JP2022034459A - Siloxane diacid anhydride and polyimide resin - Google Patents

Abstract

To provide a resin having excellent flexibility and adhesion.SOLUTION: The hydrosilylation of (A) a silicon compound having two SiH groups in one molecule and (B) a compound having one carbon-carbon double bond and one acid anhydride group in one molecule, selected from predetermined compounds, yields a siloxane diacid anhydride represented by the following formula. The siloxane diacid anhydride is reacted with a diamine compound or a diisocyanate compound to give a polyimide resin.SELECTED DRAWING: None

Description

The present invention relates to a siloxane diic acid anhydride and a polyimide resin.

Polyimide resin is a material widely used in the field of electronics, and as described in Patent Document 1, many polyimide resins having a siloxane structure in the molecule have been proposed for the purpose of imparting flexibility to the resin. There is. However, the siloxane diamine compound used during synthesis has low purity and has problems such as poor bonding in electrical wiring due to volatilization of small molecule siloxane at high temperature and lack of adhesion to various substrates. There is.

On the other hand, Patent Document 2 also proposes a technique for obtaining a polyimide resin using a diacid anhydride having a siloxane structure. However, nadic acid anhydride has very poor hydrosilylation reactivity, and it is difficult to obtain a compound having an acid anhydride group at both ends with high purity. Therefore, only a low molecular weight polyimide resin can be obtained, and adhesion is lacking. I have a problem.

Japanese Unexamined Patent Publication No. 2005-056921 Patent No. 5873529

An object of the present invention is to provide a polyimide resin having excellent flexibility and adhesion.

As a result of repeated studies to achieve the above problems, it has been found that the siloxane diic acid anhydride and the polyimide resin obtained by using the siloxane diacid anhydride have flexibility and excellent adhesion. The present invention comprises the following.

[1]. Obtained by hydrosilylating (A) a silicon compound having two SiH groups in one molecule and (B) a compound having one carbon-carbon double bond and one acid anhydride group in one molecule. Is a siloxane diic acid anhydride shown below,

(In the above chemical formula, X is an organic group having an acid anhydride group in the structure, R is an organic group represented by 1 to 20 carbon atoms, and n is an integer of 0 to 50).
Moreover, the siloxane diic acid anhydride is characterized in that the component (B) is selected from the compounds described below.

[2]. A polyimide resin obtained by reacting the siloxane diic anhydride according to [1] with a diamine compound or a diisocyanate compound.

According to the present invention, siloxane diic acid anhydride can be obtained with high efficiency. Further, by using it, a polyimide resin having excellent flexibility and adhesion can be obtained.

(Siloxane acid anhydride)
The above-mentioned siloxane diic anhydride is a siloxane diacid anhydride having an acid anhydride group at the terminal and represented by the following structure.

(In the above chemical formula, X is an organic group having an acid anhydride group in the structure, R is an organic group represented by 1 to 20 carbon atoms, and n is an integer of 0 to 50).
Further, from the viewpoint of introducing the polyimide resin without impairing the heat resistance, which is a feature of the polyimide resin, the method of introducing the acid anhydride group of X by using the hydrosilylation reaction shown below is preferable.

Hereinafter, each essential component for obtaining a siloxane diic acid anhydride using a hydrosilylation reaction will be described.

(Component (A): Silicon compound having two SiH groups in one molecule)
The component (A) can be used without particular limitation as long as it is a silicon compound having two SiH groups, that is, a compound having two SiH groups in the molecule. The most commonly available one is a SiH group-terminated linear polysiloxane, which is a single polymer of dimethylsiloxane unit, diphenylsiloxane unit, methylphenylsiloxane unit, and a copolymer of each siloxane unit. The above is not particularly limited as long as it is a polyorganosiloxane polymer whose end is closed with a dimethylhydrogensilyl group. Specifically, for example, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5,-hexamethyltrisiloxane, 1,1,5,5-tetramethyl-3. , 3-Diphenyltrisiloxane and the like are exemplified as preferable examples. Further, silicon compounds other than the polysiloxane compound at the end of the SiH group can also be used, for example, 1,4-bis (dimethylsilyl) benzene, 1,4-bis (diphenylsilyl) benzene, 1,4-bis (1,4-bis). Methylphenylsilyl) benzene, etc. are specifically mentioned.

(Component (B): A compound having one carbon-carbon double bond and one acid anhydride group in one molecule)
The component (B) is a compound having one carbon-carbon double bond and one acid anhydride group in one molecule. As the component (B), a compound having excellent reactivity with a SiH group and capable of introducing an acid anhydride group at both ends in a high yield is preferable. On the other hand, in particular, compounds such as nadic acid anhydride and maleic acid compound have poor hydrosilylation reactivity due to their molecular structure, and a siloxane diic acid anhydride having an acid anhydride group introduced at both ends can be obtained in high yield. Therefore, a polyimide resin using these compounds has a low molecular weight and lacks adhesion and strength, which is not preferable.

Preferred compound examples include itaconic acid anhydride, allylsuccinic anhydride, tetrahydrophthalic anhydride, tetrahydromethylphthalic anhydride, and tetramethylphenylphthalic anhydride. More preferably, itaconic acid anhydride and allyl succinic acid anhydride are preferable.

(Reaction of components (A) and (B))
A hydrosilylation reaction is used as a method for reacting the components (A) and (B) to obtain a siloxane diic acid anhydride. In this case, a catalyst may be used for the purpose of allowing the reaction to proceed smoothly.

As the catalyst for the hydrosilylation reaction, for example, the following can be used. Platinum alone, a carrier such as alumina, silica, carbon black, etc. on which solid platinum is supported, platinum chloride acid, a complex of platinum chloride acid with alcohol, aldehyde, ketone, etc., a platinum-olefin complex (for example, Pt (CH) ₂ = CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ), Platinum-vinylsiloxane complex (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complex (eg Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complex (eg Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ). ₄ ) (In the formula, Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are integers.), Dicarbonyldichloroplatinum, Karstedt catalyst. Also, the platinum-hydrocarbon complex described in Ashby's US Pat. Nos. 3,159,601 and 3159662, and the platinum alcoholate described in Lamoreoux's US Pat. No. 3220972. Examples include catalysts. Further, the platinum chloride-olefin complex described in Modic's US Pat. No. 3,516,946 is also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl _{2.2H 2} O, NiCl ₂ , and TiCl ₄ . , Etc. can be mentioned.

Among these, platinum chloride acid, platinum-olefin complex, platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. Further, these catalysts may be used alone or in combination of two or more.

(About polyimide resin)
The polyimide resin obtained by using the siloxane diacid anhydride of the present invention is generally obtained by reaction with a diamine compound or a diisocyanate compound, and is not particularly limited.

Examples of the diamine used for the polyimide synthesis of the present invention include [bis (4-amino-3-carboxy) phenyl] methane, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4, 4'-diaminophenyl ethane, 4,4'-diaminophenyl ether, 4,4'-didiaminophenyl sulfide, 4,4'-didiaminophenyl sulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4 , 4'-Diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindan, 6-amino-1- (4'-aminophenyl) -1,3,3- Trimethylindan, 4,4'-diaminobenzanilide, 3,5-diamino-3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 3,4'-diaminodiphenyl ether, 2,7-Diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2', 5,5'-tetrachloro- 4,4'-Diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'- Diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane , 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] ) Phenyl] Hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) -biphenyl, 1, 3'-bis (4-aminophenoxy) benzene, 1,3'-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-(p-phenylene isopropylidene) ) Bisaniline, 4,4'-(m-phenylene isopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4-( 4-Amino-2-trifluoromethyl) phenoxy] -aromatic diamines such as octafluorobiphenyl; two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and heteroatoms other than the nitrogen atom of the amino groups. Aromatic diamines with; 1,1-methoxylylene diamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4 -Diaminocyclohexane, Isophorondiamine, Tetrahydrodicyclopentadienylene diamine, Hexahydro-4,7-Metanoindanylenedimethylenediamine, Tricyclo [6,2,1,02.7] -Undecylenedimethyldiamine, 4,4 Examples thereof include aliphatic diamines such as'-methylenebis (cyclohexylamine), alicyclic diamines and derivatives thereof, and a mixture thereof alone or in any ratio can be preferably used.

Further, for the purpose of improving the solubility of the resin in the solvent and ensuring the coatability, it is preferable that the above-mentioned polyimide resin has an alicyclic structure or a sulfone group in the polymer molecule. The method for introducing the alicyclic structure into the polymer molecule is not limited, but it can be easily introduced by using a diamine as a raw material or a tetracarboxylic dian compound having these structures. Although the diamine compound has been described, a diisocyanate compound in which the amino group of the diamine compound is replaced with an isocyanate group can also be used in the same manner as the diamine compound.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.

(Adhesion evaluation)
The polyimide resin solutions obtained in Examples and Comparative Examples were spin-coated on a Cu film-forming wafer substrate with a film thickness of 5 μm and then heated on a hot plate at 250 ° C. for 1 hour to form a polyimide resin film. Next, a cross-cut test was performed according to JIS K5600-V-VI (ISO2409) to evaluate the adhesion to the Cu thin film.

● Evaluation index 0: No peeling 1: 1 to 10% peeling 2: 20 to 30% peeling 3: 50% peeling 4: 70 to 80% peeling 5: 90% or more peeling

(Heat resistance evaluation)
Using a thermogravimetric measuring device (TGA, manufactured by Shimadzu Corporation), the temperature was raised from room temperature to 500 ° C. at 10 ° C./min, and evaluation was performed using the 1% weight loss temperature as an index.

(Measurement of molecular weight)
Each of the obtained polyimide resin solutions was diluted to 0.5 wt% with DMF (dimethylformamide) and analyzed by a GPC (Gel Permeation Chromatography) system (HCL-8420, manufactured by Toso Co., Ltd.). , Weight average molecular weight (Mw) was measured in terms of standard polystyrene.

(Example 1)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixture of 12.85 g of allyl succinic anhydride, 15 g of toluene, and 0.0163 g of a xylene solution of a platinum vinyl siloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropping, it was confirmed by ¹ H-NMR that the reaction rate of the double bond was 100%, and the reaction was cooled to complete the reaction. Toluene was distilled off under reduced pressure to obtain a siloxane compound A having an acid anhydride group at the end.

Next, 20 g of N, N-dimethylformamide, 2.5 g of the siloxane compound A obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed in a 200 mL flask. Then, the mixture was stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask and the precipitate was collected. Further, washing with 500 mL of isopropyl alcohol was carried out three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution A.

(Example 2)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixture of 10.28 g of itaconic acid anhydride, 15 g of toluene, and 0.0163 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Three hours after the completion of the dropping, it was confirmed by ¹ H-NMR that the reaction rate of the double bond was 100%, and the reaction was cooled to complete the reaction. Toluene was distilled off under reduced pressure to obtain a siloxane compound B having an acid anhydride group at the end.

Next, 20 g of N, N-dimethylformamide, 2.5 g of the siloxane compound B obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed in a 200 mL flask. Then, the mixture was stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask and the precipitate was collected. Further, washing with 500 mL of isopropyl alcohol was performed three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution B.

(Example 3)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixture of 13 g of tetrahydrophthalic anhydride, 13 g of toluene, and 0.0163 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Six hours after the completion of the dropping, ¹ H-NMR was confirmed to confirm that the reaction rate of the double bond was 100%, and the reaction was cooled to complete the reaction. Toluene was distilled off under reduced pressure to obtain a siloxane compound C having an acid anhydride group at the end.

Next, 20 g of N, N-dimethylformamide, 2.5 g of the siloxane compound C obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed in a 200 mL flask. Then, the mixture was stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask and the precipitate was collected. Further, washing with 500 mL of isopropyl alcohol was carried out three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution C.

(Comparative Example 1)
In a 200 mL flask, 20 g of N, N-dimethylformamide and 1.5 g of siloxane diamine (trade name: KF-8010, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a solvent, 2,2'-hexafluoropropyridene diphthalic acid. 2.5 g of the dianhydride was added, and the mixture was stirred at room temperature and in a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask, and the precipitate was collected. Further washing with 500 mL liter of isopropyl alcohol was performed three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution D. ..

(Comparative Example 2)
Toluene (100 g) and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (15 g) were placed in a 500 mL four-necked flask, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at an internal temperature of 105 ° C. A mixture of 15.5 g of nagic acid anhydride, 15.5 g of 1,4-dioxane and 0.0163 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Twenty-four hours after the completion of the dropping, it was confirmed by ¹ H-NMR that the reaction rate of the double bond was 90% and the reaction did not proceed any further, and the reaction was cooled to complete the reaction. 1,4-Dioxane was distilled off under reduced pressure to obtain a siloxane compound D having an acid anhydride group at the end.

Next, 20 g of N, N-dimethylformamide, 2.5 g of the siloxane compound D obtained above, and 1.5 g of 2,2-bis (4-aminophenyl) hexafluoropropane were placed in a 200 mL flask. Then, the mixture was stirred at room temperature and a nitrogen atmosphere for 30 minutes. Further, 5 g of N, N-dimethylformamide, 0.8 g of pyridine and 1.5 g of acetic anhydride were sequentially put into a flask, and the mixture was stirred for 3 hours while heating at 90 ° C. After returning to room temperature, 500 mL of isopropyl alcohol was put into the flask and the precipitate was collected. Further, washing with 500 mL of isopropyl alcohol was carried out three times, and the obtained precipitate was dried under reduced pressure at 80 ° C. for 6 hours, and then diluted to 50% with N, N-dimethylformamide to obtain a polyimide resin solution E.

(result)
The polyimide resin solutions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated as described above. The results are shown in Table 1.

The present invention can be used in various fields such as insulating interlayer films for electronic devices such as semiconductors and displays, adhesives, coating agents and encapsulants.

Claims (2)

Obtained by hydrosilylating (A) a silicon compound having two SiH groups in one molecule and (B) a compound having one carbon-carbon double bond and one acid anhydride group in one molecule. Is a siloxane diic acid anhydride shown below,

(In the above chemical formula, X is an organic group having an acid anhydride group in the structure, R is an organic group represented by 1 to 20 carbon atoms, and n is an integer of 0 to 50).
Moreover, the siloxane diic acid anhydride is characterized in that the component (B) is selected from the compounds described below.

A polyimide resin obtained by reacting the siloxane diic anhydride according to claim 1 with a diamine compound or a diisocyanate compound.