JPH0455457B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a soluble polyimide resin composition in which the acid component in the repeating unit has a tricarboxycyclopentyl acetic acid structure. BACKGROUND ART Polyimide resins generally have excellent heat resistance, mechanical properties, and electrical properties, and are therefore used as film materials, coating materials, etc., particularly in the electronic industry sector. Conventional polyimide resins are produced by reacting aromatic tetracarboxylic dianhydride and aromatic diamine to obtain aromatic polyamic acid, applying a solution of this polyamic acid to a base material at an appropriate concentration, and then dehydrating it. An insoluble aromatic polyimide resin with excellent heat resistance obtained by ring closure and imidization, a polyamic acid obtained by reacting an aliphatic or alicyclic tetracarboxylic dianhydride with a diamine, and this polyamic acid They can be broadly classified into soluble polyimide resins obtained by dehydration, ring closure, and imidization in a solvent. Problems to be Solved by the Invention However, in the above-mentioned insoluble aromatic polyimide resin, its precursor, aromatic polyamic acid, has poor stability, and when stored for a long time at room temperature, the viscosity of the solution decreases, and some However, it has disadvantages such as dehydration and ring closure to form polyimide, which becomes insolubilized and becomes cloudy, so it needs to be stored at low temperature, which poses a problem in storage stability. In addition, conversion from aromatic polyamic acid to aromatic polyimide resin (hereinafter simply referred to as "conversion")
In this case, high temperatures of 300℃ or higher are usually required, and if a base material with poor heat resistance is used, conversion becomes virtually impossible.There are restrictions on the materials that can be used for the base material. . On the other hand, the above-mentioned soluble polyimide resin is soluble in organic solvents, so by adjusting its concentration and viscosity, it can be applied to a substrate at a constant thickness, and the solvent can be simply removed by heating. It is possible to form a uniform coating film by itself, and although its heat resistance is slightly inferior to that of insoluble aromatic polyimide resins, it has excellent mechanical properties, electrical properties, chemical resistance, etc. However, such soluble polyimide resins can be used as coating agents, especially for electronic material applications, such as interlayer insulating films for integrated circuits, transistors, magnetic heads, etc., insulating films for solar cells, alignment films for liquid crystal display elements, insulating films for thin film thermal heads, etc. On various types of substrates, such as passivation film, juncture coat film, moisture-proof film, buffer coat film, α-ray shielding film and other surface protection films for hermetically sealed integrated circuits, resin-sealed integrated circuits, etc. When coating, there is a problem that the adhesion to the base material used is not necessarily satisfactory, and if the adhesion between the coating film and the base material is insufficient, the high durability of the electronic equipment to be incorporated may be affected. This will cause reliability problems. The present invention was made against the background of such conventional technical problems, and it is a soluble polyimide that has excellent heat resistance, mechanical properties, electrical properties, chemical resistance, stability in solution state, etc., and has excellent adhesive properties. A resin composition is provided. Means for Solving the Problems That is, the present invention is characterized by comprising a soluble polyimide resin having a repeating unit represented by the following general formula () and a functional silane compound represented by the following general formula (). A soluble polyimide resin composition is provided. (In the formula, R represents an organic group such as a divalent aromatic group, aliphatic group, or alicyclic group.) YR ¹ SiR ² _3-n X _n ... () [In the formula, Y is CH ₃ COOC ₂ H ₄ An organic group having an NH- group, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ² is an alkyl group having 1 to 5 carbon atoms, X is an alkoxy group represented by OR ³ or an alkoxycarbonyl group represented by OCOR ⁴ (here, R ³ and R ⁴ are
is an alkyl group having 1 to 10 carbon atoms), and m represents an integer of 1 to 3. ] Such a soluble polyimide resin can be produced by, for example, imidizing polyamic acid obtained from 2,3,5-tricarboxycyclopentyl acetic dianhydride and a diamine in the presence of an organic carboxylic acid anhydride in an organic solvent solution (in particular, 1977
-199720), and by reacting 2,3,5-tricarboxycyclopentyl acetic dianhydride with a diisocyanate in an organic solvent (Japanese Patent Application No. 109239/1982). Here, 2,3,5-tricarboxycyclopentyl acetic acid (hereinafter referred to as "TCA") can be obtained by, for example, ozonolysis of dicyclopentadiene and oxidation with hydrogen peroxide [British Patent No. 872355, J.
Org.Chem., 28 , 2537 (1963)] or a method of oxidizing hydroxydicyclopentadiene obtained by hydrating dicyclopentadiene with nitric acid (West German Patent No.
1078120), and by dehydrating this TCA, 2,3,
5-Tricarboxycyclopentyl acetic acid dianhydride (hereinafter referred to as "TCA・AH") can be produced. In addition, the diamine to be reacted with TCA/AH or the diisocyanate to be reacted with TCA/AH is a compound represented by the general formula: H ₂ NR-NH ₂ or the general formula: OCNRNCO (R is a compound represented by the general formula ()). are the same and represent a divalent aromatic group, aliphatic group, or alicyclic group). Preferred R in the general formula is, for example,

【formula】

【formula】

【formula】

(In the formula, X ₁ , X ₂ , X ₃ and X ₄ may be the same or different, -H, -CH ₃ or -OCH ₃ , Y ₀ is -CH ₂ -, -C ₂ H ₄ -, -O-, -S-,

【formula】

[Formula] represents -SO ₂ - or -CONH-, and n represents 0 or 1. ), an aromatic group represented by -
( _CH2 )n-(n=2-20),

【formula】 【formula】

Examples thereof include aliphatic groups or alicyclic groups having 2 to 20 carbon atoms. In addition, in order to further improve the heat resistance of the soluble polyimide resin composition of the present invention, it is preferable that R is an aromatic group. Specific examples of the diamine include paraphenylenediamine, metaphenylenediamine, 4,4'-
Diaminodiphenylmethane, 4,4'-diaminodiphenyl ethane, benzidine, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1 , 5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,4'-
Diaminobenzarinide, 3,4'-diaminodiphenyl ether, metaxylylene diamine, paraxylylene diamine, ethylenediamine, 1,3
-propanediamine, tetramethylenediamine,
Pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, 4,4'-dimethylheptamethylene diamine, 1,4-diaminocyclohexane, tetrahydrodicyclopentadienylene diamine, hexahydro-4, Examples include 7-methanoindanilene dimethylene diamine, tricyclo[6,2,1,0 ^2,7 ]-undecylene dimethyl diamine, and the like. These can be used alone or in combination. Further, specific examples of the diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
-tolylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl sulfone diisocyanate, 4,4 '-diphenyl sulfide diisocyanate, 1,5-naphthalene diisocyanate,
2,6-naphthalene diisocyanate, tolidine isocyanate, 4,4'-biphenyl diisocyanate, p-xylylene diisocyanate, m-
Aromatic diisocyanate compounds such as xylylene diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-dicyclohexyl Alicyclic diisocyanate compounds such as ether diisocyanate, butane diisocyanate,
Hexamethylene diisocyanate, octamethylene diisocyanate, lysine diisocyanate,
Mention may be made of aliphatic diisocyanate compounds such as trimethylhexamethylene diisocyanate. These can be used alone or in combination. Intrinsic viscosity of the soluble polyimide resin used in the present invention (ηinh=nηrel/c, c=0.5g/dl, 30
°C in dimethylformamide) is preferably
0.05 dl/g or more, particularly preferably 0.05 to 5 dl/g
It is a soluble polyimide resin having preferably 50% by weight or more, particularly preferably 75% by weight or more of repeating units represented by the general formula (). The polyimide resin used in the present invention is easily soluble in organic solvents and is very stable even in a solution state.
No clouding or change in viscosity was observed even after long-term storage. Examples of the organic solvent for the soluble polyimide resin include aprotic polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, and tetramethylurea; Examples include phenolic solvents such as cresol, xylenol, and halogenated phenols, but among these, γ-butyrolactone is preferred because it has low water absorption and does not cause the coating film to become cloudy even when it absorbs water. In the present invention, a functional silane compound represented by the above general formula () is blended into such a soluble polyimide resin. As Y in the general formula (), for example,
_{CH3COOC2H4NH- may be} mentioned. In order to further improve the adhesion to the substrate and the stability of the solution state of the soluble polyimide resin composition of the present invention, Y in the general formula () is as follows:
It is necessary to be an organic group having a CH ₃ COOC ₂ H ₄ NH- group. In addition, R ¹ is a linear methylene represented by -(CH ₂ )- (represents an integer of 1 to 10) or a branched isomer thereof;

【formula】

【formula】

An arylene group represented by [Formula] etc.,

【formula】 【formula】

In _the cycloalkylene group _{represented by [ Formula ]} etc., _R ² is _a linear _or Mention may be made of branched alkyl groups. _Furthermore , as X _{, -OCH3 , -OC2H5 , -OC3H7} , _{-OC4H9 , -OC5H11 , -OC6H13} , _{-OC7H15 , -OC8H17} , _-OC9H19 , _{-OC10H21 , etc.} , _{-OCOCH3 , -OCOC2H5 , -OCOC3H7 , -OCOC4H9} , _-OCOC5 Examples include linear or branched alkoxycarbonyl groups represented by H ₁₁ , -OCOC ₆ H ₁₃ , -OCOC ₇ H ₁₅ , -OCOC ₈ H ₁₇ , -OCOC ₉ H ₁₉ , -OCOC ₁₀ H ₂₁ , etc. can. Specific examples of the functional silane compounds represented by the general formula () include 9-trimethoxysilyl-3,6-diazanonyl acetate and 9-triethoxysilyl-3,6-diazanonyl acetate. These can also be used in combination. The mixing ratio of the functional silane compound to the soluble polyimide resin is 100 parts by weight of the former,
The latter is preferably 0.05 to 30 parts by weight, particularly preferably 0.1 to 20 parts by weight; if it is less than 0.05 parts by weight, the adhesion of the soluble polyimide resin composition to the substrate will not be sufficiently improved; on the other hand, if it exceeds 20 parts by weight, When a soluble polyimide resin composition is applied as a solution, the surface properties of the coating film change significantly and migration of excess functional silane compounds occurs. The soluble polyimide resin composition of the present invention is usually applied to a substrate as a solution. The solvent used when preparing the soluble polyimide resin composition solution may be any solvent as long as it dissolves the soluble polyimide resin and does not react with the functional silane compound to cause precipitation or turbidity. Solvents that dissolve the resin are most preferred, and other common organic solvents such as alcohols, phenols, ketones, esters, lactones, ethers, halogenated, hydrocarbons, hydrocarbons such as methyl alcohol, ethyl Alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, phenol, m-cresol,
Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol iso- propyl ether,
Ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, tetrahydrofuran,
dichloromethane, 1,2-dichloroethane, 1,
4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, etc. may also be mixed with the solvent in which the soluble polyimide resin is dissolved to an extent that the soluble polyimide resin will not be precipitated. be able to. When preparing a solution of the soluble polyimide resin composition of the present invention, a functional silane compound is usually added to a solution of the soluble polyimide resin in an organic solvent, or other common organic silane compounds are added to the solution to the extent that precipitation does not occur. A solution of a functional silane compound dissolved in a solvent is mixed to prepare a solution having a solid content concentration of 0.1 to 30% by weight, preferably 0.5 to 15% by weight. The soluble polyimide resin composition solution of the present invention prepared in this manner is applied to a substrate by a roll coater method, a spinner method, a printing method, etc., and then dried at, for example, 80 to 250°C for 5 to 180 minutes. Thus, a coating film of the soluble polyimide resin composition can be formed. Effects of the Invention The soluble polyimide resin composition of the present invention has excellent heat resistance, mechanical properties, electrical properties, chemical resistance, stability in a solution state, etc., and has excellent adhesiveness to a substrate. It can be suitably used in the above-mentioned electronic material applications in the electronic industry sector, and exhibits particularly excellent performance as a coating material for organic polymer materials such as polyester, glass silicon wafers, and ITO transparent electrodes. Examples Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Reference Example 1 After dissolving 20.48 g (0.102 mol) of diaminodiphenyl ether (DDE) in 247.5 g of N,N-dimethylformamide (DMF),
23.15 g (0.103 mol) of TCA.AH was added as a powder and reacted at 25° C. with stirring. After 24 hours, a small amount of this reaction solution was sampled, and DMF was added so that the concentration of polyamic acid was 0.5 g/100 ml, and the intrinsic viscosity (30° C.) was measured. The obtained polyamic acid had an ηinh of 0.99 dl/g. Next, 30 g of a solution made by adding DMF to the reaction solution to make the polyamic acid concentration 6.1% by weight was added to 100% of the solution.
ml flask and add 1.32 g of acetic anhydride to this solution.
and 1.02 g of pyridine were sequentially added, mixed and stirred, and then reacted at 135°C for 2 hours. Next, the reaction product was poured into a large amount of methanol to solidify and collect the soluble polyimide resin, and then heated at 80°C.
and dried overnight. The viscosity ηinh of the obtained soluble polyimide resin in DMF at 30°C was 0.79 dl/g. This soluble polyimide resin was dissolved in DMF again, cast on a glass plate, dried, the film was peeled off, and the infrared absorption spectrum was measured.
Absorption based on C=0 stretching vibration of imide was observed at 1740 cm ^-1 and 1690 cm ^-1 . As a result, by heating and reacting polyamic acid solution in the presence of acetic anhydride and pyridine,
It can be seen that a soluble polyimide resin is obtained. Example 1 The soluble polyimide resin obtained in Reference Example 1 was
-Dissolve in butyrolactone to make a 5% by weight solution, and mix 2.5 phr of 9-trimethoxylyl-3,6-diazanonyl acetate to prepare a soluble polyimide resin composition solution, with a pore size of 0.22μ
The mixture was filtered through a No. m membrane filter to remove insoluble matter. This solution was applied onto a glass substrate using a spinner. After coating, it was dried at 150°C for 1 hour. The thickness of the coating film of the obtained soluble polyimide resin composition is
It was 0.20 μm. Cut the resulting coating film with a cutter knife to a width of 1 mm and a length of 11 mm.
I made 11 horizontal cuts in the book, creating a 10 x 10 grid. Paste sellotape on this grid,
A peel test was conducted. The number of peeled off grids was 0. In addition, similar 10 x 10 grid cuts were made in the resulting coating film, and the film was boiled in boiling water for 5 hours.
After drying, it was cooled to room temperature, cellophane tape was applied in a grid pattern, and a peeling experiment was performed. The number of peeled off grids was 0. Note that the obtained soluble polyimide resin composition showed no change in viscosity even after being left at room temperature for one month, and had excellent stability in the solution state. Example 2 A coating test was conducted in the same manner as in Example 1, except that the amount of the functional silane compound used in Example 1 was changed to 5 phr. The results are shown in Table 1. Example 3 A coating test was conducted in the same manner as in Example 1 except that the amount of the functional silane compound used in Example 1 was changed to 10 phr. The results are shown in Table 1. Comparative Example 1 The soluble polyimide resin obtained in Reference Example 1 was dissolved in N,N-dimethylacetamide to make a 5% by weight solution, and 3% as a functional silane compound was added to this.
A coating test similar to that in Example 1 was conducted using 2.5 phr of -aminopropyltrimethoxysilane. The results are shown in Table 1. Comparative Example 2 A coating test similar to that in Example 1 was conducted using N-(2-aminoethyl)-3-aminopropyltrimethoxysilane instead of the functional silane compound used in Comparative Example 1. The results are shown in Table 1. Comparative Example 3 A coating test similar to Example 1 was conducted using 3-aminopropyltrimethoxysilane instead of the functional silane compound used in Comparative Example 1. The results are shown in Table 1. Comparative Example 4 A coating test similar to Example 1 was conducted using 10-trimethoxysilyl-1,4,7-triazadecane instead of the functional silane compound used in Comparative Example 1. The results are shown in Table 1. Comparative Example 5 A coating test was conducted in the same manner as in Example 1, except that the functional silane compound was not used. The results are shown in Table 1. Comparative Example 6 A coating test similar to that in Example 1 was conducted using 3-isocyanatepropyltriethoxysilane instead of the functional silane compound used in Example 1. The results are shown in Table 1. Comparative Example 7 A coating test similar to that in Example 1 was conducted using 3-glycidoxylpropyltrimethoxysilane instead of the functional silane compound used in Example 1. The results are shown in Table 1. Comparative Example 8 A coating test similar to that in Example 1 was conducted using vinyltriethoxysilane instead of the functional silane compound used in Example 1. The results are shown in Table 1. Comparative Example 9 A coating test similar to that in Example 1 was conducted using 3-methacryloxypropyltrimethoxysilane instead of the functional silane compound used in Example 1. The results are shown in Table 1. Comparative Example 10 A coating test similar to that in Example 1 was conducted using 2-(3,4-epoxycyclohexyl)trimethoxysilane instead of the functional silane compound used in Example 1. The results are shown in Table 1. Comparative Example 11 A coating test similar to that in Example 1 was conducted using 3-mercaptopropyltrimethoxysilane instead of the functional silane compound used in Example 1. The results are shown in Table 1. Example 4 A coating test similar to that in Example 2 was conducted using a glass substrate on which an ITO transparent electrode was deposited instead of the glass substrate used in Example 2. The results are shown in Table 1. Comparative Example 12 A coating test was conducted in the same manner as in Comparative Example 5, using instead of the glass substrate used in Comparative Example 5 the glass substrate on which the ITO transparent electrode used in Example 4 was deposited. The results are shown in Table 1. Comparative Example 13 A coating test was conducted in the same manner as in Comparative Example 2, using a silicon wafer substrate instead of the glass substrate used in Comparative Example 2. The results are shown in Table 1. Comparative Example 14 Comparative Example instead of the glass substrate used in Comparative Example 5
A coating test was conducted in the same manner as in Comparative Example 5 using the silicon wafer substrate used in Example 13. The results are shown in Table 1.

【table】

【table】

Claims (1)

[Claims] 1. A soluble polyimide resin having a repeating unit represented by the following general formula () and the following general formula ()
A soluble polyimide resin composition comprising a functional silane compound represented by: (In the formula, R represents a divalent organic group.) YR ¹ SiR ² _3-n X _n ... () [In the formula, Y is an organic group having a CH ₃ COOC ₂ H ₄ NH- group, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ² is an alkyl group having 1 to 5 carbon atoms, X is an alkoxy group represented by OR ³ or an alkoxycarbonyl group represented by OCOR ⁴ (here, R ³ and R ⁴ are
is an alkyl group having 1 to 10 carbon atoms), and m represents an integer of 1 to 3. ]