JPH03140328A - Production of polyamic acid having high adhesivity and its cured product - Google Patents

Abstract

PURPOSE:To obtain the subject amic acid having high adhesivity to inorganic material, etc., and giving a resin having excellent storage stability by reacting a tetracarboxylic acid dianhydride, a trimellitic anhydride, a diamine and an aminosilane under specific condition. CONSTITUTION:The objective amic acid can be produced by reacting (a) A mol of a tetracarboxylic acid dianhydride of formula I (R<1> is tetravalent carbocyclic aromatic group, heterocyclic group, alicyclic group, etc.), (b) A' mol of trimellitic anhydride of formula II, (c) B mol of a diamine of formula III (R<2> is 2-12C aliphatic group, 4-30C alicyclic group or 6-30C aromatic aliphatic group) and (d) C mol of an aminosilane of formula N [R<3> is -(CH2)S- or group of formula V (S is 1-4); R<4> is 1-6C alkyl or phenyl; X is alkoxy, acetoxy, etc.; 1<=k<=3] in the presence of a solvent under a condition satisfying the relationships of formulas VI, VII and VIII.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a highly adhesive silicone polyamic acid and a method for producing a cured product thereof.

[Conventional technology]

Conventionally, polyimide resins have been widely used as protective materials, insulating materials, adhesive materials, films, and structural materials in the field of electronic equipment, mainly because of their heat resistance.

A method of using it in combination with other inorganic materials as a heat-resistant film, coating agent, or adhesive is also often used. In this case, when the inorganic material is a silicon-containing compound such as glass, many copolymers with silicon compounds have been proposed as a means to improve the adhesiveness of the inorganic material. for example,
JP-A-57-143328, JP-A-58-747
No. 3 and JP-A No. 58-13631 disclose a polyimide-siloxane copolymer using a polyimide precursor obtained by replacing a part of the diamine component as a raw material with polycytoxane terminated at both ends with diamine. A technique to do this has been proposed.

Also, Special Publication No. 58-18372, Special Publication No. 58-32
No. 162 and Japanese Patent Publication No. 58-32163 disclose a process in which a suitable carboxylic acid derivative such as a tetracarboxylic dianhydride is reacted with a diamine to produce a polyamide carboxylic acid in which the terminal groups of the acid anhydride and the like are H-condensed. Thereafter, by reacting at least 2 moles of an amino silicon compound per mole of this polyamide carboxylic acid at -20°C to +50°C, a polyamide carboxylic acid prepolymer containing silicon is obtained, and this prepolymer is not imidized. Either as is or imidized, it is chemically cyclized (imidized) in the presence of a dehydrating agent under mild conditions (at a low temperature, preferably below 50°C, especially -20°C to +25°C).
A technique is disclosed in which a silicic polyimide precursor is obtained, this precursor is heated in the presence or absence of a silane diol or siloxane diol in a solution state, and upon completion of imidization, crosslinking is performed to obtain a polyimide siloxane. .

Further, in JP-A No. 57-212230, polyamic acid or polyamide-amic acid 99.9 to 70.0% by weight
The patent discloses a polyimide resin molded product obtained by heating a polymer composition comprising 0.1 to 30.0% by weight of a specific organosilicon compound.

JP-A-56-157427 and JP-A-60-76
No. 533 discloses a method for producing a polyimide precursor by reacting a special aminosilane with a tetracarboxylic acid component to obtain a silane-modified polycarboxylic acid component, and reacting this with a diamine.

Further, JP-A-61-287926 proposes a method for producing a highly adhesive polyamic acid obtained by reacting a specific diacid anhydride, diamine and aminosilane in a specific ratio.

[Problem to be solved by the invention]

The above-mentioned JP-A-57-143328, JP-A-58-
In JP-A No. 7473 and JP-A-581-3631, some improvement in adhesion can be seen, but it is not sufficient.

Special Publication No. 58-18372, Special Publication No. 5832162
Although the methods disclosed in Japanese Patent Publication No. 58-321.63 improve the adhesion to silicon compounds to some extent, the adhesion to aluminum, for example, is insufficient. In addition, a film is formed by applying a polymer solution to the object to be bonded and baking it, and if necessary, the same polymer solution is applied on top of the film and baking is performed to form an additional film on top of the film. In practice, laminated films are often formed (such adhesion may hereinafter be referred to as "adhesion between films" in this specification), but the adhesion in such cases is unsatisfactory. Met.

In the case of JP-A-57-212230, although some improvement in adhesion to silicon compounds was observed, the adhesion between the films was not satisfactory.

JP-A-56-157427 and JP-A-60-76
Although the method disclosed in Japanese Patent Publication No. 533 improves adhesion to silicon compounds to some extent, it is not necessarily satisfactory, and it is also stated that increasing the amount of aminosilane added deteriorates the electrical properties.

The polyamic acid obtained by the method disclosed in JP-A No. 61-287926 exhibits high adhesion to many types of substrates and is a useful material, but when stored in the state of a festival, the viscosity decreases over time. It has the disadvantage of being somewhat large.

As mentioned above, there are various problems in the conventional technology, and therefore, the object of the present invention is to provide adhesives or resins for multilayer laminated composite materials with a certain level of heat resistance, and to provide adhesives for bonding between inorganic substances, metals, and coatings. The object of the present invention is to provide a precursor that provides a polyimide resin with good adhesive properties and excellent storage stability, and methods for producing a cured polyimide product obtained from the precursor.

[Failure to solve the problem]

The present invention provides A mol of tetracarboxylic dianhydride represented by the following formula (1), A' mol of trimellitic anhydride represented by the formula (IT), 8 mol of a diamine represented by the formula (III), This is a method for producing a polyamic acid by reacting C moles of aminosilane represented by (IV) in the presence of a solvent in the presence of the relationships of formulas (V), (V[) and (■).

[In formulas (I) to (IV), R1 represents a tetravalent carbocyclic aromatic group, heterocyclic group, alicyclic group, or aliphatic group, and R2 represents an aliphatic group having 2 to 12 carbon atoms. group group, alicyclic group having 4 to 30 carbon atoms, aromatic aliphatic group having 6 to 30 carbon atoms, 6 to 30 carbon atoms
30 carbocyclic aromatic group, heterocyclic group or the following formula (■)
is a borine 0 xane group represented by -(CH2
)sNH2-R-NH2 (III) NH,, -R-5iR3,Xk (IV) (where S represents an integer from 1 to 4),
R4 independently represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group having 7 to 12 carbon atoms;
X independently represents an alkoxy group, an acetoxy group, or a halogen, and k takes a value of 1≦3.

(Here, R is independently -(CH2)8 (here, S represents an integer from 1 to 4),
R6 independently represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group having 7 to 12 carbon atoms;
g takes a value of 1≦g≦100. )] The raw materials used in the method of the present invention will be explained.

First, the tetracarboxylic dianhydride and diamine represented by the formulas (1) and (III) will be described.

When R1 is a carbocyclic aromatic group, this group preferably has at least one six-membered ring.

R1 is particularly a monocyclic aromatic group, a fused polycyclic aromatic group,
or several fused or unfused rings (these rings are
Bonded to each other directly or through bridging groups. ) is a polycyclic aromatic group having

As the above bridging group, for example, the following groups are suitable.

-o--CH-CH2--CH2N Ql- and -N Ql In the above formula, Ql has 1 to 1 carbon atoms, optionally substituted with one or more halogen atoms (preferably fluorine atoms). 6, preferably represents 1 to 4 alkyl or alkylene groups, or represents a cycloalkyl group, aryl group or arylene group, and Ql represents a hydrogen atom, a cycloalkyl group or an aryl group, or in some cases It represents an alkyl group having 1 to 4 carbon atoms substituted with one or more halogen atoms.

Further, Ql and Ql may be a group in which the above groups are bonded to each other through two bridging groups, for example, two 15O7- groups.

If R1 represents a heterocyclic group, mention may be made in particular of five- or six-membered heteroaromatic groups containing oxygen, nitrogen and (or sulfur), or combinations thereof with a benzene nucleus. It is a fused cyclic group with

The carbocyclic aromatic group or heterocyclic group represented by R1 is
Further, it may be substituted with one or more of, for example, a nitro group, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom (particularly a fluorine atom), a silyl group, or a sulfamoyl group.

The group represented by R1 may be unsubstituted or substituted, for example with one or more halogen atoms (e.g. fluorine, chlorine or bromine), or C1-C4 alkyl or alkoxy groups.

When R1 is an alicyclic group, this group has at least one alicyclic group having 4 to 8 carbon atoms. When contributing multiple alicyclic groups, for example -〇--CH=-CH- or -CH2
They can also be bonded to each other through bridging groups such as -.

There may be a side chain consisting of a lower hydrocarbon such as a methyl group or an ethyl group on the carbon atom forming the alicyclic structure, or the side chains may be connected to each other to form a bicyclo or tricyclo ring. Good too.

When R1 is an aliphatic group, it is a linear or side chain aliphatic group having 4 to 12 carbon atoms.

When R2 is a carbocyclic aromatic group, preferred examples thereof include a monocyclic aromatic group, a fused polycyclic aromatic group, or a non-fused bicyclic aromatic group. In the case of this non-fused bicyclic group, the aromatic rings are bonded to each other through a bridging group. In this case, possible cross-linking groups can be exemplified by the same groups mentioned in the explanation of R1.

If R2 is a heterocyclic group, it is in particular a five- or six-membered heteroaromatic group containing 0, N and/or S.

In addition, when R2 is an aliphatic group, in particular an alkylene group having 2 to 12 carbon atoms or a heteroatom such as 0, S or N atom interposed in the alkylene chain is used. Examples include:

Examples of R2 being an alicyclic group include a cyclohexyl group or dicyclohexylmethane group, while examples of R2 being an araliphatic group include 1°3-1 .4- or 2,4
-bis-alkylenebenzene group, 4.4'-bis-alkylene diphenyl group, and 4.4'-bis-alkylene-diphenyl ether group.

Regarding R1, it is preferred that each R1 independently represents an unsubstituted monocyclic aromatic group, an unsubstituted fused polycyclic aromatic group, or an unsubstituted unsubstituted fused bicyclic aromatic group. In the last group mentioned above, the aromatic rings are mutually -0- or -CO-
A group formed by bonding through a bridging group is preferred.

On the other hand, regarding R2, each R2 is a monocyclic aromatic group or a non-fused monocyclic group which independently has one or more halogen atoms, or one or more C1-C4 alkyl groups or alkoxy groups as a substituent. It is preferably a bicyclic aromatic group or an unsubstituted monocyclic araliphatic group or an unsubstituted C2-C10 aliphatic group.

The case where R2 is a polysiloxane group has already been shown.

Examples of the tetracarboxylic dianhydride represented by the formula (1) include the following.

Pyromellitic dianhydride, 3.3', 4.4'-benzophenone-tetracarboxylic dianhydride, 2.3.3'4'-benzophenone-tetracarboxylic dianhydride, 2.2', 3 .3' ~benzophenone-tetracarboxylic dianhydride, 3.3', 4.4'-diphenyl-tetracarboxylic dianhydride, 2.2', 3.3'-diphenyl-tetracarboxylic dianhydride , bis(2,3-dicarboxyphenyl)-methannihydride, bis(3,4-dicarboxyphenyl)-methannihydride, 2.2-bis(2,3-dicarboxyphenyl)-brovanhydride, Bis(3,4-dicarboxyphenyl)-ether dianhydride, Bis(3,4-dicarboxyphenyl)-sulfone dianhydride, N,N-(3,4-dicarboxyphenyl)N-methylamine dianhydride, 3 .3',4.4'-tetracarpoxybenzoyloxybenzene dianhydride, 2.3,6.7-naphthalene-tetracarboxylic dianhydride, 1.2.5.6-naphthalene-tetracarboxylic dianhydride Anhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride, cyclobutanetetracarboxylic dianhydride , methylcyclobutanetetracarboxylic dianhydride, 1,2-dimethylcyclobutanetetracarboxylic dianhydride, 1,3-dimethylcyclobutanetetracarboxylic dianhydride, ethylcyclobutanetetracarboxylic dianhydride, bicyclo[4,2 ,0]octane-1,,6,7゜8-tetracarboxylic dianhydride, 2.7 tricyclo(6,4,0,0) dodecane 1.8,2
．． 7-tetracarboxylic dianhydride, 1,2,3,4-tetracarboxybutani dianhydride.

Known compounds can be used as the diamines represented by -Sakuhatsu (III).

Examples of carbocyclic aromatic diamines include, in particular, the following compounds:

o-, m- and p-phenylene diamines, diaminotoluenes (e.g. 2,4-diaminotoluene), 1.
4-diamino-2-methoxybenzene, 2,5. -diaminoxylenes, 1,3-diamino-4-chlorobenzene, 14-diamino-2,5-dichlorobenzene, 1,
4-diamino-2-bromobenzene, 1,3-diamino-4isopropylbenzene, N,N'-diphenyl 1,4-phenylenediamine, 4,4'-diaminodiphenyl-2,2-propane, 4.4' Diaminodiphenylmethane, 2,2'-diaminostilbene, 4
．． 4'-diaminostilbene, 4゜4'-diaminodiphenyl-ether, 4.4', diaminodiphenyl-thioether, 4,4' diaminodiphenylsulfone, 3.3'-diaminodiphenylsulfone, 4.4
'-diaminobenzoic acid phenyl ester, 2.2'
-Diaminobenzophenone, 4.4'-Diaminobenzophenone, 4.4'-Diaminobenzyl, 4-
(4'aminophenylcarbamoyl)-aniline, bis(4-aminophenyl)-phosphine oxyto, bis(
4-aminophenyl)-methyl-phosphine oxyto,
Bis(3-aminophenyl)-methylsulfine oxide, bis(4-aminophenyl)-phenylphosphine oxide, bis(4-aminophenyl)-cyclohexylphosphine oxide, N,N-bis(4-aminophenyl)N -Phenylamine, N,N-bis(4-aminophenyl)-N-methylamine, 4,4'-diaminodiphenylurea, 1,8-diaminonaphthalene, ■,
5-diaminonaphthalene, 1,5-diaminoanthraquinone, diaminofluoranthene, bis(4-aminophenyl)-diethylsilane, bis(4-aminophenyl)
-dimethylsilane, bis(4-aminophenyl)-tetramethyldisiloxane, 3.4'-diaminodiphenyl ether, benzidine, 2.2'-dimethylbenzidine, 2.2-bis[4-(4-aminophenoxy)phenyl ] Propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 4.4'-bis(4-
aminophenoxy)biphenyl, 2,2-bis(4-(
4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene,
1,3-bis(4-aminophenoxy)benzene.

Examples of the heterocyclic diamines include the following compounds.

2,6-diaminobenzyl, 2,4-diaminopyrimidine, 2,4-diamino-5-triazine, 2,7-diamitudibenzofuran, 2,7-diamitsucarbazole, 3,7-diamitufenothiazine, 2,5-diamino-1,3,4-thiadiazole, 2,4-diamino-6
-Phenyl-5-triazine.

Further, examples of aliphatic diamines include the following compounds.

Ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,2-dimethylpropylenediamine, 2゜5-dimethylhexamethylenediamine, 2. 5 dimethyl hebutamethylene diamine, 4,4
-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 3-methoxyheptamethylenediamine, 5-methylnonamethylenediamine, 2゜11-diaminododecane, 1.12-diaminooctadecane, 1.
2-bis(3-aminopropoxy)-ethane, N, N'
-dimethyl-ethylenediamine, N,N'-diethyl-1,3-diaminopropane, N,N'-dimethyl-
1,6-diamithexane, a diamine represented by the formula: % formula %).

Furthermore, compounds suitable as alicyclic diamines include 1.4
-diaminocyclohexane and 4,4'-diaminodicyclohexylmethane, and the araliphatic diamines include 1,4-bis(2-methyl-4-aminopentyl)-benzene, 1,4bis(1,1 -dimethyl-5-aminopentyl)=benzene, 1,3-bis(aminomethyl)-benzene and 1,4-bis(aminomethyl)-
Benzene is suitable.

Further, the following compounds can be mentioned as diaminopolysiloxanes.

Examples of the aminosilane represented by formula (IV) include the following compounds.

Aminomethyl-di-n-propoxy-methylsilane, (
β-aminoethyl)-di-n-propoquine-methylsilane, (β-aminoethyl)jetoxy-phenylsilane, (β-aminoethyl)tri-n-propoxysilane,
(β-aminoethyl)-dimethoxy-methylsilane, (
γ-aminopropyl)-di-n-propoxy-methylsilane, (γ-aminopropyl)-di-n-butoxy-methylsilane, (γ-aminopropyl)-trimethoxysilane, (γ-aminopropyl)-triethoxysilane ,
(γ-aminopropyl)-di-n pentoxy-phenylsilane, (γ-aminopropyl)-methoxy-rhopropoxy-methylsilane, (δ~ruaminobutyl-dimethoxy-methylsilane, (3-aminophenyl)-di-n
-propoxy-methylsilane, (4-aminophenyl)
- trilow propoxysilane, [β-(4-aminophenyl)~ethyl] -jethoxy-methylsilane, [
β-(3-aminophenyl)-ethyl]-zilowpropoxyphenylsilane, [γ-(4-aminophenyl)-propyl]-di-n-propoxy-methylsilane, [γ-(4-aminophenoxy)- propyl] -di-n-broboxy-methylsilane, [γ-(3-aminophenoxy)-propyl] -di-n-butoxy-methylsilane, (γ-aminopropyl)-methyl-dimethoxysilane, (γ-aminopropyl)- Methyl-jethoxysilane, (γ-aminopropyl)-ethyl-di-ropropoxysilane, 4-aminophenyltrimethoxysilane, 3-aminophenyltrimethoxysilane, 4-aminophenyl-methyl-di-methoxysilane, 3 -aminophenyl-dimethyl-methoxysilane, 4-aminophenyltriethoxysilane.

As a preferable solvent (hereinafter sometimes referred to as reaction solvent) used in the production method of the present invention, N-methyl-2
-pyrrolidone, N,N-dimethylacetamide, N,N
-dimethylformamide, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoramide, methylformamide, N-acetyl-2-pyrrolidone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol Seven methyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, cresol,
γ-butyrolactone, N,N-diethylacetamide,
N,N-diethylformamide, N,N-dimethylmethoxyacetamide, tetrahydrofuran, N-methyl-
Examples include ε-caprolactam and tetrahydrothiophene dioxide (sulfolane).

Moreover, this reaction can also be carried out in a mixed solvent obtained by mixing the above-mentioned organic solvents.

Furthermore, the preferred organic solvents as mentioned above may be combined with other aprotic (neutral) organic solvents such as aromatic, cycloaliphatic or aliphatic hydrocarbons or their chlorinated derivatives (e.g. benzene, toluene, xylenes, cyclohexane). , pentane, hexane, petroleum ether, methylene chloride, etc.)
Alternatively, one diluted with dioxane can also be used.

Next, the reaction method will be explained. A mole of tetracarboxylic dianhydride represented by the formula (1), A' mole of trimellitic dianhydride represented by the formula (II),
) and C moles of the aminosilane represented by the above formula (IV) are reacted in a reaction solvent. At this time, ASA'B and C are between them the above formula (V) ~
It is determined that the relationship (■) is established.

Formula (V) shows that the acid anhydride and amine in all the raw material compounds are in a nearly equivalent relationship, and deviations from this range make it difficult to obtain a high molecular weight polyamic acid, and the curing obtained from this polyamic acid is difficult. This is not preferable because it may deteriorate the electrical properties of objects. Formula (Vl) indicates the required amount of trimellitic anhydride, and if it is smaller than this range, only a material with poor adhesion to metal compounds or inorganic compounds can be obtained. Moreover, it is difficult to obtain products with good storage stability. On the other hand, if it is larger than this range, the molecular weight of the obtained polyamic acid becomes small, making it difficult to apply this polyamic acid solution to a substrate to form a film.

Further, formula (■) indicates the necessary amount of aminosilane, and outside this range, it is difficult to obtain sufficient adhesion to glass, silicon wafers, or other silicon compounds.

The reaction solvent is preferably used in an amount of 40% by weight or more based on the total amount of the reaction solvent and the added raw materials. If it is less than this, the stirring operation may be difficult. The reaction is preferably carried out at a temperature of 0°C or higher and 80°C or lower. The reaction time is preferably 0.2 to 20 hours.

Regarding the order of adding the reaction raw materials to the reaction system, all of the tetracarboxylic dianhydride, diamine, trimellitic anhydride, and aminosilane may be added to the reaction solvent at the same time and reacted, or the former two may be reacted in advance. Thereafter, the reaction product can be reacted with trimellitic anhydride and aminosilane. In the case of the latter method, a high molecular weight polymer is easily obtained. The reaction proceeds relatively quickly, producing a homogeneous and transparent reaction solution. In this way, a polymer or oligomer in which aminosilane and trimellitic acid are added to the terminals of polyamic acid is obtained. These products maintain the good adhesive properties of the highly adhesive polyamic acid proposed in JP-A No. 61-287926, and further improve the storage stability, which is a weak point.

By applying the coating solution containing the polyamic acid of the present invention to the coating object and baking it, the polyamide carboxylic acid is dehydrated and cyclized to form an imide bond, and at the same time, the hydrolyzable group at the end of the molecule, The reaction increases the molecular weight and forms a tough coating film. On the other hand, it is thought that there is also a carboxyl group of trimellitic anhydride at the polyamic acid terminal, and this and the amount of the aminosilane are expressed by the formula (V).
Only when it exists within the range regulated by (■) can polyamic acid be obtained that has excellent adhesion to many types of substrates, such as silicon compounds, metals, other inorganic compounds, and adhesion between films, and has excellent storage stability. A good varnish can be obtained.

Next, a method for producing a cured film using the polyamic acid obtained in the present invention will be described.

In most cases, the polyamic acid produced according to the present invention is
Since it is used in the form of a solution dissolved in a solvent, such as a varnish, the solution obtained by the method of the present invention is preferably used after being concentrated or diluted with a solvent.

As the solvent, the same solvent as the reaction solvent can be used. Any known method may be used to form a molded article from the polyamic acid solution obtained in the present invention; for example, after pouring the polyamic acid solution onto a glass plate, copper plate, aluminum plate, etc. By heating, the solvent is removed and the amic acid bonds are converted to imide bonds by dehydration, and crosslinking by siloxane bonds progresses to form a hard and tough film. Although it is possible to form a laminated composite material by sequentially performing such operations, it is also possible to obtain a laminated composite material by applying varnish as an adhesive between multiple dissimilar materials and firing. can.

The varnish containing polyamic acid produced according to the present invention can be further coated on a film that has been cured by firing and then baked to form a film on top of the film. It is also possible to form a laminated material using a reinforced film by impregnating filler or glass fiber with varnish and baking and hardening it.

The firing conditions vary depending on the solvent used, the thickness of the coating film, etc., but are 150 to 500°C, preferably 250 to 400°C.
, 5 to 1.5 hours is sufficient.

A silicone-based polyimide cured product can be obtained by such a method of the present invention.

The silicon-based polyimide cured product obtained by the method of the present invention can be applied to parts for electronic equipment, communication equipment, heavy electrical equipment, transportation equipment, etc., but it can also be used for electronic materials such as liquid crystal alignment agents. shows.

〔Example〕

The present invention will be explained in more detail below with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to these Examples.

Example 1 A 1 g flask equipped with a stirrer, dropping funnel, thermometer, condenser and nitrogen purging device was fixed in cold water.

After purging the inside of the flask with nitrogen gas, 500 ml of dehydrated and purified N-methyl-2-pyrrolidone (hereinafter referred to as r
It's called NMPJ. ) and 24.114g (0,120
4 mol) of 4.4'-diaminodiphenyl ether was added, and while keeping this solution at 20-25°C, 25.873
g (0,0803 mol) of 3.3', 4.4' -
Benzophenone tetracarboxylic dianhydride was added from the dropping funnel over 30 minutes, and after reacting at this temperature for 3 hours,
6.224 g (0,1365 mol) of trimellitic anhydride (hereinafter referred to as rTMAJ) was added, and 1
A time reaction was performed. After that 11.990g (0,0
562 mol) of aminophenyltrimethoxysilane (Meta/Bara-38/62, hereinafter referred to as rAPMSJ) was added, and the reaction was carried out at this temperature for 2 hours and then at 45 to 50°C for 2 hours to form a pale yellow transparent polyamic acid. A solution was obtained. The rotational viscosity of this solution at 25°C was 320 centipoise. Here, rotational viscosity refers to
This is the viscosity measured at 5°C (the same applies below).

Example 2 26.037g (0
, 0602 mol) of bis[4-(4-aminophenoxy)phenyl]sulfone kept at 30-35°C.
ml of N,N-dimethylacetamide and dissolved therein, 21.258 g (0,0723 mol) of 3.3'4.
4'-biphenyltetracarboxylic dianhydride and 6.
677 g (0,0313 mol) of APMS (meth/
After adding Bara-38/62) and reacting at this temperature for 10 hours, 1.619 g (0,00843 mol) of TMA was added and the reaction was further carried out for 3 hours. As a result, a pale yellow transparent polyamic acid solution having a rotational viscosity of 210 centipoise at 25° C. was obtained.

Example 3 41.893 g (0,16
87 mol) of 3.3'-diaminodiphenylsulfone, 62.455. (0,1406 mol) of 2,2-bis(3,4-dicarboxyphenyl)hexafluorobrovanni anhydride and 15.665 g (0,0815 mol) of TMA were added and at this temperature for 10 hours. After carrying out the reaction, 4.981 g (0,0225 mol) of 3-aminopropyltriethoxysilane was added and heated at 40-50°C.
The reaction was carried out for 3 hours. As a result, a pale yellow transparent polyamic acid solution having a rotational viscosity of 340 centipoise at 25° C. was obtained.

Example 4 47.633g (0
, 1630 mol) of 1,4-bis(4-aminophenoxy)benzene was kept at 15-20°C in 500 ml.
of NMP, and in this solution 65.687 g (
After adding 0,1833 mol) of bis(34-dicarboxyphenyl)-sulfonic dianhydride and carrying out the reaction at this temperature for 7 hours, 9.357 g (0,0489 mol)
of methyljethoxysilane and 2.348 g (0,0
122 mol) of TMA was added and the reaction was carried out at 35-40°C for 3 hours. As a result, the rotational viscosity at 25℃ is 2800.
A pale yellow transparent polyamic acid solution of centipoise was obtained.

Example 5 33.029 g (0,080
5 mol) of 2,2-bis+4-(4-aminophenoxy)phenyl)propane and 17.548 g (0,08
After adding 05 mol) of pyromellitic dianhydride and carrying out the reaction at this temperature for 5 hours, 33.029
g (0,0805 mol) of 2,2-bis+4-(4aminophenoxy)phenyl)propane, 27.459. (
0°1287 mol) of APMS (100% rose) and 5
By adding 5.643 g (0,2897 mol) of TMA and carrying out the reaction for an additional 5 hours, the rotational viscosity at 25°C became 940.
A pale yellow transparent polyamic acid solution of centipoise was obtained.

Example 6 In 500 ml of NN-dimethylformamide kept at 30-35°C using the same equipment and method as in Example 1, 43.6
3.3', 4.4' of 42K (0,1355 mol)
-benzophenonetetracarboxylic dianhydride, 14
．． 656 g (0,1355 mol) p-phenyl diamine, 8.090 g (0,0379 mol) APMS
(100% rose) and 8.326g (0,0433
mol) of TMA was added, and the reaction was carried out for 15 hours. As a result, a pale yellow transparent polyamic acid solution having a rotational viscosity of 420 centipoise at 25° C. was obtained.

Example 7 209.689r (0,98
31 mol) of APMS (rose 100%) was dissolved,
81.631 g (0,364 mol) of dimethylcyclobutanetetracarboxylic dianhydride was added to this solution and reacted for 1 hour.
By adding mol) of TMA and further carrying out the reaction for 2 hours, a pale yellow transparent polyamic acid solution having a rotational viscosity of 38 centipoise at 25° C. was obtained.

Example 8 42.092 g (
0,0812 mol) of 2.2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane and 1.
040 g (0,00541 mol) of TMA was added,
After reacting at this temperature for 1 hour, 40.067g
(0,0902 mol) of 2,2-bis(3,4-dicarboxyphenyl)hexafluorobrovanni anhydride and 5
．． 002 g (0,0235 mol) of APMS (rose 1
00%) was added thereto, and the reaction was further carried out for 6 hours. As a result, a pale yellow transparent polyamic acid solution having a rotational viscosity of 1800 centipoise at 25° C. was obtained.

Comparative Example 1 31.341 g (0,15
65 mol) of 4,4'-diaminodiphenyl ether was added and dissolved. Add 40.972g (
0.1879 mol) of pyromellitic dianhydride was added in 30 minutes and after reacting at this temperature for 3 hours, 1.203
g (0,00626 mol) of TMA was added, and the reaction was further carried out for 1 hour. After that, 14.693g (0,068
9 mol) of APMS (Meta/Bara-38/62) was added and the reaction was carried out at this temperature for 2 hours and then at 45-50°C for 2 hours to obtain a pale yellow transparent polyamic acid solution. The rotational viscosity of this solution was 680 centipoise.

Comparative Example 2 29.357 g (0,14
66 mol) of 4.4'-diaminodiphenyl ether, 35.951 g (0,1222 mol) of 3.3'
By adding 4.4'-biphenyltetracarboxylic dianhydride and 9.390 g (0,0489 mol) of TMA and carrying out the reaction at this temperature for 10 hours, the rotational viscosity at 25°C became 480 centipoise. A pale yellow transparent polyamic acid solution was obtained.

Comparative Example 3 39.348g (0
.
After adding 358 mol) of 3,3'4.4'-benzophenonetetracarboxylic dianhydride over 30 minutes and carrying out the reaction at this temperature for 6 hours, 13.413 g (0,062
9 mol) of APMS (100% bulk) was added and the reaction was carried out at this temperature for 2 hours and then at 45-50°C for 2 hours. As a result, a pale yellow transparent liquid with a rotational viscosity of 2100 centipoise at 25°C was obtained.

Comparative Example 4 29.212g (0
, 2701 mol) of p-phenylenediamine and 7.4
88+r (0,0300 mol) of 1°3-bis(3-
500 ml of N-aminopropyl)-1,1,3°3-tetramethyldisiloxane kept at 20-25°C.
After dissolving in methyl-2-pyrrolidone, 88.300 g (0,3001 mol) of 3.3', 4
．． 4'-biphenyltetracarboxylic dianhydride 3
The reaction was continued for 5 hours at this temperature, and for 4 hours at 45-50°C. As a result, a pale yellow transparent liquid with a rotational viscosity of 1300 centipoise at 25°C was obtained.

Comparative Example 5 62.530 g (0,31
23 mol) of 4,4'-diaminodiphenyl ether and 48.658 g (0.2231 mol) of pyromellitic dianhydride were added and reacted for 5 hours.
446 mol) of APMS (Para 100%) and 4.2
By adding 86 g (0,0223 mol) of TMA and further carrying out the reaction for 5 hours, a pale yellow transparent liquid with a rotational viscosity of 870 centipoise at 25° C. was obtained.

For reference, the amounts of raw materials used in Examples 1 to 8 and Comparative Examples 1 to 5, ASA' B and C (mol) and (2B
+C)/(2A+A'), A'/(A+A'
) and C/ (B+G) are shown in Table 1.

Example 9 The following adhesion test was conducted.

The various coating solutions obtained in the three examples shown in Table 1 were applied to the surfaces of glass slides, aluminum plates, and copper plates using a spinner, pre-dried at 100°C for 1 hour, and then baked at 300°C for 1 hour.
A film of 1 to 2 μm was formed.

In addition, for the adhesion test between films, the coating solutions of Examples 1 to 8 and Comparative Examples 1 and 3 were applied to the films on the slide glass formed as described above, and the coating solutions of Comparative Examples 2 and 4 were used. Regarding the liquid, the same coating liquid was applied onto each of the films formed on the aluminum plate as described above and fired under the same conditions as described above to form a laminated coating film. Each of the 4 types of coating films obtained using the 12 types of coating liquids thus obtained was cut into small square pieces of 2 m on each side, and
Cellophane tape was attached to the surface and immediately removed. Table 2 shows the number of paint film pieces that were peeled off together with the cellophane tape, expressed as a number per 100 pieces before peeling off. This clearly shows the good adhesion of polyamic acid to a wide variety of substrates by the method of the present invention.

Example 10 The following hardness measurement test was conducted.

Various coating solutions shown in Table 1 were applied to the surface of a slide glass using a spinner, dried at 100°C for 1 hour at T'41, and then baked at 200°C for 1 hour or 300°C for 1 hour.
A film of 1 to 2 μm was formed.

Table 3 shows the results of determining the pencil hardness (JIS K5400) of the surface of this film to 7111.

As is clear from the results in Tables 2 and 3, the polyimide resin obtained from the varnish obtained by the method of the present invention has the adhesive properties of the polyimide resin disclosed in JP-A No. 61-287926. It is not inferior in hardness.

Glue Example 1 Furthermore, Table 4 shows the decrease in viscosity over time when stored as a varnish. As is clear from Table 4, the varnish obtained by the method of the present invention is more stable than the polyamic acid disclosed in JP-A-61-287926 (Comparative Example 3).

〔Effect of the invention〕

The silicon-based polyimide precursor obtained by the method of the present invention can be coated on a substrate and converted into a limide by baking, so that it can be used not only for silicon compounds such as glass and silicon wafers, but also for various types of metal compounds such as aluminum and copper. Shows good adhesion to substrates. Furthermore, by similarly coating the film formed on the substrate and baking it, the interface becomes firmly bonded. Therefore, it has favorable characteristics as a multilayer or laminated material. Furthermore, the precursor of the present invention has higher storage stability and higher practical value than the precursor disclosed in JP-A-61-287926.

Claims (1)

[Claims] 1. A mole of tetracarboxylic dianhydride represented by the following formula (I), A' mole of trimellitic acid anhydride represented by the formula (II), and a diamine represented by the formula (III). B mol, formula (
A method for producing a polyamic acid, which comprises reacting C moles of aminosilane represented by IV) in the presence of a solvent in the presence of the relationships of formulas (V), (VI) and (VII). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) NH_2-R^2-NH_2(III) NH_2-R^3-SiR^4_3_-_kX_k(I
V) 0.9≦2B+C/2A+A'≦1.1 (V) 0.
9≧A'/A+A'≧0.05 (VI) C/B+C≧0.1 (VII) [In formulas (I) to (IV), R^1 is a tetravalent carbocyclic aromatic group, Represents a heterocyclic group, alicyclic group, or aliphatic group, R^2 is an aliphatic group having 2 to 12 carbon atoms, or 4 to 30 carbon atoms.
alicyclic group, aromatic aliphatic group having 6 to 30 carbon atoms, 6 carbon atoms
~30 carbocyclic aromatic groups, heterocyclic groups or the following formula (V
III), where R^3 is -(CH_2)_s-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas,
There are chemical formulas, tables, etc.▼ (where s represents an integer from 1 to 4),
R^4 independently represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group having 7 to 12 carbon atoms, X independently represents an alkoxy group, an acetoxy group, or a halogen, and k is 1≦ Takes a value of k≦3. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VIII) {Here R^5 is independently −(CH_2)_s−, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (where s represents an integer from 1 to 4),
R^6 independently represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group having 7 to 12 carbon atoms, and l takes a value of 1≦l≦100. }] 2. The aminosilane represented by the above formula (IV) has the following formula (
The method according to claim 1, characterized in that it is a compound represented by IX). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IX) (Here, R^7 independently represents a methyl group or an ethyl group.) 3. Applying the polyamic acid solution obtained by the method described in claim 1 to the substrate. A method for producing a cured polyimide product in which the solvent is volatilized and crosslinked by heating to 150 to 500°C.