product) were charged, and nitrogen gas was added. While stirring vigorously, acetylacetone 12
．． 9 g and 2.32 g of water were added at room temperature, and stirring was continued day and night to obtain a homogeneous transparent partial condensate of zirconium tetra-n-butyroxide (concentration in terms of Zr02: 12.0%).
was prepared.

Preparation Example 4 Preparation of polyamic acid solution (1) In a reactor equipped with a stirrer, a dropping funnel and a reflux device, 20.02 g of N,N-diaminodiphenyl ether and N
, N-dimethylacetamide, and 258 g of N-dimethylacetamide were cooled to 10° C. while vigorously stirring while passing nitrogen gas, and 29.42 g of biphenyltetracarboxylic dianhydride was added dropwise over 2 hours. Subsequently, the temperature was maintained at room temperature to completely dissolve the biphenyltetracarboxylic dianhydride, and the mixture was further stirred at room temperature for 6 hours to react. Thus the logarithmic viscosity is 1.58 di / g (0.5 g / 10
0 + sentence N, N-dimethylacetamide, measured at 30°C,
A polyamic acid varnish (the same applies hereinafter) was obtained.

Preparation Example 5 Preparation of polyamic acid solution (2) N,N-dimethylacetamide in Preparation Example 4 was
0g, biphenyltetracarboxylic dianhydride 4.8
A polyamic acid varnish with a logarithmic viscosity of 1.64 was obtained in the same manner as in Preparation Example 4, except that 18.40 g of pyromellitic dianhydride was used.

Preparation Example 6 Preparation of Polyamic Acid Solution (3) N,N-dimethylacetamide in Preparation Example 4 was added to 21
A polyamic acid varnish with a logarithmic viscosity of 1.8 EidQ/g was obtained in the same manner as in Preparation Example 4, except that 21.81 g of pyromellitic dianhydride was used instead of biphenyltetracarboxylic dianhydride. .

Example 1 100 g of the polyamic acid varnish obtained in Preparation Example 4 was charged into a reactor equipped with a stirrer, a dropping funnel, and a reflux condenser, and the silicon tetra prepared in Preparation Example 1 was heated at room temperature while vigorously stirring through nitrogen gas. Ethoxide 32.58
g was added dropwise over 30 minutes to obtain a brown uniform viscous liquid 1
Next, 0.19 g of 3-7 minobrobyltriethoxysilane was added to this viscous liquid, which was cast onto a glass plate using a knife coater and heated at 50°C for 1 hour and at 100°C for 1 hour.
After heating at 170°C for 1 hour and 320°C for 1 hour, the molded product was peeled off from the glass plate, and then fixed on an iron frame and further heated at 320°C for 111 hours. A film with a thickness of 50 mm was obtained by heating for a while.

The tensile strength of the film thus obtained was measured in accordance with ASTM D882-64 as mechanical strength, and the linear expansion coefficient was measured by the TMA method. Furthermore, the water absorption rate was determined to be 23% according to ASTM D 570-83.
℃, 24 hour immersion also increases the alkali resistance by 10%.
-The time for complete disappearance was measured by a NaOH aqueous solution boiling test. These results are shown in Table 1.

Example 2 In place of the polyamic acid varnish in Example 1, 100 g of the polyamic acid varnish prepared in Preparation Example 5 was used.
A film was obtained in the same manner as in Example 1 except that . The properties of this film were measured in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 27.8 g of polyamic acid varnish prepared in Preparation Example 4 instead of the polyamic acid varnish in Example 1
and the polyamic acid varnish prepared in Preparation Example 6 72.
4 g and 16.30 g of silicon tetraethoxide obtained in Preparation Example 1 and titanium-i prepared in Preparation Example 2.
A film was obtained in the same manner as in Example 1, except that 14.85 g of -propoxide was mixed and used. The characteristics of this film were measured in the same manner as in Example 1, and the results were
Shown in the table.

Example 4 Polyamic acid varnish 47.1 prepared in Preparation Example 4 was used in place of the polyamic acid varnish in Example 1.
g and the polyamic acid varnish prepared in Preparation Example 6 52.
9g and zirconium tetra-obtained in Preparation Example 3
Example 1 except that 31.25 g of n-butyroxide was used.
A film was obtained in the same manner as above. The properties of the film thus obtained were measured in the same manner as in Example 1,
The results are shown in Table 1.

Comparative Example 1 A film was obtained in the same manner as in Example 1, except that the polyamic acid prepared in Preparation Example 6 was used instead of the polyamic acid varnish in Example 1. The properties of this obtained film were measured in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 Example 2 except that the polyamic acid prepared in Preparation Example 6 was used instead of the polyamic acid varnish in Example 1, and the 3-7 minoprobyl triethoxysilane added in Example 1 was not added. A film was obtained in the same manner as in 1. The properties of this obtained film were measured in the same manner as in Example 1, and the results are shown in Table 1.

[Effects of the Invention] The present invention provides a polyimide polymer containing biphenyltetracarboxylic dianhydride as an essential component, or a polyamic acid polymer that is a precursor thereof, which can become a metal oxide under a heat treatment temperature below the decomposition temperature. A metal alkoxide is produced by heat-treating a composition consisting of a metal alkoxide and a polyimide polymer containing biphenyltetracarboxylic dianhydride as an essential component or a polyamic acid polymer, which is a precursor thereof, and forming it into a film or sheet. The molded article is characterized by the fact that the metal oxide produced by the condensation of the molded article is uniformly contained in a large amount. As a result, molded products such as films or sheets,
Mechanical strength and heat resistance 1 compared to simple polymer molded products
It is recognized that it not only has excellent dimensional stability, but also excellent water resistance, moisture resistance, and alkali resistance.

Claims (1)

[Claims] In the polyimide-based polymer molded product containing a metal oxide, the polyimide-based polymer is composed of a polymer obtained with biphenyltetracarboxylic dianhydride as an essential component or a polyamic acid-based polymer that is its precursor. 1. A molded polyimide polymer obtained by heat-treating and molding a composition containing the polymer and a metal alkoxide or a partial condensate thereof that can become a metal oxide under heat treatment at a temperature below the decomposition temperature of the polymer.