JP2021105185A - Oligoimide composition - Google Patents

Abstract

To provide an oligoimide composition that has an increased weight average molecular weight (Mw) and can be made into a solution with good moldability, wherein all or part of terminal groups of the oligoimide composition are maleimidized.SOLUTION: There is provided an oligoimide composition consisting of a terminal maleimidized oligoimide and a diamine addition body of the terminal maleimidized oligoimide, in which a dimer diamine is used as a diamine constituting the oligoimide. The oligoimide composition has a weight average molecular weight (Mw) of 6000 to 20000 inclusive.SELECTED DRAWING: None

Description

The present invention relates to oligoimide compositions.

Among the oligoimides, oligoimides in which a part or all of the terminal groups are maleimided (hereinafter, may be abbreviated as "MOI") are known. (Patent Documents 1 to 3 and Non-Patent Document 1) These MOIs can be heat-cured or photo-cured to obtain a molded product such as a film having high heat resistance and good mechanical properties based on an imide bond. .. Further, since the vinyl group of the maleimide group is active, it can be copolymerized with, for example, vinyl compounds of vinyl ethers, acrylates, and methacrylates, and these copolymers can be used as raw materials for various heat-resistant resins and adhesives. It is useful.

Among the MOIs, those using aromatic tetracarboxylic acid as the tetracarboxylic acid constituting the oligoimide and aliphatic diamine as the diamine are suitable for the passivation film of the silicon substrate, the adhesive for die bonding, the substrate for high frequency and the like. It is disclosed that it can be used for. (Patent Documents 4 to 6) As a method for producing these MOIs, an oligoimide as a terminal diamine is reacted with maleic anhydride in a solvent to produce a terminal maleamic acid oligoimide, and the terminal maleamic acid is imidized. As a dehydration catalyst, a strong acid having a pKa of less than 1 such as sulfuric acid, methanesulphonic acid, and p-toluenesulphonic acid, and an aliphatic tertiary amine such as triethylamine are coexistently heated at 100 ° C. or higher for a long time to imide. At the time of conversion, the terminal maleamic acid is imidized while removing by-product water by co-boiling, and the terminal maleamic acid is imidized (Patent Documents 3 and 5) or in a solvent containing an amide-based solvent. A method of imidizing a terminal maleamic acid while removing by-product water by co-boiling during imidization by heating the oligoimide at 100 ° C. or higher for a long time in the coexistence of the strong acid (Patent Document 6). It is disclosed. Further, in Patent Document 4, when maleimic acid is maleimided, a mixture of acetic anhydride and a basic compound (1-hydroxybenztriazole, triethylamine, sodium acetate, etc.) is used as a dehydration catalyst, and the temperature is lowered over a long period of time. Also disclosed is a method of producing MOI by reacting with. (Patent Document 4)

U.S. Pat. No. 5,096998 Japanese Unexamined Patent Publication No. 8-129914 U.S. Pat. No. 7,208566 U.S. Pat. No. 6034195 US Patent No. 2013/0228901 International Publication Patent No. WO / 2015/048575

JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY, VOL. 26, 1165-1178 (1988)

However, since the MOI disclosed in the above document has a low weight average molecular weight (Mw), when it is used as a solution and applied on a substrate, dripping or the like may occur, and from the viewpoint of moldability, it may occur. There was a point to be improved. Therefore, the present invention solves the above-mentioned problems, and an object of the present invention is to provide an MOI composition having a sufficiently increased weight average molecular weight (Mw).

It has been found that the above-mentioned problems can be solved by using MOI as a specific composition, and the present invention has been completed.

The present invention has the following object.
<1> An MOI composition comprising 80 to 99% by mass of MOI and 1 to 20% by mass of a diamine adduct of MOI (hereinafter, may be abbreviated as "MOI-DA").
<2> The MOI composition having a weight average molecular weight (Mw) of 6000 or more and 20000 or less.

Since the MOI composition of the present invention has an increased weight average molecular weight (Mw), it can be a solution having good moldability.

The MOI composition of the present invention comprises 80 to 99% by mass of MOI and 1 to 20% by mass of MOI-DA, preferably 85 to 95% by mass of MOI and 5 to 15% by mass of MOI-DA. By setting the composition ratio in this way, the weight average molecular weight (Mw) is increased and the moldability is improved.

The oligoimide forming the skeleton of MOI is an oligoma having an imide bond, and is obtained by dehydration condensation of tetracarboxylic dianhydride and diamine. As the tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride and the like can be used, and aromatic tetracarboxylic dianhydride can be used. The thing is preferable. Further, as the diamine, aromatic diamines, aliphatic diamines, alicyclic diamines and the like can be used, and aliphatic diamines are preferable.

The aromatic tetracarboxylic dianhydride is not limited as long as it is a tetracarboxylic dianhydride having an aromatic ring, and for example, pyromellitic dianhydride (PMDA), 1,2,3,4-benzene. Tetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4, 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ethertetracarboxylic dianhydride (4,4) ′ -Oxydiphthalic dianhydride), 2,3 ′, 3,4 ′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4 ′-diphenylsulfonetetracarboxylic dianhydride, 2,3 3', 4'-diphenylsulfotetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4 , 5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride and the like. , PMDA is preferably used. As the aliphatic tetracarboxylic dianhydride, for example, butanetetracarboxylic dianhydride can be used. Further, as the alicyclic tetracarboxylic dianhydride, for example, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride and the like can be used.
These aromatic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, and alicyclic tetracarboxylic dianhydrides may be used alone or in combination of two or more.

The aliphatic diamine is not limited as long as it is a diamine having an alkylene group in the main chain, but for example, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2, Examples thereof include aliphatic diamines such as 11-diaminododecane and dimadiamine, and dimadiamine is preferably used. As the diamine diamine, commercially available products such as Cognis Japan's trade names "Versamine 551" and "Versamine 552" and Croda's trade names "Priamine 1074" and "Priamine 1075" are used.
Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2'-diaminodiphenylpropane, and 4,4'-. Diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 2,3-diaminonaphthalene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'- Di (4-aminophenoxy) diphenylsulfone, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane and the like can be used. Examples of the alicyclic diamine include cyclobutane diamine, cyclohexanediamine, diaminobicycloheptane, diaminomethylbicycloheptane, diaminooxybicycloheptane, diaminomethyloxybicycloheptane, isophoronediamine, diaminotricyclodecane, and diaminomethyltricyclodecane. Etc. can be used.
These aliphatic diamines, aromatic diamines, and alicyclic diamines are used alone or in combination of two or more.

The oligoimide constituting the MOI composition of the present invention is composed of a condensate of tetracarboxylic dianhydride and diamine, and the molar ratio of tetracarboxylic acid to diamine is in the range of 0.5 or more and less than 0.9. It is preferably 0.6 or more and 0.7 or less. By setting such a molar ratio, good moldability and high heat resistance can be ensured at the same time.

The weight average molecular weight (Mw) of the MOI composition of the present invention is preferably 6000 or more and 20000 or less, and more preferably 7000 or more and 15000 or less. By setting Mw in such a range, good moldability can be ensured. The weight average molecular weight (Mw) can be confirmed, for example, by measuring GPC under the following conditions.
<GPC measurement conditions>
Column: Showa Denko Shodex (R) GPC KF-803 x 1 piece, GPC KF-804 x 2 pieces (3 pieces connected)
Eluent: THF
Temperature: 40 ° C
Flow rate: 1.0 mL / min Detector: UV detector

The MOI composition of the present invention can be produced, for example, by the following process. That is, first, a diamine and a tetracarboxylic dianhydride are reacted in a solvent to produce an oligoamic acid (oligoimide precursor) of the terminal diamine, and then maleic anhydride is reacted to produce a maleic acid at the terminal. It produces acid-modified oligoamic acid. After that, the MOI solution can be obtained by imidizing the amic acid portions of the maleamic acid and the oligoamic acid in a batch using an acid catalyst. Here, the tetracarboxylic dianhydride is preferably used in an amount of 0.5 mol or more and 0.9 mol or less, more preferably 0.6 mol or more and 0.7 mol or less, based on 1 mol of the diamine. The maleic anhydride is preferably used in an amount of 2 * (1-X) mol or more and 4 * (1-X) mol or less with respect to 1 mol of the diamine and X mol of the tetracarboxylic dianhydride used. The reaction temperature at the time of imidization is preferably 150 ° C. or lower. The reaction time during imidization is preferably 2 hours or more and 10 hours or less, and more preferably 4 hours or more and 8 hours or less. In the imidization reaction, the reaction can be carried out while distilling the water produced by the imidization out of the reaction system. The MOI solution obtained as described above is washed with an aqueous solvent, diamine is added to the MOI solution from which the acid catalyst and the like have been removed, and this is subjected to an addition reaction with a part of MOI to obtain MOI-DA. By producing, a solution consisting of a composition of MOI and MOI-DA can be obtained. The amount of diamine added to the addition reaction is preferably 0.5 mol% or more and 15 mol% or less with respect to the diamine used for MOI production. By doing so, the mass composition ratio of MOI and MOI-DA can be set to the mass composition ratio of the present invention described above. The mass composition ratio can be calculated from the masses of MOI and MOI-DA. The mass of MOI can be calculated from the measured number average molecular weight (Mn) of MOI and the number of moles of MOI remaining after the addition reaction. Here, the number of moles of the remaining MOI is calculated by subtracting twice the number of moles of the diamine used for the production of MOI-DA from the number of moles of the diamine used for the production of MOI. Further, the mass of MOI-DA can be calculated from the number average molecular weight of MOI-DA and the number of moles of diamine used for MOI-DA formation. Here, the number average molecular weight (Mn) of MOI-DA is calculated from the measured number average molecular weight (Mn) of MOI and the molecular weight of diamine because 2 mol of diamine undergoes an addition reaction with 1 mol of MOI. The diamine to be subjected to the addition reaction may be the same as or different from the diamine forming the MOI, but is preferably the same.

The reaction temperature at the time of the addition reaction is preferably 150 ° C. or lower, and more preferably 130 ° C. or lower. The reaction time is preferably 2 hours or more and 10 hours or less, and more preferably 4 hours or more and 8 hours or less. The solution thus obtained can be used as a solution comprising the composition of the present invention. Further, the MOI composition of the present invention can be obtained as a powder by adding a poor solvent or the like to this solution, reprecipitating and then drying.

In the MOI production process, it is preferable to use an aliphatic carboxylic acid having a weak acidity (pKa of 1 or more) as an acid catalyst during imidization. The amount of the aliphatic carboxylic acid used is preferably 0.1 mol or more and 3.0 mol or less, and preferably 0.2 mol or more and 2.5 mol or less, based on 1 mol of the diamine as a raw material. More preferred. If it is less than 0.1 mol, the imidization reaction may not proceed sufficiently. Further, if it exceeds 3.0 mol, side reactions such as the formation of vinyl polymer may easily occur. Here, as the aliphatic carboxylic acid, acetic acid, propionic acid, maleic acid, succinic acid, malic acid, fumaric acid and the like are used, and maleic acid is preferably used. As described above, the MOI of the present invention can be easily produced by using a specific amount of an organic carboxylic acid which is a weak acid as a dehydration catalyst. As the acid catalyst, in addition to the above-mentioned free carboxylic acid, acetic anhydride or maleic anhydride which hydrolyzes to produce a free carboxylic acid may be used.

The solvent used in the reaction is not limited as long as it is a solvent that dissolves the reaction products MOI and MOI-DA, but amide-based solvents such as N-methylpyrrolidone (NMP) and dimethylacetamide (DMAc) can be used. A hydrocarbon solvent such as toluene and xylene and an ether solvent such as glyme and diglyme are preferably used. These solvents may be used alone or in combination of two or more. Among these, a mixed solvent composed of an amide-based solvent and a hydrocarbon-based solvent is preferably used.

The solid content concentration during the reaction is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the examples.

<Example 1>
In a glass reaction vessel equipped with a reflux condenser with a water separator, a stirrer, and a thermometer, under a nitrogen atmosphere, dimadiamine (“Priamine 1075” manufactured by Crowder Japan Co., Ltd., molecular weight: 549): 1.0 mol, toluene. A mixed solvent composed of NMP (mass ratio: toluene / NMP = 80/20) was added and stirred. To the obtained solution, PMDA: 0.66 mol, followed by maleic anhydride: 0.68 mol, was added at room temperature (20 ° C.), stirred at room temperature for 1 hour, cooled, and terminally modified with maleamic acid. The obtained oligoamic acid solution (solid content concentration: 30% by mass) was obtained. Next, 2.0 mol of maleic acid was added to this solution, and the temperature of the obtained solution was raised with stirring to heat and reflux the contents. The water produced by the reaction was azeotropically separated and refluxed for 6 hours, and then cooled to obtain an orange-yellow solution. Then, the obtained solution was washed with an aqueous solvent to obtain an MOI solution. As a result of measuring the GPC of this MOI, the number average molecular weight (Mn) was 2680 and the weight average molecular weight (Mw) was 4180. 0.03 mol of the diamine diamine was added to this solution to make a uniform solution, which was reacted at about 115 ° C. for 7 hours to obtain the MOI composition of the present invention consisting of 93% by mass of MOI and 7% by mass of MOI-DA. A solution containing was obtained. As a result of measuring the GPC of this composition, the weight average molecular weight (Mw) was 10700, and a significant increase in Mw was observed. The obtained MOI composition solution was put into a methanol solution to reprecipitate the MOI, which was filtered and dried, and then NMR was measured to confirm that the MOI composition had a predetermined chemical structure. ..

<Example 2>
Example 1 and Example 1 except that a mixed solvent (mass ratio: mixed xylene / NMP = 80/20) consisting of mixed xylene (mixture consisting of orthoxylen, metaxylene, paraxylene, etc.) and NMP was used as the solvent. The same procedure was carried out to obtain an MOI solution. As a result of measuring the GPC of this MOI, the number average molecular weight (Mn) was 2960 and the weight average molecular weight (Mw) was 4600. To this solution, 0.01 mol of the diamine diamine was added to prepare a uniform solution, which was reacted at about 115 ° C. for 7 hours to obtain the MOI composition of the present invention consisting of 98% by mass of MOI and 2% by mass of MOI-DA. A solution containing was obtained. As a result of measuring the GPC of this composition, the weight average molecular weight (Mw) was 8470.

<Comparative example 1>
The MOI solution obtained in Example 1 was heated at about 115 ° C. for 7 hours without adding diaminediamine. As a result of measuring the GPC of the obtained solution, the weight average molecular weight (Mw) was 4300, and almost no increase in the weight average molecular weight (Mw) was observed.

<Comparative example 2>
0.2 mol of the diamine diamine was added to the MOI solution obtained in Example 1 to prepare a uniform solution, and an attempt was made to react at about 115 ° C., but gelation occurred during the reaction, and a uniform solution was obtained. I couldn't get it.

From the above evaluation results, by using the composition of the present invention, the weight average molecular weight (Mw) of MOI can be sufficiently increased, and the moldability of MOI can be improved.

In the MOI composition of the present invention, since the weight average molecular weight (Mw) of MOI is sufficiently increased, problems such as dripping when made into a solution are solved, and moldability is improved. Therefore, it can be suitably used for a silicon substrate passivation film, a die bonding adhesive, a high frequency substrate, and the like.

The present invention has the following object.
It consists of MOI, which uses diaminediamine as the diamine constituting the oligoimide, and a diamine adduct of the terminal maleimided oligoimide (hereinafter, may be abbreviated as "MOI-DA"), and has a weight average molecular weight (Mw). ) Is 6000 or more and 20000 or less.

The MOI composition of the present invention comprises MOI and MOI-DA, preferably MOI 80 to 99% by mass and MOI-DA 1 to 20% by mass, preferably MOI 85 to 95% by mass and MOI-DA 5 to 15% by mass. Is more preferable. By setting the composition ratio in this way, the weight average molecular weight (Mw) is increased and the moldability is improved.

Claims (1)

It is composed of a terminal maleimided oligoimide and a diamine adduct of the terminal maleimided oligoimide in which dimadiamine is used as the diamine constituting the oligoimide, and is characterized by having a weight average molecular weight (Mw) of 6000 or more and 20000 or less. Oligoimide composition.