JPS587650B2 - Jyushiso Saibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition, and more specifically, an adhesive for a heat-resistant film base used as an insulating material for electrical equipment;
Alternatively, the present invention relates to a heat-resistant curable resin composition suitable as a coating agent for pre-regs (laminate molding materials) in laminates.

Conventionally, an infusible and insoluble resin composition with excellent heat resistance has been obtained by reacting an N-Nζ monosubstituted bismaleimide with an aliphatic or aromatic polyamine having at least two primary amine groups. For example, French patent no.
It is known from No. 80955 and Japanese Patent Publication No. 45-22553.

However, when an aliphatic polyamine is used as the polyamine, the curing reaction proceeds rapidly at room temperature, making the molding operation difficult.

On the other hand, when aromatic polyamines are used as polyamines, resins with better heat resistance and other properties can be obtained than aliphatic polyamines, but the curing reaction must be performed under considerably harsh conditions, such as at 150 to 250°C for several hours to several hours. It took ten hours and was extremely impractical.

Therefore, as a result of intensive research in order to solve these drawbacks, the present inventor found that ethyl ortho- By adding orthoformate esters such as formate and methyl orthoformate, the reaction time is significantly shortened without any adverse effect on the inherent properties of the product, such as heat resistance, electrical properties, and adhesive properties. It has been found that moldability can be improved.

Furthermore, it has been discovered that by adding an orthoformic acid ester compound to the resin composition of the above product and epoxy resin, a curable resin composition with even better reaction accelerating properties and extremely good moldability can be obtained. Ta.

This invention will be explained in detail below.

The curable resin composition of the present invention is obtained by adding an orthoformic acid ester to a product obtained by reacting both an N-N' monosubstituted bismaleimide compound and a ketone compound having an acetyl group.

In this case, the amount of orthoformic acid ester added is preferably 0.2% by weight or more, preferably about 0.5 to 10% by weight, based on the product.

N. in the present invention. An example of a manufacturing method for obtaining a product of an N'-substituted bismaleimide compound and a ketone compound having an acetyl group will be described.

General formula [However, X in the formula is a divalent hydrocarbon group such as an alkylene group, cycloalkylene group, monocyclic to polycyclic arylene group, or -CH2-, -CO-, -SO2-, -C
Indicates a divalent hydrocarbon group bonded by a divalent atomic group such as ONH-.

[However, Y in the formula represents a monovalent hydrocarbon group such as a methyl group, an ethyl group, a probyl group, a butyl group, an amyl group, or a phenyl group. show.

] In addition to the ketone compound having an acetyl group represented by the above formula, an amine compound is further added as a catalyst and the reaction is carried out at room temperature to the boiling point temperature of the ketone compound, preferably from 50°C to the boiling point temperature of the ketone compound to form N-N'- Synthesize a substituted bismaleimide compound-based product.

In this reaction, when the composition ratio of the ketone compound is increased, it is desirable to carry out the reaction under the following conditions.

That is, after reacting the N-N'-substituted bismaleimide compound so that 20% or more of the total double bonds remain unreacted, the composition ratio of the unreacted ketone compound is changed to N-N/mono-substituted bismaleimide. The compound is distilled off from the reaction system under reduced pressure, or the composition ratio of the ketone compound is suppressed to such an extent that at most 80% of the double bonds of the N--N' monosubstituted bismaleimide compound are reacted.

Examples of the N-N' monosubstituted bismaleimide compound include N-N'-7-enylene bismaleimide, N-N'
-hexamethylene bismaleimide, N-N'-methylene p-phenylene bismaleimide, N-N'-oxy p-phenylene bismaleimide, N-N'-4
・4'-benzophenone-bismaleimide, N-N'-
One or more types selected from p-di7enylsulfonemaleidoimide and the like are used.

On the other hand, examples of ketone compounds having an acetyl group include those selected from acetone, methyl ethyl ketone, methyl n-probyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, acetophenone, etc. 1
A species or two or more species may be used.

Further, as the amine compound coexisting in the above reaction system, examples include tertiary amine compounds such as triethylamine, N-N-dimethyl-aniline, and N-N-dimethyl-penzylamine, or secondary amine compounds such as dimethylamine and diphenylamine. Amine compound, or aniline, p-}
Luidine, 4,4'~diaminodiphenylmethane, 4
- One or more compounds selected from polyvalent aromatic amine compounds such as 4'-diaminodiphenyl ether, 4,47-diaminodiphenyl sulfone, and diaminobenzine are used.

Note that the amount of the amine compound to be allowed to coexist in the reaction system is, for example, when a primary amine compound having the property of addition-reacting to the N-N'-substituted bismaleimide compound is coexisting, the amount of this amine compound should be determined by adjusting the amount of the amine compound to N-N' - 0.5 or less, where the chemical equivalent to the double bond of the substituted bismaleimide compound is 1,
It is desirable to add preferably 0.3 or less.

In addition, the orthoformic acid ester used in the present invention includes:
Examples include methyl orthoformate and ethyl orthoformate, and in some cases it is also possible to use higher orthoformate obtained by exchange reaction of these lower esters with esters of higher alcohols.

On the other hand, the curable resin composition, which is the second invention of the present application, contains 5 to 95% by weight of a product obtained by reacting both the above-mentioned N-N' monosubstituted bismaleimide compound and a ketone compound having an acetyl group. , an orthoformic acid ester is added to a resin component consisting of 95 to 5% by weight of an epoxy resin.

The reason why the blending ratio of the N-N'-substituted bismaleimide compound one-ton compound product and the epoxy resin is limited in this way is that if the blending ratio of these products deviates from the above range, it will lead to a decrease in heat resistance. This is because a curable resin composition suitable as an adhesive for a heat-resistant film base material used as an insulating material for electrical equipment cannot be obtained.

The amount of orthoformic acid ester added to the resin component is determined under the same conditions as when adding the orthoformic acid ester to the one-ton N-N' monosubstituted bismaleimide compound product described above, that is, the amount of orthoformic acid ester added to the resin component. 0.2% by weight
As mentioned above, it is desirable to add preferably 0.5 to 10% by weight.

The epoxy resin used in the second invention of the present application is:
Glycidyl type resin obtained by the reaction of bisphenol A and shrimp chlorohydrin, novolak type resin obtained by the reaction of novolac resin and shrimp chlorohydrin, cycloaliphatic resin, and epoxidation of polymerization of 2-polybutadiene. The resin is one or more selected from epoxidized polybutadiene type resins, epoxy acrylic type resins, and the like.

If necessary, acid anhydrides such as phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, methylnassic anhydride, and pyromellitic anhydride may be added as a curing agent for the epoxy resin at the usual addition rate, i.e. Epoxy 1
It is also possible to mix at a ratio of about 0.5 to 1 equivalent.

In the present invention, a radical polymerization type initiator such as dicumyl peroxide may be used as a reaction accelerator, if necessary.
Alternatively, a boron trifluoride amine complex may be used in combination with orthoformate.

Therefore, the curable resin composition of the present invention, which is obtained by adding an orthoformic acid ester to an N-N' monosubstituted bismaleimide compound-ketone compound product, has high reactivity, and the curing time is significantly shortened. The moldability can be significantly improved without impairing the heat resistance, electrical properties, and adhesive properties inherent in the composition.

In addition, since the curable resin composition of the present invention can be easily dissolved in a relatively low boiling point solvent such as dioxane or tetrahydrofuran, for example, when B-staged to produce a prepreg (material for forming a laminate), high-temperature heating is required. without requiring
The solvent evaporates easily and in a short time at a temperature of 80 to 130 DEG C., thereby making it possible to form a coating layer that is not sticky, easy to handle, and durable for long-term storage.

Therefore, along with the ease of preparing prepreg, it is possible to create heat-resistant laminates with excellent adhesion and adhesion, or adhesives for electrically insulating materials such as heat-resistant Fynolem base materials and Nomex paper (Dupont polyamide paper). It can be effectively used as

Furthermore, the curable resin composition of the present invention has excellent wettability when applied to a heat-resistant film base material to form a prepreg. The obtained resin solution can be applied uniformly and with good adhesion to the film base material, and therefore the adhesive strength of the obtained prepreg can be significantly improved.

On the other hand, the curable resin composition obtained by adding orthoformic acid ester to the resin components of the N-N'-substituted bismaleimide compound product and the epoxy resin, which is the second invention of the present application, has a moldability. It is possible to easily obtain a grippreg with excellent adhesiveness and adhesion, and particularly when forming a prepreg, the wettability can be significantly improved, thereby further improving the adhesive strength of the prepreg.

Examples of the present invention will be described below.

Example 1 and Comparative Example 1 First, a fourth flask (inner volume 2000 cc) equipped with a stirrer, thermometer, and reflux condenser was prepared, and in this flask dioxane 801y1 toluene 89.32, methyl ethyl ketone 1157, and 4. 4'-diaminodiphenylmethane 59f was stored, and while stirring, N-N'
- Methylene diparaphenylene bismaleimide 716v
was gradually added, the temperature was raised to 80°C, the reaction was continued under this condition for 2 hours, the temperature was further raised to 90-95°C, and the reaction was continued for 10 hours.

After the reaction was completed, the contents of the flask were cooled to 30°C, dioxane 11877 was added, and the mixture was stirred and mixed for 30 minutes to prepare product CI-1).

Next, methyl orthoformate was blended with the above product (I-1) as shown in Table 1 below to obtain six types of resin composition systems.

The results of measuring the gelation time of these resin composition systems at various temperatures are also shown in Table 1.

Note that the comparative example in the table uses only the above product [■-1].

Also, the amount of methyl orthoformate added is determined by its product [■
-1] is the ratio to the solute in

Therefore, using the curable resin composition of AI-4 in the above table and Comparative Example 1, it was made into a film with a thickness of 0.75 mm and a width of 25 m.
m, length 150 mm Kapton film (Dupont film)
It was coated on both sides of a polyimide film (manufactured by 1), air-dried, and then dried at 110° C. for 10 minutes to form a B-stage and a prepreg state.

Next, these prepregs were each made into 25mm wide pieces.
Cut into 20mm long pieces, treated with potassium dichromate-sulfuric acid mixture, cleaned and degreased.The overlapped part is 12.5mm between two stainless steel plates (thickness 1mm, width 25mm, length 150mm). 5kg/mm
Heat treated at a temperature of 200°C for 30 minutes under the pressure of 2.
Thereafter, this was transferred to a dryer and heat-treated at a temperature of 200° C. for 1 hour to obtain a test piece.

No. in the above table. When the shear fracture strength of a test piece using the curable resin composition No. 1-4 was measured at room temperature and at a tensile rate of 1.5 mm/min, it was found to be 94 kg/cm2.

In addition, after deteriorating the test piece at 200℃ and 240℃ for 240 hours, the shear fracture strength was measured under the same conditions.
240°C) was obtained.

On the other hand, the test piece of Comparative Example 1 had an initial shear fracture strength of 6.
It was 0 to 70 kg/mm2.

The surface wettability of the prepreg formed from the curable resin composition of the present invention is 46 to 47 dyne/cm using an organic solvent, whereas that of Comparative Example 1 is 42 dyne/cm.
Wetting was only possible using ~44 dyn/cm of organic solvent.

Example 2 and Comparative Example 2 A fourth flask similar to that in Example 1 was prepared, and 801v of dioxane, 89.39% of toluene, and methyl-n were added to it.
-probylketone 1377, 4,4' diaminodiphenylmethane 52 and while stirring N-N'-methylene-cyhalaphenylene bismaleimide 537v and N-N'
- After gradually adding 180 g of oxydiparaphenylene bismaleimide, the temperature was raised to 80°C, followed by a reaction for 2 hours under this condition, and the temperature was further raised to 90-95°C for 1
The reaction continued for 0 hours.

After the reaction was completed, the contents in the flask were cooled to 30°C,
Dioxane 11879 was added and mixed with stirring for 30 minutes to prepare a product CI-2) containing 50% by weight of solute.

Next, ethyl orthoformate was blended with the above product CI-2) as shown in Table 2 below to obtain a curable resin composition.

Furthermore, the gelation time of these curable resin compositions at each temperature was measured.

The results are also listed in Table 2. Incidentally, the amount of ethyl orthoformate added in the table indicates its proportion to the solute in the product (I-2).

Moreover, the comparative example in the table consists only of the above product CI-2).

However, No. in the above table. Using the curable resin compositions of 2-1 and Comparative Example 2, test pieces were prepared under the same conditions as in Example 1, and the shear fracture strength after deterioration at room temperature and at 200°C and 240°C for 240 hours was measured. When measured, No. A test piece using the curable resin composition of 62-1 was 89k9/ca at room temperature, and 106 after deterioration at 200°C.
kg/cm2, and 77 kg/c after aging at 240℃
It was the value of m2.

On the other hand, the test piece using the curable resin composition of Comparative Example 2 had an initial shear fracture strength of 60 to 70 k9/cm2.

Incidentally, the surface wettability of the prepreg formed from the curable resin composition of the present invention was extremely excellent as in Example 1 above.

Example 3 and Comparative Examples 3-1, 3-2 33% by weight of epoxy novolak resin (DEN438: Dowke S Cal brand name) was blended with the product [I-1] obtained in Example 1. Mix evenly and remove the resin component (■-
1] was adjusted.

Next, methyl orthoformate was added to this resin component (n-1) as shown in Table 3 below to obtain a curable resin composition.

Further, 4 parts by weight of BF3-monoethylamine is added to the resin component (n-1) based on the epoxy resin component,
Methyl orthoformate was blended with this as shown in Table 3 below to obtain a curable resin composition.

The results of measuring the gelation time of the curable resin composition at various temperatures are also shown in Table 3.

In addition, Comparative Example 3-1 in the table consists only of the above resin component (■-1), and Comparative Example 3-2 consists of the above resin component (■-1).
) with BF3-monoethylamine added.

Further, the amount of methyl orthoformate added in the table indicates its proportion to the solute in the resin component [■-1].

Next, test pieces were manufactured in the same manner as in Example 1 using the curable resin compositions A3-4 and A3-7 in the above table.

As a result of measuring the shear fracture strength of these test pieces at room temperature, the A3-4 test piece was 86k9/cm2, No. 3
-7 test piece had a weight of 104 kg/cm2.

In addition, after deteriorating these test pieces at 200°C for 240 hours, the shear fracture strength was measured at room temperature. 3-4
The test piece using the curable resin composition had a weight of 92 kg/cm.
2, No. The test piece using the curable resin composition No. 3-7 had a weight of 113 kg/cm2.

In contrast, the shear fracture strength of the test piece obtained using the curable resin composition of Comparative Example 3-1 was 50 kg/cm at room temperature.
2 or less, the strength of the test piece obtained using the curable resin composition of Comparative Example 3-2 was 50 to 70 kg/cm2.

As is clear from this, the curable resin composition of the present invention has extremely excellent heat resistance and adhesive properties.

Note that the surface wettability of the prepreg using the curable resin composition of the present invention is sufficient when using an organic solvent with a surface tension of 40 to 44 dyne/cm2, whereas the curable resin composition without the addition of methyl orthoformate In the case of using organic solvents, only organic solvents with a maximum surface tension of 35 to 37 dyne/cm2 could be used.

Example 4 and Comparative Example 4 50% by weight of Epicote 828 (Shell Chemical ■ trade name) was added and mixed to the product CI-2) (containing 50% by weight of solute) used in Example 2 to form a resin component [n -2) was adjusted.

Next, methyl orthoformate was blended with this resin component (■-2) as shown in Table 4 below to obtain a curable resin composition.

The results of measuring the gel time of these curable resin compositions at various temperatures are also shown in Table 4.

Note that Comparative Example 4 in the table consists only of the above resin component (■-2).

Further, the amount of methyl orthoformate added in the table indicates its proportion to the solute in the resin component (■-2).

As detailed above, according to the present invention, the inherent heat resistance of the resin,
It can increase reactivity and shorten curing time without affecting electrical properties or adhesion in any way, and has excellent wettability even when dissolved in organic solvents with high surface tension, significantly improving moldability. A curable resin that can significantly increase adhesive strength and is extremely suitable as a coating agent for prepregs in laminates used as insulating materials for electrical equipment, and as an adhesive for bonding heat-resistant film base materials. composition.

Claims (1)

[Scope of Claims] A curable resin composition obtained by adding an orthoformic acid ester to a product obtained by reacting both an I N-N'-substituted bismaleimide compound and a ketone compound having an acetyl group. 2 For a resin component consisting of 5 to 95% by weight of a product obtained by reacting both a N-N' monosubstituted bismaleimide compound and a ketone compound having an acetyl group, and 95 to 5% by weight of an epoxy resin, Curable resin composition 3 containing orthoformic acid ester