JPS601227A - Production of siloxane-modified polyamic acid - Google Patents

Abstract

PURPOSE:To produce the titled acid excellent in room-temperature storage stability, by reacting a specified diaminosiloxane as a diamine component with 2,3,5- tricarboxycyclopentylacetic acid (anhydride). CONSTITUTION:The titled acid is produced by reacting a diamine mixture comprising 1-40wt% diaminosiloxane of formula I (wherein R1 is a bivalent hydrocarbon group, R2 is a monovalent hydrocarbon group, and n is 0-100), e.g., a compound of formula II, and 99-60wt% diamine other than the above diamine (e.g., p-phenylenediamine) with 2,3,5-tricarboxycyclopentylacetic acid. Unlike conventional polyamic acids, this polyamic acid is excellent in room temperature storage stability and, in addition, a polyimide obtained by the dehydrating ring closure of this acid shows excellent heat and chemical resistance, electrical and mechanical properties and low water absorption rate as well.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a siloxane-modified polyamic acid.

Polyimide, which is generally obtained by imidizing polyamic acid, has excellent heat resistance and is therefore used in films and wire coatings used at high temperatures.

Very useful as a raw material for adhesives, paints, etc.

Conventional polyimide is produced by reacting an aromatic tetracarboxylic dianhydride such as pyromellitic anhydride with an aromatic diamine in a polar solvent to obtain an aromatic polyamic acid.Secondly, a solution of this is applied to a substrate. death.

A film-like aromatic polyimide obtained by forming the film into a film and then dehydrating and ring-closing it by a method such as heating is known.

However, traditional aromatic polyimide.

9. The aromatic polyamic acid, which is a semi-precursor, has poor stability, and if left at room temperature, the viscosity of the polyamic acid solution decreases, and if left for a long time, part of it undergoes dehydration and ring closure to form polyimide.9. It has disadvantages such as becoming insolubilized and causing cloudiness. Therefore, conventional solutions of aromatic polyamic acids have to be stored at low temperatures and must be handled with care.

Furthermore, it is known that conventional polyimide has a high water absorption rate. Therefore, when used in parts for electronic materials, there have been problems in that electrical properties deteriorate and two-dimensional stability is lacking.

As a result of intensive studies to solve these drawbacks, the present inventors have developed a polyamic acid obtained by reacting a specific diaminosiloxane as one component of a diamine with 2.3.5-tricarboxycyclopentyl acetic acid or its anhydride. The solution has excellent storage stability at room temperature, and the polyimide obtained by dehydrating and ring-closing the polyamic acid is heat resistant.

The present invention was achieved by discovering that it has excellent mechanical properties, electrical properties, chemical resistance properties, etc., and also has a low water absorption rate.

That is, the present invention provides a diamine mixture consisting of 1 to 40 weight parts of diaminosiloxane represented by the following general formula and 99 to 60 weight parts of diamines other than the diaminosiloxane; The present invention provides a method for producing a siloxane-modified polyamic acid, which is characterized by reacting a polyamic acid with a siloxane-modified polyamic acid in an organic solvent.

t2R2 ■ 2R2 (R11 is a divalent hydrocarbon group, R12 is a monovalent hydrocarbon group, n is an integer of 0 to 100) 2 3.5-) IJ carboxycyclopentyl acetic acid used in the present invention (hereinafter referred to as TCA) is a method in which evadicyclopentadiene is ozonolyzed and oxidized with hydrogen peroxide (British Patent No. 87235).

J, Org, Chern, 28.2537 (1963
)).

It can be produced by a method such as oxidizing hydroxydicyclopentadiene obtained by hydrating dicyclopentadiene with nitric acid (West German Patent No. 1078120), and by dehydrating this TCA, 2,3,5 ．． −)
Licarboxycyclopentyl acetic anhydride (hereinafter TCA-
AH) can be produced.

R1 in the diaminosiloxane used in the present invention is a divalent hydrocarbon group selected from aliphatic, alicyclic, and aromatic groups.2 For example, trinothylene group, tetramethylene group, and pentamethylene group.

Cyclohexylene group, phenylene group rings are vignetted. Further, R2 is a monovalent hydrocarbon group and is an aliphatic group.

It is selected from alicyclic groups and aromatic groups, such as evamethyl, ethyl, phenyl, and cyclohexyl groups. Further, n is O to 100, and n
If it exceeds 100, the mechanical strength decreases, which is not preferable. A specific example of diaminosiloxane is:

H3CH3 H2N+CHzt'3Si-0-Si +C'H2-)
3NH□■ H3CH3 CH3C113 H2N-f C1-12+, -8 i -0-S i
-f C1-129N1-I21 CH2Cl (3 H3CH3 CH3CH3 etc. can be mentioned.

The diamine other than the diaminosiloxane has the general formula: l
-12N-R-N1-I2 (R represents a divalent aromatic group, aliphatic group, or alicyclic group).

A preferable example of R in the above general formula is 2, for example.

1 (In the formula, X1.X2.X3 and X4 may be the same or different (, -H, -CH5-j or -CH3, Y is -C
H2, -C2H4-+-〇-, -8-.

CH3CFa 1] represents 0 or 1).

-(CH2)n=(n=2-20).

CH3 (”H2)3 C(CH2)3.

Examples include an aliphatic group or alicyclic group having 2 to 20 carbon atoms and represented by CH3.

In order to further improve the heat resistance of the polyimide obtained by imidizing the polyamic acid obtained in the present invention, it is preferable that R is aromatic.

Specific examples of the above-mentioned diamine include phenylene diamine, metaphenylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-diamitediphenylethane, benzidine, 4,4'-diaminodiphenyl sulf(t+4) .4' 7-amino diphenyl sulfone, 4,4'-diaminodiphenyl ether, L5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,4'-diaminobenzanilide,
3.4'-diaminodiphenyl ether, metaxylylene diamine, paraxylylene diamine, ethylene diamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine.

Hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, 4.4
'-Dimethylhebutamethylenediamine.

1.4-diaminocyclohexane, tetrahydrodicyclopentadienylene diamine, hexahythro 4.7-
Methanoindanilene symethylene diamine.

Tricyclo[6,2,1,02.7]-landecylenedimethyldiamine and the like can be mentioned. These can be used alone or in combination.

The ratio of the diaminosiloxane to the diamine other than the diaminosiloxane is 1 to 40% by weight:99 to 60% by weight. If the diaminosiloxane is less than 1% by weight, the water absorption rate cannot be improved, and if it exceeds 40% by weight, the heat resistance and mechanical strength will decrease when the resulting polyamic acid is imidized.

The reaction solvent used in the present invention is N-methyl-2-
pyrrolidone, N,N-dimethylformamide, N,N-
Dimethylacetamide, N-alkylpyrrolidones such as N,N'-dimethylsulfoxide, and dipolar polar solvents such as N,N-dialkylamides are preferred, but general organic solvents such as alcohols, phenols, and ketones are preferred. esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons 1 such as methyl alcohol.

Ethyl alcohol, inglobil alcohol, ethylene glycol, propylene gellicol, L4-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, γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, L2-dichloroethane, ■, 4-dichlorobutane, trichloroethane, chlorobenzene, 0-dichlorobenzene, hexane, heptane, octane.

Benzene, toluene, xylene, etc. can also be used. In particular, when the above polar solvent and a general organic solvent are mixed and used, it is easy to obtain a high molecular weight polyamic acid.

For example, when TCA-AH and diamine are reacted using a solvent of about 7/3 (volume ratio) of acetone/dimethylformamide, the reaction system becomes uniform and it becomes easy to obtain a polyamic acid having a particularly high molecular weight.

The reaction ratio of the above TCA4 or TCA-AH and diamine is preferably carried out in equimolar amounts; however, as long as the purpose of the present invention is achieved, there may be a slight excess or deficiency.2 For example, TCA
or TCA-AH-mol to diamine mixture 0.
The reaction can be carried out at a ratio of about 7 to 1.3 moles.

Moreover, the molecular weight of the polyamic acid can also be adjusted by adding a monoamine or a dicarboxylic acid anhydride.

The amount of solvent used is preferably TCA4'I'CA・A
It is 0.5 to 20 times the weight of the total amount of H and diamine mixture.

In the present invention, the reaction temperature for producing polyamic acid varies depending on whether TCA or TCA-AH is used as a starting material, and when rCA is used as a starting material, the reaction temperature is usually 2 to perform dehydration condensation.

It is effective to carry out the reaction at 50-300°C, preferably 100-250'C. On the other hand, when TCA/AH is used as a raw material, addition polymerization is performed, and the reaction does not necessarily have to be carried out at a high temperature; it is usually sufficient to carry out the reaction at a temperature of 20 to 100°C.

In general, 'I'CA and 'l'CA-A) (and TC
It is preferable to use dianhydride for A.AH,%.

It becomes easy to produce polyamic acid that is soluble in organic solvents.

Intrinsic viscosity ηi of the polyamic acid obtained in this way
n b (concentration 0.5 g/100 ml 1. solvent N.

N'-dimethylacetamide, measurement temperature 30'C) is preferably 0.05 dl/g or more, particularly preferably 0.0
It is 5 to 20 dl/g. Note that the intrinsic viscosity ηinh is.

(t is the flow rate of the polymer solution, to is the flow rate of N,N'-dimethylacetamide).

The polyamic acid obtained according to the present invention is easily soluble in a solvent, and even if some of the amide bonds are imidized, it is soluble in the solvent, so it is very stable in a solution state.

The obtained organic solvent solution of polyamic acid was used as it was.
Or after recovering polyamic acid from an organic solvent solution by a conventional method and purifying it as necessary.

The diimidization reaction can also be carried out by dissolving the mixture in an organic solvent again, adding a tertiary amine if desired in the presence of an organic carboxylic acid anhydride, and heating in the organic solvent. Soluble polyimide can be easily produced. Examples of the organic solvent in this case include the same organic solvents as mentioned above, and the concentration of the organic solvent solution of polyamic acid is preferably 1 to 50% by weight, particularly preferably 1 to 30% by weight. Furthermore, the boiling point of the organic carboxylic acid anhydride used during the imidization reaction is 250°C.
It is preferable that the following is true. If the boiling point of the organic carboxylic acid anhydride exceeds 250°C, the organic carboxylic acid anhydride will not be removed at the same time during the process of removing the solvent by heating during film formation, and will remain in the film, resulting in adverse effects on physical properties, etc. have a negative impact. As described above, as an organic carboxylic acid anhydride.

For example, acetic anhydride, propionic anhydride, butyric anhydride.

Inbutyric anhydride, valeric anhydride, etc. are used. Mixed acid anhydrides 9 of these organic carboxylic acids, such as acid anhydrides obtained from acetic acid and propionic acid, can also be used. The amount of the organic carboxylic acid anhydride added is preferably 0.2 to 20 moles per mole of repeating structural unit of polyamic acid. 0.2
When the amount is less than 2 times the mole, the imidization reaction progresses slowly, and when it exceeds 20 times the amount, the solubility of the polyamic acid in the organic solvent decreases. Furthermore, in order to promote the imidization reaction, a tertiary amine can be added as a catalyst if desired. In addition to promoting the imidization reaction, the tertiary amine also has the effect of suppressing a decrease in the solution viscosity of the resulting polyimide. Tertiary amine.

The boiling point is 250 for the same reason as in the case of organic carboxylic acid anhydrides.
℃ or less, preferably 9. For example, aliphatic tertiary amines such as triethylamine, tripropylamine, and tributylamine, aromatic 3R amines such as N,N-dimethylaniline, pyridine, 2-methylpyridine, N-methylimidazole, and quinoline. Examples include heterocyclic compounds such as. The amount of the tertiary amine added is preferably 920 times or less per mole of repeating structural unit of the polyamic acid. When the amount exceeds 20 times the mole, the solubility of polyamic acid in organic solvents tends to decrease. The reaction temperature of the imidization reaction is preferably 60 to 200°C, particularly preferably 100 to 170°C. If the temperature is lower than 60°C, the progress of the imidization reaction will be delayed, and if the temperature exceeds 200°C, the molecular weight of the polyimide will decrease significantly. The organic carboxylic acid anhydride and the tertiary amine may be added in either order, or they may be added after being mixed together.

The polyimide thus obtained is produced by casting an organic solvent solution of the polyimide after two reactions onto a base material such as a glass plate or a metal plate, and then applying the organic solvent and organic carboxylic acid by heating or other methods. Film formation can be achieved by removing the anhydride and tertiary amine. Furthermore, after the polyimide is recovered from the organic solvent solution of the polyimide after the reaction, it can be redissolved in the organic solvent and then formed into a film by the above method. In addition to the above-mentioned polar solvents, the organic solvent used for this redissolution includes the solvent 2 that dissolves polyimide.
For example, phenol, metacresol.

Examples of imidization methods for polyamic acids include para-cresol and phenolic solvents that are a mixture of these. An example is a method of heating at 100 to 500° C. while or after removing.

In the polyamic acid obtained according to the present invention, a stabilizer such as an antioxidant is added to the polyamic acid, for example, 1.0. About 1 to 5 parts by weight of O may be added, and about 1 to 100 parts by weight of an additive such as a filler may be added, for example, to 100 parts by weight of polyamic acid.

The polyimide using polyamic acid as a precursor obtained by the present invention exhibits excellent properties such as heat resistance, 9 mechanical properties, electrical properties, and chemical resistance, and furthermore has a low water absorption rate. It is useful for films, adhesives, paints, etc. Specifically, it is useful for printed wiring boards, surface protective films or glabellar insulating films for flexible semiconductor integrated circuit elements, coating materials for enameled electric wires, various laminates, gaskets, etc. .

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

(CH2)3NH20. 47 g and 4.11 g of diaminodiphenyl ether were added, 46.2 g of N,N-dimethylformamide (DMF') was added and stirred, and then 4.75 g of TCA-AH was added as a powder and reacted at room temperature for 24 hours. . The obtained polyamic acid has a ηInh in DMF of 1. 8 7 dl/g
Met. DMF51.
After diluting by adding 1 g, add acetic anhydride 9, 4 while stirring.
After adding 10.2 g of pyridine, the mixture was reacted at 120° C. for 2 hours. The obtained polyimide was poured into a large amount of methanol and coagulated. After collecting this polyimide, it was heated to 80℃ for 1
Vacuum drying was performed for 2 hours.

The ηinh of this polyimide in DMF at 30°C is 1.29
It was de/g. This polyimide was dissolved again in DMF and cast onto a glass plate, and then dried at 80°C for 1 hour.
The film was peeled off and vacuum dried at 150°C for 24 hours. The film thickness at this time was about 50 μm. This film was cut into a certain area and immersed in distilled water at 23°C for 10 hours. After taking out the film, both sides of the film were wiped off. After being left at room temperature for 2 hours, the weight increase of this film was measured. did. As a result, the water absorption rate was 2.9%. After vacuum drying this film at 100°C overnight,
Results of tensile test according to JISK6911.

Tensile strength8. 5 Kg/crJ, and elongation was 25%.

Example 2 The same procedure as in Example 1 was carried out except that 0.97 g of diaminosiloxane and 3.99 g of diaminodiphenyl ether were used in Example 1, and ηinh was 1.48 at/
After synthesizing the polyamic acid (g), it was imidized in the same manner as in Example 1. ηinh of polyimide is 1.04 dl/g
Met. The water absorption rate of this polyimide was 1.8.

Example 3 A polyamic acid with an ηinh of 0.95 dl/g was synthesized in the same manner as in Example 1 except that 2.11 g of diaminosiloxane and 3.72 g of diaminodiphenyl ether were used in Example 1, and then the same as in Example 1 was used. It was imidized in the same way. The ηinh of the polyimide was 0.68 dl/g. The water absorption rate of this polyimide was 1.1%.

Comparative Example 1 Polyamic acid with ηinh of 2.34 dl/g was synthesized in the same manner as in Example 1 except that 4.23 g of diaminodiphenyl ether was used instead of the diamine mixture of Example 1, and then It was imidized in the same way. The ηinh of the polyimide was 1.26 dl/g. The water absorption rate of this polyimide was 4.2.

Patent application/person Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Scope of Claims] A diamine mixture consisting of 1 to 40% by weight of a diaminosiloxane represented by the following general formula and 99 to 60% by weight of a diamine other than the diaminosiloxane, and 2.35-)licarboxycyclopentyl acetic acid or its anhydride. A method for producing a siloxane-modified polyamic acid R2R, which comprises reacting the above in an organic solvent. 1 R, 2R2 (R1 is a divalent hydrocarbon group, 几2 is a monovalent hydrocarbon group, n is an integer from 0 to 100)