JPH0841200A - Polyimide silicone and its production - Google Patents

Abstract

PURPOSE:To obtain a polyimide silicone excellent in adhesion, heat resistance and solvent resistance, too. CONSTITUTION:This silicone essentially consists of structural units represented by formula I (wherein X is a tetravalent organic group; Y is a bivalent organic group; and n is an integer of 1 or greater) and structural units represented by formula II (wherein R<1> is a 1-6 C monovalent organic group; (m) is an integer of 2-8; and (a)is an integer of 0-2).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide silicone having excellent adhesiveness and heat resistance and a method for producing the polyimide silicone.

[0002]

2. Description of the Related Art Polyimide is excellent in heat resistance, mechanical strength, pattern formability, etc., and can be highly purified, so that it is widely used in the electronic industry field.

Polyimide generally has a drawback that it has poor adhesion to an inorganic material substrate such as a silicone wafer. As a polyimide having improved adhesion to an inorganic material substrate, a polyimide silicone having a siloxane bond introduced into its skeleton has been proposed. For example, US Pat.
Japanese Patent No. 325,450 discloses a method for producing a polyimide silicone by using diaminosiloxane as a diamine component which is a starting material for producing a polyimide and reacting the diaminosiloxane with a tetracarboxylic acid component. . Further, in JP-A-64-85220 and JP-A-61-159425, a tetracarboxylic acid dianhydride having a siloxane bond is used as a tetracarboxylic acid component, and the tetracarboxylic acid dianhydride and diamine are used. A method of producing a polyimide silicone by reacting with components is disclosed.

[0004]

However, although the polyimide silicone obtained by the above method has improved adhesiveness, it has a problem that it is inferior in heat resistance as compared with a polyimide having no siloxane bond in the skeleton. is there.

Therefore, the object of the present invention is to provide excellent adhesiveness,
Moreover, it is to provide a polyimide silicone having excellent heat resistance and a method for producing the polyimide silicone.

[0006]

In order to solve the above problems, the present invention provides at least the following general formula (1):

[Chemical 12] (In the formula, X is a tetravalent organic group, and when there are a plurality of X, they may be the same or different. Y is a divalent organic group, and when there are a plurality of Y, they are May be the same or different. N is an integer of 1 or more) and the following general formula (2):

[Chemical 13] (In the formula, R ¹ is a monovalent organic group having 1 to 6 carbon atoms, and when plural R ¹ are present, they may be the same or different. M is an integer of 2 to 8; And particularly preferably 3. a is an integer of 0 to 2) is provided.

The present invention also has the following general formula (3):

Embedded image (In the formula, X is as described above, and when there are a plurality of X, they may be the same or different. Y is as described above, and when there are a plurality of Y, they are the same or different. And n is as described above.) And a polyamic acid represented by the following general formula (4):

[Chemical 15] (In the formula, R ¹ is as described above, and when plural R ¹ are present, they may be the same or different. M and a are also as described above. R ² and R ³ are the same. Or may be different, and each has a hydrogen atom or a carbon atom number of 1 to 3.
Is a monovalent organic group. However, at least one of R ² and R ³ is a hydrogen atom. And a polysiloxane having a unit represented by the formula (3) is mixed and heated.

Further, the present invention provides X in the general formula (1).
However, the following equation (5):

Embedded image A group represented by the following formula (6):

[Chemical 17] And a group represented by the following formula (7):

Embedded image Is at least one group selected from the group consisting of groups represented by: and Y is the following formula (8):

[Chemical 19] And a group represented by the following formula (9):

Embedded image (In the formula, a plurality of R ⁶ may be the same or different and are a divalent organic group, and a plurality of R ⁷ may be the same or different,
It is a monovalent organic group. ) A method for producing the above-mentioned polyimide silicone, which is at least one group selected from the group consisting of groups represented by the following general formula (10):

[Chemical 21] (In the formula, X'is at least one group selected from the group consisting of groups represented by the above formulas (5) to (7), and Y'is
It is at least one group selected from the group consisting of groups represented by the above formulas (8) and (9), and n is as described above. And a polysiloxane having a unit represented by the above general formula (4) is mixed and heated.

Polyimide Silicone The polyimide silicone of the present invention contains at least the constitutional unit represented by the general formula (1) and the constitutional unit represented by the general formula (2).

X in the general formula (1) is a tetravalent organic group, and when a plurality of Xs are present, they may be the same or different. As a typical example of X,

[Chemical formula 22] However, the present invention is not limited to these.

Y in the general formula (1) is a divalent organic group, and when a plurality of Y's are present, they may be the same or different. Examples of Y include, for example, the following general formula (11):

[Chemical formula 23] (In the formula, plural R ^{4 s} may be the same or different, and are —H,
-Cl, -CONH ₂ or _{example, -CH 3, -C 2 H 5} , -C
It is an alkyl group having 1 to 3 carbon atoms such as ₃ H ₇ . ) Group represented by

The following general formula (12):

[Chemical formula 24] (In the formula, a plurality of R ⁴ may be the same or different and are as described above. R ⁵ is a single bond, —O—, —SO ₂ —, —S.
- or, for _{example, -CH 2 -, - C (} CH 3) 2 -, - C (CF 3)
_{It is} a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms such as 2-. ) Group represented by

The following general formula (13):

[Chemical 25] (In the formula, a plurality of R ⁴ may be the same or different as described above, and a plurality of R ⁵ may be the same or different as described above.),

The following general formula (14):

[Chemical formula 26] (In the formula, a plurality of R ⁴ may be the same or different and are as described above, and R ⁵ is as described above.),

The following general formula (15):

[Chemical 27] (In the formula, a plurality of R ⁶ may be the same or different, and examples thereof include an alkylene group having 3 to 4 carbon atoms (eg, -C _{3
H 6 -, - C 4 H} 8 - , etc.), a phenylene group, the formula:

[Chemical 28] It is a divalent organic group such as a group represented by. A plurality of R ^7's may be the same or different, and include, for example, an alkyl group having 1 to 3 carbon atoms (eg, —CH ₃ , —C ₂ H ₅ , —C ₃ H).
₇ ), monovalent organic groups such as phenyl groups. k is 1
It is an integer of 40. Group having a siloxane bond represented by

The following general formula (16):

[Chemical 29] (In the formula, a plurality of R ⁷ may be the same or different as described above. R ⁸ is an ethylene group or a phenylene group. A plurality of R ⁹ may be the same or different.
C ₃ H ₆ -, - an alkylene group having 3-4 carbon atoms, such as - C ₄ H _8. And a group having a silethylene bond or a silphenylene bond.

In the above general formula (1), n is an integer of 1 or more, preferably 4 to 70.

R ¹ in the general formula (2) is ¹ carbon atom.
In the case where a plurality of R ^1's are present, they may be the same or different. As R ¹ ,
Specific examples thereof include a methyl group, an ethyl group and a phenyl group.

The content ratio of the structural unit represented by the above general formula (1) is usually 50 to 99% by weight, preferably 7
5 to 98% by weight. The content of the structural unit represented by the general formula (2) is usually 1 to 50% by weight, preferably 2 to 25% by weight.

The polyimide silicone of the present invention has, in addition to the constitutional unit represented by the general formula (1) and the constitutional unit represented by the general formula (2), for example, the constitutional unit shown below. Good. (R ¹⁰ ) _b SiO _{(4-b) / 2} units (where
A plurality of R ^10's may be the same or different and each is a hydrogen atom or 1
It is a valent organic group, and is an alkyl group such as a methyl group, an ethyl group or a propyl group, or an aryl group such as a phenyl group. b is an integer of 0-3. ),

Embedded image A unit (where R ¹ , a and m are as described above),

[Chemical 31] A unit (where X is the same as X in the general formula (1)),

Embedded image Unit (where X and Y are the same as X and Y in the general formula (1)).

The molecular weight of the polyimide silicone of the present invention is usually in the range of 1,000 to 30,000, preferably 2,000 to 20,000.

Method for Producing Polyimide Silicone The polyimide silicone of the present invention can be produced , for example, by the above general formula.
The polyamic acid represented by the formula (3) and the polysiloxane having the unit represented by the general formula (4) are usually used in the amount of 250
It can be produced by heating at ~ 400 ° C for 0.5 to 3 hours. Both reaction components are usually used in the reaction in a well mixed state.

Polyamic Acid The polyamic acid represented by the above general formula (3) can be produced by a conventional method. For example, the following general formula (17):

[Chemical 33] (In the formula, X is as described above.) And a tetracarboxylic dianhydride represented by the following general formula (18): H ₂ N—Y—NH ₂ (18) (In the formula, Y is the above. And a diamine compound represented by the formula (1), tetracarboxylic dianhydride is usually 0.98 to 1.02 mol, preferably 0.99 to 1.01 per 1 mol of the diamine compound. When dissolved in a suitable inert solvent so as to have a molar ratio and mixed and stirred at 0 to 80 ° C., preferably 25 to 40 ° C., the viscosity of the solution gradually rises and is represented by the above general formula (3). Polyamic acid is generated. However, the manufacturing method is not limited to this.

Examples of the inert solvent used for producing the polyamic acid include tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Triethylene glycol dimethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, γ-butyrolactone, butyl cellosolve acetate, butyl acetate,
Ethyl acetate, N-methyl-2-pyrrolidone, N,
Examples thereof include N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoramide, toluene and xylene. These are used alone or in combination of two or more.

Examples of the tetracarboxylic dianhydride represented by the above general formula (17) include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propanoic acid dianhydride, 2,2-bis (3,4) -Dicarboxyphenyl) perfluoropropanoic acid dianhydride, bis (3,4-dicarboxyphenyl)
Dimethylsilane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, bis (3,4-dicarboxyphenyl) sulfone, etc. And these can be used alone or
Combinations of more than one species can be used.

Examples of the diamine compound represented by the above general formula (18) include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and 2,2 '.
-Bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-amino) Phenoxy)
Benzene, 1,4-bis (m-aminophenylsulfonyl) benzene, 1,4-bis (p-aminophenylsulfonyl) benzene, 1,4-bis (m-aminophenylthioether) benzene, 1,4-bis ( p-aminophenyl thioether) benzene, 2,2-bis [4-
(4-Aminophenoxy) phenyl] propane, 2,2
-Bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4-
(4-Aminophenoxy) phenyl] propane, 1,1
-Bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- ( 4-aminophenoxy) phenyl] ethane,
1,1-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4
-(4-aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] methane, bis Aromatic diamine compounds such as [4- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane;

For example, the following formula:

Embedded image A diamine compound having a siloxane bond such as

For example, the following formula:

Embedded image Examples thereof include diamine compounds having a silethylene bond or a silphenylene bond, but are not limited thereto. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

Polysiloxane Polysiloxane has a unit represented by the above general formula (4). R ² and R ³ in the general formula (4) are each a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and specific examples of the monovalent organic group include a methyl group. , An alkyl group such as an ethyl group and a propyl group; for example, a vinyl group,
An alkenyl group such as an allyl group is exemplified. Preferred among the monovalent organic groups are a methyl group and an ethyl group. R ² and R ³ may be the same or different, but at least one of R ² and R ³ must be a hydrogen atom. In addition, the above-mentioned general formula (4) is added to the polysiloxane.
When a plurality of units represented by are included, a plurality of R ² may be the same or different, and a plurality of R ³ may be the same or different.

The polysiloxane preferably contains the unit represented by the general formula (4) in an amount of 5 mol% or more, and more preferably 20 to 100 mol% in all units.

The polysiloxane is represented by the general formula (4) above.
In addition to the unit represented by, for example, the following general formula (19): (R ¹⁰ ) _b SiO _{(4-b) / 2} (19) (In the formula, plural R ¹⁰ may be the same or different, An atom or a monovalent organic group, an alkyl group such as a methyl group, an ethyl group and a propyl group, an aryl group such as a phenyl group, and b is an integer of 0 to 3). can do.

Polysiloxane can be obtained, for example, by the following general formula (2
0):

Embedded image (In the formula, R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and when a plurality of R ¹¹ are present, they may be the same or different. R ¹ is as described above, and R ¹ is When a plurality of them are present, they may be the same or different. A and m are as described above) and, if necessary, for example, the following general formula (21): (R _{^{10) b Si (OR 11)}} (4-b) (21) ( wherein, R ¹⁰ is as defined above, may .R ¹¹ or different from those of the same in the case where R ¹⁰ there are a plurality of As described above, when a plurality of R ^11's are present, they may be the same or different. B is as described above.) It is produced by hydrolyzing and condensing an alkoxysilane. be able to.

The alkoxysilane represented by the general formula (20) is

Embedded image When

[Chemical 38] (Here, R ¹ , R ¹¹ and a are as described above.)
It is produced by hydrosilylation of and with a transition metal catalyst, particularly a platinum-based catalyst.

The polyimide silicone of the present invention comprises one kind or a combination of two or more kinds of the polyamic acid represented by the general formula (3) and a polysiloxane having a unit represented by the general formula (4). It can be produced by mixing and heating the seeds or a combination of two or more kinds. In that case, the amount of the polysiloxane is preferably 1 to 50 parts by weight, more preferably 2 to 25 parts by weight, based on 100 parts by weight of the polyamic acid.

When the polyamic acid and the polysiloxane are heated, first, the following formula (a) and
(b):

[Chemical Formula 39] And then react with the following formula (c):

[Chemical 40] It is presumed that they react with each other to produce polyimide silicone.

A solution of the polyamic acid represented by the general formula (3) and the polysiloxane having the unit represented by the general formula (4) in an appropriate organic solvent is prepared in advance. It is possible to save it. The solution is prepared, for example, by adding a solution prepared by dissolving the polysiloxane in an organic solvent to the solution prepared by producing the polyamic acid and mixing them.

Any organic solvent can be used without particular limitation as long as it can dissolve the polyamic acid and the polysiloxane, and examples thereof include inert solvents used in the production of the polyamic acid. . The organic solvent is used alone or as a mixed solvent of two or more kinds. The amount of the organic solvent used is not particularly limited, but is such that the total concentration of the polyamic acid and the polysiloxane is usually 1 to 60% by weight, preferably 3 to 40% by weight. And Further, the viscosity of the solution at 25 ° C. is preferably 5 to 15,000 cP.

The above solution has little change in viscosity even after 3 months from preparation, does not gel, and has excellent storage stability. This solution is applied to a substrate such as a glass plate, dried by heating at 100 to 200 ° C. for 0.5 to 3 hours, and then heat-cured at 250 to 400 ° C. for 0.5 to 3 hours to obtain adhesiveness. Also, a polyimide silicone coating having excellent heat resistance can be formed.

Method for Producing Polyimide Silicone Among the polyimide silicones of the present invention, X in the general formula (1) is at least one selected from the group consisting of groups represented by the above general formulas (5) to (7). And Y is at least one selected from the group consisting of the groups represented by the general formulas (8) and (9) (hereinafter referred to as polyimide silicone II) is represented by the general formula (10). It can be produced by mixing the polyimide represented by the formula (1) and the polysiloxane having the unit represented by the general formula (4), and generally heating at 100 to 300 ° C. for 0.5 to 4 hours.

Polyimide Polyimide is represented by the above general formula (10). Generally, polyimide is insoluble in general-purpose organic solvents except some high-boiling organic solvents, polyimide represented by the general formula (10), various organic solvents, for example, polyamic acid of the above. It is soluble in the inert solvent used in production.

The polyimide represented by the general formula (10) is
It can be manufactured according to a conventional method. For example, in the general formula (17), X is at least one tetracarboxylic dianhydride which is a group represented by the general formula (5), (6) or (7), and the general formula (18) ), Y is at least one diamine compound represented by the general formula (8) or (9), and tetracarboxylic dianhydride is 0.5 to 0 per 1 mol of the diamine compound. 0.99 mol, preferably 0.8
It is dissolved in the inert solvent used in the production of the polyamic acid so as to be ˜0.99 mol, and usually -20 to 80
The polyamic acid is produced by mixing and stirring at 0 ° C., preferably 0 to 50 ° C.
It is produced by heating at 00 to 200 ° C. to perform dehydration ring closure. In the case of dehydration ring closure, it is preferable to use an azeotropic dehydrating agent such as toluene or xylene in order to facilitate dehydration.

In the production of polyimide silicone II,
The amount of the polyimide compounded is preferably such that the ratio of the amine equivalent of the terminal amino group of the polyimide to the carboxy equivalent of the polysiloxane is 1: 2, and further 100 to 100 parts by weight of the polysiloxane. 10,000
The amount is preferably parts by weight, and particularly preferably in the range of 300 to 5000 parts by weight.

When the polyimide and the polysiloxane are heated, the polysiloxane first reacts as in the above formula (a) and then as in the above formula (c) to form polyimide silicone II. It is estimated that

A solution prepared by dissolving the polyimide represented by the general formula (10) and the polysiloxane in a suitable organic solvent is stable as a varnish. The solution is prepared, for example, by adding a solution prepared by dissolving the polysiloxane in an organic solvent to the solution used for producing the polyimide.

The above solution is coated on a substrate, and 100-2
Heat drying at 00 ° C for 0.5-3 hours, then 100-3
By heat-curing at 00 ° C. for 0.5 to 2 hours, a film of polyimide silicone II having excellent adhesiveness and heat resistance can be formed.

Utility The polyimide silicone of the present invention is excellent in adhesiveness and heat resistance, and is also excellent in solvent resistance. Also, the dielectric constant,
Physical properties such as mechanical strength, dielectric breakdown strength, and volume resistivity are also excellent as in the conventional ones. Therefore, for example, a junction coat film, a passivation film, a buffer coat film, an α-ray shielding film such as an LSI, an interlayer insulating film of a multi-layer wiring, and a conformal printed circuit board on the surface of a semiconductor element such as a diode, a transistor, an IC, an LSI It is extremely useful as a coating, an alignment film for liquid crystal display devices, a protective film for electric / electronic parts such as an ion implantation mask, and the like.

[0047]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Preparation of polysiloxane Preparation of polysiloxane 5- (3-trimethoxysilylpropyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride 16.32 g of methylisobutyl In ketones,
Hydrolysis and condensation were carried out by adding a 3-fold molar amount of water. The obtained product was washed with water and dried.

Thus, the following formula:

Embedded image 10.8 g of polysiloxane having a unit represented by the following formula was obtained. The weight average molecular weight of the polysiloxane measured by GPC was about 3,000.

Preparation of polysiloxane 4.8 g of methanol was added to 16.32 g of 5- (3-trimethoxysilylpropyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride. , 8
Heated at 0 ° C. for 1 hour. 2.7 g of water was added to the reaction product in methyl isobutyl ketone for hydrolysis and condensation,
The obtained product was washed with water and dried.

Thus, the following formula:

Embedded image as well as

[Chemical 43] Thus, 9.2 g of polysiloxane having a unit represented by the following formula was obtained. The weight average molecular weight of the polysiloxane was about 2,800 as measured by GPC.

Preparation of polysiloxane 16.32 g of 5- (3-trimethoxysilylpropyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride in methylisobutylketone. Hydrolysis / condensation was carried out by adding 3-fold molar amount of water. The obtained product was washed with water.

Thus, the formula:

[Chemical 44] 10.8 g of polysiloxane having a unit represented by the following formula was obtained. The weight average molecular weight of the polysiloxane measured by GPC was about 3,000.

Example 1 In 75.0 g of N-methyl-2-pyrrolidone, 3,
15.42 g of 3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride and 9.58 g of 4,4'-diaminodiphenyl ether were reacted at room temperature to give the following formula:

Embedded image (In the formula, n ¹ has an average value of about 26.) N-methyl-2-pyrrolidone solution 100 of polyamic acid
g was obtained.

N-methyl-2 of the obtained polyamic acid
-To the pyrrolidone solution, add 1.25 g of polysiloxane N
A solution obtained by dissolving 5.0 g of -methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature for 1 hour to obtain a composition.
The nonvolatile concentration of the composition was 23.8% by weight (measured by heating at 200 ° C. for 1 hour), and the viscosity at 25 ° C. was 6300 cP.

Further, in order to investigate the storage stability of the obtained composition, the viscosity at 25 ° C. after storing at 5 ° C. for 3 months was measured. Table 1 shows the results.

Next, the obtained composition was applied onto a substrate, heated at 150 ° C. for 1 hour, and further heated at 350 ° C. for 1 hour to be cured to form a polyimide silicone film. A glass plate and a silicone wafer were used as the substrate.

The polyimide silicone obtained was analyzed by IR spectrum, and the following formula was obtained:

Embedded image (Wherein n ¹ is as described above) (93.5% by weight), the following formula:

[Chemical 47] The structural unit represented by (1.8% by weight), the following formula:

Embedded image as well as

[Chemical 49] It was confirmed to consist of the structural unit represented by (4.7% by weight).

The adhesiveness of the obtained polyimide silicone film to each substrate was examined by a cross-cut peeling test as described below. Table 1 shows the results.

Cross-cut peeling test In accordance with JIS K 5400, 100 cross-cuts were provided on the cured film at intervals of 1 mm, and the number of squares remaining when the adhesive tape was attached and peeled off was counted. .

The heat resistance of the obtained polyimide silicone film was examined using a differential thermal balance. Table 1 shows the thermal decomposition start temperature.

Example 2 N-methyl-2-polyamic acid used in Example 1
100 g of pyrrolidone solution, 1.25 polysiloxane
A solution obtained by dissolving 5.0 g of N-methyl-2-pyrrolidone in 5.0 g was added, and the mixture was stirred at room temperature for 1 hour to obtain a composition. The nonvolatile concentration of the composition is 23.9% by weight (20%
Measured by heating at 0 ° C for 1 hour), 25 ° C
The viscosity at was 6320 cP.

The storage stability of the obtained composition was examined in the same manner as in Example 1. Table 1 shows the results.

A polyimide silicone film was formed in the same manner as in Example 1 by using the obtained composition.

The obtained polyimide silicone was analyzed by IR spectrum, and the following formula:

Embedded image (In the formula, n ¹ is as described above.) A structural unit (93.6% by weight) represented by the following formula:

[Chemical 51] The structural unit represented by (1.8% by weight), the following formula:

Embedded image as well as

Embedded image Was confirmed to consist of the structural unit represented by (4.6% by weight).

The adhesion of the obtained polyimide silicone film to each substrate was examined in the same manner as in Example 1. Table 1 shows the results.

Further, the heat resistance of the obtained polyimide silicone film was examined by using a differential thermal balance. Table 1 shows the thermal decomposition start temperature.

Comparative Example 1 N-Methyl-2-polyamic acid used in Example 1
A composition prepared by adding 1.25 g of 3-aminopropyltriethoxysilane in 5.0 g of N-methyl-2-pyrrolidone to 100 g of the pyrrolidone solution was prepared.
The viscosity of the composition at 25 ° C. was 5800 cP.

The storage stability of the obtained composition was examined in the same manner as in Example 1. Table 1 shows the results.

Further, using the obtained composition, Example 1
A polyimide silicone film was formed in the same manner as in. The adhesiveness of the obtained polyimide silicone film to each substrate was examined in the same manner as in Example 1. Table 1 shows the results.

Further, the heat resistance of the obtained polyimide silicone film was examined by using a differential thermal balance. Table 1 shows the thermal decomposition start temperature.

Comparative Example 2 In 75.0 g of N-methyl-2-pyrrolidone, 3,
At room temperature, 15.42 g of 3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 8.62 g of 4,4'-diaminodiphenyl ether and 1.19 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane. The following formula:

[Chemical 54] (In the formula, p, q, and r are integers of 1 or more, and p: q =
100 g of an N-methyl-2-pyrrolidone solution of a polyamic acid represented by 9: 1) was obtained. 25 ° C of the solution
The viscosity at 6200 was 6200 cP.

The storage stability of the above solution was examined in the same manner as in Example 1. Table 1 shows the results.

A polyimide silicone film was formed in the same manner as in Example 1 by using the obtained solution. The adhesiveness of the obtained polyimide silicone film to each substrate was examined in the same manner as in Example 1. Table 1 shows the results.

Further, the heat resistance of the obtained polyimide silicone film was examined by using a differential thermal balance. Table 1 shows the thermal decomposition start temperature.

[0076]

[Table 1]

Example 3 22.7 g (0.051 mol) of 2,2-bis (3,4-dicarboxyphenyl) perfluoropropanoic acid dianhydride and 90 g of diethylene glycol dimethyl ether were added to a reaction vessel under a nitrogen atmosphere. And then 2,2-
A solution of 24.6 g (0.060 mol) of bis [4- (4-aminophenoxy) phenyl] propane dissolved in 70 g of diethylene glycol dimethyl ether was added dropwise, and the resulting mixture was stirred for 12 hours to obtain a polyamic acid. . Next, after attaching a reflux condenser with a water receiver to the reaction vessel, 20 g of xylene was placed in the reaction vessel.
Was added, and the mixture in the reaction vessel was heated to 150 ° C.,
The polyamic acid was imidized by heating at this temperature for 4 hours. After the reaction was completed, the solution in the reaction vessel was cooled and then reprecipitated with methanol.

Thus, the following formula:

[Chemical 55] 45.2 g of a polyimide compound represented by (n ² is about 6 on average) is obtained.

After dissolving 40 g of the obtained polyimide compound in 160 g of diethylene glycol dimethyl ether, a solution of 4.2 g of polysiloxane in 15 ml of tetrahydrofuran was added thereto, and the mixture was stirred until it became uniform. The resulting composition was a homogeneous solution.

Next, the obtained composition was applied onto a substrate, heated at 150 ° C. for 1 hour, and further heated at 250 ° C. for 1 hour to be cured to form a polyimide silicone film. A silicon wafer was used as the substrate.

The polyimide silicone obtained was analyzed by IR spectrum, and the following formula was obtained:

[Chemical 56] (N ² is as described above), a structural unit (83.2% by weight) represented by the following formula:

[Chemical 57] The structural unit represented by (9.2% by weight), the following formula:

Embedded image as well as

Embedded image It was confirmed that the polymer was composed of a structural unit represented by (7.6% by weight).

The adhesiveness of the obtained polyimide silicone film to a silicone wafer was examined by a cross-cut peeling test as described below. The results are shown in Table 2.

Cross-cut peeling test According to JIS K 5400, 100 cross-cuts were formed on the cured film at 1 mm intervals, and the number of squares remaining when the adhesive tape was peeled off was counted.

The heat resistance of the obtained polyimide silicone film was examined using a differential thermal balance. Table 2 shows the thermal decomposition start temperature.

Further, in order to examine the solvent resistance of the obtained polyimide silicone film, it was immersed in diethylene glycol methyl ether, and whether or not it was dissolved was visually observed. The results are shown in Table 2.

Comparative Example 3 Under a nitrogen atmosphere, 22.2 g (0.05 mol) of 2,2-bis (3,4-dicarboxyphenyl) perfluoropropanoic acid dianhydride and 80 g of diethylene glycol dimethyl ether were added to a reaction vessel. And then 2,2-bis [4- (4-aminophenoxy) phenyl] propane
A solution of 20.5 g (0.05 mol) dissolved in 60 g of diethylene glycol dimethyl ether was added dropwise, and the resulting mixture was stirred for 12 hours to obtain a polyamic acid.
Next, after attaching a reflux condenser with a water receiver to the reaction vessel, 20 g of xylene was added to the reaction vessel, the mixture in the reaction vessel was heated to 150 ° C., and heated at that temperature for 4 hours. By doing so, the polyamic acid was imidized. After the reaction was completed, the solution in the reaction vessel was cooled and then reprecipitated with methanol.

Thus, the following formula:

Embedded image 37.2 g of a polyimide compound represented by (n ³ is about 18 on average) was obtained.

10 g of the obtained polyimide compound was dissolved in 40 g of diethylene glycol dimethyl ether to prepare a polyimide composition solution.

Next, using the composition thus obtained, Example 3 was used.
A polyimide silicone film was formed in the same manner as in. The adhesion of the obtained polyimide silicone film to a silicone wafer was examined in the same manner as in Example 3. The results are shown in Table 2.

The heat resistance of the obtained polyimide silicone film was examined using a differential thermal balance. Table 2 shows the thermal decomposition start temperature.

Further, in order to examine the solvent resistance of the obtained polyimide silicone film, it was immersed in diethylene glycol methyl ether, and whether or not it was dissolved was visually observed. The results are shown in Table 2.

Comparative Example 4 Under a nitrogen atmosphere, 80 g of diethylene glycol dimethyl ether was added to 22.2 g (0.05 mol) of 2,2-bis (3,4-dicarboxyphenyl) perfluoropropanoic acid dianhydride in a reaction vessel. And then 2,2-bis [4- (4-aminophenoxy) phenyl] propane 1
4.37 g (0.035 mol) and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 3.73 g (0.015 mol) were dissolved in 60 g of diethylene glycol dimethyl ether. The solution was added dropwise, and the resulting mixture was stirred for 12 hours to obtain a polyamic acid. Next, after attaching a reflux condenser with a water receiver to the reaction vessel, 20 g of xylene was added, the mixture in the reaction vessel was heated to 150 ° C., and heated at that temperature for 4 hours to obtain a polyamic acid. Was imidized. After completion of the reaction, cool the solution in the reaction vessel,
It was reprecipitated with methanol.

Thus, the following formula:

[Chemical formula 61] (In the formula, s, t, and u are integers of 1 or more,
s: t = 7: 3) polyimide compound 3 represented by
2.5 g was obtained.

10 g of the obtained polyimide compound was dissolved in 40 g of diethylene glycol dimethyl ether to prepare a polyimide composition solution.

Next, using the composition thus obtained, Example 3
A polyimide silicone film was formed in the same manner as in. The adhesion of the obtained polyimide silicone film to a silicone wafer was examined in the same manner as in Example 3. The results are shown in Table 2.

The heat resistance of the obtained polyimide silicone film was examined using a differential thermal balance. Table 2 shows the thermal decomposition start temperature.

Further, in order to examine the solvent resistance of the obtained polyimide silicone film, it was immersed in diethylene glycol methyl ether and visually observed whether or not it was dissolved. The results are shown in Table 2.

[0098]

[Table 2]

[0099]

The polyimide silicone of the present invention is excellent in adhesiveness and heat resistance, and is also excellent in solvent resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideki Akiba 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (3)

[Claims] 1. At least the following general formula (1): (In the formula, X is a tetravalent organic group, and when there are a plurality of X, they may be the same or different. Y is a divalent organic group, and when there are a plurality of Y, they are May be the same or different. N is an integer of 1 or more) and the following general formula (2): (In the formula, R ¹ is a monovalent organic group having 1 to 6 carbon atoms, and when plural R ¹ are present, they may be the same or different. M is an integer of 2 to 8; And a is an integer of 0 to 2.). 2. The following general formula (3): (In the formula, X is a tetravalent organic group, and when there are a plurality of X, they may be the same or different. Y is a divalent organic group, and when there are a plurality of Y, they are May be the same or different. N is an integer of 1 or more.) And a polyamic acid represented by the following general formula (4): (In the formula, R ¹ is a monovalent organic group having 1 to 6 carbon atoms, and when plural R ¹ are present, they may be the same or different. M is an integer of 2 to 8; , a is .R ² and R ³ is an integer of 0 to 2 may be the same or different, are each a monovalent organic group hydrogen atom or a carbon atoms 1-3. However, R ² and R ^At least one of the ^three
It is a hydrogen atom. The method for producing a polyimide silicone according to claim 1, which comprises heating a polysiloxane having a unit represented by the formula (1). 3. In the general formula (1), X is the following formula (5): A group represented by the following formula (6): And a group represented by the following formula (7): Is at least one group selected from the group consisting of groups represented by: and Y is represented by the following formula (8): And a group represented by the following formula (9): (In the formula, a plurality of R ⁶ may be the same or different and are a divalent organic group, and a plurality of R ⁷ may be the same or different,
It is a monovalent organic group. The method for producing a polyimide silicone according to claim 1, which is at least one group selected from the group consisting of groups represented by the following general formula (10): (In the formula, X'is at least one group selected from the group consisting of groups represented by the above formulas (5) to (7), and Y'is
It is at least one group selected from the group consisting of groups represented by the above formulas (8) and (9), and n is an integer of 1 or more. ) And a polyimide represented by the following general formula (4): (In the formula, R ¹ is a monovalent organic group having 1 to 6 carbon atoms, and when plural R ¹ are present, they may be the same or different. M is an integer of 2 to 8; , a is .R ² and R ³ is an integer of 0 to 2 may be the same or different, are each a monovalent organic group hydrogen atom or a carbon atoms 1-3. However, R ² and R ^At least one of the ^three
It is a hydrogen atom. ) A method for producing, which comprises mixing with a polysiloxane having a unit represented by the formula and heating.