JPS62100529A - Modified polyimide composition - Google Patents

Abstract

PURPOSE:A composition that is prepared by uniformly dissolving a modified modified polyimide resulting from the reaction between a soluble aromatic polyimide and a specific amine, in an organic polar solvent, thus forming thin films with high adhesion to a variety of materials such as metal, high light transmission and heat resistance. CONSTITUTION:(A) A soluble aromatic polyimide prepared by polycondensation reaction between an aromatic tetracarboxylic acid an an aromatic diamine and imidization is allowed to react with (B) an amine containing polar groups of R1-NH-R2 (R1 is H, 1-6C alkyl; R2 is 1-6C hydrocarbon or 6-13C aromatic hydrocarbon which bears polar groups such as hydroxyl, cyano, nitro, carboxyl or epoxy) to give a modified polyimide in which at least 5% of the imide ring in component A is ring-opened with component B. Then, the resultant modified polyimide is dissolved in an organic polar solvent in a concentration of 1-50wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method in which the imide ring bond of the above-mentioned aromatic polyimide obtained by reacting a soluble aromatic f-soliimide [- with a specific amine compound] is 7" 8. Modified polyimine F' ring-opened with a ring compound is dissolved uniformly in an organic polar solvent. The large bo1,1-imide composition of
Various inorganic or -C11 + A materials -% ':':' J
<Spread it on the blood, dry the coated layer, heat treat it, and then crush it tightly.
It is a lever to form a coating layer (thin film layer) with transparent resistance (j, Ij'llf!!, transparency) and a thin external resistance and iTh, 'I <'ii'x edge property. \、＋＝'j! This liquid crystal aligning film is formed at t4, and it is easy to see how the liquid crystal aligning film is formed at t4.

[Jousai's technique (1・f and its problems) +i ri ・imi 卜 G, white is heat 1 cow and electric layer!!
r, electric layer; +1 electron 4-■, etc.:,
2, insulating protective films for liquid crystal alignment films and electronics (insulating for solid-state devices, insulation for solid-state devices, interlayers for semiconductors (J'': fii circuits, etc.) Absolute V! membrane, etc.) is used in j [S formation +, objectives ゛1 and l, etc.).

Generally, polyimide is difficult to dissolve in organic polar solvents, so a solution of a polyimide precursor (polyamic acid) is used to form a coating film, and the coating is then dried and imidized. Therefore, it is necessary to heat-treat the material at a considerably high temperature for a long time to form a polyimide maintenance film.
Polyimide protective films can be formed with good reproducibility at relatively low temperatures, but there is a problem in that the electrical or electronic materials themselves that should be protected by polyimide protective films may be thermally degraded. .

On the other hand, there are polyimides that are compatible with organic polar solvents,
Conventionally known polyimides of this kind have problems such as being soluble only in very specific solvents or having poor solubility in organic polar solvents, such as requiring a long time to dissolve and not being uniformly dissolved.

Furthermore, a conventionally known protective film formed of polyimide has a problem in that it has insufficient adhesion to an inorganic or metal substrate such as glass or aluminum.

Historically, conventionally known polyimides have poor light transmittance (colorless i! brightness), and are designed to be used in four colors (generally yellow), and for applications that do not like coloring (cannot be used, There is a problem that +i) is limited.

(Means for Solving the Problems) As a result of intensive research in order to provide a polyimide that solves the above-mentioned problems, the inventors of the present invention have developed a method for reacting a iiJ-soluble aromatic polyimide with a specific amine compound. The modified polyimide, in which the imide ring bond of the aromatic polyimide L is ring-opened with the above amine compound, has excellent solubility in an organic polar medium (excellent in hot temperatures). In addition, it has excellent adhesion to inorganic or metal plates, and has a heat-resistant and electrically insulating coating: W layer (thin (; found that it is possible to form a thin layer).

Ta.

The present invention was made based on the above knowledge, and therefore, a soluble aromatic polyimide obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component and an aromatic diamine component,
General formula R+N,! (R2 (where R1 is hydrogen or an alkyl group having 1 to G carbon atoms, and R2 is a hydroxyl group, an ano group, a nitro group, or a carboxyl group) having a polar group selected from the group consisting of 3 and an epoxy group with a carbon number of 1 -6 hydrocarbon groups or aromatic hydrocarbon groups having 6 to 13 carbon atoms) At least 5% of the imide ring bonds of the above-mentioned soluble aromatic polyimide obtained by reacting with a polar exhaust-containing amine compound represented by The above provides a modified polyimide composition in which the modified polyimide ring-opened with the polar group-containing amine compound is uniformly mixed in an organic polar solvent at a concentration of 1 to 50% by weight. .

The i+'r polyimide composition of the present invention will be described in detail below.

The soluble aromatic polyimide used in the production of the modified polyimide constituting the &[1 product] of the present invention may contain, for example, an aromatic tetracarboxylic acid component and an aromatic diamine component in approximately equal moles and an organic polar solvent. at a fairly high temperature (preferably a temperature of about 100 to 300°C, particularly preferably 120 to 25°C)
It can be produced by polymerization and imidization in one step by heating to a temperature of 0° C.), or it can be produced by polymerizing and imidizing the above two components in approximately equimolar amounts in an organic polar solvent. Aromatic polyamic acid (precursor of aromatic polyamic acid) is produced by heating at a layer weight of about 100°C or less, especially at a temperature of 20 to 70°C, and the aromatic polyamic acid is Manufactured by imidization under reasonable conditions.

+6i aromatic tetracarboxylic acid component, for example, 2.3.3', 4'-biphenyltetracarboxylic acid or its acid dianhydride, 3,3", 4゜4゛-biphenyltetracarboxylic acid or its acid anhydride; 2.
2', 3.3'-carboxylic acid or dianhydride thereof, 2.3.3'.

4'-henzophenone detracarboxylic acid or its acid dianhydride, 3.3', 4.4'-henzofe, nontetracarboxylic acid or its acid dianhydride, pyromellitic acid or its acid dianhydride, etc. The above-mentioned aromatic tetracarboxylic acids may be esterified products, salts, etc., but biphenyltetracal 1ζ acid dianhydride, especially 2.3.3', =
1'-Biphenyltetracarboxylic dianhydride f
Delicious.

11i Z-Aromatic diamine component; for example, bis(4-aminone, tri3/phenyl) sulpone, 2.
2-di(4-aminophenoxophenyl)brohane, 4
．． 4'-di(4-aminophenoxo)biphenyl,
1.4-di(4-aminophenoxo)henzen, anisidine, tolidine, 9.10-bis(4-7minophenyl)anthracene, 9゜9-bis(4-aminophenyl)
Polycyclic aromatic diamines having a large number of aromatic rings such as fluorene are preferred, but aromatic diamine compounds having the following photosensitive groups and the like can also be used.

3.5-diaminobenzoic acid ethyl acrylate, 2,4-diaminobenzoic acid ethyl acrylate, 3,5-diaminobenzoic acid ethyl methacrylate, 2,4-diaminobenzoic acid ethyl methacrylate acid ester, 3,5-diaminobenzoic acid glycidyl acrylate ester, 24-diaminobenzoic acid glycidyl acrylate ester, 3,5-diaminobenzoic acid glycidyl methacrylate ester, 2,4-diaminobenzoic acid glycidyl methacrylate 1 - ester, 3.
5-diami/'benzocyanic acid, 2,4-
Anthin Q cyanide varnish such as Diamino Angu Cyanide Gay Leather Varnish Wool: 3.5-27mm, 2' Ruacrylate 1
．． 3.5- Diaminohensyl methacrylate-1- etc.
, acryl acrylate 1 to f, i-acrylamide --
-3゜4゛-Noaminochaconyl ether, 2-acrylamide-3,4°-diaminodiphenyl ether, 4-nnnamamide-3,? ' -diaminodiphenyl ether, 3.4'-so'acrylamide-
3', 4-diaminodiphenyl l-thyl, 3,4'-jinnam°? mil"3", 4-diamino 7; phenylgothyl, 4-methyl-2' (:2-methacryloyloxocarbonyl)-3,4°-diaminodiphenyl ether, 4-7,000-2'-(2-acryloyl Schiff L ethers such as oxocarbonyl)-3°4°-diaminodiphenyl ether, 3,3°-diaminochalcone, 3.4°-diaminochalcone, 3'. 4-diaminochalcone, 4゛-methyl-
3'. 4-diaminochalcone, 4”-methquin-3′
, 4-diaminochalcone, 3′--methyl-3.5
-Chalcones such as diaminochalcone.

When a polyimide obtained by using a combination of the polycyclic aromatic-2 amine and the aromatic diamine compound having a photosensitive group is used as the aromatic diamine component, cracking performance becomes good.

Examples of the organic polar solvent used in the polymerization of the aromatic tetracarboxylic acid component and the aromatic diamine component include sulfokid solvents such as dimethyl sulfoxide and noethyl sulfokind; N-dimethylformamide, N. Formamide-based solvents such as N-diethylformamide, N. N-dimethylacetamide, N. N-
Acetamide solvents such as diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, hex-methylene sulfoxide, γ-butyrolactone, etc., or phenol, o-,
m- or p-cresol, kylnol, halogenated fluoride L
Phenolic solvents such as , nol, nol, orthochlorophenol, parabromophenol, catechol, etc. can be used.

N. of the present invention. The soluble aromatic polyimide 1' used in the production of the modified polyimide 1' constituting the [I acid product] is a polymeric bond, for example, -1 degree: 0.5 degrees,
7100m e I'8 medium (N-methyl-2-pyrroli(,N)) was measured at a measurement temperature of 30°C.
−da logarithm ↑? i 1 degree (measures the degree of polymerization of the polymer)
J'-) is 0.1 to 2.

A value of 0, 2, and especially 0, 3 to 1.5 is preferable.

In addition, the variable 1't'+'s1 constituting the composition of the present invention
'Used in the production of mido 4'1,ru+'+i+ki-Shizuyo R
1 -N11-R2 represents polar group J (conversion: "I: i and j- are monolamine, It is possible to remove hydrogen, prussic acid, etc.

Therefore, the crude polyimide constituting the composition of the present invention is
6. Soluble aromatic polyimide parent polyimide dispersion (by reacting with an amine compound containing an m-group, at least 5% or more of the imide ring bonds of the soluble aromatic polyimide, preferably 1
It is obtained by ring-opening about 0 to 60% with the polar group-containing amine compound.

If the rate of ring opening of imide ring bonds (sometimes referred to as the reaction rate of 2 or less rings opened per 100 imide ring bonds) is less than 5%, the modification of the polyimide is insufficient and the present invention The desired modified polyimide composition cannot be obtained.

In the reaction between the soluble aromatic polyimide and the polar group-containing amine compound, for example, the soluble aromatic polyimide is dissolved in a reaction solvent, the polar group-containing amine compound is added thereto, and the reaction temperature is usually 10 to 100°C. Reaction time 0.5~
It is carried out under conditions of 50 hours.

The concentration of soluble aromatic polyimide in the reaction solvent solution was 3
The content is preferably about 50% by weight.

Further, the amount of the polar group-containing amine compound used is preferably approximately equimolar to the imide ring bond of the soluble aromatic polyimide.

Opening ratio of imide ring bonds in modified polyimide (
The reaction rate (reaction rate) can be controlled by appropriately adjusting the reaction condition (a') in L.

Examples of the reaction solvent used in the reaction between the soluble aromatic polyimide and the polar amine compound include:
N-methylpyrrolidone, N-vinylpyrrolidone, N,N
-dimethylformamide, N,N--dimethylacetamide, dimethylformoquinde, p-cresol, p--
Examples include chlorophenol.

Therefore, the modified polyimide of the present invention and the acid compound (faith) are prepared by adding the modified -1ξ rimide obtained as described above to an organic polar solvent in an amount of 1 to 50% by weight, preferably 2 to 30% by weight.
It can be obtained by uniformly dissolving it at a concentration of .

Examples of the bipedal organic polar solvent include organic polar solvents similar to the reaction solvent used in the production of the modified polyimide described above.

The modified polyimide composition of the present invention preferably has a rotational viscosity of about 0.1 to 5000 poise, particularly about 0.2 to 2000 poise at 25°C.

The modified polyimide composition of the present invention can be coated uniformly on the surface of the object to be coated (circuit board, optical sensor, etc.) by an appropriate method such as using a rotary coater or a printing machine at room temperature or under heating. to form a coating film of the composition,
Next, the coating film is heated to about 100°C or higher, particularly at 120°C to 4°C.
A solidified membrane of modified polyimide can be produced by drying at a temperature of 50°C.

〔Example〕

EXAMPLES The present invention will be explained in more detail by giving examples below.

EXAMPLES Soluble aromatic polyimide powder having the logarithmic viscosity shown in Table 1 below was obtained using the scale shown in Table 1 below.

In a separable flask (with stirring bar, nitrogen inlet, and water metering receiver), add 2.3.3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) ) Sulfone (B A P S)
was added, and nitrogen was flowed through this for 1 hour to replace the air in the reaction system. Next, N-methyl-2-pyrrolidone (
NMP) is added, and the flask is immediately immersed in an oil bath at 190°C, and stirred while flowing nitrogen. - Collect the water formed in a water metering receiver along with excess NMP. Let the reaction run for 8 hours to form aromatic poly-1j imide.

Next, after cooling the reaction solution, 2 mL of NMP was added to the reaction solution.
Yes, I understand. After that, 1 p of methanol was put in a mixer, and the reaction solution was added little by little to the methanol being stirred with the mixer to precipitate the formed aromatic polyimide, which was then filtered.

; After passing through J2, the obtained aromatic polyimide was diluted with methanol 4
Wash in MIKI 4F- containing 00ml. After repeating this washing twice, the aromatic polyimide was dried under reduced pressure.
iiJ soluble aromatic polyimide powder is obtained.

Table 1 The soluble aromatic polyimide powder obtained as described above was reacted with N-methylethanolamine under the reaction conditions shown in Table 2 below to obtain a modified polyimide. still,
The resulting modified polyimide was precipitated in the same manner as the soluble aromatic polyimide described above, and the modified polyimide was obtained as a powdery polymer.

Table 2 below shows the relationship between the synthesis reaction t, the reaction time, and the ratio of opening of the imide ring bond (reaction/d). 11 Aromatic polyimide powder “'110l1008N
Reaction solvent)■ 525gN-methylethanolamine amount 21.75g nitrogen flow (ml/min)
100 Reaction temperature (''-) 25-30 Reaction time (l
lr) Reaction rate ゛2(%)・,4mi)≧1,
Upper 1st scratch L4! 1 grain + 2 E No. - 1'
``Kawa-〃 (manufactured by Kodo-1 - Modified polyimide obtained as described above) [Rate of ring opening of imide ring bond (
(reaction rate): 36%] was uniformly dissolved in NMP at a concentration of 9 12 doublets to obtain a modified polyimide composition (faith) of the present invention.

Adhesion and heat resistance of the modified polyimide composition of the present invention to various substrates were measured as follows.

[Adhesion] The modified polyimide composition of the present invention with a concentration of 12% by weight prepared as described above was subjected to a spin cord (2000 rpm).
was applied onto the substrate and dried at 20σ°C for 30 minutes to create a 0.5 μm thick coating film made of aromatic polyimide 1.
Cross-cut tape to check the adhesion of this coating film to the substrate?
It was investigated by separation.

The results are shown in Table 3 below. In Table 3 below, the adhesion test results are expressed as the area percentage of the coating film that adhered to the substrate after the test.

Table 3 1cul ”: ”
'+11 1'' 1 alumina 1J/l rr □ ・
・1, 1 ・ 1 ・ 1 ITO・ll Note] * 24 hours 1:i, 120°C, 2 atm [Heat resistance] Modified polyimide composition of the invention with 12% concentration prepared as described above Created: '171 m J
VX film at 200'C for 30η・axis +'A
7'lt, by T G A, poem 59'
Oσ (oil temperature [9:] was measured. The temperature of the oil was as follows.

σN chamber starting temperature 240°C 59・δ戎! I±Temperature f375'C Also, TMA was measured after drying one 12 μm thick film made from the pot-shaped polyimide composition of the present invention at 200°C for 30 minutes. The result is B, L, 5.2 X
The expansion coefficient was 10-5 (/'CI+).

Example 2 Using the aromatic tetracarboxylic acid component and the aromatic diamine component shown in Table 4 below, a soluble aromatic polyimide powder having a logarithmic viscosity (T) shown in Table 4 below was obtained in the same manner as in Example 1. These soluble aromatic polyimide powders were reacted with polar group-containing amine compounds shown in Table 4 below under the same reaction conditions as in Example 1 to open the imide ring bonds shown in Table 4 below. A modified polyimide powder having a ring ratio (reaction rate) was obtained.

These modified polyimide powders were added to NMP with 9/12 doublets.
They were uniformly dissolved between the layers to obtain modified polyimide composition 1 varnishes of the present invention.

(;Tranejin Niki's invention 2 go 2+'l, i milli
・I Mi 1)■「戊′l″′ri? , and the various stems 'n +' 4 (+E = &l -4-A dense i'i sex wo Jfs l-10202 ni)
', iil. The results are shown in Table 4 below.

〔Effect of the invention〕

The modified polyimide composition of the present invention is a heat-resistant modified polyimide which is obtained by modifying a soluble aromatic polyimide with a specific amine compound and is soluble in an organic polar solvent. It is uniformly dissolved,
By applying it to the surface of various inorganic or metal materials (such as O-1), and drying and heat-treating the cloth layer, it has excellent adhesion and light transmittance (4!!! color brightness). (l
It is possible to form a heat-resistant and electrically insulating coating layer (7J film layer) that is transparent and uniformly thick without whitening due to moisture. It is suitable as a film forming material, and other inks are also available! It is also used for 4 purposes.

Permit applicant: Ube Industries Co., Ltd. Shi-,-yoj

Claims (1)

[Claims] A soluble aromatic polyimide obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component and an aromatic diamine component has the general formula R_1-NH-R_2 (where R_1 is hydrogen or an alkyl group having 1 to 6 carbon atoms). , R_2 is a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 13 carbon atoms and having a polar group selected from the group consisting of hydroxyl group, cyano group, nitro group, carboxyl group, and epoxy group. A modified polyimide in which at least 5% or more of the imide ring bonds of the soluble aromatic polyimide are ring-opened with the polar group-containing amine compound, which is obtained by reacting with the polar group-containing amine compound represented by In polar solvents, 1 to
A modified polyimide composition that is uniformly dissolved at a concentration of 50% by weight.