JPH0220523A - Silicone imide copolymer and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain a copolymer having excellent heat resistance and softening temp. and moldability adjustable to a desired level by reacting bis(m- aminophenyl)-1,1,3,3-tetraalkyl-disiloxane with a plurality of arom. carboxylic acid dianhydrides. CONSTITUTION:A silicone imide copolymer having repeating units of formula I or II is obtd. by reacting bis(m-aminophenyl)-1,1,3,3-tetraalkyldisilosxane with a plurality of arom. carboxylic acid dianhydrides. In the formulas, R1 and R2 are each formula III or IV; X is a direct bonding, -O-, -CO-, -S-, -SO2-; R<1> and R<2> are groups different from each other; R<0> is an alkyl. Said copolymer has heat resistance and its properties, such as softening temp. and flexibility, are easily adjustable. Therefore, it is suitably used for not only a film for a flexible printed circuit board, an insulating material for heavy electric instruments, a heat-resistant electric wire coating for airplanes but also varnishes, tapes, a matrix resin for fiber-reinforced composite materials etc., in accordance with required characteristics.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a flexible printed wiring board film,
The present invention relates to a novel silicone imide copolymer suitable for insulating materials for heavy electrical equipment, carrier tapes, heat-resistant wire coating materials for aircraft, as well as varnishes, tapes, matrix resins for fiber-reinforced composite materials, and a method for producing the same.

[Conventional technology]

Polyimide, that is, a polymer containing an imide group in one molecular chain, can be used as a resin film, adhesive, molded product, M
Applied to various uses of A-edge varnish.

Taking advantage of its heat resistance, it is also used in aircraft structural materials and flexible circuits (FPC). In particular, polyimide, which has a high proportion of aromatic rings in its molecules, is known as an excellent heat-resistant material, but on the other hand.

It has drawbacks such as poor flexibility and solubility in various solvents, and therefore lacks processability. In order to solve this drawback, various methods for producing modified polyimides have been developed that include amide, ester bonds, siloxane bonds, etc. in the main chain of polyimide. , polyesterimide, polysiliconimide, and various modified polyimides such as polyetherimide exhibiting thermoplasticity have been developed and manufactured.

In particular, polysilicon imide is produced by reacting a diaminosiloxane compound with a tetracarboxylic acid dianhydride such as pyromellitic anhydride, biphenyltetracarboxylic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, etc. A method for producing polysilicon imide to obtain an imide and a polysilicon imide obtained by such a production method are disclosed in Japanese Patent Publication No. 43-27439, Japanese Patent Publication No. 47-9268, etc., and diaminosiloxane, respectively. Various proposals have been made depending on the type and composition of the compound, the type of polysilicon imide obtained, etc.

The present inventor recently discovered bis(n+-aminophenyl)-1,1
, 3゜By reacting 3-tetraalkyldisiloxane with an aromatic tetracarboxylic acid dianhydride, the tetraalkyldisiloxane imparts high flexibility and freedom to the molecular chain bonded to the meta position of the aromatic ring having an amino group. (Japanese Patent Application No. 1982-202764).

[Problem that the invention seeks to solve]

However, even with these modified polysilicon imides, it is extremely difficult to adjust various physical properties such as softening temperature as desired, and sometimes flexibility and solubility in various solvents are poor, resulting in insufficient processability. There was no
Alternatively, it has been pointed out that heat resistance and softening point are too low, and various components can be selected arbitrarily and various physical properties such as softening temperature can be adjusted at will. Development of new modified imide or imide copolymer. is desired.

Therefore, an object of the present invention is to provide a novel imide copolymer which has excellent heat resistance and whose softening temperature and processability can be appropriately adjusted as desired, and a method for producing the same.

[Means for solving problems]

The above object of the present invention is to obtain a silicone imide copolymer having the following repeating unit (RI) and a repeating unit (II), a silicone imide copolymer having the following repeating unit (1) and a repeating unit (III), and a silicone imide copolymer having the following repeating unit (III) and the following repeating unit. (1), repeating unit (II), repeating unit (III) and repeating unit (
IV) and their production methods.

(In the formula, R", R";
However, R1 and R2 represent different groups.

Ro: alkyl group) X: direct bond, -can, -C-1-S-1-50, -where R1 and R2 represent different groups.

Y;-(h,-),-5-,-3Q,-,-CH2-5
-C(CI43)2-1"c (CF3)2-1-3
L(CI et al.) 2-) Various types of alkyl groups are used, and there are no particular restrictions on the number of carbon atoms; however, lower alkyl groups such as methyl, ethyl, propyl, or butyl groups are usually used. is used, and methyl group is particularly preferably used.

That is, the silicon-containing imide copolymer of the present invention has a silicon moiety made of tetraalkyldisiloxane as described above, and has phenyl groups bonded to both ends of this silicon moiety, and further has phenyl groups bonded to both ends of the silicon moiety. It contains as a repeating unit a structure having an imide bond that is bonded to the phenyl nucleus via a carbonyl bond (-C-) at the meta position of the phenyl group, but in this way, it is Regarding imide copolymers having silicon imide units having imide bonds, there are no examples specifically described in the publications introduced above or in other publications.

In order to obtain a heat-resistant plastic with excellent processability, particularly flexibility, the inventors first made the molecular chains as flexible as possible. It is important to develop modified polyimides that satisfy requirements such as ■reducing the amount of imide components in the polymer chain, and ■introducing other thermally stable groups into the main chain. In the case of (1) and (2), it is effective to make sure that the bonds are in meta-coordination with each other, and that the bonded aromatic rings maintain a structure in which they cross each other. We assumed that this would be the case, and used bis(m-aminophenyl)1,1,3.3-tetraalkyldisiloxane as the diamino component for polyimide production, and reacted it with aromatic tetracarboxylic acid dianhydride. When a polyimide was produced using this method, it was found that a polyimide with good flexibility and solvent solubility and excellent heat resistance could be obtained.

As a result of further research, this diamine component...
React with two or more types of aromatic tetracarboxylic acid dianhydrides. ■Methods such as reacting with one type of aromatic tetracarboxylic acid/dianhydride together with other types of aromatic diamines, or ■Reacting with two or more types of aromatic tetracarboxylic acids/dianhydrides together with other types of aromatic diamines. We have developed a new polyimide copolymer containing the silicone imide unit obtained by the above method, and have also established a method for producing the same.

The second silicon imide unit is present in the polyimide chain and increases the flexibility and mobility of the molecular chain, thereby increasing flexibility. For example, the softening temperature of polyimide obtained by the reaction of pyromellitic anhydride and oxydianiline is 350°C or higher, whereas the diamine component is bis(m-aminophenyl)-1,1,3,3
- using a mixture containing mole percent of tetraalkyldisiloxane. The softening temperature of the imide copolymer according to claim 2 obtained by reacting this with pyromellitic anhydride is 218°C.
Therefore, there was almost no decrease in thermogravimetric loss or humidity, and a significant decrease in softening point was observed.

Moreover, the silicon-containing imide copolymer of the present invention described above is
Manufactured by using bis(m-aminophenyl) 1,1.3.3-tetraalkyldisiloxane as part or all of the diamine component and reacting it with aromatic tetracarboxylic acid dianhydride. .

still. Bis(m-aminophenyl) used in this case 1,
1,3,3-tetraalkyldisiloxanes such as bis(
(m-aminophenyl)-1.1,3.3-tetramethyldisiloxane can be produced by a method according to the following reaction formula.

■.

b, p. 162.4℃/11. OmmHg 72.
5% b. P. 166, 0℃/10-'mmHg 8
8.0% To explain the method for producing the silicon imide copolymer of the present invention more specifically, bis(m-aminophenyl)-1, l, 3 produced by the above method etc.
, 3-tetraalkyldisiloxane and the following formula (VI
) is represented by the following formula (V) in equimolar amounts together with at least one aromatic diamine represented by (V).

~su2 b. p. 67, 0℃10. Nasaratane 54.4% (however,
R1 is as described above. ) H, N-R3-NH.
(VI) (However, R3 is as above) Polyamide 35, / After producing 1% tsucic acid, this polyamic acid solution is applied by casting onto a support such as a glass plate, and then heated to remove the solvent and perform an imidization reaction to form a film-like imide copolymer. can be manufactured. Further, a resin-like imide copolymer can also be produced by reprecipitating and isolating polyamic acid from the polyamic acid solution using diethyl ether or the like, and then heating it.

Furthermore, this resin-like silicone imide copolymer can be molded into a predetermined shape by a method such as a hot press method or the like, either directly or after being pulverized into powder.

The aromatic tetracarboxylic acid dianhydride represented by the formula (V) used in this case is as follows.

For example, diphenylsulfone-3,3', 4,4'
-Tetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride,
Examples include one or a mixture of two or more selected from dianhydride and pyromellitic acid dianhydride.

In addition, examples of the aromatic diamine represented by the above formula (VI) include para-phenylene diamine, meta-phenylene diamine, and compounds represented by the following formula, which may be used alone or as a mixture of two or more. You can also do that.

(In the formula, Y is -0-, -CH, -1-CO-, -5-1
-SO, -1-C(CH,), -1-C(CF3)z-
or -5i (C1(3)a-). In the present invention, when two or more aromatic diamines or two or more aromatic tetracarboxylic acid dianhydrides are used, two or more aromatic dianhydrides are used. They may be mixed and reacted at the same time, or the two types may be reacted separately. In the former case, the imide copolymer has a random unit arrangement, and in the latter case, the imide copolymer has a block-like unit arrangement, but no specific change in physical properties is observed between the two.

〔Effect of the invention〕

As explained above, the imide copolymer having a silicon component of the present invention has a highly thermally stable silicon moiety introduced therein, and has an imide bond at the meta position of both terminal phenyl groups of the silicon moiety, and has excellent flexibility. Since silicon imide units have been introduced, it has heat resistance and can easily adjust properties such as softening temperature and flexibility.

Therefore, depending on the desired performance, it can be suitably used for films for flexible printed wiring boards, insulating materials for heavy electrical equipment, carrier tapes, heat-resistant wire coating materials for aircraft, as well as varnishes, tapes, matrix resins for fiber-reinforced composite materials, etc. be able to.

Furthermore, according to the production method of the present invention, the imide copolymer of the present invention can be produced easily and efficiently.

〔Example〕

Examples will be shown below to explain the present invention in more detail.
The invention is not limited to these examples.

Example 1 0.17 g of bis(m-aminophenyl)-1,1,3,3-tetramethyldisiloxane (+m-APMSi) (
While stirring 0.56mmoQ) at 0°C, add 0.12g of pyromellitic dianhydride (PMOA) (0.28m+
A solution of N,N-dimethylacetamide (DMAc) l- containing 0.2 g (0.28 mmoQ) of diphenylsulfone tetracarboxylic acid dianhydride (DSTA) was added dropwise in a nitrogen stream over 10 minutes. After completion of 'a', the solution was stirred at room temperature for 6 hours and then heated under reduced pressure (1 mmHg).
) and continued stirring for 2 hours to obtain a viscous solution. This solution was cast onto a glass plate and heated in a nitrogen stream at 150°C for 2 hours and at 200°C for 2 hours to remove the solvent and imidize it to obtain a yellow transparent film (thickness 30-50/411). . The IR spectrum of this film was determined by aI; '3.1780cm-1,1720c+a-
1 has an imide group, 1350c+a-' has a sulfone group,
Eleven absorptions of 5i-0 bonds were observed at 105105O'. Furthermore, when an IINMR spectrum was measured using dimethylformamide (hereinafter referred to as -DMF) in which six hydrogen atoms were deuterated, a singlet based on 5i-Cf13 was found at δfrjio of 3 ppm, and a δ value of 7.8 to 9. ,0p
A multiplet based on aromatic hydrogen was observed at pm, and the integral ratio of the two was 1:1.

From the above results, the structure of the produced polymer is determined by the following formula (■a
) and formula (■b) were copolymerized in a ratio of 1=1 to an imide copolymer. Also, the relative viscosity of this polymer in 0MAc (concentration = 0.5 g/dQ
) was 0.35 dQ/g.

220-1 without significantly affecting heat resistance.
It can be seen that the temperature can be adjusted arbitrarily between 40°C.

Table-1 Similarly, by changing the mixing ratio of PMDA and DSTA, the formula (■a
) and formula (■b) with different copolymerization compositions were synthesized. These properties were compared with those of polyimides consisting only of repeating units (■a) and (■b). The results are shown in Table-1. From this result, the flow initiation temperature of the copolymer can be adjusted by changing the composition of DSTA.
bis(m-aminophenyl)-1,1, while stirring mmoQ) at 0°C.

3.3-Tetramethyldisiloxane (m-APMSi)
0.15 g (0,46 mmoU and 0.83 g (4,12 mmoU) of 4,4'-diaminodiphenyl ether (ODA)
oQ) containing N,N-dimethylacetamide (DMAc)
) 10 mQ of the solution was added dropwise in a nitrogen stream over 30 minutes. After completion of the dropwise addition, this solution was stirred at room temperature for 6 hours to obtain a viscous yellow homogeneous solution. This solution was then poured into a large amount of diethyl ether, and a pale yellow resinous product was isolated by reprecipitation. The weight after drying is 1.95g, and the relative viscosity of the liquid in 0MAc (0.5g/2 degrees Fahrenheit)
dQ) was 0.69 d12/gte.

Furthermore, the IR spectrum of the above resinous product was measured using the KBr tablet method and was found to be 3400-2500 cm-1 and 1
carboxyl group at 710 cm-1, 1670 cm-”
Absorption of an amide group was observed at 1050cn+-1, and absorption of a SiO bond was observed at 1050cn+-1. Furthermore, using DG-DMF as a solvent")
When all INMR values were determined, the δ value was 0.3 ppm.
A single line based on -C1l, and a multi-lane line based on aromatic hydrogen at a δ value of 7.5-8.7 ppm are observed, and the integral ratio of both is 1.
．． It was 2:11. From the above results, this product has the following formula (■a) and formula (■b) as repeating units and the ratio is 1=
It was confirmed that it was an amic acid copolymer of No. 9.

On the other hand, the 0 MAc solution of polyamic acid obtained in the above reaction was cast on a glass plate and heated in a nitrogen stream at 150°C for 2 hours and 200°C for 3 hours to remove the solvent and imidize. Yellow transparent film (thickness approx. 30~
50 μl) ρ was obtained. This film was insoluble in the solvent, but when its IR spectrum was measured, it was found to be 1780c
1050C1 with imide group at m-1, 1720 cm-1
Absorption of 81-0 binding to ll-1 was observed. From this result, in this film, formula (■a) and formula (■b)
The imide of the repeating unit is almost completed, and the following formula (IXa)
It was found that this is an imide copolymer in which the formula (■b) is used as a repeating unit and the ratio thereof is 1:9.

When the softening point of this film was analyzed by the TMA method using the needle penetration method, it was found to be 328°C. In addition, the breaking strength in the tensile test is 7.5 Kg/mm2, the breaking elongation is 10%, and the 1 elastic modulus is 100 Kg/mm'', and the trade name K a p t o n' that does not include formula (■a) The softening point was about 21°C lower than that of a polyimide film consisting only of repeating units of formula (■b) corresponding to .The temperature at which weight loss started was 460°C.Those with other compositions were synthesized in the same way. and obtained various physical properties.The results are shown in the table.
Shown in 2. This result also shows that the inclusion of the siloxane unit of formula (IX a ) sharply lowers the softening point of the amide copolymer.

Example 3 Pyromellitic acid dianhydride (PMDA) 0.43 g (2
, 34a + moQ) and diphenylsulfone tetracarboxylic acid °2 anhydride (0.53 g (2,34 mmoQ)) were dissolved in 10 d of dimethylacetamide (DMAc), and bis(11-7 minophenyl)-1 was dissolved in dimethylacetamide (DMAc) with stirring at 0°C in a nitrogen stream. , 1,3,3-tetramethyldisiloxane (m
-APMSi)O, 11 g (0,47 mmoQ), and 4
．． 4'-diaminophenyl ether (ODA) 0.65
g (4,23a+moff) was added. This solution was then stirred at room temperature for 3 hours, resulting in a viscous yellow solution.

This solution was cast on a glass plate and heated at 150°C for 2 hours.
When the mixture was heated at 200° C. for 3 hours to remove the solvent and imidize, a transparent yellow film (about 35 pm thick) was obtained. This film exhibited swelling behavior in solvents such as DMAc, but did not completely dissolve.

When we measured its IR spectrum, we found that it was 1780 cm-
Absorption of an imide group at '1720 cm-1, a sulfone group at 1350 cm-1, and a 5i-0 bond at 1050 cm-1 was observed.From these results, this film was found to have the above formula (■a), (■ It is thought to consist of an imide copolymer having four repeating units: b), ([a), and (■b) (ratio: 1:9:1:9).

The softening point of this film was measured using the needle penetration method described above.
93° C. and the formula (IX a ) described in Example 2
Imide copolymer containing formula (■b) in a ratio of 1:9 (experiment NQ
It can be seen that the softening point is lowered by 30°C compared to 3).

Patent applicant: Toa Fuel Industries Co., Ltd.

Claims (5)

[Claims] (1) A silicone imide copolymer having the following repeating unit (I) and repeating unit (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1, R^2; ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ X; Direct bond, -O-, -CO-, -S-, -SO_2
-However, R^1 and R^2 represent different groups. R^0; alkyl group) (2) A silicone imide copolymer having the following repeating unit (I) and repeating unit (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1; ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ X: Direct bond, -O-, -CO-, -S-, -SO_2
-R^0; Alkyl group) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [In the formula, R^1; ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ X: Direct bond, -O-, -C-, -S-, -SO_2-
R^2; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Y; -O-, -CO-, -S, -SO_2-, -CH_
2-, -C(CH_3)_2-, -C(CF_3)_2
−, −Si(CH_3)_2−] (3) A silicone imide copolymer having the following repeating units (I), repeating units (II), repeating units (III) and repeating units (IV). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1, R^2; ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ X; Direct bond, -O-, -CO-, -S-, -SO_2
-However, R^1 and R^2 represent different groups. R^0; alkyl group) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) [In the formula, R^1, R^2; ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ X: Direct bond, -O-, -C-, -S-, -SO_2-
However, R^1 and R^2 represent different groups. R^3; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Y; -O-, -CO-, -S-, -SO_2-, -CH
_2-, -C(CH_3)_2-, -C(CF_3)_
2-, -Si(CH_3)_2-] (4) Bis(m-aminophenyl)1,1,3,3-tetraalkyldisiloxane and multiple aromatic carboxylic acids.
A method for producing a silicon imide copolymer as set forth in claim 1 by reacting with dianhydride. (5) Aromatic tetracarboxylic acid dianhydride, aromatic diamine and bis(m-aminophenyl) 1,1,3,3-
A method for producing a silicone imide copolymer as set forth in claim 2 and/or claim 3 by reacting with tetraalkyldisiloxane.