JP2022052049A - Atmospheric temperature liquid solventless thermosetting composition and method for producing the same - Google Patents

Abstract

To provide an atmospheric temperature liquid solventless thermosetting composition which provides a cured product excellent in heat resistance, and a method for producing the same.SOLUTION: An atmospheric temperature liquid solventless thermosetting composition is obtained by charging an atmospheric temperature solid bisphenol A type cyanate resin and P-d type benzoxazine into an atmospheric temperature liquid bisphenol A type epoxy resin, heating and mixing the mixture at 100°C for 4 hours, and cooling the mixture to an atmospheric temperature. A compatible material is obtained by charging atmospheric temperature solid 4,4'-diphenylmethane bismaleimide into an atmospheric temperature liquid bisphenol A type epoxy resin, heating and mixing the mixture at 150°C for 3 hours, and cooling the mixture. An atmospheric temperature liquid solventless thermosetting composition is obtained by charging an atmospheric temperature solid bisphenol A type cyanate resin and P-d type benzoxazine into the compatible material, heating and mixing the mixture at 100°C for 4 hours, and cooling the mixture to an atmospheric temperature. A cured product excellent in heat resistance is obtained by heating the thermosetting composition to 150°C to temporarily cure the composition, and then heating the composition to 200°C to finally cure the composition.SELECTED DRAWING: None

Description

The present invention relates to a thermosetting composition that can be used as a sealing material, an impregnating material, an adhesive, or the like for an electric / electronic material such as a semiconductor or a printed wiring board.

Conventionally, a cured product having excellent heat resistance has been adopted as a sealing material for electric / electronic materials such as semiconductors. As a thermosetting composition for obtaining such a cured product, one composed of an epoxy compound, a polyfunctional cyanate compound, a benzoxazine compound and a polyfunctional maleimide compound is known (Patent Document 1). However, most of the compounds are generally solid at room temperature, and in the technique described in Patent Document 1, each compound is dissolved and used in a slurry in which a filler such as silica is dispersed in a solvent. .. Therefore, the thermosetting composition will be provided in the form of a slurry containing a solvent.

However, such a thermosetting composition has a drawback that the solvent must be evaporated at the time of use and the working environment is deteriorated. In addition, the evaporation of the solvent may cause the volume of the cured product to shrink or cracks to occur in the cured product.

Japanese Patent No. 6301473

An object of the present invention is to provide a solvent-free thermosetting composition which is liquid at room temperature and a method for producing the same.

Regardless of the form, the epoxy compound, the polyfunctional cyanate compound, and the benzoxazine compound are compatible with each other well when mixed under specific conditions, and can maintain a uniform liquid state at room temperature without using a solvent. , The present inventors have discovered. For example, when a solid polyfunctional cyanate compound and a solid benzoxazine compound are added to an epoxy compound that is liquid at room temperature and mixed under specific conditions, the solid compound is well compatible with the epoxy compound and becomes liquid at room temperature. I found. It was also discovered that when a solid polyfunctional maleimide compound is added to an epoxy compound that is liquid at room temperature and mixed under specific conditions, the solid polyfunctional maleimide compound is well compatible with the epoxy compound and becomes liquid at room temperature. .. The present invention has been made on the basis of such findings. That is, the present invention relates to a room temperature liquid solvent-free thermosetting composition in which an epoxy compound, a polyfunctional cyanate compound and a benzoxazine compound are compatible with each other.

[Definition of terms]
In the present invention, "normal temperature" means a temperature of 10 to 30 ° C. Therefore, "normal temperature liquid" means that it is liquid in the entire temperature range of 10 to 30 ° C.
In the present invention, the "solvent-free type" means that the components are not dissolved using a solvent. Therefore, the solvent-free thermosetting composition is a composition in which the active ingredient in the composition is not dissolved by the solvent.

The epoxy compound used in the present invention may be solid or liquid at room temperature. In the present invention, it is particularly preferable to use an epoxy compound that is liquid at room temperature. The epoxy compound that is liquid at room temperature is a state that is liquid at room temperature as a state peculiar to the epoxy compound. That is, it is liquid at room temperature without using a solvent. As the room temperature liquid epoxy compound, a room temperature liquid bisphenol A type epoxy compound, a room temperature liquid bisphenol F type epoxy compound, or the like is used. As the bisphenol A type epoxy compound which is liquid at room temperature, EPICLON 850S, EPICLON 850, EPICLON 840, EPICLON 840S, EPICLON 850LC, etc. manufactured by DIC Corporation are used alone or in combination. Further, as the bisphenol F type epoxy compound which is liquid at room temperature, EPICLON 830S, EPICLON 830, EPICLON 835LV and the like manufactured by DIC Corporation are used alone or in combination. A room temperature liquid bisphenol A type epoxy compound and a room temperature liquid bisphenol F type epoxy compound may be mixed and used.

In the present invention, when a room temperature solid epoxy compound is used, the product of the epoxy equivalent and the number of epoxy groups contained in one molecule of the epoxy compound (hereinafter, simply referred to as “the number of epoxy groups”) is 700 or less, more preferably 600. It is preferable to adopt the following. Such an epoxy compound has a molecular weight of about 700 or less and has a low molecular weight. Therefore, even if the polyfunctional cyanate compound and the benzoxazine compound are mixed and heated to form a compatible state and then cooled to room temperature, the entanglement between the molecules of the epoxy compound is inhibited and no solid substance is produced. be. When the product of the epoxy equivalent and the number of epoxy groups exceeds 700, a solid substance tends to be produced when cooled to room temperature. Examples of the room temperature solid epoxy compound include TEPIC-S manufactured by Nissan Chemical Industries, Ltd., which has a product of epoxy equivalent and epoxy group number of about 300, and EPICLON HP4770 manufactured by DIC Corporation, which has a product of epoxy equivalent and epoxy group number of about 400. Is used alone or in combination.

As the polyfunctional cyanate compound, a compound which is solid at room temperature is generally used. As the polyfunctional cyanate compound which is solid at room temperature, a bisphenol A type cyanate compound which forms a triazine ring and is cured is used.

As the benzoxazine compound, a solid at room temperature is generally used. As the benzoxazine compound which is solid at room temperature, those described in JP-A-2014-141426 such as Pd-type benzoxazine or Fa-type benzoxazine manufactured by Shikoku Chemicals Corporation are used. Further, BS-BXZ, BF-BXZ and the like manufactured by Konishi Chemical Industry Co., Ltd. are also used. Further, these benzoxazine compounds may be mixed and used.

The compounding ratio of each of the above-mentioned compounds in the composition is preferably as follows. That is, the content of the epoxy compound is 10 to 70% by mass and the content of the polyfunctional cyanate compound is 10 to 80% by mass with respect to the total amount of the epoxy compound, the polyfunctional cyanate compound and the benzoxazine compound, that is, benzo. The content of the oxazine compound is preferably 3 to 30% by mass, more preferably 10 to 30% by mass. When the content of the epoxy compound is less than 10% by mass, it becomes difficult to make the solid polyfunctional cyanate compound and the benzoxazine compound compatible with each other, and crystals tend to be easily generated in the obtained composition. When the content of the epoxy compound exceeds 70% by mass, the heat resistance of the obtained cured product tends to decrease. When the content of the polyfunctional cyanate compound is less than 10% by mass, the heat resistance of the obtained cured product tends to decrease. When the content of the polyfunctional cyanate compound exceeds 80% by mass, the content of the epoxy compound is relatively small, and crystals tend to be easily generated in the obtained composition. When the content of the benzoxazine compound is less than 3% by mass, the heat resistance of the obtained cured product tends to decrease. When the content of the benzoxazine compound exceeds 30% by mass, the composition tends to thicken and the pot life tends to decrease.

It is preferable that the room temperature liquid solvent-free thermosetting composition according to the present invention further contains a generally solid polyfunctional maleimide compound in phase with each other. This is because the time for temporary curing can be shortened by containing the polyfunctional maleimide compound. Examples of the polyfunctional maleimide compound include 4,4'-diphenylmethane bismaleimide, bis- (3 ethyl-5 methyl-4-maleimidephenyl) methane, bisphenol A diphenyl ether bismaleimide, phenylene bismaleimide, 4-methyl-1,3-. Phenylene bismaleimide or 1,6'-bismaleimide- (2,2,4-trimethyl) hexane or the like may be used alone or in admixture. Further, a polymer obtained by polymerizing these may be used.

The polyfunctional maleimide compound is preferably contained in the composition in an amount of 5 to 30% by mass. When the content of the polyfunctional maleimide compound is less than 5% by mass, it tends to be difficult to shorten the temporary curing time. When the content of the polyfunctional maleimide compound exceeds 30% by mass, the composition becomes highly viscous and the workability tends to decrease.

The room temperature liquid thermosetting composition according to the present invention is produced by heating each of an epoxy compound, a polyfunctional cyanate compound, a benzoxazine compound and, if desired, a polyfunctional maleimide compound to a temperature equal to or higher than the melting point and mixing them. can do. In particular, the preferred production method is as follows. That is, a room temperature solid epoxy compound, a room temperature solid polyfunctional cyanate compound, and a room temperature solid benzoxazine compound are heated and mixed to form a uniform liquid, and then cooled to room temperature to provide a room temperature liquid solvent-free thermosetting. A method for obtaining a sex composition. At this time, as described above, it is preferable to use a room temperature solid epoxy compound having a product of the epoxy equivalent and the number of epoxy groups of 700 or less. A heating temperature of about 90 to 140 ° C. and a heating and mixing time of about 10 minutes to 24 hours are sufficient. By such a method, an epoxy compound, a polyfunctional cyanate compound and a benzoxazine compound are well compatible with each other, and a solid substance does not precipitate even when cooled, so that a room temperature liquid solvent-free thermosetting composition can be obtained. ..

In addition, a polyfunctional cyanate compound that is solid at room temperature and a benzoxazine compound that is solid at room temperature are added to an epoxy compound that is liquid at room temperature, then heated and mixed to form a uniform liquid, and then cooled to room temperature so that there is no liquid at room temperature. A method for obtaining a solvent-type thermosetting composition is also preferable. The heating temperature and the heating and mixing time are about the same as above, the heating temperature is about 90 to 140 ° C., and the heating and mixing time is about 10 minutes to 24 hours. By this method, the polyfunctional cyanate compound which is solid at room temperature and the benzoxazine compound which is solid at room temperature are well compatible with the epoxy compound which is liquid at room temperature, and the solid substance does not precipitate even when cooled, and the solvent-free heat which is liquid at room temperature is used. A curable composition is obtained.

The room temperature liquid solvent-free thermosetting composition containing the polyfunctional maleimide compound is preferably produced by the following method. That is, in the first step of heating and mixing a room temperature solid epoxy compound and a room temperature solid polyfunctional maleimide compound to form a uniform liquid, and then cooling the compound to obtain a compatible product. After adding the polyfunctional cyanate compound and the benzoxazine compound which is solid at room temperature, the compound is heated at a temperature lower than the temperature at the time of heating in the first step, mixed to form a uniform liquid, and then cooled to room temperature from the second step. It is a method to become. At this time, as described above, it is preferable to use a room temperature solid epoxy compound having a product of the epoxy equivalent and the number of epoxy groups of 700 or less. The heating temperature in the first step is about 150 to 200 ° C., and the heating and mixing time is about 10 minutes to 24 hours, which is sufficient. It is sufficient that the heating temperature in the second step is about 90 to 140 ° C. and the heating and mixing time is about 10 minutes to 24 hours.

Further, in the first step of adding a polyfunctional maleimide compound which is solid at room temperature to an epoxy compound which is liquid at room temperature, heating and mixing to make a uniform liquid, and then cooling to obtain a compatible product, the compatible product is used. , A method consisting of a second step of adding a room temperature solid polyfunctional cyanate compound and a room temperature solid benzoxazine compound, then heating to a temperature lower than the temperature at the time of heating in the first step, mixing, and cooling to room temperature. be. The heating temperature and heating mixing time in the first step and the second step are about the same as above.

In these methods, the first step and the second step are divided because the compatibility with the epoxy compound is different between the polyfunctional maleimide compound and the polyfunctional cyanate compound and the benzoxazine compound. That is, in order for the polyfunctional maleimide compound to be compatible with the epoxy compound, the heating temperature must be 150 ° C. or higher. On the other hand, the polyfunctional cyanate compound and the benzoxazine compound are compatible with the epoxy compound at a heating temperature of less than 150 ° C. When a polyfunctional maleimide compound, a polyfunctional cyanate compound, and a benzoxazine compound are mixed with an epoxy compound at once and heated to 150 ° C. or higher, a curing reaction is likely to occur, and it becomes difficult to obtain a composition in a room temperature liquid state.

Various additives may be added to the thermosetting composition according to the present invention as long as the effects of the present invention are not impaired. For example, fillers such as silica, alumina, aluminum nitride, boron nitride, aluminum hydroxide, glass, talc, clay, mica, calcium carbonate or carbon; fibrous reinforcing agents such as glass fiber or carbon fiber; dyes, pigments and the like. Coloring agent; A mold release agent such as silicone or a fluorine-based compound may be added.

The thermosetting composition according to the present invention is pre-cured at 130 to 170 ° C. for about 10 minutes to 2 hours, and then main-cured at 180 to 270 ° C. for about 2 to 7 hours. It can be used as a sealing material for electrical / electronic materials or as an impregnating material for circuit boards or the like. The cured product after the main curing has excellent heat resistance.

The solvent-free thermosetting composition according to the present invention is used as a sealing material for electronic components, a casting material, an impregnating material for a circuit board, a laminated material, a paint, an adhesive, a resist ink, and the like.

Since the solvent-free thermosetting composition according to the present invention does not contain a solvent that is liquid at room temperature, it does not deteriorate the working environment and has the effect that volume shrinkage and cracking of the cured product due to evaporation of the solvent are less likely to occur. Play. Therefore, by using the solvent-free thermosetting composition according to the present invention, it is possible to efficiently produce electronic parts and the like that require heat resistance.

Example 1
In 14 g of a room temperature liquid bisphenol A type epoxy compound (manufactured by DIC: product name EPICLON850S), 28 g of a room temperature solid bisphenol A type cyanate compound [Mitsubishi Gas Chemical Co., Ltd .: product name triazine (TA)] and room temperature solid diaminodiphenylmethane 13.8 g of type benzoxazine (manufactured by Shikoku Kasei Co., Ltd .: product name: Pd type benzoxazine) was added, mixed for 4 hours while heating at 100 ° C., and then cooled to 23 ° C. As a result, a room temperature liquid solventless thermosetting composition in which a bisphenol A type epoxy compound, a bisphenol A type cyanate compound and a diaminodiphenylmethane type benzoxazine were compatible was obtained.

Example 2
Room temperature liquid solvent-free thermosetting by the same method as in Example 1 except that the amount of diaminodiphenylmethane type benzoxazine (manufactured by Shikoku Kasei Co., Ltd .: product name Pd type benzoxazine) solid at room temperature was changed to 8 g. A sex composition was obtained.

Example 3
Room temperature solid bisphenol A type cyanate compound [Mitsubishi Gas Chemical Co., Ltd .: product name Triazine (TA)] 21 g instead of room temperature solid bisphenol A type cyanate compound [Mitsubishi Gas Chemical Co., Ltd .: product name Triazine (TA)] 21 g And a room temperature liquid diallyl bisphenol A type cyanate compound [manufactured by Mitsubishi Gas Chemicals, Inc .: product name A211], except that a mixture of 7 g was used, a room temperature liquid solvent-free thermosetting composition was prepared by the same method as in Example 2. Obtained.

Example 4
Room temperature solid bisphenol A type cyanate compound [Mitsubishi Gas Chemical Co., Ltd .: product name Triazine (TA)] 14 g instead of room temperature solid bisphenol A type cyanate compound [Mitsubishi Gas Chemical Co., Ltd .: product name Triazine (TA)] 14 g And a room temperature liquid diallyl bisphenol A type cyanate compound [manufactured by Mitsubishi Gas Chemicals, Inc .: product name A211], except that a mixture of 14 g was used, a room temperature liquid solvent-free thermosetting composition was prepared by the same method as in Example 2. Obtained.

Example 5
Same as Example 1 except that the amount of diaminodiphenylmethane type benzoxazine (manufactured by Shikoku Kasei Co., Ltd .: product name Pd type benzoxazine) solid at room temperature was changed to 2 g and the mixing time was changed to 24 hours. A solvent-free thermosetting composition which is liquid at room temperature was obtained by the above method.

Example 6
Same as Example 2 except that the room temperature liquid bisphenol F type epoxy compound (DIC: product name EPICLON830S) was used instead of the room temperature liquid bisphenol A type epoxy compound (DIC: product name EPICLON850S). By the method, a solvent-free thermosetting composition which was liquid at room temperature was obtained.

Example 7
In 14 g of a room temperature liquid bisphenol A type epoxy compound (manufactured by DIC: product name EPICLON850S), 28 g of a room temperature liquid bisphenol E type cyanate compound (manufactured by Mitsubishi Gas Chemicals Co., Ltd .: product name P201) and a room temperature liquid benzoxazine compound (Shikoku) Chemical company property: 8 g of product name ALP-d type benzoxazine) was added and mixed to obtain a room temperature liquid solvent-free thermosetting composition.

Comparative Example 1
Instead of the room temperature liquid bisphenol A type epoxy compound (DIC: product name EPICLON850S), a room temperature solid epoxy compound (Mitsubishi Chemical: product name jER1002; product of epoxy equivalent and epoxy group number: about 1300) is used. Obtained a solvent-free thermosetting composition by the same method as in Example 2. This composition was in a solid state at room temperature.

Comparative Example 2
Instead of the room temperature liquid bisphenol A type epoxy compound (DIC: product name EPICLON850S), a room temperature solid epoxy compound (Mitsubishi Chemical: product name jER1004; product of epoxy equivalent and epoxy group number: about 1850) is used. Obtained a solvent-free thermosetting composition by the same method as in Example 2. This composition was in a solid state at room temperature.

The solvent-free thermosetting compositions obtained in Examples 1 to 7 were provisionally cured at 150 ° C. for 1 hour, and then main-cured at 200 ° C. for 5 hours to obtain a cured product. rice field. This cured product was subjected to a dynamic viscoelasticity measuring machine (manufactured by AntonioPaar, product name MCR302) at the peak top of tan δ under the measurement conditions of a frequency of 1 Hz, a shear strain of 0.05%, and a heating rate of 2 ° C./min. The seen glass transition point (° C) (hereinafter, simply referred to as "tanδ glass transition point (° C)") was measured. The results are shown in Table 1. Since the compositions obtained in Comparative Examples 1 and 2 are solid at room temperature, a cured product has not been obtained.
[Table 1]
━━━━━━━━━━━━━━━━━━━━━━
tanδ glass transition point (° C)
━━━━━━━━━━━━━━━━━━━━━━
Example 1 221.8
Example 2 220.2
Example 3 211.5
Example 4 200.1
Example 5 232.5
Example 6 210.1
Example 7 206.0
━━━━━━━━━━━━━━━━━━━━━━

As is clear from Table 1, the cured product obtained by curing the room temperature liquid solvent-free thermosetting composition according to Examples 1 to 7 has a high glass transition point and is excellent in heat resistance.

Example 8
In 14 g of a room temperature liquid bisphenol A type epoxy compound (manufactured by DIC: product name EPICLON850S), 6 g of room temperature solid 4,4'-diphenylmethane bismaleimide (manufactured by Keiai Kasei Co., Ltd .: product name BMI) was added to 150. After mixing for 3 hours while heating at ° C., the mixture was cooled to 100 ° C. to obtain a liquid companion product in which a bisphenol A type epoxy compound and 4,4'-diphenylmethane bismaleimide were compatible (first step). With the temperature of this companion maintained at 100 ° C, 28 g of a bisphenol A-type cyanate compound [manufactured by Mitsubishi Gas Chemicals, Inc .: product name Triazine (TA)] solid at room temperature and diaminodiphenylmethane solid at room temperature were contained in the composure. 8 g of type benzoxazine (manufactured by Shikoku Kasei Co., Ltd .: product name Pd type benzoxazine) was added, mixed for 4 hours, and then cooled to 23 ° C. (second step). As a result, a room temperature liquid solventless thermosetting composition in which bisphenol A type epoxy compound, bisphenol A type cyanate compound, diaminodiphenylmethane type benzoxazine and 4,4'-diphenylmethane bismaleimide were compatible with each other was obtained.

Example 9
The same method as in Example 8 except that the amount of 4,4'-diphenylmethanebismaleimide (manufactured by KI Kasei Co., Ltd .: product name BMI) solid at room temperature was changed to 3 g, and the same method as in Example 8 was used for room temperature liquid solvent-free heat. A curable composition was obtained.

Example 10
The same method as in Example 8 except that the amount of 4,4'-diphenylmethanebismaleimide (manufactured by KI Kasei Co., Ltd .: product name BMI) solid at room temperature was changed to 12 g, and the same method as in Example 8 was used for room temperature liquid solvent-free heat. A curable composition was obtained.

Example 11
A solvent-free thermosetting composition that is liquid at room temperature is obtained by the same method as in Example 8 except that the amount of the bisphenol A type epoxy compound (manufactured by DIC: product name EPICLON850S) that is liquid at room temperature is changed to 8 g. rice field.

Example 12
A solvent-free thermosetting composition that is liquid at room temperature is obtained by the same method as in Example 8 except that the amount of the bisphenol A type epoxy compound (manufactured by DIC: product name EPICLON850S) that is liquid at room temperature is changed to 28 g. rice field.

Example 13
A solvent-free thermosetting composition that is liquid at room temperature is obtained by the same method as in Example 8 except that the amount of the bisphenol A type epoxy compound (manufactured by DIC: product name EPICLON850S) that is liquid at room temperature is changed to 42 g. rice field.

Example 14
A solvent-free thermosetting composition that is liquid at room temperature is obtained by the same method as in Example 8 except that the amount of the bisphenol A type epoxy compound (manufactured by DIC: product name EPICLON850S) that is liquid at room temperature is changed to 56 g. rice field.

Example 15
Room temperature liquid solvent-free thermosetting by the same method as in Example 8 except that the amount of bisphenol A type cyanate compound [manufactured by Mitsubishi Gas Chemical Company: product name triazine (TA)] solid at room temperature was changed to 14 g. A sex composition was obtained.

Example 16
Implemented except that the input amount of bisphenol A type cyanate compound [manufactured by Mitsubishi Gas Chemical Company: product name triazine (TA)] solid at room temperature was changed to 56 g, and the mixing time in the second step was changed to 18 hours. A solvent-free thermosetting composition liquid at room temperature was obtained by the same method as in Example 8.

Example 17
Implemented except that the input amount of bisphenol A type cyanate compound [manufactured by Mitsubishi Gas Chemical Company: product name triazine (TA)] solid at room temperature was changed to 65 g, and the mixing time in the second step was changed to 24 hours. A solvent-free thermosetting composition liquid at room temperature was obtained by the same method as in Example 8.

Example 18
Instead of 6 g of room temperature solid 4,4'-diphenylmethanebismaleimide (manufactured by Keiai Kasei Co., Ltd .: product name BMI), room temperature solid 4,4'-diphenylmethanebismaleimide (manufactured by Keiai Kasei Co., Ltd .: product name BMI) ) 4.2 g and 1.8 g of room temperature solid bis- (3 ethyl-5 methyl-4-maleimidephenyl) methane (manufactured by Keiai Kasei Co., Ltd .: product name BMI-70) are added, as in Example 8. By the same method, a room temperature liquid solvent-free thermosetting composition was obtained.

Example 19
Room temperature solid bisphenol A type cyanate compound [Mitsubishi Gas Chemical Company: product name Triazine (TA)] 21 g instead of room temperature solid bisphenol A type cyanate compound [Mitsubishi Gas Chemical Company: product name Triazine (TA)] 21 g And a room temperature liquid solvent-free thermosetting composition is obtained by the same method as in Example 18 except that 7 g of the diallyl bisphenol A type cyanate compound (manufactured by Mitsubishi Gas Chemical Company, product name A211) which is liquid at room temperature is added. rice field.

Example 20
Room temperature solid bisphenol A type cyanate compound [Mitsubishi Gas Chemical Company: product name Triazine (TA)] 14 g instead of room temperature solid bisphenol A type cyanate compound [Mitsubishi Gas Chemical Company: product name Triazine (TA)] 14 g A room temperature liquid solvent-free thermosetting composition is obtained by the same method as in Example 18 except that 14 g of the diallyl bisphenol A type cyanate compound (manufactured by Mitsubishi Gas Chemical Company, product name A211) which is liquid at room temperature is added. rice field.

Example 21
Room temperature solid bisphenol A type cyanate compound [Mitsubishi Gas Chemical Company: product name Triazine (TA)] 14 g instead of room temperature solid bisphenol A type cyanate compound [Mitsubishi Gas Chemical Company: product name Triazine (TA)] 14 g A room temperature liquid solvent-free thermosetting composition was obtained by the same method as in Example 18 except that 14 g of a room temperature liquid bisphenol E-type cyanate compound (manufactured by Mitsubishi Gas Chemical Company, product name P201) was added. ..

Example 22
Implementation except that the input amount of diaminodiphenylmethane type benzoxazine (manufactured by Shikoku Kasei Co., Ltd .: product name Pd type benzoxazine) solid at room temperature was changed to 4 g, and the mixing time in the second step was changed to 18 hours. A solvent-free thermosetting composition liquid at room temperature was obtained by the same method as in Example 8.

Example 23
Same as Example 8 except that the bisphenol A type epoxy compound (manufactured by DIC: product name EPICLON850S) liquid at room temperature was replaced with the bisphenol F type epoxy compound (manufactured by DIC: product name EPICLON830S) liquid at room temperature. By the method, a solvent-free thermosetting composition which was liquid at room temperature was obtained.

Example 24
A liquid phase solution was obtained by the same method as in the first step of Example 8. To this companion, 28 g of a room temperature liquid bisphenol E-type cyanate compound (manufactured by Mitsubishi Gas Chemicals Co., Ltd .: product name P201) and 8 g of a room temperature liquid benzoxazine compound (Shikoku Kasei Co., Ltd .: product name ALP-d type benzoxazine) were added. The mixture was charged and mixed to obtain a solvent-free thermosetting composition which was liquid at room temperature.

Example 25
The same method as in Example 20 except that the room temperature liquid epoxy compound (Mitsubishi Chemical Corporation: product name jER630) is used instead of the room temperature liquid bisphenol A type epoxy compound (manufactured by DIC: product name EPICLON850S). A solvent-free thermosetting composition was obtained.

Example 26
Instead of the room temperature liquid bisphenol A type epoxy compound (DIC: product name EPICLON850S), the room temperature solid epoxy compound (Nissan Chemical Industries, Ltd .: product name TEPIC-S. Product of epoxy equivalent and number of epoxy groups: about 300) A solvent-free thermosetting composition was obtained by the same method as in Example 20 except that the above was used.

Example 27
Instead of the room temperature liquid bisphenol A type epoxy compound (DIC: product name EPICLON850S), a room temperature solid epoxy compound (DIC: product name EPICLON HP4770, product of epoxy equivalent and epoxy group number: about 400) is used. Obtained a solvent-free thermosetting composition by the same method as in Example 20.

Comparative Example 3
Same as Example 8 except that diaminodiphenylmethane type benzoxazine (manufactured by Shikoku Kasei Co., Ltd .: product name Pd type benzoxazine) solid at room temperature was not added and the mixing time in the second step was changed to 24 hours. A solvent-free thermosetting composition was obtained by the above method. A solid substance remained in this composition.

Comparative Example 4
A solvent-free thermosetting composition that is liquid at room temperature is obtained by the same method as in Example 8 except that the bisphenol A type cyanate compound [manufactured by Mitsubishi Gas Chemical Company: product name triazine (TA)] that is solid at room temperature is not added. rice field.

Comparative Example 5
Instead of the room temperature liquid bisphenol A type epoxy compound (DIC: product name EPICLON850S), a room temperature solid epoxy compound (Mitsubishi Chemical: product name jER1002, product of epoxy equivalent and epoxy group number: about 1300) is used, etc. Obtained a solvent-free thermosetting composition by the same method as in Example 8. This composition was in a solid state at room temperature.

Comparative Example 6
Instead of the room temperature liquid bisphenol A type epoxy compound (DIC: product name EPICLON850S), a room temperature solid epoxy compound (Mitsubishi Chemical: product name jER1031S, product of epoxy equivalent and epoxy group number: about 800) is used, etc. Obtained a solvent-free thermosetting composition by the same method as in Example 20. This composition was in a solid state at room temperature.

The solvent-free thermosetting compositions obtained in Examples 8 to 27 and the solvent-free thermosetting compositions obtained in Comparative Example 4 were temporarily cured at 150 ° C. for 1 hour, and then 200. Main curing was carried out at ° C. for 5 hours to obtain a cured product. This cured product was subjected to a dynamic viscoelasticity measuring machine (manufactured by AntonioPaar, product name MCR302) under the measurement conditions of a frequency of 1 Hz, a shear strain of 0.05%, and a heating rate of 2 ° C./min. ℃) was measured. The results are shown in Table 2. Since the composition obtained in Comparative Example 3 has a solid substance remaining, and the compositions obtained in Comparative Examples 5 and 6 are solid at room temperature, a cured product has not been obtained.
[Table 2]
━━━━━━━━━━━━━━━━━━━━━━
tanδ glass transition point (° C)
━━━━━━━━━━━━━━━━━━━━━━
Example 8 228.6
Example 9 222.5
Example 10 235.2
Example 11 234.0
Example 12 224.1
Example 13 223.8
Example 14 212.4
Example 15 228.6
Example 16 242.4
Example 17 239.4
Example 18 236.5
Example 19 231.4
Example 20 228.5
Example 21 233.4
Example 22 231.4
Example 23 218.5
Example 24 227.2
Example 25 268.5
Example 26 280.1
Example 27 242.3
Comparative Example 4 193.4
━━━━━━━━━━━━━━━━━━━━━━

As is clear from Table 2, the cured product obtained by curing the room temperature liquid thermosetting composition according to Examples 8 to 27 is the room temperature liquid solventless thermosetting composition according to Comparative Example 4. It can be seen that the glass transition point is higher and the heat resistance is excellent as compared with the cured product obtained by curing.

Claims (10)

A room temperature liquid solvent-free thermosetting composition in which an epoxy compound, a polyfunctional cyanate compound, and a benzoxazine compound are compatible with each other. A room temperature liquid solvent-free thermosetting composition obtained by dissolving a polyfunctional cyanate compound and a benzoxazine compound in a room temperature liquid epoxy compound. The content of the epoxy compound is 10 to 70% by mass and the content of the polyfunctional cyanate compound is 10 to 80% by mass with respect to the total amount of the epoxy compound, the polyfunctional cyanate compound and the benzoxazine compound. The solvent-free thermosetting composition according to claim 1 or 2, wherein the content of the benzoxazine compound is 3 to 30% by mass. The solvent-free thermosetting composition according to claim 1 or 2, wherein the polyfunctional maleimide compound is further dissolved. The content of the epoxy compound is 10 to 70% by mass with respect to the total amount of the epoxy compound, the polyfunctional cyanate compound, the benzoxazine compound and the polyfunctional maleimide compound, and the content of the polyfunctional cyanate compound is 10 to 80% by mass. The solvent-free thermosetting composition according to claim 4, wherein the content of the benzoxazine compound is 3 to 30% by mass, and the content of the polyfunctional maleimide compound is 5 to 30% by mass. A room temperature solid epoxy compound, a room temperature solid polyfunctional cyanate compound, and a room temperature solid benzoxazine compound in which the product of the epoxy equivalent and the number of epoxy groups possessed by one molecule of the epoxy compound is 700 or less are heated and mixed. The method for producing a solvent-free thermosetting composition according to claim 1, wherein the compound is made into a uniform liquid and then cooled to room temperature. A room temperature solid epoxy compound having a product of the epoxy equivalent and the number of epoxy groups contained in one molecule of the epoxy compound is 700 or less, and a room temperature solid polyfunctional maleimide compound are heated and mixed to form a uniform liquid. The first step of cooling to obtain a compatible compound,
After adding a room temperature solid polyfunctional cyanate compound and a room temperature solid benzoxazine compound to the phase solution, the mixture is heated at a temperature lower than the temperature at the time of heating in the first step and mixed to form a uniform liquid. The method for producing a solvent-free thermosetting composition according to claim 4, which comprises a second step of cooling to room temperature. The solvent-free thermosetting according to claim 2, wherein the polyfunctional cyanate compound and the benzoxazine compound which are solid at room temperature are added to the epoxy compound which is liquid at room temperature, then heated and mixed to form a uniform liquid, and then cooled to room temperature. A method for producing a sex composition. The first step of adding a room temperature solid polyfunctional maleimide compound to a room temperature liquid epoxy compound, heating and mixing to make a uniform liquid, and then cooling to obtain a compatible product.
After adding a room temperature solid polyfunctional cyanate compound and a room temperature solid benzoxazine compound to the companion, the mixture is heated at a temperature lower than the temperature at the time of heating in the first step and mixed to form a uniform liquid. The method for producing a solvent-free thermosetting composition according to claim 4, which comprises a second step of cooling to room temperature. The method for producing a solvent-free thermosetting composition according to claim 7 or 9, wherein the heating temperature in the first step is 150 to 200 ° C. and the heating temperature in the second step is 90 to 140 ° C.