JPH0214242A - Polyamic acid composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain a polyamic acid composition providing a polyimide polymer molded article having excellent dimensional stability, heat-resistance, etc., and suitable as electric or electronic parts, etc., by compounding a specific polyamic acid with a metal alkoxide (or its partial condensate) and a polar organic solvent. CONSTITUTION:The objective composition is produced by compounding (A) a polyamic acid produced by reacting an aromatic tetracarboxylic acid dianhydride (e.g., biphenyltetracarboxylic acid dianhydride) with an aromatic diamine (e.g., 4,4'-diaminodiphenyl ether) in the presence of a silane coupling agent (e.g., gamma-aminopropyltrimethoxysilane) with (B) a metal alkoxide (e.g., silicon tetramethoxide) and/or partial condensate of metal alkoxide and (C) a polar organic solvent.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a polyamic acid composition that is a precursor of polyimide as a heat-resistant resin suitably used in the electrical and electronic fields, and a method for producing the same. be.

[Prior art] Polyimide-based intermediates have excellent mechanical properties in a wide temperature range, as well as good electrical properties and chemical resistance, so they are used in electrical and electronic parts, automobile parts, and sanitary and food equipment. Used for parts, medical device parts, etc. Particularly in the field of electrical and electronic components mentioned above, polyimide polymer films are used as electrical insulators or semiconductor integrated circuits used in flexible printed circuit boards, various electric motors, transformers, generators, etc. due to their excellent heat resistance. It has been put to practical use in film carrier tapes, etc.

However, in general, inorganic small polymers have the disadvantage of having a higher coefficient of thermal expansion than inorganic materials, and polyimide polymers are no exception to this. Therefore, when applying to flexible printed circuit boards, for example, when bonding metal foil to polyimide film, it is necessary to place a layer between the polyimide film and the metal foil to prevent curling caused by the difference in thermal expansion coefficients. It is necessary to provide an adhesive layer. However, the materials used for such adhesive layers generally have poor heat resistance, and there is a problem in that the heat resistance fj 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 with various structures have been proposed. For example, in JP-A-60-250031, a polyimide obtained from a polyamic acid using a diamine component selected from the following is mentioned as having low expansion property. In addition, as another example, attempts have been made to improve dimensional stability by using a compound with a special structure in the acid dianhydride or diamine component, which is a component of polyimide. However, the use of compounds with special structures as described in I. still leaves problems with respect to the strength and fj properties of the raw materials.

[Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned problems. A polyamic acid composition comprising a polyamic acid obtained by reaction in the presence of a polyamic acid, a metal alkoxide and/or a partial condensate of a metal alkoxide, and a 41 polar solvent, and the! ! J
This provides a method for manufacturing.

Since the polyimide polymer molded product obtained from the polyamic acid composition of the present invention has excellent properties such as dimensional stability, heat resistance, and mechanical strength, it is suitable for electrical and electronic applications. The object of the present invention is to provide a new polyamic acid composition and a method for producing the same, which can be suitably used as various parts or structural materials, including r-parts, and which can provide a polyimide-based i1i composite molded product having a tensile property. be.

[Means for Solving the Problems] That is, the present invention provides polyamic acids, metal alkoxides and/or metal alkoxides obtained by reacting aromatic tetracarboxylic dianhydrides and aromatic diamines in the presence of a silane coupling agent. The present invention provides a polyamic acid composition comprising a partial condensate of a metal alkoxide and an organic polar solvent.

Furthermore, the present invention provides a method for producing the polyamic acid composition described in 1.1 and 1.1, one of which is to react an aromatic tetracarboxylic dianhydride and an aromatic diamine, and then add a silane coupling agent. It is characterized in that after reacting to obtain a polyamic acid, a metal alkoxide and/or a partial condensate of a metal alkoxide is blended therein,
After reacting another dipping aromatic tetracarboxylic dianhydride with a silane coupling agent and then reacting with an aromatic diamine to obtain a polyamic acid, a metal alkoxide and/or a partial condensate of the metal alkoxide is added to the polyamic acid. This is a method for producing a polyamic acid composition characterized by blending the following.

The aromatic tetracarboxylic dianhydride used in the present invention is a compound represented by the following general formula [l], and suitable examples include pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, pen Examples include zophenonetetracarboxylic dianhydride, and two or more of these can be used in combination. In the aromatic tetracarboxylic dianhydride exemplified above, chemical resistance, water resistance, and moisture resistance are improved by including biphenyltetracarboxylic dianhydride.

It is preferable to include this as an essential component.

Further, the aromatic diamine used in the present invention is selected from the above general formula [ ] % formula % [11: R represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group, or a halogen: X represents a bond in the mouthpart, - o-, -3-, -3o, -, -C-, an alkylene group having 6 to 6 carbon atoms, and a perfluoroalkylene group; m and n each represent an integer of 0 to 2; ), and two or more of these can be used in combination. Suitable aromatic diamines include 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl-propane, etc.].

Furthermore, the silane coupling agent used in the present invention is
nm is used to improve the dispersibility and mixability of metal alkoxides and other substances blended into polyamic acid, and the coefficient of thermal expansion, etc. of molded products from the composition is improved compared to molded products that do not contain it. The dimensional stability based on the properties is significantly improved. Various known silane coupling agents may be used as the silane coupling agent, but they do not only act as a dispersion improver or dispersion stabilizer that improves dispersibility and mixability, but also act as a dispersion stabilizer with suitable functional groups. 11) By selecting the one that binds to the functional group possessed by the 1o polymer, it becomes possible to bond with the functional group possessed by the 1o polymer, and the physical properties of the resulting molded product can be further improved. Such silane coupling agents may contain one or more amine groups, especially primary and/or secondary amino groups, such as γ-
Aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, e.g. γ-glycidoxypropyltrimethoxysilane with one or more glycidyl groups, or e.g. γ-mercapto with one or more [- mercapto groups. Preferred examples include propyltriethoxysilane. Others: Phenyltrime I・
Phenyl silane coupling agents such as xysilane, halogen silane coupling agents such as trimethylchlorosilane, silylamine silane coupling agents such as dimethyltrimethylsilylamine, acyloxysilane silane coupling agents such as vinyltriacetoxysilane, N- An acetamidosilane-based silane coupling agent such as trimedelsilylacetamide can also be used. Among these silane coupling agents, functional groups 1 of polyamic acid or polyimide polymers, such as -COOI+, -NI+8. -NI
15 is to use a silane coupling agent that is reactive with IC-shun etc.

Furthermore, the same effect can be obtained 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 metal alkoxide in the polyamic acid composition.

The composition ratios of aromatic tetracarboxylic dianhydride, aromatic diamine, and silane coupling agent are each in molar ratio I
QQ/99.9-80/Q, preferably 01-40.

Examples of the metal alkoxide in the polyamic acid composition of the present invention include Si alkoxide compounds such as silicon tetramethoxide and silicon tetraethoxide, Zr alkoxide compounds such as zirconium tetrapropoxide and zirconium tetrabutoxide, and titanium tetrarib compounds. Ti alkoxide compounds such as oxide, titanium tetrabutoxide, AI alkoxide compounds such as aluminilatri-5ec-butoxy, Sn alkoxide compounds such as chintetrabutoxide, and partial condensates obtained by precondensing these can be used.

These metal alkoxides undergo a synthesis reaction and become metal oxides when the composition is heat-treated and formed into a molded article. Here, in order to make the condensation reaction proceed smoothly, while water and a catalyst are added to hydrolyze the metal alkoxide, the condensation can be further proceeded by heat treatment.

The amount of the metal oxide derived from the metal alkoxide contained in the polyamic acid composition of the present invention is preferably 1 to 200 parts by weight based on 100 parts by weight of the polyimide component formed from the polyamic acid. In addition, when molding a composition into a film shape, for example, the solid content concentration of the composition depends on the viscosity of 10.
It is preferable that the amount is 50% by market weight. The heat resistance and dimensional stability improve in response to the electric charge of the metal oxide in the molded product, but
If it is too small, it is difficult to achieve the desired effect, and if it is too large, it tends to become brittle. Therefore, preferably 10
~+001 parts by weight.

The following two methods can be applied to the method for producing the polyamic acid composition of the present invention.

The first method is to react an aromatic tetracarboxylic dianhydride with an aromatic diamine, then react with a silane coupling agent to obtain a polyamic acid, and add a metal alkoxide and/or a metal alkoxide to the polyamic acid. The partial condensate of In this method, it can be produced by a two-step reaction as described above, but it is more preferable to adopt a production method using the following three-step reaction. The amount (mol) of aromatic diamine is increased relative to the amount (mol) of carboxylic dianhydride, preferably +00/105 to 145, and then the aromatic diamine is added to the reaction system as the second stage reaction. The molar ratio of aromatic tetracarboxylic dianhydride and aromatic diamine was adjusted to <100/99 as described above.
．． React so that it becomes 9 to 80. Next, in the third stage reaction, a silane coupling agent is reacted with the residue of the aromatic tetracarboxylic dianhydride in the second stage reaction. In the first stage reaction, the aromatic tetracarboxylic dianhydride and the aromatic diamine are equivalent in molar ratio to the aromatic tetracarboxylic dianhydride and aromatic diamine. ! There are no residues of water, and no reaction with the silane coupling agent takes place.

The second method is to react an aromatic tetracarboxylic dianhydride with a silane coupling agent, then react with an aromatic diamine to obtain a polyamic acid, and add a metal alkoxide and/or a metal alkoxide moiety to the polyamic acid. A condensate is blended. In this method, an aromatic diamine is reacted with -t (mol) of an aromatic tetracarboxylic dianhydride by increasing its charge.Meanwhile,
A product obtained by reacting an aromatic tetracarboxylic dianhydride with a silane coupling agent in advance is reacted with a product obtained by reacting the aromatic tetracarboxylic dianhydride with an aromatic diamine to form a polyamic acid. Acid. In this case, the final molar ratio of aromatic tetracarboxylic dianhydride and aromatic diamine is set to 99.9 to 80, as in the first method.

A metal alkoxide and/or a partial condensate of a metal alkoxide is blended into the polyamic acid product thus obtained. The blending method is not particularly limited and can be carried out by any conventional method. Since polyamic acid has a varnish-like structure as a small coalesce solution depending on the organic polar solvent used in the reaction, the method of mixing metal alkoxide or its partial condensate with this small coalesce solution is the most uniformly dispersed composition. It is suitable in that it can be obtained.

The metal alkoxide or its partial condensate used here can be used without any special treatment, but
A suitable solvent may also be added for the purpose of improving miscibility and dispersibility. In addition, further condensation may be carried out by adding water or a catalyst, or by heat treatment.

When adding water, the amount added is not particularly limited, but 1 part of alkoxy of metal alkoxide! 0.1 to 4 for d
An equivalent amount is preferable; if the amount is larger than this, the stability of the polyimide polymer or polyamic acid polymer as a composition decreases. Examples of the catalyst include acids known as hydrolysis catalysts, such as hydrochloric acid, sulfuric acid, 6rI acid, acetic acid, toluenesulfonic acid, and inorganic bases such as sodium hydroxide and 41-organic bases such as alkyl amines.

The polyamic acid composition of the present invention can be obtained by the above-mentioned production method, but since an organic polar solvent is used during production, the 1rC combined solution has a varnish-like appearance due to the solvent. Therefore, the solid content concentration is 5QiTjja
% F or less, and the concentration can be adjusted separately using an organic polar solvent. Examples of organic polar solvents include N,N-dimethylacetamide (hereinafter referred to as DM8), N-methyl-2-pyrrolidone (hereinafter referred to as NM
), N,N-dimethylformamide (referred to as
It is preferable to use DMF (hereinafter referred to as DMF).

The polyamic acid composition of the present invention can be made into a polyimide molded article by molding and heat treating it. The molding method is not particularly limited, but a cast molding method such as casting onto a flat glass surface or a steel belt is suitable. As for the heat treatment conditions in cast molding, it is desirable to heat to 50 to 50C, at which time imidization and polycondensation of the metal alkoxide are carried out.If the heating temperature is too low, the above-mentioned The heating temperature is preferably 100° C. to 400° C., since heating is less sensitive to the reaction, and thermal decomposition occurs if the temperature is too high.The molded product obtained by this method may be subjected to post-treatments such as stretching and hardening. By doing so, the physical properties can be further improved.

Examples of molded products in the present invention include films that have heat resistance and high strength, and can be laminated with metal foil to make printed wiring boards, and for electrical insulation such as insulating films for various motors and insulating films for transformers and generators. It can be suitably used as a film. Furthermore, a molded article can be obtained by impregnating glass cloth, carbon fiber aramid cloth, glass vapor, carbon vapor, aramid vapor, etc. with the composition, or by dispersing it in the composition and molding it. In addition, the above-mentioned compositions can be applied directly to metal foil for flexible wiring boards, liquid crystal alignment films, passivation films for Sl, alpha-ray shielding films, multilayer wiring interlayer insulating films for semiconductor elements such as silicon and gallium arsenide, etc. It can be applied.

[Function] Although the mechanism of action regarding the high heat resistance, high strength, and excellent -r stability of molded products obtained by cast molding the polyamic acid composition of the present invention is not necessarily clear, Because it is mixed with the polyimide component in the form of a lump or partial cotton mixture, the metal oxide produced by condensation during heat treatment during molding is dispersed in an extremely uniform state, and it also contains a silane coupling agent. From this, it is presumed that this is due to the fact that the metal oxide promotes some kind of mutual interaction or chemical bonding with the polyimide component.

[Example 1] Next, the present invention will be explained in more detail with reference to Examples, but 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, stirred vigorously, and then ρ-toluenesulfone l'1 l120.
A mixture of 69 g and 24.0 g of water was added dropwise at room temperature over 30 minutes. Furthermore, stirring was continued day and night to produce a homogeneous and transparent partial condensate of silicone tetraethoxide (SiO□).
(equivalent concentration: 11.5%) was prepared.

Preparation Example 2 Preparation of Metal Alkoxide (2) In a reactor similar to Preparation Example 1, 56.0 g of N,N-dimethylacetamide and ditanetetra i-propoxide (
11 Wood Ill/Tatsusha product) 71.4g, and while stirring vigorously, add 25.1g of acetylacetone and 44g of water.
．． 5 g of titanium tetra-1-propoxide were added at room temperature, and stirring was continued day and night to prepare a homogeneous and transparent partial condensate of titanium tetra-1-propoxide (concentration in terms of TiOz: 12.8%).

Preparation Example 3 Preparation of Metal Alkoxide (3) Into the same reactor as in Preparation Example 1, 67.6 g of N,N-dimethylacetamide and 49.4 g of zirconium tetra-n-butyroxide (Matsuki Koshosha product) were charged and heated vigorously. While stirring, add 12.9 g of acetylacetone and 2.
32 g was added at room temperature, and stirring was continued day and night to prepare a homogeneous and transparent partial condensate of zirconium tetrarope thyroxide (concentration in terms of Zr0z: 12.0%).

Example 1 19.8 g of 4,4'-diamino diphenyl ether was placed in a reactor equipped with a stirrer and a reflux condenser.

213 g of DM8 was charged as a solvent, and 18.2 g of pyromellitic dianhydride was added thereto over 2 hours at 10° C. while stirring vigorously through nitrogen gas. After continuing the reaction for 2 hours, pyromellitic dianhydride 3.
After 61 g was added and the reaction was carried out for 1 hour, 0.44 g of γ-aminopropyltriethoxysilane was added, and stirring was continued for 6 hours at room temperature to obtain a silane-modified polyamic acid solution.

100 g of the silane-modified polyamic acid solution thus obtained was charged into the same reactor as in Section L, and while nitrogen gas was passed through and vigorously stirred, the metal alkoxide (1) (silicon tetraethoxide) prepared in Preparation Example 1 was heated. Partial condensate) 32.8g was added dropwise over 30 minutes to give a uniform brown color.
- A viscous liquid was obtained. This was cast on glass temporary -F using a knife coater, and heated at 50℃, 100℃, 170℃,
The mixture was heated to 320° C. and then heated for 2 hours at each temperature. After cooling, the film-like molded product was peeled off from the temporary glass to obtain a film with a thickness of 50 μm.

Regarding the properties of the film obtained in this way, the tensile strength is expressed as the mechanical strength.
, : , t: S, bending resistance (M i” 'T') is A
The linear expansion coefficient was further measured by the 1' MA method using STM D 2+76-631'. The results are shown in Table 1.

Example 2 20.02 g of 4,4'-diaminodiphenyl ether and 220 g of N,N-dimethylacetamide were placed in the same reactor as in Example 1, and pyromellitic acid dihydrogen was added at 10° C. while vigorously stirring while passing nitrogen gas. Anhydride 15
．． 2g and biphenyltetracarboxylic dianhydride 4.60
g was added over a period of 2 hours. After continuing the reaction for 2 hours, pyromellitic dianhydride 3. After adding Zg and reacting for 1 hour, 1.42 g of γ-glycidoxypropyltrimethoxysilane was added and stirred at room temperature for 6 hours to obtain a silane-modified polyamic acid solution.

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 then cast onto a glass plate and heat treated to obtain a film with a thickness of 50 μm.

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

Example 3 Silane-modified polyamic acid solution 10 obtained in Example 1
0g and metal alkoxide (1) prepared in Preparation Example 1
(Partial condensate of silicone tetraethoxide) 18.6
g and metal alkoxide (2) prepared in Preparation Example 2 (
Partial condensate of titanium tetra-1-propoxide) 39
．． A viscous liquid was prepared in the same manner as in Example 1, except that a mixed solution with Og was used, and a 50 μm thick film was obtained by casting onto a glass plate 1- and subjecting it to heat treatment.

Regarding this film, the specific PI was measured in the same manner as in Example 1. The results are shown in Table 1.

Example 4 Silane modified polyamic acid solution obtained in Example 1 14!
1. +00g and metal alkoxide (1) prepared in Preparation Example 1 (partial condensate of silicone detraethoxide)
18.6g and Preparation Example (3) (zirconium tetra n-
A viscous liquid was prepared in the same manner as in Example 1 except that 39.4 g of the mixed solution (partial condensate of butyloxide) was used, and then cast onto a glass plate and heat treated to form a 50μ thick film. I got it.

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

Example 5 20.02 g of 4.4゛-diaminodiphenyl needle and 190 g of DMAC were placed in the same reactor as in Example 1, and 14.1 g of pyromellitic dianhydride and biphenyltetracarboxylic acid were added while stirring vigorously through nitrogen gas. 8.9 g of acid dianhydride was added over a period of 2 hours. Subsequently, the reaction was continued for 2 hours.

On the other hand, 1.2 g of pyromellitic dianhydride, 0.5 g of γ-anilinopropyltrimethoxysilane, and 30 g of 1) M were charged into the same reactor as in Example 1, and the reaction was carried out for 3 hours. Next, this was added to the solution from the previous reaction, and then the reaction was carried out for 6 hours.

100 g of the silane-modified polyamic acid solution obtained in this manner was charged into the same reactor as in Section t, and while nitrogen gas was passed through and vigorously stirred, the metal alkoxide (I) (silicon detraethoxide) prepared in Preparation Example 1 was added. (partial condensate) was added dropwise over 30 minutes to obtain a brown uniform viscous liquid. Using this viscous liquid, a film with a thickness of 50 μm was obtained in the same manner as in Example 1.

The properties 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 Example 1, except that γ-aminopropyltriethoxysilane was not added.

A viscous liquid was prepared using this polyamic acid solution in the same manner as in Example 1, and further cast onto a glass plate and heat treated.

A film with a thickness of 50μ was obtained.

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

Comparative Example 2 Glass plate 1- was cast and heat treated in the same manner as in Example 1 using only the polyamic acid solution prepared in Comparative Example 1 without adding any metal alkoxide to the polyamic acid solution. A film with a thickness of 50 μm was obtained.

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

Table 1 [Effects of the Invention] The present invention provides a polyamic acid composition comprising a polyamic acid i9 combination, which is a 1111 precursor of a polyimide polymer containing a silane coupling agent, and a metal alkoxide, and a polyamic acid composition comprising a metal alkoxide. ! A metal oxide-containing polyimide-based composite molded product formed by molding the composition, preferably a film or sheet formed by cast molding. It is characterized by the fact that the metal oxide is contained uniformly and in a large amount. In this way, molded products such as films or sheets have excellent mechanical strength as well as heat resistance, and in particular, the dimensional stability is greatly improved compared to molded products made from polyimide-based I (I combined lit products). This effect is produced by the inclusion of the silane coupling agent together with the metal oxide, and the patent attorney (patent attorney)

Claims (4)

[Claims] (1) A polyamic acid obtained by reacting an aromatic tetracarboxylic dianhydride and an aromatic diamine in the presence of a silane coupling agent, a metal alkoxide and/or a partial condensate of a metal alkoxide, and an organic polar solvent. A polyamic acid composition comprising: (2) Claim 1 in which the aromatic tetracarboxylic dianhydride contains biphenyltetracarboxylic dianhydride as an essential component.
The polyamic acid composition described. (3) After reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine and then reacting with a silane coupling agent to obtain a polyamic acid, a metal alkoxide and/or a partial condensate of the metal alkoxide is added to the polyamic acid. 1. A method for producing a polyamic acid composition, which comprises blending the polyamic acid composition. (4) After reacting an aromatic tetracarboxylic dianhydride with a silane coupling agent and then reacting an aromatic diamine to obtain a polyamic acid, a metal alkoxide and/or a partial condensate of the metal alkoxide is added to the polyamic acid. 1. A method for producing a polyamic acid composition, which comprises blending the polyamic acid composition.