JPH0352930A - Polyimide - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having an improved solubility, excellent in adhesion properties, heat resistance and mechanical strength and useful as an adhesives, etc., by introducing dimethylsiloxy group into the main chain and introducing an endomethylenetetraphthalimide group to the terminals of the main chain skeleton. CONSTITUTION:An objective polymer having a structure of formula I [Z is substituent having promotion activity of crosslinkage of terminal group; R02 is substituent selected from CH3, CH3CH2, CH3O, etc.; R01 is substituent selected from CH3, CH3CH2, H and Ph; n is 0-4; m is 1-6; Ar' is tetravalent organic group; Ar is divalent organic group; X and Y are positive integer]. In addition, the objective compound is recommendably obtained, e.g. by reacting an organic tetracarboxylic acid dianhydride of formula II with H2N-Ar-NH2 in an organic polar solvent, then adding an organic diamine compound of formula III thereto, reacting a norbornenic acid anhydride derivative therewith and carrying out ring closure of the resultant amic acid copolymer by dehydration.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel heat-resistant polyimide polymer. More specifically, the present invention relates to a polyimide polymer that is particularly excellent in adhesiveness, heat resistance, and mechanical strength, and is useful as a base resin for laminated materials, a heat-resistant adhesive, and the like.

[Prior Art and Problems to be Solved] Generally, polyimide is well known as a polymer having excellent heat resistance. This polymer also has excellent chemical resistance, electrical properties, and mechanical properties. Generally, polyimide resins or films are composed of polyimide obtained by reacting aromatic tetracarboxylic dianhydride and aromatic diamine. As a typical example,
There are those using pyromellitic dianhydride as the aromatic tetracarboxylic acid and oxydianiline as the diamine. These polyimide resins are known to have high heat resistance and excellent electrical insulation properties, and are widely used as electrical insulation materials such as IC sealing materials.

By the way, it has been pointed out that although polyimide has a rigid structure and has good stability at high temperatures, it has poor flexibility and poor adhesion to metals and plastics. In addition, in order to mold polyimide into films and structural members, since it is poorly soluble in organic solvents in the imide state, N,N-dimethylformamide, N,N''-dimethylacetamide, N-methyl-2- Because polyamic acid is soluble in high-boiling organic polar solvents such as pyrrolidone and dimethyl sulfoxide and is used by dissolving it in these solvents, water is generated during thermal dehydration and ring closure for imidization, resulting in the formation of molded products. voids and cracks are likely to occur in the adhesive, and there are problems with the reliability of the adhesive when it is adhered to metals, plastics, etc.

In order to solve these problems, Japanese Patent Laid-Open No. 84-2292
Publication No. 6 discloses a polyimide characterized by using a diamine containing a siloxane group and norborneneic anhydride as an end capping agent. However, although this method improves adhesion and mechanical strength,
There was a problem in terms of heat resistance due to the increased number of aliphatic groups and the low crosslink density of intermolecular crosslinks involving the norbornene skeleton. [Means for Solving the Problems] In view of the above-mentioned circumstances, the present inventors have made extensive studies to solve these technical problems, and as a result, they have arrived at the present invention.

That is, the present invention provides general formula (V)
2 is CHs, CH3 CH2, CHIO, CI
, B', F, CN, NO2 , CFs , CF3 CF
R.2, a substituent selected from CF,0, which may be the same or different; , is CH, cHs CH
2, H, Ph, n is an integer of 0 to 4, m is an integer of 1 to 6, Ar'' is a tetravalent organic group, Ar is 2
a valent organic group, X and Y are positive integers].

An example of a method for producing this polyimide polymer will be explained.

An organic tetracarboxylic dianhydride (A) represented by the general formula (I) [wherein Ar'' is the same as above], a minor molar amount relative to this, preferably 50 to 90 mol%,
More preferably, 75 to 90 mol% of the organic diamine compound (B) represented by the general formula (n) H, NA r-NH, [where Ar is the same as above] in an organic polar solvent. The reaction is carried out to obtain a prebolimer having acid anhydride groups at both ends, and then the general formula CI [[] [wherein Ro2 is CH, , CH3 CH, , CH,
0, C I S B r S FS CN, N
R. is a substituent selected from O2, CFs, CF3CF2, CF,0 and may be the same or different; , is CH3, CH)CH2, H, Pl
a substituent randomly selected, n is an integer of 0 to 4, m is 1 to
An organic diamine compound (C) represented by [an integer of 6]
was added to cause a reaction, and further a norbornenic anhydride derivative (D) represented by the general formula (IV) U [wherein Z is a substituent having the ability to promote crosslinking] as a terminal amine group capping agent was added to each mole of The ratio is (A) : ((B) + (C))
: (D)-ISR+172 [1 is a positive integer of 2 or more, preferably 1 to 9, more preferably 2 to 8] When added and reacted, it is expressed by the above general formula. A polyamic acid copolymer which is a precursor of a polyimide polymer is obtained. A polyimide polymer can be obtained by thermally or chemically dehydrating and ring-closing this copolymer.

Next, in order to obtain a polyimide copolymer from the solution of the polyamic acid copolymer, which is the precursor, a method of thermally dehydrating and ring-closing or a method of chemically dehydrating and ring-closing can be used.

Further, any processing method can be applied to this polyimide polymer, and here, as an example, a method of press molding into a sheet shape will be described.

In the method of thermally dehydrating and ring-closing (imidization) to obtain a polyimide powder, it is preferable to carry out ring-closing by heating a solution of the above-mentioned polyamic acid copolymer at a temperature of 150 DEG C. or less for about 5 to 90 minutes. Next, the obtained polyimide solution is poured into distilled water after cooling, and the filtrate is heated and dried under reduced pressure to obtain a polyimide powder made of the polyimide copolymer of the present invention. This powder is put into a predetermined mold and then heated and press-molded to obtain a polyimide sheet. The temperature during heating in the heating press is preferably in the range of 100 to 250°C, more preferably in the range of 150 to 250°C, particularly 200 to 230°C. Although there is no particular limitation on the heating rate during heating, it is preferable to heat gradually so that the maximum temperature reaches the above temperature.

Further, the molding pressure during heating is not particularly limited and can be appropriately set in relation to the desired thickness of the sheet. The heating time varies depending on the thickness of the sheet and the maximum temperature, but is generally preferably within a range of 10 to 30 minutes after reaching the maximum temperature.

In the method of chemically dehydrating and ring-closing (imidization) to obtain polyimide powder, polyimide powder can be obtained in the same manner as in the case of adding a catalytic amount of tertiary amine to the polyamide described above and thermally dehydrating it. .

As the organic tetracarboxylic dianhydride used in the present invention, organic tetracarboxylic dianhydride having any structure can be used. I can give you the following:

The organic tetracarboxylic dianhydride represented by these Ar- groups may be used alone or 2F! It is also possible to use a combination of the above.

Among these, in view of the balance of various properties, those containing at least one of the following groups as a main component are preferred.

As the Ar group in the aromatic diamine compound (B) represented by the general formula (n) mentioned above, essentially any divalent organic group can be used, but specific examples include the following: can be given.

-(CH2)6- Among them, Like What's new is CF3 less of It is preferable to use one or more of these as main components.

The repeating number X in the block unit of the polyimide copolymer is 1 to 9, preferably 1 to 7, more preferably 1 to 7.
It is 4. This is because if the number of repetitions, X, exceeds 9, the copolymerization ratio will be biased, and the effect of copolymerization will be reduced.

Moreover, although units with different values of X may exist in one molecule of the copolymer, it is preferable that the value of X is constant.

Y in general formula (V) is 1 to 20, preferably 1 to 20
15, more preferably an integer of 1 to 8. If Y is less than 1, the adhesiveness and flexibility of polyimide with other substances will be poor, and if it exceeds 20, the effect of the dimethylsilyl group will be strong, so the effect of the imide ring, which has excellent heat resistance, will be weakened. This results in poor thermal stability.

The substituent Z having the ability to promote crosslinking in general formulas (IV) and (V) is such that the polymer of the present invention is photo- or thermally cured by the terminal group derived from the compound represented by general formula (IV). There are no particular restrictions as long as the substituent has the ability to promote Ph-So-Ph-S
- Ph-Se -Ph-SO2 - P
It is particularly desirable that h-Se −↓ 0 .

Although the details of how this substituent Z is involved in the crosslinking of the polymer of the present invention are unknown, it is believed that because the hydrogen bonded to the carbon to which Z is bonded is activated. It is presumed that the crosslinking reaction progresses more easily.

Examples of organic/organic polar solvents used in the production reaction of the polyamic acid composition include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N,N
Examples include formamide solvents such as dimethylformamide and N,N-diethylformamide, and acetamide solvents such as N,N-dimethylacetamide and N,N-diethylacetamide. It can be used alone or as a mixed solvent of two or more, or as a mixed solvent with a non-solvent for polyamic acid such as methanol, ethanol, isobrobyl alcohol, benzene, toluene, xylene, methyl cellosolve, etc. More preferably. , N,N-dimethylformamide as a solvent, the aforementioned polyamic acid composition was
From the viewpoint of handling, it is desirable that the amount dissolved is 40% by weight, preferably 5 to 30% by weight.

The viscosity of this solution can be adjusted by changing the type or concentration of the solvent depending on the situation of use.

Chemical dehydration and ring closure (imidization) of polyamic acid copolymer
Examples of dehydrating agents used in this process include aliphatic acid anhydrides such as acetic anhydride, aromatic acid anhydrides, and the like. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples in any way.

Production Example 1 A 5000 ml four-necked flask was equipped with a serum cap, a thermometer, an external stirrer, and a N2 inlet tube.

After sufficient N2 substitution, dry diethyl ether 300m
1.4 g of lithium was added thereto, and the mixture was cooled to -5°C. p-
40.4 g of nitrobenzyl bromide was placed in a 50 ml syringe and added dropwise over 30 minutes while being careful not to generate heat. 18.7 g of dichlorotetramethyldisilane was dissolved in 30 ml of diethyl ether and added dropwise with a syringe. After the dropwise addition, the reaction was continued for 3 hours, then poured into 200 ml of water, neutralized with diluted hydrochloric acid, and extracted with ethyl acetate.

1.56 gs of the obtained dinitro compound, 25 ml of glacial acetic acid,
50 ml of concentrated hydrochloric acid containing 12-5 gs of tin chloride was added to a 300 ml four-necked flask equipped with a serum cap, a thermometer, an external stirrer, and a N2 inlet tube, and the mixture was stirred at 100° C. for 4 hours. 40% by weight aqueous sodium hydroxide solution 67
．． 5 ml was added and the mixture was stirred for 30 minutes.

It was poured into 200 ml of water and extracted with ethyl acetate.

The structure obtained from IR,'H-NMR measurements was the following diamine [1].

CH3 [1] Production Example 2 A 5000 ml four-necked flask was equipped with a serum cap, a thermometer, an external stirrer, and a N2 inlet tube.

The atmosphere was sufficiently replaced with N2, and the reaction system was cooled to below 10°C. Add 250 ml of dry carbon tetrachloride, and add 26.94 g of thallium pentadiene (hereinafter referred to as Cp-TI).
was added under a stream of N2. 23. Phenylselenium bromide (PhSeBr) in 25 ml of dry carbon tetrachloride.
60 g was added dropwise over 1 hour. After stirring for 20 minutes,
While keeping the reaction system at the above temperature, maleic anhydride 9.8
g was dissolved in 25 ml of dry carbon tetrachloride, and then added dropwise to the reaction system.

After stirring for 84 hours, the precipitate was collected by filtration and purified by column chromatography to obtain 14.3 g of compound [2]. The structure of the obtained compound is IR,'
Identification was made by H-NMR measurement.

Example 1 A 5000 ml four-necked flask was equipped with a serum cap, a thermometer, an external stirrer, and a N2 inlet tube. Paraphenylenediamine (hereinafter referred to as p-PDA) 6.4
g was collected, and 231.0 g of N,N-dimethylacetamide (hereinafter referred to as DMAc) was added to dissolve it. On the other hand, 21.8 g of pyromellitic anhydride (hereinafter referred to as PMDA) was collected in a 50 ml eggplant flask, and the p-
It was added in solid form into the PDA solution. Furthermore, this 50
10 ml of PMDA remaining on the wall of the eggplant flask. The mixture was poured into a reaction system (4-necked flask) with DMAc of 100 mL, and stirring was continued for an additional hour to obtain an acid anhydride-terminated amic acid prebolimer.

On the other hand, 8.89 g of diamine [1 piece] was collected in a 50 ml Erlenmeyer flask, and 12.0 g of DM Ac was added thereto to dissolve it. This solution was added into the reaction system (4 neck flask) and then dissolved in DMAclOml. The acid anhydride [2] was quickly added to obtain an endomethylenetetraphthalimide group end-capped copolymer polyamic acid solution having a bulk viscosity of 25 voids.

In the above reaction operations, PMDA, p-PDA, diamine [1], and acid anhydride [2] were handled and the inside of the reaction system was carried out under a stream of dry nitrogen.

The obtained polyamic acid solution was stirred at 35 to 45°C for 4 to 5 hours, and further refluxed and reacted at 150 to 180°C for 4 to 5 hours to obtain a polyimide solution.

This polyimide solution was poured into 300 ml of distilled water, and the filtrate was dried under vacuum at 150°C for 480 hours to obtain a yellow polyimide powder. Put 2.5 g of this powder into a mold with a cross-sectional area of 16.3 cd,
After preheating at 0° C. for 30 minutes, press molding was performed at 195° C. for 25 minutes under a pressure of 230 kg/C to obtain a sheet with a thickness of 100 μm. The physical properties of this sheet are
It was as shown in Table 1.

Production Example 3 1 g of dichlorotetramethyldisilane. 7. 10.2 g of diamine [3] was obtained in the same manner as in Production Example 1, except that 12.9 g of dichlorodimethylsilane was used.

CH3 [3] Production Example 4 12.56 g of acid anhydride [4] was obtained according to the same method as Production Example 2, except that 23.60 sr of PhSeBr was changed to 14.46 g of phenylsulfenyl chloride (PhSC 1). Ta.

Example 2 8.89 g of diamine [1] was added to 7.17 g of diamine [3]
g, further add 7.09 g of acid anhydride [2] to acid anhydride [4
] Example 1 except that each was changed to 46.05 g.
Polyimide sheets were obtained according to the method described in . The physical properties of this sheet were as shown in Table 1.

Example 3 A polyimide molecule was obtained in accordance with the method of Example 1, except that 21.8 g of PMDA was replaced with 29.4 g of penzophenone tetracarboxylic anhydride (hereinafter referred to as s-BPDA). The physical properties of this sheet were as shown in Table 1.

Example 4 A polyimide sheet was obtained according to the method of Example 2, except that 21.8 g of PMDA was changed to 29.4 g of s-BPDA. The physical properties of this sheet were as shown in Table 1.

Implementation N5 6.04g of p-PDA was added to oxydianiline (hereinafter referred to as OD
A polyimide sheet was obtained in accordance with the method of Example 1, except that the amount was changed to 11.9 g.

The physical properties of this sheet were as shown in Table 1.

Example N6 A polyimide sheet was obtained according to the method of Example 2, except that 6.04 g of p-PDA was changed to 1.9 g of ODAI. The physical properties of this sheet were as shown in Table 1.

Example 7 The method of Example 1 was followed, except that 21.8 g of PMDA was changed to 44.4 g of 4,4°-hexafluoroisobutylidene bisphthalic dianhydride (hereinafter referred to as 6-FDA). A polyimide sheet was obtained. The physical properties of this sheet were as shown in Table 1.

Implementation N8 PMDA21. A polyimide sheet was obtained according to the method of Example 2, except that 8rr was changed to 6-FDA44.4tr. The physical properties of this sheet were as shown in Table 1.

Table 1 *) 389 19.2 178 1g53
99 16.9 166 18941
5 17.9 179 199425
21.3 181 221402
20.6 171 201384
20.8 168 185356
20.9 156 191343
21.2 163 211Tg temperature was recorded with a Shimadzu DT-407GA measurement device [Effects of the invention] The polyimide of the present invention has a dimethylcytoxy group introduced into the main chain and an endomethylenetetraphthalimide group at the end of the main chain skeleton. This improves solubility, and the polyimide resin obtained by heat-treating this polyimide has a highly three-dimensional crosslinked structure, so it has improved mechanical, electrical, and other properties such as tensile strength, insulation, and adhesive properties. has improved thermal properties and can be used in a wide range of applications such as heat-resistant adhesives, heat-resistant paints, and polymeric materials for electronic devices.

Claims (1)

[Claims] 1) General formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Z is a substituent having the ability to promote crosslinking of the terminal group, R_
0_2 is CH_3, CH_3CH_2, CH_3O, C
l, Br, F, CN, NO_2, CF_3, CF_3C
R_0_1 is a substituent selected from F_2, CF_3O and may be the same or different;
, CH_3CH_2, H, a substituent selected from Ph, n
is an integer of 0 to 4, m is an integer of 1 to 6, Ar' is a tetravalent organic group, Ar is a divalent organic group, and X and Y are positive integers.] Combined. 2) Z is Ph-SO-, Ph-Se-, Ph-S-,
Claim 1 selected from Ph-Se-, Ph-SO_2-
The polyimide polymer described in . 3) The polyimide polymer according to claim 1, wherein Ar is a numerical formula, a chemical formula, a table, etc. 4) The polyimide polymer according to claim 1, wherein Ar is a numerical formula, a chemical formula, a table, etc. 5) The polyimide polymer according to claim 1, wherein Ar is a numerical formula, a chemical formula, a table, etc. 6) The polyimide polymer according to claim 1, wherein Ar is a numerical formula, a chemical formula, a table, etc. 7) The polyimide polymer according to claim 1, wherein Ar' is ▲a numerical formula, a chemical formula, a table, etc.▼. 8) The polyimide polymer according to claim 1, wherein Ar' is ▲a numerical formula, a chemical formula, a table, etc.▼. 9) The polyimide polymer according to claim 1, wherein Ar' is ▲a numerical formula, a chemical formula, a table, etc.▼. 10) The polyimide polymer according to claim 1, wherein Ar is a numerical formula, a chemical formula, a table, etc. 11) The polyimide polymer according to claim 1, wherein X is an integer of 1 to 9. 12) The polyimide polymer according to claim 1, wherein Y is an integer of 1 to 20.