JP2000080272A - Polymer composition having low dielectric constant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of presenting a polymer material having a low dielectric constant and excellent in heat resistance and adhering properties by bringing the composition to contain a polymer constituted of a specific organic group and a specific group. SOLUTION: This polymer composition having a low dielectric constant is brought to contain a polymer constituted of 5-35 mole % of (A) a 3-4 valent 3-30C organic group and one or more of groups selected from (B) formula I [Q1 and Q3 are each a 3-4 valent organic group having >2C; Q2 is a divalent organic group having >2C; Q4 and Q5 are each H, a monovalent organic group having 1-10C; (p) is 1-100; (q) and (r) are each 1 or 2], formula II [Q6 and Q8 are each a tetravalent organic group having >2C; Q7 is a divalent organic group having >2C; (s) is 0-100], formula III [Q9 and Q11 are each a tetravalent organic group having >2C; Q10 is a divalent organic group having >2C; (t) is 0-100], formula IV [Q12 and Q14 are each a 2-4 valent organic group having >2C; Q13 is a 3-6 valent organic group having >2C; Z is O, S or NH; (u) is 1-100; (v) and (w) are each 1 or 2], formula V [Q15 and Q17 are each a divalent and >2C organic group; Q16 is a tetravalent and >2C organic group (x) is 0-100], etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant polymer material having a low dielectric constant and good adhesion.

[0002]

2. Description of the Related Art Fluoroalkyl resins and polyolefin resins are well known as heat-resistant materials having a low dielectric constant. However, such materials have problems such as difficulty in pattern processing, poor adhesion, and low glass transition temperature, and have not been put to practical use. Conventionally, materials having a low dielectric constant include a spin-on glass film containing fluorine atoms, a silicon oxide film containing fluorine atoms formed by plasma CVD, and a heat-resistant organic polymer such as polyimide. Materials have been used in the semiconductor field. However, the dielectric constant of such a film is almost 3 or more in most cases, and it is expected that an electric capacity due to an interlayer insulating film will become a problem when the speed of a semiconductor is increased in the future.

In view of the foregoing, the present invention has been intensively studied in order to develop a heat-resistant polymer material having a low dielectric constant and excellent adhesiveness. As a result, a polymer skeleton having a specific structure has been obtained. Thus, a material having a low dielectric constant and excellent heat resistance and adhesiveness was found.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide a heat-resistant polymer material having a low dielectric constant.

[0005]

According to the present invention, a trivalent to tetravalent organic group having 3 to 30 carbon atoms and a compound represented by any of the general formulas (1) to (9)
Wherein the content of the trivalent to tetravalent group having 3 to 30 carbon atoms in the polymer is 5 to 35 mol%, the polymer comprising at least one group represented by the following formula: A dielectric constant polymer composition, wherein the polymer is represented by (1) a trivalent to tetravalent crosslinking component and a compound represented by the following general formulas (1) to (9):
Is reacted with at least one of the groups represented by the formula (1) to obtain N1. (2) The N1 is reacted with a trivalent to tetravalent crosslinking component to form N2.
(3) Reaction of N2 with at least one of the groups represented by formulas (1) to (9) to obtain N3 (4) Reaction of N3 with a trivalent group from 3 to obtain N4 2n + 1 times (n is an integer from 0 to 100)
A low dielectric constant polymer composition obtained by performing a reaction repeatedly and sequentially.

[0006]

Embedded image (Q ¹ and Q ³ are trivalent to tetravalent organic groups containing at least ^two carbon atoms, Q ² is a divalent organic group containing at least ^two carbon atoms, and Q ⁴ and Q ⁵ are hydrogen atoms And / or a monovalent organic group having 1 to 10 carbon atoms, p is 1 to 1
An integer of 00, q and r represent 1 or 2. )

Embedded image (Q ⁶ and Q ⁸ are tetravalent organic groups containing at least two carbon atoms, Q ⁷ is a divalent organic group containing at least two carbon atoms, and s is an integer from 0 to 100.)

Embedded image (Q ⁹ and Q ¹¹ are tetravalent organic groups containing at least two carbon atoms, and Q ¹⁰ is a tetravalent organic group containing at least two carbon atoms.
A valent organic group, t represents an integer of 0 to 100; )

Embedded image (Q ¹² and Q ^{14 each} have at least two carbon atoms.
To a tetravalent organic group, Q ¹³ is a trivalent to hexavalent organic group containing at least two carbon atoms, and Z is selected from an oxygen atom, a sulfur atom, or NH. u represents an integer of 1 to 100, and v and w represent 1 or 2. )

Embedded image (Q ¹⁵ and Q ¹⁷ are a divalent organic group containing at least 2 or more carbon atoms, Q ¹⁶ is a tetravalent organic group containing at least 2 or more carbon atoms, Z is an oxygen atom, a sulfur atom, Represents NH, and x represents an integer from 0 to 100.)

Embedded image (Q ¹⁹ and Q ²¹ are divalent organic groups containing at least two carbon atoms, Q ²⁰ is a trivalent to tetravalent organic group containing at least two carbon atoms, and Q ²² is a hydrogen atom and / or A monovalent organic group having 1 to 10 carbon atoms, y is 1 to 10
Integer of 0, a represents 1 or 2. )

Embedded image (Q ²³ and Q ²⁵ are divalent organic groups containing at least two carbon atoms, and Q ²⁴ is a divalent organic group containing at least two carbon atoms.
A valent organic group, b represents an integer from 0 to 100; )

Embedded image (Q ²⁷ and Q ²⁹ are a trivalent to hexavalent organic group containing at least two carbon atoms, Q ²⁸ is a divalent organic group containing at least two carbon atoms, Z is an oxygen atom, a sulfur atom, Or NH. C is an integer of 1 to 100, d, e
Represents 1 or 2. )

Embedded image (Q ³⁰ , Q ³² , Q ³⁴ are tetravalent organic groups containing at least 2 or more carbon atoms, Q ³¹ , Q ³³ are divalent organic groups containing at least 2 or more carbon atoms, Z is Represents an oxygen atom, a sulfur atom, and NH, and f represents an integer from 0 to 100.)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a trivalent to tetravalent group is used to form a branch in a polymer structure. As such a compound, those shown in the following general formula (11) are preferable. However, other trivalent to tetravalent groups can also be used. Further, when the group is trivalent or less, branching is not obtained, which is not preferable. Further, if the group has a valence of 5 or more, it is not preferable because it may gel.

[0008]

Embedded image The trivalent to tetravalent group accounts for 5 to 3 mol% of the polymer component.
It is preferable that 5 mol% is blended. More preferably, it is 10 mol% to 25 mol%. If the amount is less than 5 mol%, the obtained polymer approaches the properties of the linear polymer, and if it is more than 35 mol%, gelation may occur during the reaction.

In the present invention, as the group to be reacted with the above-mentioned crosslinking group, those listed in the general formulas (1) to (9) can be preferably used.

In the general formula (1), Q ¹ and Q ^{3 each} have 2 carbon atoms.
It represents the above trivalent or tetravalent organic group. Such things as benzophenonetetracarboxylic acid,
Tetravalent aromatic-containing groups such as 4,4 '-(hexafluoroisopropylidene) diphthalic acid, diphenylethertetracarboxylic acid, and diphenylsulfonetetracarboxylic acid residues, and trivalent aromatic-containing groups such as trimesic acid are preferred. Examples can be given. More preferably,
Pyromellitic acid having a bond axis deviation within 30 degrees,
Examples thereof include a tetravalent group such as a 3,3 ′, 4,4′-biphenyltetracarboxylic acid residue and a trivalent group such as a trimellitic acid residue.

Q ² represents a divalent organic group having 2 or more carbon atoms. Preferred examples of 4,4′-
Diaminodiphenyl ether, aminophenoxybenzene, bis (4-aminophenoxyphenyl) propane,
Aromatic diamine residues such as bis (4-aminophenoxyphenyl) sulfone residues are preferred. More preferred are paraphenylenediamine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl and 4,4'-bis (trifluoromethyl) -4 having a rigid structure in which the bond axis shifts within 30 degrees. '-Diaminoterphenyl, 3,3'-dimethoxybenzidine and the like. In addition, 1 to 30 mol% of the Q ¹ and Q ³ components is an aliphatic diamine residue such as ethylenediamine, cyclohexyldiamine residue, or siloxane-containing diamine residue 1,1.
A 3-bis (3-aminopropyl) tetramethyldisiloxane residue or the like can also be blended.

Q ⁴ and Q ^{5 each} represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Q ⁴ and Q ⁵ may be the same or different.

In the general formula (2), Q ⁶ and Q ^{8 each} have 2 carbon atoms.
It represents the above tetravalent organic group. Preferred examples thereof include tetravalent aromatic-containing groups such as benzophenonetetracarboxylic acid, 4,4 ′-(hexafluoroisopropylidene) diphthalic acid, diphenylethertetracarboxylic acid, and diphenylsulfonetetracarboxylic acid residue. be able to. More preferably, pyromellitic acid whose bond axis shift is within 30 degrees, 3,3 ′,
A tetravalent group such as a 4,4′-biphenyltetracarboxylic acid residue can be exemplified.

As Q ⁷ , those similar to Q ² in the general formula (1) can be used. The general formula (3) represents one having an isoimide structure. , Q ⁹ and Q ¹¹ represent a tetravalent organic group having 2 or more carbon atoms. The same one as Q ⁶ in the general formula (2), which is a tetracarboxylic acid residue, can be used. Q ¹⁰ represents a divalent organic group having 2 or more carbon atoms. It can be used of the general formula identical to Q ⁷ (2) as such.

In the general formula (4), Q ¹² and Q ¹⁴ represent a divalent to tetravalent organic group having 2 or more carbon atoms. Z is selected from an oxygen atom, a sulfur atom, and NH. Such materials include hydroxydiaminobenzene, dihydroxydiaminobenzene, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'- Dihydroxy-4,4'-diaminobiphenyl, thiohydroxydiaminobenzene, dithiohydroxydiaminobenzene, bis (3-amino-4-thiohydroxyphenyl) hexafluoropropane, 3,3'-diamino-
4,4'-dithiohydroxybiphenyl, 3,3'-dithiohydroxy-4,4'-diaminobiphenyl, tetraaminobenzene, tetraaminobiphenyl residues and the like can be mentioned. Further, 2,5-diaminohydroxybenzene, in which the displacement of the bonding axis is within 30 degrees, 1,4
-Diamino-2,5-dihydroxybenzene, 3,3 '
-Diamino-4,4'-dihydroxybiphenyl, 3,
3'-dihydroxy-4,4'-diaminobiphenyl,
2,5-diaminothiohydroxybenzene, 1,4-diamino-2,5-dithiohydroxybenzene, 3,3 ′
-Diamino-4,4'-dithiohydroxybiphenyl,
3,3′-dithiohydroxy-4,4′-diaminobiphenyl, 1,2,4,5-tetraaminobenzene,
3 ', 4,4'-tetraaminobiphenyl residue and the like can be mentioned.

[0016] Q ^12, Q ¹⁴ component as the divalent radical in which the general formula (1) the same as Q ² in Q ^{1 1,} Q ¹³ may be from 1 to 30 mole% denaturation of ingredients.

Q ¹³ represents a trivalent to hexavalent organic group having 2 or more carbon atoms. These include phthalic acid,
Examples thereof include aromatic dicarboxylic acid residues such as diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, and biphenyl dicarboxylic acid residues, and aliphatic dicarboxylic acid residues such as adipic acid and cyclohexane dicarboxylic acid residues. From the viewpoint of heat resistance, it is preferable to use an aromatic dicarboxylic acid residue. Also, the displacement of the coupling axis is 3
It is more preferable to use terephthalic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenyl sulfone dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, or the like, which is within 0 degrees.

In the general formula (5), Q ¹⁵ and Q ¹⁷ represent a tetravalent organic group having 2 or more carbon atoms. Such materials include hydroxydiaminobenzene, dihydroxydiaminobenzene, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy -4,4'-diaminobiphenyl, thiohydroxydiaminobenzene, dithiohydroxydiaminobenzene, bis (3-amino-4-thiohydroxyphenyl) hexafluoropropane, 3,3'-diamino-
4,4'-dithiohydroxybiphenyl, 3,3'-dithiohydroxy-4,4'-diaminobiphenyl, tetraaminobenzene, tetraaminobiphenyl residues and the like can be mentioned. Further, 2,5-diaminohydroxybenzene, in which the displacement of the bonding axis is within 30 degrees, 1,4
-Diamino-2,5-dihydroxybenzene, 3,3 '
-Diamino-4,4'-dihydroxybiphenyl, 3,
3'-dihydroxy-4,4'-diaminobiphenyl,
2,5-diaminothiohydroxybenzene, 1,4-diamino-2,5-dithiohydroxybenzene, 3,3 ′
-Diamino-4,4'-dithiohydroxybiphenyl,
3,3′-dithiohydroxy-4,4′-diaminobiphenyl, 1,2,4,5-tetraaminobenzene,
Those obtained by a dehydration ring-closing reaction of a 3 ′, 4,4′-tetraaminobiphenyl residue and the like can be mentioned.

As Q ^16, the same tetravalent Q ¹³ as Q ¹³ in formula (4) can be used. In the general formula (6), Q ¹⁹ and Q ²¹ can be the same as Q ^{2 in the} general formula (1). Q ²⁰ can be the same as Q ^{1 in the} general formula (1). Q ²² may be the same as the Q ⁴ of the general formula (1). y represents an integer from 1 to 100, and a represents 1 or 2.

In the general formula (7), the same Q ²³ and Q ²⁵ as Q ^{7 in the} general formula (2) can be used.
Q ²⁴ can be the same as Q ^{6 in the} general formula (2). In general formula (8), Q ²⁷ and Q ²⁹ can be the same as Q ^{13 in} general formula (4). Q ²⁸
It can be the same as the Q ¹² of the general formula (4). Z is selected from an oxygen atom, a sulfur atom, and NH. c represents an integer from 1 to 100, and d and e represent 1 or 2. In the general formula (9), Q30, Q32, Q
34 can be the same as Q16 in general formula (5). The same Q31 and Q33 as Q15 in the general formula (5) can be used. Z is selected from an oxygen atom, a sulfur atom, and NH. f represents an integer from 1 to 100.

In the present invention, as the monovalent group, those described in the general formula (10) can be used. Also. Other monovalent organic groups having 3 to 30 carbon atoms or monovalent organic groups having 3 to 30 carbon atoms including a silicon atom are shown. Particularly, a compound containing a silicon atom is preferable because it also has an effect of improving adhesiveness. These groups can be used in combination, and other groups can also be used.

Further, the low dielectric constant polymer composition of the present invention comprises:
First, a branched group is reacted with a divalent group. It is presumed that by repeating this operation, a material close to a radially branched polymer as shown in the general formula (12) can be obtained. Such a polymer having an appropriate degree of branching and spreading has a structure in which polymer chains do not approach each other as compared with a linear polymer obtained by polymerizing only a divalent monomer, and the volume of the polymer per unit volume is small. The rate can be reduced. If a trivalent to tetravalent group is first reacted with other raw materials without performing such a reaction,
It is not preferable because gelation may occur.

[0023]

Embedded image (N is an integer from 1 to 100; R ⁰ , R ² ,..., R ²ⁿ are a trivalent to hexavalent organic group, a silicon atom-containing group, R ¹ , R ³ ,
.. R ^{2n + 1} is a divalent group, n is an integer from 1 to 100,
r0 is an integer from 3 to 6, r ₂ ,..., r _2n is 2 to 5
Represents an integer up to. The polymer of the present invention has a branched structure,
Since the polymer chains do not approach each other, the volume fraction occupied by the polymer chains in the bulk polymer decreases. Such a polymer having a small volume fraction tends to have a lower dielectric constant than a polymer having a large volume fraction. This is because the lowest dielectric constant among insulators is vacuum, followed by air. This volume fraction can be estimated from the ratio of the specific gravity of the linear polymer having the same structure as the branched polymer. That is, the specific gravity, which is the weight of the polymer per unit volume, is divided by the molecular weight of the structural unit of the polymer, and can be estimated by the ratio of the number of molecules per unit volume. That is, it is considered that the polymer having the specific gravity decreased by 10% has the porosity increased by 10%.

In view of the above, the low dielectric constant polymer composition of the present invention comprises R ⁰ , R ² ,
By measuring the specific gravity of the linear polymer using the same component and the crosslinked polymer of the present invention without using the crosslinking component of R ⁴ , the dielectric constant decreases when the volume fraction as described above increases. The dielectric constant is reduced by 5% or more when the specific gravity is reduced by 5% or more with respect to the linear polymer. From the viewpoint of the dielectric constant, it is preferable that the specific gravity falls within a range of 5% or more and less than 90%. From the viewpoint of the strength of the obtained film, the specific gravity is 90%.
% Is not preferable.

In the method for producing a polymer of the present invention, first, a crosslinking component R ⁰ is reacted with a branch component R ¹ to obtain an oligomer N1. Subsequently, the crosslinking component R ² is reacted to obtain N 2. N3
Obtain N4 reacted branches component R ³ and. Such a reaction is obtained by repeating 2n + 1 times. At the end of the reaction, a monovalent organic group may be used as a terminal blocking group. Examples of such compounds include monovalent amine compounds such as aniline and propylamine, and monovalent acid anhydrides such as phthalic anhydride and succinic anhydride.
Furthermore, it has a reactive multiple bond such as a monovalent amine compound having a reactive multiple bond such as ethynylaniline and vinylaniline, and a reactive multiple bond such as maleic anhydride and nadic anhydride, which are reactive with heat. And the like. In addition, aminopropyltriethoxysilane, silicon atom-containing amine compounds such as aminophenyltrimethoxysilane, and silicon atom-containing acid anhydride compounds such as trimethoxysilyl phthalic anhydride also have an effect of improving adhesion to a substrate, and preferable. These compounds may be used alone, or a plurality of them may be used in combination. As described above, by sequentially reacting the cross-linking component and the branch component alternately, it is possible to obtain a polymer radially spread from the center.

The molecular weight and molecular weight distribution of the polymer of the present invention can be determined by the GPC method. For example, a system in which two columns (TSK-Gel2000) manufactured by Tosoh Corporation are connected to a system using a 510 type pump manufactured by Waters and a 990J type photodiode array detector can be used. For molecular weight calibration, standard polystyrene having a molecular weight of 1,000 to 100,000 was used. The molecular weight of the polymers according to the invention is between 5000 and 10
It is preferably in the range of 10,000. The molecular weight distribution can be represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), preferably in the range of 1.02 <Mw / Mn <2.0, and more preferably 1.05 <Mw. / Mn <1.
5

The dielectric constant of the low dielectric constant composition of the present invention is expressed as a ratio to the dielectric constant of vacuum. The dielectric constant of a heat-resistant resin composition such as a general polyimide resin is about 3. The dielectric constant of the low dielectric constant composition of the present invention is preferably 2.7 or less, more preferably 2.5 or less.

In the measurement of the specific gravity of the present invention, the obtained low dielectric constant polymer composition is spin-coated on thin glass whose weight has been accurately measured in advance, and a uniform film thickness (thickness unevenness is 10% or less) is applied to the glass. ) And cured under the required heat treatment conditions. The specific gravity can be measured by measuring the weight of the glass plate and the film thickness of the low dielectric constant polymer composition.

In the measurement of the dielectric constant of the present invention, a low dielectric constant polymer composition is spin-coated on an aluminum foil in a uniform film thickness, cured under a necessary heat treatment condition, and coated with aluminum or gold. It can be measured by depositing a metal such as nickel or the like on an electrode.

The dependence of the dielectric constant of the low dielectric constant composition of the present invention on temperature is preferably 0.1% / ° C. or less. If the temperature change of the dielectric constant is larger than this, when the low dielectric constant composition of the present invention is used as an insulating material of an actual device or substrate, the dielectric constant changes with temperature, and the temperature change of the device or substrate It is not preferable because the signal transmission state changes.

The low dielectric constant polymer composition of the present invention comprises a non-proton such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide and the like. Polar solvents, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, meta-cresol, p-chlorophenol And the like, or dissolved in an organic solvent such as a phenol or a mixture thereof. In general, when the trivalent to tetravalent crosslinking monomers are contained in an amount of 5 mol% or more, a network structure is formed and most of the monomers are not dissolved in an organic solvent. However, in the low dielectric constant composition of the present invention, the reaction is sequentially performed. The polymer is dissolved in an organic solvent by controlling the structure of the obtained polymer.

Some of the low dielectric constant polymer compositions of the present invention can be melt-molded. In general, when the trivalent to tetravalent crosslinking monomers are contained in an amount of 5 mol% or more, a network structure is formed, and the glass transition temperature of the obtained polymer becomes as high as 400 ° C. or more. If the polymer is heated to a temperature equal to or higher than the glass transition temperature of the polymer for performing the melt molding, a thermal decomposition reaction, a thermal crosslinking reaction, and the like occur, and the polymer is hardly melted. However, in the low dielectric constant composition of the present invention, by sequentially performing the reaction and controlling the structure of the obtained polymer, the glass transition temperature of the obtained polymer becomes around 300 ° C.,
What can be melt-molded can also be obtained.

If necessary, a surfactant may be mixed for the purpose of improving the wettability between the low dielectric constant polymer composition of the present invention and a substrate. In addition, inorganic particles such as silicon dioxide and titanium oxide, or powder of polyimide can also be added.

For the purpose of improving the adhesion to the substrate, a silane coupling agent, a titanium chelating agent, or an aluminum chelating agent may be added to the varnish of the low dielectric constant polymer composition, or the substrate may be pretreated.

Next, a method for forming a pattern using the low dielectric constant polymer composition of the present invention will be described.

The low dielectric constant polymer composition of the present invention is applied on a substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, or the like is used, but is not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, and roll coating. The coating thickness is different depending on the coating method, the solid content concentration of the composition, the viscosity, etc.
It is applied so as to have a thickness of 0.1 to 150 μm.

In order to form a pattern of the low dielectric constant polymer composition of the present invention, a photoresist is applied to a resin film which has been heat-treated at a temperature of 100 ° C. to 500 ° C. The photoresist pattern is obtained by exposing and developing the photoresist. Using this pattern as a mask, a desired pattern of the low dielectric constant polymer composition film can be obtained by a method such as plasma etching, reactive ion etching, or laser ablation. Moreover, it can also be scientifically etched with a chemical such as hydrazine. Subsequently, both cases where heat treatment is performed and cases where heat treatment is not performed are conceivable, but both can be used. This heat treatment converts the film into a heat-resistant film by applying a temperature of 200 ° C. to 500 ° C. This heat treatment is carried out for 5 minutes to 5 hours while selecting the temperature and increasing the temperature stepwise, or while selecting a certain temperature range and continuously increasing the temperature. For example, at 140 ° C., 2
Heat treatment at 00 ° C. and 400 ° C. for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be used.

The heat-resistant film formed by the low dielectric polymer composition according to the present invention is used for a passivation film of a semiconductor, a protective film of a semiconductor element, an interlayer insulating film of a semiconductor, an interlayer insulating film of a multilayer wiring for high-density mounting, and the like. Used for

[0039]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. Method for Measuring Characteristics Measurement of Dielectric Constant A varnish of the low dielectric constant polymer composition of the present invention is spin-coated on an aluminum foil having a thickness of 25 μm using a 1H-D2S spin coater manufactured by Mikasa. Using a hot plate of SKW-636 made by Dainippon Screen,
Prebake at 100 ° C for 5 minutes. The number of revolutions in spin coating is adjusted so that the film thickness after prebaking is 5 μm.

The aluminum foil spin-coated with the low dielectric constant polymer composition thus obtained was coated with DH-42 manufactured by Yamato Scientific Co., Ltd.
Heat-treat in an inert oven under a nitrogen stream. The heat treatment conditions are as follows: after treating at 200 ° C. for 30 minutes,
The temperature was raised at 350 ° C. for 1 hour, and when the temperature in the oven became 200 ° C. or less, it was taken out of the oven.

About 100 nm of aluminum was deposited on the film surface of the low dielectric constant polymer composition to form an electrode on the film. EBH-6 type manufactured by ULVAC, Inc. was used for vapor deposition.

Using this sample, the permittivity was measured at a frequency of 1 kHz using an LCR meter 4288A manufactured by Hewlett-Packard Company and a measuring electrode 14865A for a film.

Measurement of Specific Gravity A slide glass (40 mm × 50 mm, manufactured by Matsunami Glass Co., Ltd.)
The surface having a thickness of 0.12 to 0.17 mm (No. 1) was washed with isopropyl alcohol. It was dried in a ventilation oven DT-42 manufactured by Yamato Scientific Co., Ltd. at 100 ° C. for 4 hours, and cooled with a glass desiccator containing silica gel. After cooling to room temperature, AD precision balance ER-182A
Was used to measure the weight of this glass plate. A varnish of the low dielectric constant polymer composition was spin-coated on the glass plate whose weight was measured using a spinner 1H-DS manufactured by Mikasa Co., Ltd., so that the film thickness after the heat treatment was about 5 μm.

The spin-coated glass plate was heated at 80 ° C. for 5 minutes and at 120 ° C. for 5 minutes using a hot plate portion of a coater developer SKW-636 manufactured by Dainippon Screen.
Prebaked for minutes. Furthermore, using an inert oven DT-42 manufactured by Yamato Scientific Co., Ltd., the mixture was heated at 140 ° C. for 30 minutes, then heated to 350 ° C. and heat-treated in nitrogen for 1 hour (oxygen concentration: 20 ppm or less). After that, the oven temperature is 200
When the temperature fell below ℃, it was taken out of the oven.

The sample taken out of the oven was placed in a desiccator, allowed to cool, allowed to cool to room temperature, and then weighed using a precision balance ER-182A manufactured by AD. From this weight and the weight of the glass plate alone, the weight of the applied film was determined. Next, a part of the coated surface was scratched with a single-tooth razor, and the part with and without the scratch was measured using “Surfcom” 1500 manufactured by Tokyo Seimitsu Co., Ltd. to determine the step.

The specific gravity was obtained by dividing the weight (g unit) of this film by the area (4.0 cm × 5.0 cm), which is the volume, multiplied by the film thickness (cm unit).

Adhesion Measurement (PCT Adhesion Test) A varnish of the low dielectric constant polymer composition of the present invention was coated on a 4-inch silicon wafer by SCW-63 manufactured by Dainippon Screen.
6 is spin-coated using the spin coater. SCW-63 manufactured by Dainippon Screen Co., Ltd.
Prebake at 100 ° C. for 5 minutes using the hot plate of No. 6. The number of revolutions in spin coating is adjusted so that the film thickness after prebaking is 5 μm.

The silicon wafer spin-coated with the low dielectric constant polymer composition thus obtained is heat-treated in an inert oven INH-15 manufactured by Koyo Lindberg Co. under a nitrogen stream (oxygen concentration: 20 ppm or less). The heat treatment conditions were as follows: after treatment at 140 ° C. for 30 minutes, the temperature was raised to 350 ° C. in 1 hour, the treatment was performed at 350 ° C. for 1 hour, and when the temperature in the oven became 200 ° C. or less, it was taken out of the oven.

The film of the silicon wafer coated with the low dielectric constant polymer composition was scratched in a grid pattern with a width of 2 mm and five in a horizontal and vertical direction with a single-tooth razor. The adhesion of the film was peeled off using "Cellotape" manufactured by Nichiban Co., Ltd. At this point (initial stage), those having peeled off have very poor adhesion. What was not peeled off at this time was 500 ° C under 121 ° C and 2.1 atm of saturated steam.
Time processed. After 500 hours, a similar peeling test was performed to examine whether or not the film was peeled. If no peeling is observed at this time, the adhesion is good.

Measurement of Film Thickness A sample coated and heat-treated on a silicon wafer or a glass plate is scratched with a single-tooth razor, and a surface roughness meter Surfcom 1500A manufactured by Tokyo Seimitsu Co., Ltd. is used. The level difference was measured and used as the film thickness.

Measurement of heat resistance 1 g of a varnish to be measured was placed in a tin plate. This is heat-treated in a nitrogen stream (oxygen concentration 20 ppm or less) in an inert oven DT-42 manufactured by Yamato Scientific Co., Ltd. This heat treatment is performed at 80 ° C. for 30 minutes and then at 200 ° C. for 30 minutes.
Minutes, and then the temperature is raised to 350 ° C. in one hour,
After a time treatment, when the temperature in the oven became 200 ° C. or less, it was taken out of the oven.

The powder of the low dielectric constant polymer composition thus obtained was collected and measured from room temperature to 600 ° C. at a heating rate of 10 ° C./min using a thermal balance apparatus TG-50 manufactured by Shimadzu Corporation. The temperature at which the weight decreased by 5% from the point at which the temperature reached 300 ° C. was defined as the thermal decomposition temperature. When the thermal decomposition temperature is lower than 450 ° C., gas may be generated in a process in which heat of about 450 ° C. is applied in a semiconductor manufacturing process, and there is a problem in heat resistance.

Synthesis Example 1 Synthesis of Crosslinking Monomer (1) 500 ml equipped with a nitrogen inlet tube, a stirring blade and a thermometer
12.6 g (0.1 mol) of 1,3,5-trihydroxybenzene was dissolved in 150 g of N-methyl-2-pyrrolidone (NMP), and 24.2 g (0.175 mol) of potassium carbonate was added thereto. ) And dispersed at 70 ° C. Here, para-nitrochlorobenzene 47.3
g (0.3 mol) was added, and the reaction was carried out at 150 ° C. for 6 hours. After completion of the reaction, the inorganic salt was removed by filtration after the temperature of the solution was sufficiently lowered, and the filtrate was poured into 3 l of water to form a precipitate. The precipitate was collected by filtration and dried in vacuo at 70 ° C. for 12 hours (yield: 35 g, 71.5%).

30 g of the vacuum-dried product was dispersed in 1000 g of ethanol, and 1.5 g of 5% palladium carbon was added thereto, and a balloon containing hydrogen was attached thereto.
For 8 hours until the absorption of hydrogen ceased.

After completion of the reaction, the filtrate was collected by filtration and evaporated to obtain the desired crosslinked monomer (1) (yield: 2).
2g, 90% yield).

Synthesis Example 2 Synthesis of Crosslinking Monomer (2) 3 equipped with a nitrogen inlet tube, a stirring blade, a thermometer, and a distillation tube
In a 00 ml four-necked flask, 37.4 g (0.3 mol) of 3-aminopropyldiethoxymethylsilane (APDS) was added to 30 g of gamma-butyrolactone and 3-methyl-3-methyl-3-butyrolactone.
Dissolved in 27.4 g of methoxybutanol, 3.6 g (0.2 mol) of water was added thereto, and the mixture was stirred at 30 ° C., and the temperature of the solution was gradually increased, followed by stirring at 110 ° C. for 2 hours. Discharge water and ethanol from the distillation tube. The solution was cooled to obtain a 50% solution of a trivalent crosslinking monomer (2) to which an average of three molecules of APDS were bound. This solution was used as it was for the reaction.

Synthesis Example 3 Crosslinking monomer (3) (tri (4
-Aminophenyl) amine) 24.5 g (0.1 mol) of triphenylamine was added to sulfuric acid 7
Dissolved in 0 g. Here, 35 g of 61% nitric acid was gradually added. After adding nitric acid, the mixture was stirred for 2 hours, poured into 3 L of a 5% aqueous sodium hydrogen carbonate solution containing ice, and the obtained solid was collected by filtration. After the collected solid was sufficiently washed with water, it was dried in a vacuum dryer at 50 ° C. for 20 hours (yield 26 g).

20 g of the dried solid was placed in a 500 ml autoclave, and 300 ml of methyl cellosolve was added together with 1.5 g of 5% palladium-carbon. The inside of the container was replaced with hydrogen gas, and then the hydrogen pressure was increased to 8 kgf /
A reduction treatment was performed while stirring at 70 ° C. for 2 hours. After the reaction, when the internal temperature became 30 ° C. or less, the pressure in the vessel was removed, and palladium-carbon was removed from the internal solution by filtration. The filtrate was concentrated with a rotary evaporator to obtain tri (4-aminophenyl) amine (yield: 14 g).

Example 1 In a nitrogen stream, 0.215 g (1 mmol) of 3,4,4'-triaminodiphenyl ether (TPE), which is a branched component, was placed in a 1000 ml four-necked flask under N, N-
Dimethylacetamide (DMAc)). Here, pyromellitic anhydride (PMDA) 0.654
g (3 mmol) together with 15 g of NMP,
For 5 minutes. Subsequently, 2,2′-dimethyl-4,
0.636 g of 4'-diaminobiphenyl (DMB) (3
mmol) and stirred at 30 ° C. for 1 hour.

Thereafter, 0.646 g of TPE (3 mmo
l) was added along with 5 g of DMAc, and 0.654 PMDA was added.
g (3 mmol) was added. After the addition, the mixture was stirred at 30 ° C. for 1 hour. Then, 1.272 g (6 mmol) of DMB was added and dissolved together with 8 g of DMAc, and then PMDA1.
309 g (6 mmol) was added, and the mixture was stirred at 30 ° C. for 1 hour.

Thereafter, 1.292 g of TPE (6 mm
l) was added along with 15 g of DMAc and PMDA 1.30
9 g (6 mmol) were added. After the addition, the mixture was stirred at 30 ° C. for 1 hour. Then 2.544 g of DMB (12 mmo
l) was added and dissolved together with 30 g of DMAc, and then PM
2.617 g (12 mmol) of DA were added, and 1
Stirred for hours.

Thereafter, 2.584 g of TPE (12 mmo
l) was added along with 20 g of DMAc and PMDA 2.61 was added.
7 g (12 mmol) were added. After adding, 1 at 30 ° C
Stirred for hours. Then 5.167 g of DMB (24 mmo
l) was added and dissolved together with 30 g of DMAc, and then PM
5.235 g (24 mmol) of DA were added, and 1
Stirred for hours.

Finally, 1.32 g of aniline (14 mmo)
l), 3-Aminopropyltrimethoxysilane 2.21
3 g (10 mmol) were added, and 5.235 g of PMDA was added.
(24 mmol) together with 20 g of DMAc,
The mixture was stirred at 2 ° C. for 2 hours.
Mol%).

The obtained reaction solution was evaluated by using a solution filtered through a polytetrafluoroethylene membrane filter (FP-100, manufactured by Sumitomo Electric Industries) having a pore size of 1 μm.

The dielectric constant is 2.21 and the specific gravity is 1.53
Met. There was no problem with the adhesiveness, and it did not peel off even after 500 hours. The heat resistance was 530 ° C.

Example 2 Under a nitrogen stream, 0.126 g (1 mmol) of melamine, which is a branched component, was put into a 1000 ml four-necked flask together with 40 g of metacresol and 0.2 g of isoquinoline. 0.883 g of 4'-biphenyltetracarboxylic dianhydride (BPDA) (3 mmol
l) was added and reacted at 70 ° C. for 30 minutes, then at 150 ° C. for 1 hour. Next, the temperature of the liquid was cooled to 70 ° C.,
0.961 g (3 mmol) of 2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl (TFMB)
, And reacted at 70 ° C. for 10 minutes and then at 150 ° C. for 30 minutes. The temperature of the solution was cooled again to 70 ° C., and BPDA was added.
0.883 g (3 mmol) was added and the mixture was added at 70 ° C. for 10 minutes.
The reaction was performed at 150 ° C. for 30 minutes. Thus, a compound corresponding to N1 described in claim 2 was obtained.

Further, 0.378 g of melamine (3 mmo
1) was added and reacted at 100 ° C. for 10 minutes and at 150 ° C. for 30 minutes to obtain a compound corresponding to N2 according to claim 2. Then, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) 2.66
6 g (6 mmol) together with 40 g of meta-cresol and 0.2 g of isoquinoline are added at 70 ° C. for 30 minutes, and then 15 minutes.
The reaction was performed at 0 ° C. for 1 hour. Then, the temperature of the liquid was cooled to 70 ° C., and 1.921 g (6 mmol) of TFMB was added.
The reaction was carried out at 70 ° C. for 10 minutes and then at 150 ° C. for 30 minutes, the temperature of the solution was cooled to 70 ° C., and 2.666 g of 6FDA (6.
mmol) and reacted at 70 ° C. for 10 minutes and at 150 ° C. for 30 minutes. As a result, a compound corresponding to N3 described in claim 2 was obtained.

Further, 0.756 g of melamine (6 mm
1) was added and reacted at 100 ° C. for 10 minutes and at 150 ° C. for 30 minutes to obtain a compound corresponding to N4 according to claim 2. Next, 5.333 g (12 mmol) of 6FDA was added together with 60 g of meta-cresol and 0.1 g of isoquinoline, and the mixture was reacted at 70 ° C. for 30 minutes and then at 150 ° C. for 30 minutes. Then, the temperature of the solution was cooled to 70 ° C., and TFMB3.
842 g (12 mmol) was added, and the mixture was reacted at 70 ° C. for 10 minutes and then at 150 ° C. for 30 minutes. The temperature of the solution was cooled to 70 ° C., and 6.333 g (12 mmol) of 6FDA was added. The reaction was performed for 30 minutes. Thus, a compound corresponding to N5 described in claim 2 was obtained.

Further, 1.512 g of melamine (12 mm
ol) and reacted at 100 ° C. for 10 minutes and at 150 ° C. for 30 minutes to obtain a compound corresponding to N6 according to claim 2. Then, 10.67 g (24 mmol) of 6FDA
Was added together with 80 g of meta-cresol and 0.1 g of isoquinoline, and reacted at 70 ° C. for 30 minutes, and then at 150 ° C. for 30 minutes. Then, the temperature of the solution was cooled to 70 ° C.
7.685 g (24 mmol) were added, and 10
And then react at 150 ° C for 30 minutes.
Cool to 0 ° C. and 10.67 g (24 mmol) of 6FDA
And reacted at 70 ° C. for 10 minutes and at 150 ° C. for 30 minutes. As a result, a compound corresponding to N7 described in claim 2 was obtained.

Further, 3.024 g of melamine (24 mm
ol) and reacted at 100 ° C. for 10 minutes and at 150 ° C. for 30 minutes to obtain a compound corresponding to N8 according to claim 2. Then 14.14 g (48 mmol) of BPDA
Was added together with 100 g of metacresol and 0.2 g of isoquinoline, followed by a reaction at 70 ° C. for 30 minutes and then at 150 ° C. for 1 hour. Then, the temperature of the solution was cooled to 70 ° C.
15.37 g (48 mmol) were added, and 10
And then react at 150 ° C for 30 minutes.
Cool to 0 ° C. and 21.33 g (48 mmol) of 6FDA
And reacted at 70 ° C. for 10 minutes and at 200 ° C. for 30 minutes. Thus, a compound corresponding to N9 described in claim 2 was obtained. Thereafter, the temperature of the solution was raised to 70 ° C., and 1.155 g (5 mmol) of 3-aminopropyltriethoxysilane, 1.404 g (12 mmol) of 4-ethynylaniline, and 2.14 g of aniline as terminal blocking components (corresponding to Rm). 883 g (31 mmol) was added,
The mixture was reacted for 0 minutes to synthesize a radially branched polyimide solution.

After the completion of the reaction, when the temperature of the solution became 30 ° C. or less, the reaction solution was poured into 5 l of methanol to precipitate a polymer, which was collected by filtration. The collected polymer is
Washed twice with methanol and air dried. 100 g of N-methyl-2-pyrrolidone (NMP)
And precipitated in 5 l of water containing 30% methanol to precipitate the polymer. The precipitated polymer was collected, washed twice with water, and dried in vacuum at 100 ° C. for 24 hours (blending amount of crosslinking monomer: 12.3 mol%).

3 g of the vacuum-dried sample was dissolved in 30 g of NMP and filtered through a 1 μm-pore-diameter filter made of tetrafluoroethylene (FP-100 manufactured by Sumitomo Electric Industries, Ltd.) to prepare a solution for measurement.

The dielectric constant is 2.28 and the specific gravity is 1.54
Met. The specific gravity was reduced by about 7% as compared with Comparative Example 1. The heat resistance was 510 ° C., which was good. There was no problem in the adhesion at the initial stage and after 500 hours.

Comparative Example 1 TFMB was placed in a 500 ml four-necked flask under a nitrogen stream.
6.4 g (20 mmol) was added together with 50 g of meta-cresol and 0.2 g of isoquinoline, and heated to 70 ° C. After all are completely dissolved, 6.88 g of 6FDA (20 m
mol) and reacted at 70 ° C. for 30 minutes, then at 150 ° C. for 1 hour, and then at 200 ° C. for 3 hours to obtain a linear polyimide solution (blending amount of crosslinking monomer: 0).
Mol%). After completion of the reaction, a measurement solution was prepared using the above polyimide solution in the same manner as in Example 2.

The dielectric constant is 2.81 and the specific gravity is 1.66.
Met. Adhesion had a problem from the initial stage, and peeled off from the substrate. Heat resistance was 520 ° C.

Example 3 0.290 g (1 mmol) of tris (4-aminophenyl) amine (TMPA) as a branching component was added to NMP1.
Dissolve in 0 g. 0.883g of BPDA (3m
mol), and the mixture was stirred at room temperature for 30 minutes. Where 3,
3'-dimethoxy-4,4'-diaminobiphenyl (D
(MOB) 0.732 g 3 mmol was added along with NMP 5 g. After adding 0.883 g (3 mmol) of BPDA, 0.870 g (3 mmol) of TMPA was added, followed by stirring at room temperature for 30 minutes.

Subsequently, 1.765 g (6 mmo) of BPDA
l), and 1.464 g (6 mmol) of DMOB was added to N
After being added together with 10 g of MP, the mixture was stirred for 30 minutes. Thereafter, 1.765 g (6 mmol) of BPDA was added, and TM was added.
1.740 g (6 mmol) of PA was added, and the mixture was stirred at room temperature for 30 minutes.

3.530 g (12 mmol) of BPDA was added, and 2.928 g (12 mmol) of TMOB was added to NMP.
After being added together with 30 g, the mixture was stirred at room temperature for 1 hour. Further, 3.530 g (12 mmol) of BPDA was added to NMP1
0g and TMPA 3.480g (12mmo
l) was added and the mixture was stirred at room temperature for 1 hour.

Thereafter, 7.061 g of BPDA (24 mm
ol) and 7.680 g (24 mmol) of TFMB
Was added together with 30 g of NMP, and the mixture was stirred at room temperature for 1 hour.
Then, 7.061 g (24 mmol) of BPDA was added to NMP.
6.960 g of TMPA (24 mm
ol) and stirred at room temperature for 1 hour.

Thereafter, 14.12 g of BPDA (48 mm
ol) and 15.36 g (48 mmol) of TFMB, and the mixture was stirred at room temperature for 1 hour. After that, TFMB1
5.36 g (48 mmol), BPDA 14.12 g
(48 mmol) was added together with 50 g of NMP, and the mixture was stirred at room temperature for 2 hours. Then, 0.980 g of maleic anhydride
(10 mmol), 5.624 g of phthalic anhydride (38 m
mol), and the mixture was stirred at 40 ° C for 2 hours. To this solution was added 39.06 g (186 mmol) of trifluoroacetic anhydride.
l) was added together with 100 g of NMP, and the mixture was stirred at room temperature for 10 hours to perform isoimidization.

This polymer solution was put into 10 l of water,
A polymer powder having a radially branched isoimide structure was obtained (the blending amount of the crosslinking monomer: 10.9 mol%).

This powder was vacuum dried at 80 ° C. for 20 hours. 3 g of the polymer dried in vacuum is dissolved in 30 g of dimethylimidazoline, and a polytetrafluoroethylene membrane filter having a pore diameter of 1 μm (Sumitomo Electric Industries, Ltd.)
FP-100) was used for evaluation.

The dielectric constant was 2.34, the specific gravity was 1.53, and the heat resistance was 510 ° C. Adhesion is PCT adhesion test 100
There was no problem until time.

Example 4 3,3 ′, 4,4′-Tetraaminobiphenyl (TA
B) 0.214 g (1 mmol), 3,3′-dihydroxy-4,4′-diaminobiphenyl (HAB) 0.8
64 g (4 mmol) and pyridine 0.632 g (8 mm
ol) was dissolved in 10 g of DMAc and cooled to -10 ° C. Here, terephthalic acid chloride (TPC) 0.812
g (4 mmol) gamma-butyrolactone (GBL)
A solution dissolved in 10 g was gradually added dropwise so that the internal temperature did not exceed 0 ° C. After stirring this solution at −10 ° C. for 30 minutes, 0.856 g (4 mmol) of TAB was added to DMAc20.
g, pyridine 0.632 g (8 mmol). 0.812 g (4 mmol) of TPC was added to this solution in G
A solution dissolved in 10 g of BL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, the mixture was stirred for 30 minutes. HAB2.
592 g (12 mmol), pyridine 1.896 g (2
4 mmol) and 40 g of DMAc. Here TPC
A solution of 2.436 g (12 mmol) dissolved in 20 g of GBL was gradually added dropwise so that the internal temperature did not exceed 0 ° C. This solution was stirred at −10 ° C. for 30 minutes.

Thereafter, 2.568 g of TAB (12 mm
l) 70 g of DMAc, 1.896 g of pyridine (24 mm
ol). 2.436 g of TPC was added to this solution.
(12 mmol) dissolved in 30 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After dropping, 30
Minutes. 7.776 g (36 mmol) of HAB, 5.688 g (72 mmol) of pyridine, DMAc100
g was added. Here, TPC 7.308g (36mmo
A solution of l) dissolved in 70 g of GBL was gradually added dropwise so that the internal temperature did not exceed 0 ° C. This solution was cooled at -10 ° C for 3 hours.
Stirred for 0 minutes. Thereafter, BAHF 13.18 g (36 m
mol) and 5.688 g (72 mmol) of pyridine in D
Added with 80 g of MAc. Here TPC 7.308
g (36 mmol) dissolved in 70 g of GBL was gradually added dropwise so that the internal temperature did not exceed 0 ° C. This solution was stirred at −10 ° C. for 30 minutes. Thereafter, the temperature of the solution was reduced to 3
0 ° C. and 0.980 g of maleic anhydride (10
mmol), 2.960 g of phthalic anhydride (20 mmol
l), 2-trimethoxysilyl phthalic anhydride 1.608
g (6 mmol) was added, and the mixture was stirred at 30 ° C. for 2 hours. After completion of the stirring, the precipitate was removed by filtration, and the filtrate was used for the evaluation as it was (the blending amount of the crosslinking monomer: 6.9 mol%).

The dielectric constant was 2.41, the specific gravity was 1.55, and the heat resistance was 480 ° C. Adhesion did not have any problem at the beginning and after 500 hours.

Example 5 0.960 g (3 mmol) of TFMB, TEA 0.30
3 g (3 mmol) was dissolved in 15 g of NMP, and -10
Cooled to ° C. Here trimesic acid chloride (TMC)
A solution prepared by dissolving 0.2655 g (1 mmol) in 10 g of GBL was gradually added dropwise so that the internal temperature did not exceed 0 ° C.

After the dropwise addition, the temperature of the solution was raised to 30 ° C.
0.8826 g (3 mmol) of PDA was added. Thereafter, 0.960 g (3 mmol) of TFMB was added, and 3
Stirred at 0 ° C. for 1 hour.

1.920 g (6 mmol) of TFMB, T
0.909 g (9 mmol) of EA was added together with 20 g of NMP, and the solution was cooled again to −10 ° C.
A solution obtained by dissolving 965 g (3 mmol) in 15 g of GBL was gradually added dropwise so that the internal temperature did not exceed 0 ° C.

After the completion of the dropwise addition, the temperature of the solution was raised to 30 ° C.
1.309 g (6 mmol) of PMDA was added, and further, 3,3′-dimethoxybenzidine (TLD) 1.464.
g (6 mmol) was added and the mixture was stirred at 30 ° C. for 1 hour.
2.928 g (12 mmol) of TLD, 1.81 of TEA
8 g (18 mmol) was added together with 20 g of NMP, and the solution was cooled again to -10 ° C, and 1.593 g of TMC (6
(mmol) in 25 g of GBL.
The solution was gradually dropped so as not to exceed ° C.

After the completion of the dropwise addition, the temperature of the solution was raised to 30 ° C.
2.617 g (12 mmol) of PMDA was added, and 2.928 g (12 mmol) of TLD was further added.
For 1 hour. After the completion, 0.740 g of phthalic anhydride
(5 mmol), 1.640 g of nadic anhydride (10 m
mol), and the mixture was stirred at 50 ° C. for 1 hour (blending amount of crosslinking monomer: 13.2 mol%).

The dielectric constant is 2.45, the specific gravity is 1.58,
Heat resistance was 520 ° C. Adhesion is PCT adhesion test 2
There was no problem until after 00 hours.

Example 6 Tri (4-aminophenyl) methane (TAM) 0.28
9 g (1 mmol) was dissolved in 15 g of NMP. 0.6534 g (3 mmo) of pyromellitic anhydride (PMDA)
l), and after 10 minutes, 0.960 g of TFMB (3 mm
ol) and stirred at 30 ° C. for 1 hour.

Subsequently, 0.867 g of TAM (3 mmo)
l) was added along with 10 g of NMP and BPDA 0.882
6 g (3 mmol) were added. Stirred at 30 ° C. for 1 hour.

Thereafter, 1.920 g of TFMB (6 mmo
l) was added along with 10 g of NMP and BPDA 1.765
g (6 mmol) was added and the mixture was stirred at 30 ° C. for 1 hour.
Subsequently, 1.734 g (6 mmol) of TAM was added to NMP1.
5.765 g of BPDA (6 mmo)
l) was added and the mixture was stirred at 30 ° C for 1 hour.

Thereafter, 3.840 g of TFMB (12 mm
ol) was added along with 45 g of NMP, and BPDA 3.53 was added.
1 g (12 mmol) was added, and the mixture was stirred at 30 ° C. for 1 hour. Subsequently, 3.468 g (12 mmol) of TAM was added to N
MP50g and BPDA 3.531g (12
mmol). Stirred at 30 ° C. for 1 hour.

Thereafter, 7.680 g of TFMB (24 mm
ol) along with 50 g of NMP and 5.23 PMDA
5 g (24 mmol) was added, and the mixture was stirred at 30 ° C. for 1 hour. Subsequently, 6.936 g (24 mmol) of TAM was added to N
MP was added together with 80 g, and 7.728 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (24 g) was added.
mmol) and stirred at 30 ° C. for 1 hour. Thereafter, 15.36 g (48 mmol) of TFMB was added to NMP1.
14.12 g of BPDA (48 mm
ol) and stirred at 30 ° C. for 1 hour.

Finally, 3.315 g (15 mmol) of 3-aminopropyltriethoxysilane and 3.06 of aniline were added.
9 g (33 mmol) was added, and the mixture was stirred at 30 ° C. for 1 hour, and then stirred at 50 ° C. for 1 hour (blending amount of crosslinking monomer:
14.2 mol%).

The dielectric constant is 2.45, the specific gravity is 1.58,
Heat resistance was 510 ° C. The adhesion was good both at the beginning and after 500 hours.

Example 7 0.290 g (1 mmol) of tri (4-aminophenyl) amine (TAPA) prepared in Synthesis Example 3 was added to NMP30.
Dissolve in g. Here, 3,3′-dihydroxy-
0.648 g of 4,4'-diaminobiphenyl (HAB)
(3 mmol) and glycidyl methyl ether (GME)
3.168 g (36 mmol) were added and the solution was cooled to -10 ° C.
And cooled. Here, terephthalic acid chloride (TPC)
A solution in which 0.609 g (3 mmol) of GBL was dissolved in 8 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C.

After completion of the dropwise addition, the mixture was stirred at -10 ° C for 30 minutes.
Subsequently, 0.870 g (3 mmol) of TAPA and GME
3.168 g (36 mmol) were added along with 15 g of NMP. A solution in which 0.609 g (3 mmol) of TPC was dissolved in 8 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, the mixture was stirred at -10 ° C for 1 hour.
Then, 1.296 g (6 mmol) of HAB, GME6.
336 g (72 mmol) were added along with 25 g of NMP. Here, 1.218 g (6 mmol) of TPC was added to GB
A solution dissolved in 15 g of L was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, the mixture was stirred at -10 ° C for 30 minutes.

Subsequently, 1.740 g of TAPA (6 mmo
l) and 6.336 g (72 mmol) of GME in NMP3
Added with 0 g. Here, 1.218 g of TPC (6
(mmol) in 15 g of GBL.
The solution was dropped so as not to exceed ° C. After completion of dropping, it is 1
Stirred for hours.

Further, bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) 4.3
92 g (12 mmol) and GME 12.67 g (144
mmol) along with 40 g of NMP. Where T
A solution prepared by dissolving 2.436 g (12 mmol) of PC in 30 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C.
After completion of the dropwise addition, the mixture was stirred at -10 ° C for 30 minutes.

Subsequently, 3.480 g of TAPA (12 mm
ol) and 12.67 g (144 mmol) of GME in NM
Added with P50g. Here, 2.436 g of TPC
(12 mmol) dissolved in 30 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. -10 after completion of dropping
Stirred at 30 ° C for 30 minutes. Then 5.184 g of HAB (24
mmol), 25.3 g (288 mmol) of GME
Added with 70 g of MP. Here, TPC4.872
g (24 mmol) dissolved in 50 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After dropping -1
Stirred at 0 ° C. for 1 hour.

Subsequently, 6.960 g of TAPA (24 mm
ol) and 25.3 g (288 mmol) of GME in NMP
Added with 100 g. Here, TPC 4.872 g
(24 mmol) dissolved in 50 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. -10 after completion of dropping
Stirred at C for 1 hour. Then, HAB 10.37 g (48
mmol) and 33.79 g (384 mmol) of GME. Here, 9.744 g (48 mmol) of TPC
Was dissolved in 80 g of GBL, and the solution was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, the mixture was stirred at -10 ° C for 30 minutes.

Subsequently, 4-ethynylaniline 2.808
g (24 mmol), 2.210 g (10 mmol) of 3-aminopropyltriethoxysilane, 1.3 aniline
02g (14 mmol) and GME 33.79 gg (38
4 mmol) was added along with 40 g of NMP. 9.744 g of isophthalic acid chloride (IPC) (48 mm
ol) in 50 g of GBL was gradually added dropwise so that the internal temperature did not exceed 0 ° C. After dropping, -10 ° C
For 1 hour, and then gradually raise the temperature to room temperature for 2 hours.
The mixture was stirred for a period of time (the amount of the crosslinking monomer: 12.3 mol%).

A sample obtained by filtering this polymer solution with a polytetrafluoroethylene membrane filter having a pore size of 1 μm was used.

The dielectric constant was 2.33, the specific gravity was 1.55, and the heat resistance was 478 ° C. There was no problem in the adhesion at the initial stage and after 500 hours.

Example 8 0.960 g (3 mmol) of TFMB was added to 15 g of NMP,
Dissolved in 0.237 g (3 mmol) of pyridine,
Cooled to 0 ° C. To this solution is added trimesic acid chloride (T
A solution in which 0.265 g (1 mmol) of MC) was dissolved in 5 g of GBL was added dropwise. After completion of the dropwise addition, the mixture was stirred at -10 ° C for 30 minutes.

Thereafter, the temperature of the solution was gradually raised to 30 ° C., and 0.960 g (3 mmol) of TFMB was added.
Further, 0.883 g (3 mmol) of BPDA was added to NMP5
g together and stirred at 30 ° C. for 1 hour. Then, TF
MB 1.920 g (6 mmol), pyridine 0.711
g (9 mmol) was added and the solution temperature was cooled to -10 ° C. 0.796 g (3 mmol) of TMC was added to this solution.
Was dissolved in 10 g of GBL, and the solution was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, the temperature of the solution was gradually increased to 30 ° C., and 1.920 g of TFMB (6 mm
l), 1.765 g (6 mmol) of BPDA was added to NMP2
0 g together, and the mixture was stirred at 30 ° C. for 1 hour.

Subsequently, the crosslinking agent 4.78 synthesized in Synthesis Example 1 was used.
8 g (6 mmol), 5.296 g of BPDA (18 mm
ol) was added together with 20 g of NMP and stirred at 30 ° C. for 15 minutes, and 7.680 g (12 mmol) of TFMB was further added.
Was added. 1.036 g (7 mmol) of phthalic anhydride and 0.490 g (5 mmol) of maleic anhydride were added, and 50
Stirred at C for 2 hours. Thereafter, 9.66 g (46 mmol) of trifluoroacetic anhydride was added together with 30 g of NMP, and the mixture was stirred at 30 ° C. for 3 hours, and then left overnight, and 5 l of water was added.
And a precipitate of a polymer composition having an isoimide structure was obtained. This was vacuum-dried at 80 ° C. for 20 hours (blending amount of crosslinking monomer: 12.3 mol%).

The dielectric constant was 2.44, the specific gravity was 1.58, and the heat resistance was 470 ° C. Adhesion is PCT adhesion test 100
No problem until hours later.

Example 9 HAB (0.648 g, 3 mmol) is dissolved in DMAC (20 g). Glycidyl methyl ether (GME)
Add 584 g (18 mmol) and cool to -10 ° C. Here, 0.265 g (1 mmol) of TMC was added to GBL
A solution dissolved in 5 g was gradually added dropwise. After dropping,
Stirring was continued for 30 minutes. Further, HAB 0.64
8 g (3 mmol), 1.584 g of GME (18 mmo
l) was added along with 10 g of DMAc. This solution contains T
A solution in which 0.609 g (3 mmol) of PC was dissolved in 5 g of GBL was added dropwise. After completion of the dropwise addition, the mixture was stirred for 1 hour.

Thereafter, 1.296 g of HAB (6 mm
l), 4.752 g (54 mmol) of GME was added to DMAc
Added with 30 g. 0.796 g of TMC is added to this solution.
(3 mmol) dissolved in 8 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, the mixture was stirred for 1 hour. Further, 1.296 g (6 mmol) of HAB,
6.336 g (72 mmol) of GME was added to 30 g of DMAc.
Added with. 1.593 g of TPC (6 m
(mol) in 10 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C.

Then, HAB 2.592 g (12 mmo)
l), 9.504 g (108 mmol) of GME in DMA
Added with 40 g of c. Here, 1.593 g of TMC
A solution of (6 mmol) dissolved in 15 g of GBL was added dropwise. After completion of the dropwise addition, the mixture was stirred for 1 hour. After that, HAB
5.184 g (12 mmol), 9.504 g of GME
(108 mmol) was added along with 60 g of DMAc.
Here, 2.436 g (12 mmol) of TPC was added to GBL1.
A solution dissolved in 5 g was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, the mixture was stirred for 1 hour.

5.184 g (24 mmol) of HAB, G
19.01 g (216 mmol) of ME was added to 60 g of DMAc.
Added with. Here, 3.186 g of TMC (12 m
mol) was dissolved in 30 g of GBL.
After completion of the dropwise addition, the mixture was stirred for 1 hour. Then, HAB 5.18
4 g (24 mmol), GME 12.67 g (144 m
mol) was added along with 80 g of DMAc. Here TP
A solution in which 4.872 g (24 mmol) of C was dissolved in 35 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C.

To this solution was added 1.355 g of benzoic acid chloride.
A solution of (10 mmol) dissolved in 10 g of GBL was added dropwise. After stirring for 1 hour, the temperature was raised to 30 ° C. and 0.980 g (10 mmol) of maleic anhydride was added.
1.072 g of trimethoxysilyl-phthalic anhydride (4
mmol), and the mixture was stirred at 30 ° C. for 2 hours (blending amount of crosslinking monomer: 14.0 mol%).

The dielectric constant was 2.31, the specific gravity was 1.52, and the heat resistance was 490 ° C. There was no problem in the adhesion at the initial stage and after 500 hours.

Example 10 0.744 g (3 mmol) of 3,3'-dithiohydroxy-4,4'-diaminobiphenyl (SAB) is dissolved in 30 g of dimethylacetamide (DMAC). Add 0.237 g (3 mmol) of pyridine and cool to -10 ° C. Here, 0.265 g (1 mmol) of TMC was added to G
A solution dissolved in 8 g of BL was gradually dropped. After completion of the dropwise addition, stirring was continued for 30 minutes. Furthermore, SAB0.
744 g (3 mmol), pyridine 0.474 g (6 m
mol) was added along with 20 g of DMAc.

To this solution was added 0.609 g of TPC (3 mm
ol) in 10 g of GBL was added dropwise. After the completion of the dropwise addition, the mixture was stirred for 30 minutes. Then SAB 1.488g
(6 mmol), 0.711 g (9 mmol) of pyridine
Was added along with 30 g of DMAc. Here, TMC0.
A solution of 796 g (3 mmol) dissolved in 10 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was performed for 30 minutes.

1.488 g (6 mmol) of SAB and 0.948 g (12 mmol) of pyridine were added together with 30 g of DMAc. 1.218 g of TPC (6 mm
ol) in 15 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 30 minutes. Then, 2.976 g (12 mmol) of SAB and 2.844 g (36 mmol) of pyridine were added to 50 g of DMAc.
Added with. 1.593 g of TMC (6 m
mol) was dissolved in 20 g of GBL.
It was dropped so as not to exceed. After dropping is complete, leave
Stirring was continued for minutes.

2.976 g (12 mmol) of SAB and 1.896 g (24 mmol) of pyridine were added to 35 g of DMAc.
Added with. 2.436 g of TPC (12
(mmol) in 25 g of GBL.
The solution was dropped so as not to exceed ° C. After completion of the dropwise addition, stirring was continued for 30 minutes. Then, 5.952 g of SAB (24 mmo
l), 0.711 g (36 mmol) of pyridine in DMA
Added with 70 g of c. Here, 3.186 g of TMC
(12 mmol) dissolved in 40 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After dropping, 30
For a minute.

5.952 g (24 mmol) of SAB and 3.792 g (48 mmol) of pyridine were added to 70 g of DMAc.
Added with. 4.872 g of TPC (24
(mmol) in 55 g of GBL.
The solution was dropped so as not to exceed ° C. After completion of the dropwise addition, stirring was continued for 30 minutes. Then SAB 11.90g (48mmo
l), 5.688 g (72 mmol) of pyridine in DMA
c was added together with 120 g. TMC 1.59 was added to this solution.
A solution of 3 g (24 mmol) dissolved in 20 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After dropping,
Stirring was continued for 30 minutes.

11.90 g (48 mmol) of SAB and 7.584 g (96 mmol) of pyridine were added to DMAc120.
g. 9.744 g of TPC (4.
(8 mmol) dissolved in 100 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After dropping, stirring was continued for 1 hour. Then SAB 23.81 g (96 mmo
l), 11.38 g (144 mmol) of pyridine were added to DM
Ac was added with 250 g of Ac. Here, TMC12.7
A solution of 4 g (48 mmol) dissolved in 150 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was performed for 30 minutes.

23.81 g (96 mmol) of SAB and 15.17 g (192 mmol) of pyridine were added to DMAc25.
Added with 0 g. 19.49 g of TPC was added to this solution.
(96 mmol) dissolved in 200 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After dropping, 1
Stirring was continued for hours.

To this solution was added 8.430 g of benzoic acid chloride.
(60 mmol) dissolved in 20 g of cyclohexanone was added dropwise. After completion of the dropping, stirring was continued for 1 hour.

The temperature of the solution was raised to 30 ° C.
11.16 g (36 mmol) of 4,4'-diphenylethertetracarboxylic dianhydride was added. After 10 minutes, 2.210 g of 3-aminopropyltriethoxysilane
(10 mmol), 1.170 g of 4-ethynylaniline
(10 mmol), 1.488 g (16 mmol) of aniline
l) was added and the mixture was stirred at 40 ° C for 2 hours. After completion of the stirring, the solution from which the precipitate was removed by filtration was filtered again through a membrane filter made of polytetrafluoroethylene having a pore diameter of 1 μm (manufactured by Sumitomo Electric Industries, Ltd.). 8 mol%).

The dielectric constant was 2.29, the specific gravity was 1.61, and the heat resistance was 470 ° C. Adhesion did not have any problem at the beginning and after 500 hours.

Example 11 0.399 g of the crosslinked monomer (1) synthesized in Synthesis Example 1
(1 mmol) and 0.1 g of isoquinoline were dissolved in 30 g of meta-cresol. 0.883 g of BPDA here
(3 mmol) was added and reacted at 150 ° C. for 1 hour.
The solution was cooled to 50 ° C. and TFMB 0.960
g (3 mmol), 0.883 g of BPDA (3 mmol
l) and 0.2 g of isoquinoline were added together with 10 g of meta-cresol, and reacted at 70 ° C. for 15 minutes and then at 150 ° C. for 1 hour. Thus, a compound corresponding to N1 described in claim 2 was obtained.

Again, the solution was cooled to 50 ° C., and 1.198 g (3 mmol) of the crosslinking monomer (1) was added.
For 30 minutes and at 150 ° C. for 30 minutes. This allows
A compound corresponding to N2 described in claim 2 was obtained. Thereafter, the solution was cooled to 50 ° C. and 3.530 g of BPDA was obtained.
(12 mmol) and 1.920 g (6 mmol) of TFMB
l) and 0.2 g of isoquinoline were added together with 50 g of meta-cresol, reacted at 70 ° C. for 15 minutes, and reacted at 150 ° C. for 1 hour. Thereby, the N3 described in claim 2
A compound corresponding to was obtained.

Further, the solution was cooled to 50 ° C., and 2.395 g (6 mmol) of the crosslinking monomer (1) was added.
And then reacted at 150 ° C. for 1 hour. Thus, a compound corresponding to N4 described in claim 2 was obtained. Subsequently, the solution was cooled to 50 ° C. and 6FDA 10.66
7 g (24 mmol), 3.84 g TFMB (12 mm
ol) and 0.2 g of isoquinoline
g, and reacted at 70 ° C. for 15 minutes, then at 150 ° C. for 2 hours. Thus, a compound corresponding to N5 described in claim 2 was obtained.

Further, the solution was cooled to 50 ° C., and 4.790 g (12 mmol) of the crosslinking monomer (1) was added.
Reaction was carried out at 15 ° C. for 15 minutes. As a result, a compound corresponding to N6 described in claim 2 was obtained. 6FDA 21.31
g (48 mmol) and 7.680 g of TFMB (24 mm
ol) and 0.5 g of isoquinoline
g, and reacted at 70 ° C. for 15 minutes, then at 200 ° C. for 2 hours. As a result, a compound corresponding to N7 described in claim 2 was obtained. After this, the solution is brought to 100 ° C.
And cooled to 2.656 g (12 mmo) of 3-aminopropyltriethoxysilane as a terminal blocking component (Rm).
l) and 1.116 g (12 mmol) of aniline were reacted for 1 hour to obtain a radially branched polyimide solution having a silicon atom at the terminal (blending amount of crosslinking monomer: 12.1).
5 mol%).

After completion of the reaction, a measurement solution was prepared in the same manner as in Example 2 using the above polyimide solution.

The dielectric constant is 2.15 and the specific gravity is 1.48.
Met. The specific gravity was reduced by about 11% as compared with Comparative Example 1. Heat resistance was 480 ° C. Adhesion is initial, 50
There was no problem after 0 hours.

Example 12 0.265 g (1 mmol) of TMC as a branched component
Was dissolved in 5 g of GBL, and 0.648 g of HAB was added.
(3 mmol) in 30 g of DMAc and 0.237 in pyridine
g (3 mmol) and added dropwise to the solution at −15 ° C. After this, HAB 0.674 g (3 mmol),
0.474 g (6 mmol) of pyridine, 10 g of DMAc
Was added. 0.609 g of TPC (3 mmo) was added to this solution.
A solution of l) dissolved in 8 g of GBL was added dropwise. Further, 0.711 g (9 mmol) of pyridine, BAHF2.1
96 g (6 mmol) and 20 g of DMAc were added. Thus, a compound corresponding to N1 described in claim 2 was obtained.

In this solution, 0.796 g (3 mmo) of TMC was added.
A solution of l) dissolved in 10 g of GBL was added dropwise. Thus, a compound corresponding to N2 described in claim 2 was obtained. After completion of the dropwise addition, 30 g of DMAc and 0.47 of pyridine were used.
4g (6mmol), BAHF 2.196g (6mmo
l) was added. Thereafter, 1.218 g of TPC (6 mmo
A solution of l) dissolved in 15 g of GBL was added dropwise. Further, 1.422 g (18 mmol) of pyridine and BAHF
4.392 g (12 mmol) were added along with 50 g of DMAc. As a result, a compound corresponding to N3 described in claim 2 was obtained. Here, 1.593 g of TMC (6
(mmol) in 20 g of GBL was added dropwise. Thus, a compound corresponding to N4 described in claim 2 was obtained. After completion of the dropwise addition, 50 g of DMAc, 0.948 g (12 mmol) of pyridine, 2.592 g of HAB
(12 mmol) was added. After this, TPC 2.436
g (12 mmol) dissolved in 30 g of GBL was added dropwise. Thus, a compound corresponding to N5 described in claim 2 was obtained. Here, 1.176 g (12 mmol) of maleic anhydride was added as a terminal blocking component (Rm), and the mixture was stirred at 20 ° C. for 3 hours. Thus, radially branched polyhydroxyamide was obtained. After completion of the stirring, the solution from which the precipitate was removed by filtration was poured into 2 l of water to obtain a polymer powder. After washing the polymer with water,
For 20 hours. 3 g of a vacuum-dried sample was dissolved in 30 g of NMP, and a filter made of tetrafluoroethylene having a pore diameter of 1 μm (FP- manufactured by Sumitomo Electric Industries, Ltd.)
100) to prepare a solution for measurement (11.8 mol% of the crosslinking monomer).

The dielectric constant is 2.35 and the specific gravity is 1.51
Met. The heat resistance was 460 ° C. Adhesion is PCT
There was no problem until 50 hours after the adhesion test.

Comparative Example 2 29.76 g (93 mmol) of TFMB, melamine5.
802 g (46 mmol) and 0.5 g of isoquinoline
-Dissolved in 1000 g of cresol. 6FDA82.
66 g (186 mmol) of m-cresol were added together with 64 g, and after stirring at 50 ° C. for 30 minutes, the temperature of the solution was raised to 150 ° C., and the system gelled (the blending amount of the crosslinking monomer: 14.1 mol%). ).

Example 13 The same reaction as in Example 2 was carried out except that the branched monomer synthesized in Synthesis Example 2 was used instead of melamine.

The dielectric constant is 2.18 and the specific gravity is 1.52
Met. The specific gravity was reduced by about 8% as compared with Comparative Example 1. The heat resistance was 470 ° C., which was good. There was no problem in the adhesion at the initial stage and after 500 hours.

Example 14 0.960 g (3 mmol) of TFMB was added to DMAc30.
g, dissolved in 0.303 g (3 mmol) of TEA,
Cooled to 10 ° C. Here, TMC 0.265g (1m
mol) was dissolved in 5 g of GBL.
The solution was dropped so as not to exceed ° C. After dropping, it is 30
Minutes. Subsequently, 1.920 g of TFMB (6 mmo
l) was prepared by adding 30 g of DMAC and 0.909 g of TEA (9 mmo).
l). 0.796 g of TMC is added to this solution.
(3 mmol) dissolved in 10 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After the dropwise addition, the mixture was stirred at −10 ° C. for 30 minutes.

3.840 g (12 mmol) of TFMB was added to 50 g of DMAc and 1.818 g (18 mmol) of TEA.
Added with. Here, 1.593 g of TMC (6 mmo
A solution of l) dissolved in 20 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, the mixture was stirred at -10 ° C for 30 minutes.

7.680 g (24 mmol) of TFMB was added to 100 g of DMAc and 3.636 g (36 mmol) of TEA.
l). Here, 3.186 g of TMC (12
(mmol) in 35 g of GBL.
The solution was dropped so as not to exceed ° C. After completion of the dropwise addition, the mixture was stirred at -10 ° C for 30 minutes.

TFMB (12.80 g, 40 mmol) and 1,988 g (8 mmol) of 1,3-bis (3-aminopropyltetramethyldisiloxane) were added to 150 g of DMAc.
And 7.272 g (72 mmol) of TEA. Here, 6.372 g (24 mmol) of TMC was added to GB
A solution dissolved in 60 g of L was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, the mixture was stirred at -10 ° C for 30 minutes.
Thereafter, the temperature of the solution was raised to room temperature, and after stirring for 1 hour, the precipitate was removed by filtration (blending amount of crosslinking monomer: 3).
3.1 mol%).

This dielectric constant was 2.45. The heat resistance was as good as 550 ° C. There was no problem in the adhesion at the initial stage and after 500 hours.

Comparative Example 3 0.960 g (3 mmol) of TFMB was added to 50 g of DMAc.
And 0.33 g (3 mmol) of TEA
Cooled to 0 ° C. Here, TMC 0.265g (1mmo
A solution of l) dissolved in 5 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 30 minutes.

1.291 g (6 mmol) of TPE was added to DM
Ac was added together with 50 g of Ac and 0.909 g (9 mmol) of TEA. A solution of 0.796 g (3 mmol) of TMC dissolved in 10 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 30 minutes.

5.162 g (24 mmol) of TPE was added to D
It was added together with 80 g of MAc and 3.636 g (36 mmol) of TEA. Here, 3.186 g of TMC (12 mmo
A solution of l) dissolved in 40 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 30 minutes.

8.928 g (96 mmol) of aniline was added to 200 g of DMAc and 14.54 g (144 mmol) of TEA.
l). Here, TMC 12.74 g (48
(mmol) in 150 g of GBL was gradually added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, if the stirring was continued, the inside of the system gelled (the blending amount of the crosslinking monomer: 48.7 mol%).

[0150]

According to the present invention, a heat-resistant resin film having a low dielectric constant and excellent adhesiveness can be obtained.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 2, 1999 (1999.9.2)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0023

[Correction method] Change

[Correction contents]

[0023]

Embedded image (R ⁰ , R ² ,... R ²ⁿ is a trivalent to hexavalent organic group, a silicon atom-containing group, R ¹ , R ³ ,... R ^{2n + 1} is a divalent group, and n is 1
An integer from to 100, r ₀ is an integer from 3 to 6,
r ₂ ,... r _2n represents an integer of 2 to 5. R ^m is hydrogen
It represents an atom, a monovalent organic group having 1 to 30 carbon atoms. The polymer of the present invention has a branched structure,
Since the polymer chains do not approach each other, the volume fraction occupied by the polymer chains in the bulk polymer decreases. Such a polymer having a small volume fraction tends to have a lower dielectric constant than a polymer having a large volume fraction. This is because the lowest dielectric constant among insulators is vacuum, followed by air. This volume fraction can be estimated from the ratio of the specific gravity of the linear polymer having the same structure as the branched polymer. That is, the specific gravity, which is the weight of the polymer per unit volume, is divided by the molecular weight of the structural unit of the polymer, and can be estimated by the ratio of the number of molecules per unit volume. That is, a polymer having a specific gravity reduced by 10% is considered to have a porosity increased by 10%.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0025

[Correction method] Change

[Correction contents]

In the method for producing a polymer of the present invention, first, a crosslinking component R ⁰ is reacted with a branch component R ¹ to obtain an oligomer N1. Subsequently, the crosslinking component R ² is reacted to obtain N 2. N3
Obtain N4 reacted branches component R ³ and. Such a reaction is obtained by repeating 2n + 1 times. At the end of the reaction, a monovalent organic group may be used as a terminal blocking group. In the general formula (21), R ^m corresponds to this portion
You. When R ^m is a hydrogen atom, there is no terminal blocking group,
In the case of a monovalent organic group having a prime number of 1 or more and 30 or less,
The functional group becomes a terminal blocking group. Examples of such compounds include monovalent amine compounds such as aniline and propylamine, and monovalent acid anhydrides such as phthalic anhydride and succinic anhydride. Furthermore, it has a reactive multiple bond such as a monovalent amine compound having a reactive multiple bond such as ethynylaniline and vinylaniline, and a reactive multiple bond such as maleic anhydride and nadic anhydride, which are reactive with heat. And the like.
In addition, aminopropyltriethoxysilane, a silicon atom-containing amino compound such as aminophenyltriethoxysilane, and a silicon atom-containing acid anhydride compound such as trimethoxysilyl phthalic anhydride have an effect of improving adhesion to a substrate, and are more preferable. . These compounds may be used alone, or a plurality of them may be used in combination. As described above, by sequentially reacting the cross-linking component and the branch component alternately, it is possible to obtain a polymer radially spread from the center.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA10 AA14 AB16 CB23 CB25 CB26 CC20 4J002 CL061 CL071 CQ001 EC006 EE026 EH006 EJ006 EL066 EL086 EL106 EP016 EU026 EV206 GQ01

Claims (6)

[Claims] 1. A trivalent to tetravalent organic group having 3 to 30 carbon atoms and at least one of groups represented by general formulas (1) to (9).
Including a polymer composed of species, wherein the content of the trivalent to tetravalent group having 3 to 30 carbon atoms in the polymer is 5 to 3;
A low dielectric constant polymer composition characterized by being 5 mol%. Embedded image (Q ¹ and Q ³ are trivalent to tetravalent organic groups containing at least ^two carbon atoms, Q ² is a divalent organic group containing at least ^two carbon atoms, and Q ⁴ and Q ⁵ are hydrogen atoms And / or a monovalent organic group having 1 to 10 carbon atoms, p is 1 to 1
An integer of 00, q and r represent 1 or 2. ) (Q ⁶ and Q ⁸ are tetravalent organic groups containing at least two carbon atoms, Q ⁷ is a divalent organic group containing at least two carbon atoms, and s is an integer from 0 to 100.) Embedded image (Q ⁹ and Q ¹¹ are tetravalent organic groups containing at least two carbon atoms, and Q ¹⁰ is a tetravalent organic group containing at least two carbon atoms.
A valent organic group, t represents an integer of 0 to 100; ) (Q ¹² and Q ^{14 each} have at least two carbon atoms.
To a tetravalent organic group, Q ¹³ is a trivalent to hexavalent organic group containing at least two carbon atoms, and Z is selected from an oxygen atom, a sulfur atom, or NH. u represents an integer of 1 to 100, and v and w represent 1 or 2. ) (Q ¹⁵ and Q ¹⁷ are a divalent organic group containing at least 2 or more carbon atoms, Q ¹⁶ is a tetravalent organic group containing at least 2 or more carbon atoms, Z is an oxygen atom, a sulfur atom, Represents NH, and x represents an integer from 0 to 100.) (Q ¹⁹ and Q ²¹ are divalent organic groups containing at least two carbon atoms, Q ²⁰ is a trivalent to tetravalent organic group containing at least two carbon atoms, and Q ²² is a hydrogen atom and / or A monovalent organic group having 1 to 10 carbon atoms, y is 1 to 10
Integer of 0, a represents 1 or 2. ) (Q ²³ and Q ²⁵ are divalent organic groups containing at least two carbon atoms, and Q ²⁴ is a divalent organic group containing at least two carbon atoms.
A valent organic group, b represents an integer from 0 to 100; ) (Q ²⁷ and Q ²⁹ are a trivalent to hexavalent organic group containing at least two carbon atoms, Q ²⁸ is a divalent organic group containing at least two carbon atoms, Z is an oxygen atom, a sulfur atom, Or NH. C is an integer of 1 to 100, d, e
Represents 1 or 2. ) (Q ³⁰ , Q ³² , Q ³⁴ are tetravalent organic groups containing at least 2 or more carbon atoms, Q ³¹ , Q ³³ are divalent organic groups containing at least 2 or more carbon atoms, Z is Represents an oxygen atom, a sulfur atom, and NH, and f represents an integer from 0 to 100.) 2. The branched polymer according to claim 1, wherein (1) a trivalent to tetravalent crosslinking component and a compound represented by the general formulas (1) to (9).
Is reacted with at least one of the groups represented by the formula (1) to obtain N1. (2) The N1 is reacted with a trivalent to tetravalent crosslinking component to form N2.
(3) Reaction of N2 with at least one of the groups represented by formulas (1) to (9) to obtain N3 (4) Reaction of N3 with a trivalent group from 3 to obtain N4 2n + 1 times (n is an integer from 0 to 100)
The low dielectric constant polymer composition according to claim 1, which is obtained by performing a reaction repeatedly and sequentially. 3. A low dielectric constant polymer composition, wherein the polymer according to claim 1 is dissolved in an organic solvent. 4. A low dielectric constant polymer composition, wherein the polymer according to claim 1 can be melt-molded. 5. The low dielectric constant polymer composition according to claim 1, wherein the relative dielectric constant with respect to vacuum is 2.7 or less. 6. The method according to claim 1, wherein after repeating the reaction 2n + 1 times, a monovalent group having 3 to 20 carbon atoms represented by the general formula (10) is reacted. Low dielectric constant polymer composition. Embedded image (D represents a monovalent organic group having 1 to 10 carbon atoms, and J represents a divalent organic group having 2 to 30 carbon atoms.)