JPH11181281A - Polyimide composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyimide composition hardly generating a metal oxide at the interface of a metal and the polyimide, and suitable for screen printing. SOLUTION: This polyimide composition comprises a polyimide obtained by mixing or reacting an aromatic tetracarboxylic acid component with an aromatic diamine component and the oxygen-containing solvent, and substantially imidated, and the solvent, further contains an additive, and has >=1.5 thixotropy coefficient, which is the value obtained by dividing an apparent viscosity [η0.5 ] at 20 sec<-1> constant shear rate by an apparent viscosity [η20 ] at 20 sec<-1> constant shear rate, 150-50,000 poise apparent viscosity [η0.5 ] and 50-5,000 poise apparent viscosity [η20 ]. The additive is benzotriazole.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide composition suitable for screen printing, and more particularly to a polyimide composition having improved adhesion strength to metal.

[0002]

2. Description of the Related Art Polyimide, which is suitable for forming a surface protective film for electronic parts and as an interlayer insulating material for electronic parts and other heat-resistant parts, is widely used in the electronic and electric industries. Polyimide is used not only as a bulk material but also for coating or patterning to cover the surface of a substrate. As a method of forming a relief pattern,
A method of performing patterning by wet or dry processing after spin coating, a method of performing patterning simultaneously with coating by screen printing, and the like are known, but the latter screen printing method is desired from the viewpoint of shortening the process. .

[0003] Compositions suitable for screen printing of polyimide include kneading inorganic or organic powder with a varnish of polyamic acid or polyimide, or a method disclosed in
A paste and the like having a thixotropic property by appropriately imidizing a polyamic acid as disclosed in JP-A-149895 are known.

On the other hand, JP-A-2-228359 discloses a composition containing benzotriazole and 1,2,4-triazole in a polyamic acid and having a rust-preventing ability against copper and copper alloys.

[0005]

In the case of coating a polyimide on a substrate, in the case of a polyamic acid which is a precursor of the polyimide, it is necessary to complete the reaction to convert the polyimide into a polyimide and to coat the polyimide varnish. However, heating is necessary to remove the solvent. When the substrate is made of a metal such as copper, the substrate is easily oxidized when heated by air or a carboxyl group contained in the polyamic acid, and the interface between the metal and the polyimide becomes an oxide. When the metal polyimide coating thus formed is subjected to a wet process such as gold plating thereafter, the processing solution infiltrates along the oxide generated at the interface, and finally the metal and polyimide are separated. Will be.

Accordingly, the present invention provides a polyimide composition suitable for screen printing in which no metal oxide is formed at the interface between metal and polyimide.

[0007]

The present inventors have intensively studied to solve the above-mentioned problems, and found that adding an antioxidant such as benzotriazole to a polyamic acid solution prevents oxidation of the interface. However, it has been found that since a high temperature is required to convert the polyamic acid to the polyimide, the antioxidant effect is diminished and a sufficient improvement in adhesiveness may not be observed. However, the present inventors have found that a specific composition having a thixotropic property composed of a polyimide which has been completely imidized in advance and a solvent can form a strong coating film at a relatively low temperature and can reduce the oxidation of the interface, and have reached the present invention.

That is, the present invention further relates to a composition comprising a substantially completely imidized polyimide obtained by mixing or reacting an aromatic tetracarboxylic acid component, an aromatic diamine component and an oxygen-containing solvent, and a solvent. A thixotropy coefficient of 1.5 or more, an apparent viscosity [η _0.5 ] of 150 to 50,000 poise, and an apparent viscosity [η ₂₀ ] of 50 to 5,000 poise. A polyimide composition in which the additive is a benzotriazole derivative. Here, the thixotropy coefficient, steady shear rate an apparent viscosity [eta _0.5] in 0.5 sec ^-1, the steady shear rate is a value obtained by dividing the apparent viscosity [eta _20] in 20sec ^-1.

The polyimide according to the present invention is a polyimide obtained by heating a polyamic acid solution obtained by mixing or reacting an aromatic tetracarboxylic acid component, an aromatic diamine component and an oxygen-containing solvent. , B
Is a polyimide composition containing a component consisting of

A: benzenetetracarboxylic dianhydride,
Benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, terphenyl tetracarboxylic dianhydride or an aromatic tetracarboxylic acid component in which its reactive derivative is 50 mol% or more.

B: at least 70 mol% is bis (4- (3-aminophenoxy) phenyl) sulfone or a reactive derivative thereof, and the siloxydiamine compound is at least 0.5 mol% to at most 10 mol%; diaminopolysiloxane A diamine component having a compound content of 1 mol% or more and 20 mol% or less, in an amount of 0.95 to 1.05 mol based on 1 mol of the tetracarboxylic acid component (A).

The polyimide composition contains an oxygen-containing solvent having a boiling point of 180 ° C. or more and 300 ° C. or less as the oxygen-containing solvent. The polyimide composition of the present invention is a polyimide composition comprising the above-mentioned polyimide, a solvent and a benzotriazole derivative as constituent elements. Considering the shape retention of the relief pattern when used as a paste for screen printing, its solid content (refers to the sum of the aromatic diamine component and the aromatic tetracarboxylic acid component; the same applies hereinafter) has a concentration of 20% by weight. % Or more, preferably 25% by weight or more, and is 60% by weight or less, preferably 50% by weight or less from the upper limit of the viscosity range in consideration of the filling property to the plate pattern opening.

[0013] Of the aromatic tetracarboxylic acid component used in the present invention, preferably 50% by mole or more of benzenetetracarboxylic acid, for example, pyromellitic acid, trifluoromethylbenzenetetracarboxylic acid, bistrifluoromethylbenzenetetracarboxylic acid. Acid, difluorobenzenetetracarboxylic acid, benzophenonetetracarboxylic acid,
One or more selected from reactive derivatives such as biphenyltetracarboxylic acid or terphenyltetracarboxylic acid or dianhydrides and esters thereof. The tetracarboxylic acid which can be used as the other tetracarboxylic acid component at less than 50 mol% is not particularly limited, but hexafluoroisopropylidene diphthalic acid, oxydiphthalic acid, cyclobutanetetracarboxylic acid, bicyclo
Reactive derivatives such as (2,2,2) oct-7-ene-2,3,5,6-tetracarboxylic acid or its anhydrides and esters can be exemplified, and these two or more can be used in combination. If these are used in an amount exceeding 50 mol%, sufficient adhesion to various substrates cannot be obtained.

In the diamine component used in the polyimide composition of the present invention, 70% by mole or more of bis (4- (3-
Aminophenoxy) phenyl) sulfone or a reactive derivative thereof, preferably 0.5% to 10% by mole of siloxydiamine, and 1% to 20% by mole of diaminopolysiloxane is preferred. Although not particularly limited, 1,3-bis (3
-Aminopropyl) -1,1,2,2-tetramethyldisiloxane, 1,3-bis (3-aminobutyl) -1,
1,2,2-tetramethyldisiloxane, bis (4-
Aminophenoxy) dimethylsilane, 1,3-bis (4
Examples of diaminopolysiloxanes such as -aminophenoxy) tetramethyldisiloxane include a compound represented by the following general formula:

[0015]

Embedded image

(Wherein Z is an alkylene group or phenylene group having 1 to 8 carbon atoms, and Rs are the same or different from each other, and may be an alkyl group, alkoxy group or substituent group having 1 to 8 carbon atoms which may have a branch. And d represents an integer of 4 to 60).

The amount of siloxydiamine used is preferably 1 to 10 mol% of the diamine component, more preferably 1 to 5 mol% of the diamine component used. If the siloxydiamine component is less than 1 mol%, the effect of improving the adhesiveness is poor, and
If it exceeds 0 mol%, the adhesiveness is not improved and a decrease in heat resistance is observed, which is not preferred.

The amount of the diaminopolysiloxane used is preferably 0.5 to 20 mol% of the diamine component, more preferably 1 to 15 mol% of the diamine component used. If the diaminopolysiloxane component is less than 0.5 mol%, the effect of improving the adhesiveness is poor, and if it exceeds 20 mol%, the adhesiveness is not improved and a decrease in heat resistance is observed, which is not preferable.

The diamine component which can be used at less than 30 mol% is not particularly limited, but may be O-, m-, p-phenylenediamine, 2,4-diaminotoluene, 2,5-
Diaminotoluene, 2,4-diaminoxylene, 2,4
-Diaminodulene, dimethyl-4,4'-diaminodiphenyl, dialkyl-4,4'-diaminodiphenyl, dimethoxy-4,4'-diaminodiphenyl, diethoxy-4,4'-diaminodiphenyl, 4,4 ' -Diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether,
4,4'-diaminodiphenylsulfone, 3,3'-
Diaminodiphenylsulfone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone,
1,3-bis (3-aminophenoxy) benzene, 1,
3-bis (4-aminophenoxy) benzene, 1,4-
Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4-
(4-aminophenoxy) phenylsulfone, 2,
2'-bis (4- (4-aminophenoxy) phenyl)
Propane, 2,2-bis (4- (4-aminophenoxy) phenylhexafluoropropane, 2,2-bis (4- (3-aminophenoxy) phenyl) propane,
2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4
-Amino-2-trifluoromethylphenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (3
-Amino-5-trifluoromethylphenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,
2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-
Methylphenyl) hexafluoropropane, 4,4'-
Bis (4-aminophenoxy) octafluorobiphenyl, 2,2′-bis (trifluoromethyl) diaminodiphenyl, 3,5-diaminobenzotrifluoride,
2,5-diaminobenzotrifluoride, 3,3'-bistrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-bistrifluoromethyl-5,5'-diaminobiphenyl, bis (trifluoromethyl)- 4,
4'-diaminodiphenyl, bis (fluorinated alkyl)
-4,4'-diaminodiphenyl, dichloro-4,4 '
-Diaminodiphenyl, dibromo-4,4'-diaminodiphenyl, bis (fluorinated alkoxy) -4,4'-
Diaminodiphenyl, diphenyl-4,4'-diaminodiphenyl, 4,4'-bis (4-aminotetrafluorophenoxy) tetrafluorobenzene, 4,4'-bis (4-aminotetrafluorophenoxy) octafluorobiphenyl, 4,4'-binaphthylamine, 4,
4'-diaminobenzanilide, 4,4'-diamino (N-alkyl) benzanilide and the like can be presented, and two or more of these can be used in combination.

In a solvent mainly composed of an amide-based solvent such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, etc., which are generally employed as a solvent for polyimide or its precursor and have a high solubility, No thixotropy required for screen printing is observed.

As preferred oxygen-containing solvents, lactones such as γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone and ε-caprolactone can be presented.
In addition, carbonates such as ethylene carbonate and propylene carbonate, esters such as butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethers such as dibutyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, methyl isobutyl ketone, cyclohexanone, acetophenone Such as ketones such as butanol, octanol, and alcohol such as ethyl cellosolve, as well as linear or cyclic amide, urea, sulfoxide, sulfone, hydrocarbon, and halogen solvents, and the stability of polyimide composition. Can be added in a range that does not affect the content.

The benzotriazole derivative used in the polyimide composition of the present invention includes benzotriazole, and is not particularly limited, and examples thereof include the following compounds.

[0023]

Embedded image

These compounds are 1H-benzotriazolecarboxylic acid (CBT-1 manufactured by Johoku Chemical Co., Ltd.
same as below. ), 1- (2,3-dihydroxypropyl)
Benzotriazole (BT-GL), 1-hydroxymethylbenzotriazole (BT-OH), or BTD
-HD, BTD-DP, BTT-DP, BT-MA, B
TM, BT-U, BTD-U, BT-341, BT-
It is available as LX (a product of Johoku Chemical Co., Ltd.). It is also possible to use two or more of the above benzotriazole derivatives in combination.

The addition of the benzotriazole derivative in the polyimide composition of the present invention is effective in improving the adhesion to various substrates, but is particularly applied to a substrate having copper foil and copper wiring, and is subjected to solvent removal and / or firing. The effect of improving the adhesiveness is particularly remarkable when subjected to a step of performing post-wet acid washing, alkali washing, water washing, and / or gold plating.

The amount of the benzotriazole derivative used is preferably in the range of 2 to 15 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the solid content as the total amount of the tetracarboxylic acid component and the diamine component. is there. When the amount is less than 2 parts by weight, the adhesive effect is poor, and when the amount is more than 15 parts by weight, the thermal effect of the formed film is lowered without improving the adhesive effect.

The production of the polyimide composition of the present invention is carried out by charging a diamine component and a tetracarboxylic acid component in advance in a reactor such that they are substantially equimolar, adding a solvent, and heating. The addition of the benzotriazole derivative may be performed before or after performing the heating / reaction.

The heating conditions vary depending on the combination of the diamine component, the tetracarboxylic acid component, the solvent, etc., the solid content concentration, the volume and the polyimide composition to be produced, and are determined by the heating temperature and time. And more preferably in the range of 160 ° C to 180 ° C for 1 hour to 2 hours.
It is preferable to heat for about 4 hours. If the temperature is lower than 140 ° C., the conversion rate is low. The temperature may be higher than 200 ° C., but there is no particular advantage.

Further, depending on the combination of the diamine component, the tetracarboxylic acid component, the solvent, etc., the polyimide is substantially completed by heating under the above-mentioned conditions. It may be necessary to stand still for a certain period of time. Normally, cooling need not be particularly controlled, and natural cooling may be used. However, in some cases, it is preferable to adjust the cooling rate. The term "around room temperature" means that it is not necessary to have a particularly limited temperature.
The temperature may be about 0 ° C. The standing is performed for one hour to several tens of days, but there is no need to add operations such as stirring, so there is no difference from ordinary storage.

[0030] The polyimide composition of the present invention produced in this manner is manufactured by RHEOLAB MC20 manufactured by Physica.
(Cone / plate method or cylinder method, 22 ° C. The following conditions are the same unless otherwise noted.)
Difference in apparent viscosities indicated at the time and 0.5 sec ^-1 of steady shear rate 20sec ^-1 indicates a large remarkable thixotropy.

As a value representing the thixotropic property, a thixotropic coefficient [η _0.5 / η ₂₀ ] (when the steady shear rate is 0.
The apparent viscosity [eta _0.5] in 5 sec ^-1, the steady shear rate and divided by the apparent viscosity [eta _20] in 20sec ^-1. This value is preferably 1.5 or more for good screen printability.
0 is more preferable, and 1.5 to 250 is further preferable.

The polyimide composition of the present invention can form a relief pattern having a thickness of 0.1 to 100 μm after desolvation, and can be used by setting conditions such as selection of adopted components and setting of solid content concentration. The appropriate viscoelastic properties for the desired plate shape and desired film thickness can be adjusted over a wide range. The range of preferred viscoelastic properties of the polyimide composition of the present invention is 0.5 sec.
The apparent viscosity [η _0.5 ] at ^-1 is about 150 poise to 50,000 poise, and the apparent viscosity [η ₂₀ ] at ₂₀ sec ^-1 is about 50 to 500 poise.
0 poise or less. If [η _0.5 ] is less than 150 poise or [η ₂₀ ] is less than 50 poise, pattern shape retention is inferior, and [η _0.5 ] is 50,000 poise or [η ₂₀ ] is 5
If it exceeds 000 poise, the use of a high mesh plate of 400 mesh or more causes clogging of the plate, which is not preferable.

Various methods for measuring the imidation ratio are known, such as nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR), and a method for quantifying water accompanying imide ring closure. Although there is a carboxylic acid neutralization titration method, nuclear magnetic resonance spectroscopy (NMR) was applied for quantification of the imidation ratio of the polyimide composition of the present invention.

That is, it was calculated from the integral ratio of ¹ H attributable to the amide group at around 9 to 11 ppm and ¹ H attributable to the aromatic at around 6 to 9 ppm. As a nuclear magnetic resonance spectrometer, JNW-WIN300 manufactured by JEOL Ltd.
It was used.

By selecting a paste having this viscoelastic characteristic range, from a thin film to a thick film, under appropriate screen printing conditions, the filling property into the plate pattern opening, which is excellent in practicality, and the shape of the formed relief pattern Retention is obtained.

With respect to the relief pattern of the paste-form polyimide composition of the present invention formed by screen printing, a polyimide film pattern can be obtained only by removing the solvent. Desolvation conditions depend on the coating film thickness.
30 ~ 250 ℃ by oven or hot plate
However, the temperature may be constant over the entire processing time, or may be performed while gradually increasing the temperature. The maximum temperature in the desolvation treatment is in the range of 100 ° C. to 200 ° C., and 1 to 150 ° C. It is preferable to perform the heating by heating in an inert atmosphere such as air or nitrogen for minutes. .

If necessary, firing may be performed. The firing conditions are as follows: the heating temperature is 120 ° C. by an oven or a hot plate depending on the coating film thickness.
To 450 ° C, preferably 150 to 400 ° C, more preferably 180 to 350 ° C. The time required for baking depends on the coating film thickness, but is 10 minutes to 5 hours, preferably 20 minutes to 3 hours, and more preferably 30 minutes to 2 hours.

Particularly preferred embodiments of the polyimide composition of the present invention are as follows: (a) 1,3-bis (3-aminopropyl) -1,
1 to 10% by mole of 1,2,2-tetramethyldisiloxane (b) diaminopolysiloxane (represented by the formula 1;
A propylene group, R is a methyl group, and d is 8. ) 8
(C) 75-90 mol% of (4- (3-aminophenoxy) phenylsulfone (d), 0-10 mol% of ODA, and (e) pyromellitic dianhydride 50 (F) benzophenonetetracarboxylic dianhydride 20-
A polyimide obtained by reacting a 50 mol% tetracarboxylic acid component in substantially equimolar amounts with each other in a γ-butyrolactone or n-methylpyrrolidone solvent in an amount such that the resin solid content becomes 30 to 45 wt%. Include solvent. That the imidization of polyimide is substantially completed. The polyimide and the solvent further contain 2 to 5 parts by weight of a benzotriazole derivative based on 100 parts by weight of the solid content. The composition has a thixotropy coefficient of 1.5 or more and an apparent viscosity [η _0.5 ] of 150 to 50,000 poise,
The apparent viscosity [η ₂₀ ] is 50 to 5,000 poise. Use of 1H-benzotriazolecarboxylic acid, 1- (2,3-dihydroxypropyl) benzotriazole as the benzotriazole derivative. Screen-printing the composition of claim 1 on copper or a copper alloy. Desolvating the printed pattern at 150 to 220 ° C. However, the present invention is not limited to this embodiment.

As the substrate on which the polyimide composition of the present invention is coated, a substrate composed of copper or a copper alloy is particularly suitable, but is not limited to this. Of course, aluminum, silicon or their alloys or metals such as stainless steel , Alumina, glass, borosilicate glass, quartz, zirconia, mullite, ceramics such as silicon nitride, barium titanate, lithium niobate, tantalum niobate,
Semiconductor materials such as gallium arsenide and indium phosphide can be used without limitation. In addition, a substrate coated with a heat-resistant polymer compound such as polyimide, aromatic polyamide, polyphenylene, polyxylylene, polyphenylene oxide, polysulfone, polyamideimide, polyesterimide, polybenzimidazole, polyquinazolinedione, or polybenzoxazinone. Can be coated.

More specific examples of the application of the polyimide composition of the present invention include, but are not limited to, monolithic ICs on substrates made of silicon wafers, gallium arsenide, etc., such as DRAM, SRAM, CPU, ceramic substrates, glass, and the like. Devices such as hybrid ICs, thermal heads, image sensors, multi-chip high-density mounting boards formed on substrates, interlayer insulating films or surface protection for various wiring boards such as TAB tapes, flexible boards, and rigid wiring boards, α-rays Although it can be used as a protective film having various purposes such as shielding, it is particularly preferable to use it at a portion in contact with the surface of copper or a copper alloy.

Hereinafter, the present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto.

[0042]

EXAMPLES Example 1 1.688 g of 1.688 g of a diamine component and a tetracarboxylic acid component were placed in a glass four-neck separable flask equipped with a thermocouple, a stirrer, and a reflux condenser so as to have an equimolar amount of a diamine component and a tetracarboxylic acid component. , 3-Bis (3-aminopropyl) -1,1,2,2-tetramethyldisiloxane (hereinafter referred to as "TMDS"; 6.791 mmol), 2
5.91 g of diaminopolysiloxane (represented by the formula 1
Z is an n-propylene group, R is a methyl group, and d is 8.
Hereinafter, it is called “DAPS”. 27.16 mmol), 8
3.22 g of (4- (3-aminophenoxy) phenylsulfone (hereinafter referred to as “BAPS”; 192.4 m)
mol), 34.56 g of pyromellitic dianhydride (hereinafter, referred to as “PMDA”; 158.5 mmol), 2
1.88 g of benzophenonetetracarboxylic dianhydride (hereinafter referred to as “BTDA”, 67.91 mmol) was charged, and 273.5 g of γ-butyrolactone was added thereto.
Stirred at 0 ° C. for 4 hours. Separately, 10.05 g of 1H-benzotriazolecarboxylic acid (CBT-
1) was dissolved in 30.20 g of 1,3-dimethyl-2-imidazolidinone to prepare an additive solution. Then about 1
When cooled to 00 ° C., 26.95 g of the prepared additive solution was added to the polymerization solution, and the mixture was sufficiently stirred. When cooled down to room temperature, the obtained polyimide solution was analyzed by ¹ H-NMR.
The apparent viscosity at ^-1 was 480 poise and the thixotropic coefficient was 1.

Thereafter, the mixture was allowed to stand at room temperature.
thixotropic factor apparent viscosity at each of 10,000 poise and 1,650 poise at sec ^-1 and 20sec ^-1 was 6.1.

The printability of the paste was evaluated as 200 μm
Forming 100 via holes at 250 μm intervals 400
When 100 sheets were continuously printed on a copper surface TAB tape using a mesh screen printing plate, a good pattern was obtained without any defects such as missing, chipping, stringing and bleeding. The printed matter was placed in an oven, kept at 40 ° C. for 30 minutes, then heated to 180 ° C. for 30 minutes, and then heated for 2 minutes.
The film thickness after holding for a time was 8 μm. The substrate surface dimension of the formed pattern was ± 3 for each pattern.
0 μm or less, and the difference between the printing plate surface dimensions and the substrate surface dimensions is within 50 μm for any substrate surface pattern.
The shape retention of the pattern was also good.

The evaluation of the adhesiveness was performed according to a gold plating process generally performed at the time of preparing a wiring board. That is, alkali washing (immersing in a 10% KOH aqueous solution, irradiating with ultrasonic waves for 1 minute at room temperature, and then rinsing with water), and acid washing (immersing in a 10% aqueous sulfuric acid solution and irradiating ultrasonic waves for 1 minute at room temperature). Rinsing with water.), And then immersing it in a non-cyanide-based gold plating solution (Microfab 100, manufactured by Tanaka Kikinzoku) at 65 ° C for 1 minute. As a result, it was confirmed that the treatment liquid did not penetrate into the opening of the pattern and was not peeled off, and showed good adhesion. The results are shown in Tables 1 and 2.

[0046]

[Table 1]

TMDS: 1,3-bis (3-aminopropyl) -1,1,2,2-tetramethyldisiloxane DAPS: diaminopolysiloxane (represented by the formula
Is an n-propylene group, R is a methyl group, and d is 8. BAPS: (4- (3-aminophenoxy) phenylsulfone ODA: 4,4'-diaminodiphenylether PMDA: pyromellitic dianhydride BTDA: benzophenone tetracarboxylic dianhydride NMP: N-methylpyrrolidone CBT-1: 1H-benzotriazolecarboxylic acid (Johoku Chemical Co., Ltd. product) BT-GL: 1- (2,3-dihydroxypropyl) benzotriazole (Johoku Chemical Co., Ltd. product)

[0048]

[Table 2]

Example 2 Preparation of a polyimide composition in the same manner as in Example 1 except that 1- (2,3-dihydroxypropyl) benzotriazole (BT-GL manufactured by Johoku Chemical Co., Ltd.) was used as the benzotriazole derivative. In addition, pattern formation and testing were performed, and the results are shown in Tables 1 and 2. About 226 mmol was used for each of the diamine component and the tetracarboxylic acid component. The same applies to the following examples and comparative examples.

Example 3 A polyimide composition was prepared and a pattern was formed and tested in the same manner as in Example 1 except that the ratio of BTDA and BPDA and the solid content were changed as shown in Table 1. Are shown in Tables 1 and 2.

Example 4 A polyimide composition was prepared and a pattern was formed in the same manner as in Example 1 except that the diamine component, the tetracarboxylic acid component, and the solid (resin) component concentration were changed as shown in Table 1. The test was performed, and the results are shown in Tables 1 and 2.

[Comparative Example 1] A similar test was conducted in Example 1 without using any additives. However, the gold plating solution permeated the interface, and the polyimide film was peeled off. The results are shown in Tables 1 and 2.

Comparative Example 2 A polyimide solution was prepared in the same manner as in Example 1 except that the solvent was N-methylpyrrolidone and the ratio between TMDS and DAPS and the solid (resin) content were changed as shown in Table 1. Then, the plate was allowed to stand for 30 days, but had a thixotropy coefficient of 1.1, which was not suitable for screen printing. The results are shown in Tables 1 and 2.

[0054]

The polyimide composition of the present invention can prevent the formation of metal oxide at the interface between polyimide and metal by adding a benzotriazole derivative as an additive. Since a polyimide coating film can be formed only by applying a solvent at a relatively low temperature after being applied to a material, a synergistic effect of these can be obtained, and a remarkable effect of improving adhesiveness can be obtained.

Claims (5)

[Claims] A composition comprising a solvent and a substantially completely imidized polyimide obtained by mixing or reacting an aromatic tetracarboxylic acid component, an aromatic diamine component and an oxygen-containing solvent, further comprising an additive. A polyimide composition having a thixotropy coefficient of 1.5 or more, an apparent viscosity [η _0.5 ] of 150 to 50,000 poise, and an apparent viscosity [η ₂₀ ] of 50 to 5,000 poise, defined below. And a polyimide composition wherein the additive is a benzotriazole derivative. The thixotropy coefficient is an apparent viscosity [η _0.5 ] at a steady shear rate of _0.5 sec ⁻¹ .
And the apparent viscosity [η at a steady shear rate of 20 sec ^-1 ]
₂₀ ]. 2. The aromatic tetracarboxylic acid component is benzenetetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, terphenyltetracarboxylic dianhydride or a reactivity thereof. 50 mol% or more of the derivative and 50 mol% of the other tetracarboxylic dianhydride or its reactive derivative
The polyimide composition according to claim 1, comprising: 3. The method according to claim 1, wherein the aromatic diamine component is bis (4- (3
-Aminophenoxy) phenyl) sulfone or a reactive derivative thereof, comprising at least 70 mol%, a siloxydiamine compound at 0.5 to 10 mol%, a diaminopolysiloxane compound at 1 to 20 mol%, and another diamine. The polyimide composition according to claim 1 or 2, wherein 4. A benzotriazole derivative comprising an aromatic tetracarboxylic acid component and an aromatic diamine component in a total amount of 100
The polyimide composition according to any one of claims 1 to 3, wherein the amount is 2 to 15 parts by weight based on parts by weight. 5. An article having a polyimide coating obtained by printing the polyimide composition according to claim 1 on a substrate made of copper or a copper alloy, and removing the solvent and / or baking.