JP2022104654A - Solventless thermosetting composition which is liquid at ordinary temperature and production method thereof - Google Patents

Abstract

To provide a solventless thermosetting composition which is liquid at ordinary temperature and gives a cured product having excellent heat resistance.SOLUTION: A bisphenol-A type cyanate resin which is solid at ordinary temperature is heat-melted to obtain a molten liquid. To this molten liquid is added and mixed trimethylolpropane diallyl ether which is liquid at ordinary temperature to obtain a liquid mixture. To this liquid mixture is added and mixed P-d type benzoxazine which is solid at ordinary temperature and the P-d type benzoxazine is melted, Thereafter, the mixture is cooled to room temperature to obtain a solventless thermosetting composition which is liquid at ordinary temperature and in which a reaction product of a polyfunctional cyanate compound and a hydroxyl group-containing compound, a polyfunctional cyanate compound, and a benzoxazine ring-containing compound are compatibilized. By using, as the molten liquid, a material obtained by heat-melting a bisphenol-A type cyanate resin which is solid at ordinary temperature and a polyfunctional maleimide compound which is solid at ordinary temperature, there is obtained a solventless thermosetting composition which is liquid at ordinary temperature and in which further a polyfunctional maleimide compound is compatibilized.SELECTED DRAWING: None

Description

There is an application for exception of loss of novelty

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 substrate.

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, a composition obtained by mixing a polyfunctional maleimide compound, a benzoxazine ring-containing compound and a polyfunctional aromatic cyanate compound is known (Non-Patent Document 1). .. However, each compound described in Non-Patent Document 1 is solid at room temperature. Therefore, in order to obtain a cured product, a method of heating this composition, melting and mixing each compound, and then heat-curing at a higher temperature is adopted (Non-Patent Document 1, P.96, left column 2.2). See section 2).

However, since each compound is solid, each compound must be melted and uniformly mixed at a temperature lower than the curing temperature before heat curing, which has a drawback of inconvenience. It is also conceivable to dissolve each compound in a solvent to form a liquid composition, but in this case, the solvent must be evaporated during heat curing, which causes a problem that the working environment deteriorates. rice field.

Makoto Okamoto, Akio Takahashi, Toshiyuki Oyama, "Highly Heat Resistant Resin Based on Maleimide / Benzoxazine / Cyanic Acid Ester Reaction", Network Polymer Vol. 35 No. 3 (2014) P.I. 94-101

An object of the present invention is to provide a room temperature liquid solvent-free thermosetting composition and a method for producing the same, in which the above-mentioned compounds are compatible with each other.

Each compound of polyfunctional maleimide compound, benzoxazine ring-containing compound and polyfunctional aromatic cyanate compound is generally solid at room temperature, and is heated and melted to uniformly mix each compound to make it liquid, and then to room temperature. Upon cooling, each compound returns to solid again. However, if a specific compound (reaction product) is blended when it is liquefied, each compound will maintain a compatible state for a certain period of time even when cooled to room temperature, and will not return to a solid state. The inventors have discovered it. The present invention is based on such findings.

That is, the present invention is a room temperature liquid solvent-free heat in which a reaction product of a polyfunctional aromatic cyanate compound and a hydroxyl group-containing compound, a polyfunctional aromatic cyanate compound and a benzoxazine ring-containing compound are compatible with each other. It relates to a curable composition and a method for producing the same. Further, the present invention is a room temperature liquid in which a reaction product of a polyfunctional aromatic cyanate compound and a hydroxyl group-containing compound, a polyfunctional maleimide compound, a polyfunctional aromatic cyanate compound and a benzoxazine ring-containing compound are compatible with each other. The present invention relates to a solvent-free thermosetting composition and a method for producing the same.

[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 each compound is not dissolved by using a solvent. Therefore, the solvent-free thermosetting composition is a composition in which each compound in the composition is not dissolved by the solvent.

The room temperature liquid solvent-free thermosetting composition according to the present invention is compatible with a reaction product of a polyfunctional aromatic cyanate compound and a hydroxyl group-containing compound, a polyfunctional aromatic cyanate compound and a benzoxazine ring-containing compound. Being done.

As the polyfunctional aromatic cyanate compound, a solid at room temperature is generally used. As the polyfunctional aromatic cyanate compound which is solid at room temperature, a bisphenol A type cyanate compound which forms a triazine ring and is cured is used. Specifically, various bisphenol A-type cyanate compounds manufactured and sold by Mitsubishi Gas Chemical Company under the registered trademark "CYTESTER" can be used. Exceptionally, a room temperature liquid polyfunctional aromatic cyanate compound can be used alone or in combination with a room temperature solid compound.

The hydroxyl group-containing compound is a compound having a hydroxyl group in the molecule, and is particularly preferably a monool compound having one hydroxyl group in the molecule. The hydroxyl group of the hydroxyl group-containing compound may be a phenolic hydroxyl group bonded to an aromatic ring or an alcoholic hydroxyl group bonded to an alkyl. Specifically, isodecyl alcohol, isotridecyl alcohol, 2-ethyl-1-hexanol, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monohexyl ether, octanol, 3-methoxy-3-methyl-1-butanol, glycerol diglycidyl ether, pentaerythritol triallyl ether, trimethylolpropanediallyl ether, cumylphenol, hydroxydicyclopentadiene, benzyl alcohol, diallylbisphenol A, glycidol or α, α -Bis (trifluoromethyl) benzyl alcohol or the like is used alone or in combination.

When the hydroxyl group of the hydroxyl group-containing compound is phenolic, the reaction product of the polyfunctional aromatic cyanate compound and the hydroxyl group-containing compound is produced by reacting by the mechanism shown in Chemical formulas 1 to 4. The polyfunctional aromatic cyanate compound is N≡C—O—Ar—O—C≡N (where Ar is a group having an aromatic ring and O—C≡N is bonded to the aromatic ring. ), And the hydroxyl group-containing compound having one hydroxyl group is represented by Ph-OH (where Ph is a group having an aromatic ring and OH is bonded to the aromatic ring).

First, the polyfunctional aromatic cyanate compound and the hydroxyl group-containing compound react with each other by the reaction formula as shown in Chemical formula 1 to produce an iminocarbonate compound.

Next, the imino carbonate compound produced in Chemical formula 1 and the polyfunctional aromatic cyanate compound are reacted by the reaction formula as shown in Chemical formula 2 to form a trimer.

This trimer is dephenol-condensed by the reaction formula shown in Chemical formula 3 to produce a heterocyclic compound.

Further, in this trimer, the cyanate monomer is desorbed by the reaction formula as shown in Chemical formula 4, and a heterocyclic compound different from the heterocyclic compound shown in Chemical formula 3 is produced.

When the hydroxyl group of the hydroxyl group-containing compound is alcoholic, the reaction product of the polyfunctional aromatic cyanate compound and the hydroxyl group-containing compound is produced by reacting by the mechanism shown in Chemical formulas 5 to 9. A hydroxyl group-containing compound having one alcoholic hydroxyl group is represented by Alc-OH (wherein, Alc is a group having a hydrocarbon group and OH is bonded to a carbon atom of a hydrocarbon).

ここで、Ｎ≡Ｃ－Ｏ－Ａｒ－ＯＨはフェノール性水酸基を持つ化合物であるので、以下、Ｐｈ’－ＯＨと表記する。また、Ａｌｃ－Ｏ－Ｃ≡Ｎは、殆どそのまま残存する。
First, the polyfunctional aromatic cyanate compound and the hydroxyl group-containing compound undergo an exchange reaction as shown in Chemical formula 5, and the cyanate group and the hydroxyl group are exchanged.

Here, since N≡C—O—Ar—OH is a compound having a phenolic hydroxyl group, it is hereinafter referred to as Ph ′ -OH. Further, Alc—O—C≡N remains almost as it is.

The exchanged phenolic hydroxyl group and the disianate group react with each other by the reaction formula shown in Chemical formula 6 to produce an iminocarbonate compound.

Next, the imino carbonate compound produced in Chemical formula 6 and the polyfunctional aromatic cyanate compound are reacted by the reaction formula as shown in Chemical formula 7 to form a trimer.

This trimer is dephenol-condensed by the reaction formula shown in Chemical formula 8 to produce a heterocyclic compound.

Further, in this trimer, the cyanate monomer is desorbed by the reaction formula as shown in Chemical formula 9, and a heterocyclic compound different from the heterocyclic compound shown in Chemical formula 8 is produced.

Therefore, the reaction product of the polyfunctional aromatic cyanate compound and the hydroxyl group-containing compound is mainly composed of the heterocyclic compound produced by Chemical formula 3 or Chemical formula 4 or the heterocyclic compound produced by Chemical formula 8 or Chemical formula 9, and is mainly composed of Chemical formulas 1 to 1. It contains various intermediates produced in Chemical formula 9. In the present invention, when such a reaction product is present in the composition, when the heat-melted polyfunctional aromatic cyanate compound, the benzoxazine ring-containing compound and / or the polyfunctional maleimide compound is cooled to room temperature, each compound is subjected to. It is believed that crystallization is inhibited and the composition remains liquid at room temperature.

As the benzoxazine ring-containing compound, a compound which is solid at room temperature is generally used. As the benzoxazine ring-containing compound which is solid at room temperature, those described in JP-A-2014-141426 such as Pd-type benzoxazine or Fa-type benzoxazine are used. Further, BS-BXZ, BF-BXZ, etc. manufactured by Konishi Chemical Industry Co., Ltd. are also used. In the present invention, ALP-d type benzoxazine which is a viscous liquid at room temperature may be used. Further, these benzoxazine ring-containing compounds may be mixed and used.

As the polyfunctional maleimide compound, a solid at room temperature is generally used. The polyfunctional maleimide compound is not an essential compound constituting the room temperature liquid solvent-free thermosetting composition according to the present invention, but when the main curing is performed after the temporary curing to obtain a cured product, the time for the temporary curing is set. Since it can be shortened, it is preferable to use in the present invention. 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 compounding ratio of each of the above-mentioned compounds in the composition is preferably as follows. That is, the reaction product of the polyfunctional aromatic cyanate compound and the hydroxyl group-containing compound is preferably blended in an amount of 0.0001 to 0.3 mol with respect to 1 mol of the polyfunctional aromatic cyanate compound. The benzoxazine ring-containing compound is preferably blended in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the polyfunctional aromatic cyanate compound. When the polyfunctional maleimide compound is blended, it is preferable to blend 1 to 30 parts by mass of the polyfunctional maleimide compound with respect to 100 parts by mass of the polyfunctional aromatic cyanate compound.

The room temperature liquid solvent-free thermosetting composition according to the present invention is a polyfunctional aromatic cyanate compound obtained by heating and melting a generally solid polyfunctional aromatic cyanate compound and a benzoxazine ring-containing compound. It can be obtained by adding a reaction product of a hydroxyl group and a hydroxyl group, mixing the mixture uniformly, and then cooling to room temperature. Further, after heating and melting a polyfunctional aromatic cyanate compound, a benzoxazine ring-containing compound and a polyfunctional maleimide compound which are generally solid, a reaction product of the polyfunctional aromatic cyanate compound and a hydroxyl group-containing compound is produced. It can be obtained by adding, mixing uniformly, and then cooling to room temperature.

The following method is particularly preferable as a method for producing a room temperature liquid solvent-free thermosetting composition according to the present invention. That is, a benzoxazine ring-containing compound that is solid at room temperature is added to a mixture of a melt that is obtained by heating and melting a polyfunctional aromatic cyanate compound that is solid at room temperature and a hydroxyl group-containing compound that is liquid at room temperature. This is a method in which the benzoxazine ring-containing compound is melted and then cooled to room temperature. In the case of this method, a reaction product of the polyfunctional aromatic cyanate compound and the hydroxyl group-containing compound and the polyfunctional aromatic cyanate compound can be obtained in the mixed solution. That is, a part of the polyfunctional aromatic cyanate compound is reacted with the hydroxyl group-containing compound to obtain a reaction product, and the rest of the polyfunctional aromatic cyanate compound remains as it is. Therefore, the hydroxyl group of the hydroxyl group-containing compound must be in a very small amount with respect to the cyanate group of the polyfunctional aromatic cyanate compound. Specifically, it is preferable to prepare a mixed solution so that the hydroxyl group of the hydroxyl group-containing compound has a ratio of 0.00005 to 0.1 mol with respect to 1 mol of the cyanate group of the polyfunctional aromatic cyanate compound.

When a polyfunctional maleimide compound is further added to the composition, a melt obtained by heating and melting both a room temperature solid polyfunctional aromatic cyanate compound and a room temperature solid polyfunctional maleimide compound and a room temperature liquid hydroxyl group-containing compound It is preferable to adopt a method in which a benzoxazine ring-containing compound solid at room temperature is added to a mixed solution of the above, the benzoxazine ring-containing compound is melted in the mixed solution, and then the mixture is cooled to room temperature. In this case as well, a reaction product of the polyfunctional aromatic cyanate compound and the hydroxyl group-containing compound, the polyfunctional aromatic cyanate compound and the polyfunctional maleimide compound can be obtained in the mixed solution. Therefore, as in the above case, the hydroxyl group of the hydroxyl group-containing compound must be in a very small amount with respect to the cyanate group of the polyfunctional aromatic cyanate compound in the mixed solution, and the polyfunctional aromatic cyanate must be contained. It is preferable to prepare a mixed solution so that the hydroxyl group of the hydroxyl group-containing compound has a ratio of 0.00005 to 0.1 mol with respect to 1 mol of the cyanate group of the compound.

In order to melt a room temperature solid polyfunctional aromatic cyanate compound, a room temperature solid benzoxazine compound, and a room temperature solid polyfunctional maleimide compound, it is sufficient to heat them to a temperature equal to or higher than their respective melting points. Specifically, it is about 90 to 140 ° C, preferably around 120 ° C. Further, the mixing time for obtaining the mixed solution or the composition is about 10 minutes to 24 hours, which is sufficient. After obtaining the thermosetting composition according to the present invention, if the storage period is long, for example, one week or more, it is frozen at a temperature of −15 ° C. to −70 ° C. or lower to prepare a frozen product. It is preferable to store it. This is because after a lapse of one week or more, a curing reaction between the reaction product and the polyfunctional aromatic cyanate compound, the benzoxazine ring-containing compound or the polyfunctional maleimide compound gradually occurs even at room temperature, and the reaction product is cured.

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, by adding a solvent-free liquid phenol resin (such as Reditop ELPC75 manufactured by Gun Ei Chemical Industry Co., Ltd. or MEH-8000H manufactured by Meiwa Kasei Co., Ltd.), the curing temperature can be lowered or the electrical characteristics can be improved. Also, 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 230 ° 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 is liquid at room temperature, it is not necessary to melt and mix the cured product before curing, and it is possible to work efficiently. Further, since it does not contain a solvent, it does not deteriorate the working environment and has an effect that volume shrinkage and cracking of the cured product due to evaporation of the solvent are less likely to occur. Needless to say, when the solvent-free thermosetting composition according to the present invention is supplied as a frozen product, it may be thawed and used as a liquid. 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
Trimethylolpropane diallyl ether 15 which is liquid at room temperature in a melt obtained by heating and melting 278 g (1 mol) of a bisphenol A-type cyanate compound (manufactured by Mitsubishi Gas Chemicals, Inc .: product name "Triazine (TA)") which is solid at room temperature at 120 ° C. .0 g (0.07 mol) was added and mixed at the same temperature for 2 hours to obtain a mixed solution. To this mixed solution, 30.4 g (0.07 mol) of Pd-type benzoxazine (manufactured by Shikoku Chemicals Corporation) solid at room temperature was added, and the mixture was melt-mixed at the same temperature for 1 hour. Then, the mixture was cooled to room temperature and stored for 7 days to obtain a stable room temperature liquid solvent-free thermosetting composition. Further, this room temperature liquid solvent-free thermosetting composition was frozen to obtain a frozen product, which was then stored.

Example 2
The same method as in Example 1 except that 17.9 g (0.07 mol) of pentaerythritol triallyl ether, which is liquid at room temperature, is used instead of 15.0 g (0.07 mol) of trimethylolpropane diallyl ether, which is liquid at room temperature. To obtain a stable room temperature liquid solvent-free thermosetting composition and a frozen product thereof.

Example 3
Stable by the same method as in Example 1 except that 0.21 g (0.002 mol) of benzyl alcohol which is liquid at room temperature is used instead of 15.0 g (0.07 mol) of trimethylolpropane diallyl ether which is liquid at room temperature. A solvent-free thermosetting composition which is liquid at room temperature and a frozen product thereof were obtained.

Example 4
Room temperature solid bisphenol A type cyanate compound (manufactured by Mitsubishi Gas Chemicals Co., Ltd .: product name "Triazine (TA)") 278 g (1 mol) and room temperature solid 4,4'-diphenylmethane bismaleimide (manufactured by Keiai Kasei Co., Ltd .: product) 15.0 g (0.07 mol) of trimethylolpropane diallyl ether, which is liquid at room temperature, is added to a melt obtained by heating and melting 35.8 g (0.1 mol) of the name “BMI” at 120 ° C., and at the same temperature. The mixture was mixed for 2 hours to obtain a mixed solution. To this mixed solution, 30.4 g (0.07 mol) of Pd-type benzoxazine (manufactured by Shikoku Chemicals Corporation) solid at room temperature was added, and the mixture was melt-mixed at the same temperature for 1 hour. Then, the mixture was cooled to room temperature and stored for 7 days to obtain a stable room temperature liquid solvent-free thermosetting composition. Further, this room temperature liquid solvent-free thermosetting composition was frozen to obtain a frozen product, which was then stored.

Example 5
The same method as in Example 4 except that 17.9 g (0.07 mol) of pentaerythritol triallyl ether, which is liquid at room temperature, is used instead of 15.0 g (0.07 mol) of trimethylolpropane diallyl ether, which is liquid at room temperature. To obtain a stable room temperature liquid solvent-free thermosetting composition and a frozen product thereof.

Example 6
The same method as in Example 4 except that 35.8 g (0.14 mol) of pentaerythritol triallyl ether, which is liquid at room temperature, is used instead of 15.0 g (0.07 mol) of trimethylolpropane diallyl ether, which is liquid at room temperature. To obtain a stable room temperature liquid solvent-free thermosetting composition and a frozen product thereof.

Example 7
By the same method as in Example 4, except that 10.5 g (0.07 mol) of hydroxydicyclopentadiene which is liquid at room temperature is used instead of 15.0 g (0.07 mol) of trimethylolpropane diallyl ether which is liquid at room temperature. , A stable room temperature liquid solvent-free thermosetting composition and a frozen product thereof were obtained.

Example 8
By the same method as in Example 4, except that 4.73 g (0.04 mol) of ethylene glycol monobutyl ether, which is liquid at room temperature, is used instead of 15.0 g (0.07 mol) of trimethylolpropane diallyl ether, which is liquid at room temperature. , A stable room temperature liquid solvent-free thermosetting composition and a frozen product thereof were obtained.

Example 9
Except for using 9.8 g (0.04 mol) of α, α-bis (trifluoromethyl) benzyl alcohol which is liquid at room temperature instead of 15.0 g (0.07 mol) of trimethylolpropane diallyl ether which is liquid at room temperature. By the same method as in Example 4, a stable room temperature liquid solvent-free thermocurable composition and a frozen product thereof were obtained.

Example 10
Stable by the same method as in Example 4 except that 0.54 g (0.005 mol) of benzyl alcohol which is liquid at room temperature is used instead of 15.0 g (0.07 mol) of trimethylolpropane diallyl ether which is liquid at room temperature. A solvent-free thermosetting composition which is liquid at room temperature and a frozen product thereof were obtained.

Example 11
Stable by the same method as in Example 4 except that 1.54 g (0.005 mol) of room temperature liquid trimethylolpropane diallyl ether is used instead of 15.0 g (0.07 mol) of room temperature liquid trimethylolpropane diallyl ether. A solvent-free thermosetting composition which is liquid at room temperature and a frozen product thereof were obtained.

Example 12
Stable by the same method as in Example 4 except that 0.37 g (0.005 mol) of glycidol which is liquid at room temperature is used instead of 15.0 g (0.07 mol) of trimethylolpropane diallyl ether which is liquid at room temperature. A solvent-free thermocurable composition liquid at room temperature and a frozen product thereof were obtained.

Example 13
Room temperature solid bisphenol A type cyanate compound (manufactured by Mitsubishi Gas Chemicals, Inc .: product name "Triazine (TA)") 278 g (1 mol) and room temperature solid bis- (3-ethyl-5-methyl-4-maleimidephenyl) methane (Manufactured by KAI Kasei Co., Ltd .: Product name "BMI-70") 15.4 g (0) of pentaerythritol triallyl ether, which is liquid at room temperature, in a melt obtained by heating and melting 110.6 g (0.25 mol) at 120 ° C. .06 mol) was added and mixed at the same temperature for 2 hours to obtain a mixed solution. To this mixed solution, 30.4 g (0.07 mol) of Pd-type benzoxazine (manufactured by Shikoku Chemicals Corporation) solid at room temperature was added, and the mixture was melt-mixed at the same temperature for 1 hour. Then, the mixture was cooled to room temperature and stored for 7 days to obtain a stable room temperature liquid solvent-free thermosetting composition. Further, this room temperature liquid solvent-free thermosetting composition was frozen to obtain a frozen product, which was then stored.

Example 14
Room temperature solid bisphenol A type cyanate compound (Mitsubishi Gas Chemical Co., Ltd .: product name "Triazine (TA)") 278 g (1 mol), room temperature liquid cyanate compound (Mitsubishi Gas Chemical Co., Ltd .: product name "P-201" 26 .4 g (0.1 mol) and 35.8 g (0.1 mol) of 4,4'-diphenylmethane bismaleimide (manufactured by KI Kasei Co., Ltd .: product name "BMI") solid at room temperature were heated and melted at 120 ° C. To the melt, 15.0 g (0.07 mol) of trimethylolpropanediallyl ether, which was liquid at room temperature, was added and mixed at the same temperature for 2 hours to obtain a mixed solution. In this mixed solution, P, which was solid at room temperature. -D-type benzoxazine (manufactured by Shikoku Kasei Co., Ltd.) was added in an amount of 30.4 g (0.07 mol) and melt-mixed at the same temperature for 1 hour. Then, the mixture was cooled to room temperature and stored for 7 days. A room temperature liquid solvent-free thermocurable composition was obtained. Further, the room temperature liquid solvent-free thermocurable composition was frozen to obtain a frozen product, which was then stored.

Comparative Example 1
Room temperature solid bisphenol A type cyanate compound (Mitsubishi Gas Chemical Company: product name "triazine (TA)") 278 g (1 mol) and room temperature solid 4,4'-diphenylmethane bismaleimide (manufactured by Keiai Kasei Co., Ltd .: product) 35.8 g (0.1 mol) of the name "BMI") was heated and melted at 120 ° C. and mixed for 2 hours to obtain a melt. When this melt was cooled to room temperature, each compound was precipitated and only a solid composition was obtained.

Comparative Example 2
Room temperature solid bisphenol A type cyanate compound (manufactured by Mitsubishi Gas Chemicals Co., Ltd .: product name "Triazine (TA)") 278 g (1 mol) and room temperature solid 4,4'-diphenylmethane bismaleimide (manufactured by Keiai Kasei Co., Ltd .: product) 30.4 g (0.07 mol) of Pd-type benzoxazine (manufactured by Shikoku Kasei Co., Ltd.) solid at room temperature in a melt obtained by heating and melting 35.8 g (0.1 mol) of the name "BMI" at 120 ° C. Was added and melt-mixed at the same temperature for 2 hours to obtain a mixed solution. When this mixed solution was cooled to room temperature, each compound was precipitated and only a solid composition was obtained.

Comparative Example 3
Room temperature solid bisphenol A type cyanate compound (manufactured by Mitsubishi Gas Chemical Company: product name "Triazine (TA)") 278 g (1 mol) and room temperature solid Pd type benzoxazine (manufactured by Shikoku Kasei Co., Ltd.) 30.4 g (0) .07 mol) was heated and melted at 120 ° C. and mixed for 2 hours to obtain a melt. When this melt was cooled to room temperature, each compound was precipitated and only a solid composition was obtained.

Comparative Example 4
Trimethylolpropane diallyl ether 15 which is liquid at room temperature in a melt obtained by heating and melting 278 g (1 mol) of a bisphenol A-type cyanate compound (manufactured by Mitsubishi Gas Chemicals, Inc .: product name "Triazine (TA)") which is solid at room temperature at 120 ° C. .0 g (0.07 mol) was added and mixed at the same temperature for 2 hours to obtain a mixed solution. When this mixed solution was cooled to room temperature, the cyanate compound was precipitated, and only a solid-liquid type composition was obtained.

The room temperature liquid solvent-free thermosetting compositions obtained in Examples 1 to 12 and 14 were provisionally cured at 150 ° C. for 1 hour, and then main-cured at 200 ° C. for 2 hours. , A cured product was obtained. The room temperature liquid solvent-free thermosetting composition obtained in Example 13 was provisionally cured at 150 ° C. for 1 hour, and then main-cured at 220 ° C. for 3 hours. The obtained cured product was obtained. Since the compositions according to Comparative Examples 1 to 4 are not liquid at room temperature, a cured product has not been obtained.

These cured products were subjected to a tensile type dynamic viscoelasticity measuring device (manufactured by Hitachi High-Tech Science Co., Ltd .: product name "DMA7100") at a frequency of 1 Hz and a heating rate of 2 ° C./min under the measurement conditions of normal temperature to 300 ° C. Dynamic viscoelasticity up to was measured. The peak top of the obtained tan δ was set as the glass transition point (° C.), and the results are shown in Table 1.
[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━
tanδ glass transition point (° C)
━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 1 236.3
Example 2 244.5
Example 3 273.1
Example 4 243.7
Example 5 249.8
Example 6 204.9
Example 7 238.3
Example 8 251.9
Example 9 256.0
Example 10 271.3
Example 11 274.5
Example 12 281.6
Example 13 244.5
Example 14 244.0
━━━━━━━━━━━━━━━━━━━━━━━━━━

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 14 has a high glass transition point and is excellent in heat resistance.

Claims (11)

A room temperature liquid solvent-free thermosetting composition comprising a reaction product of a polyfunctional aromatic cyanate compound and a hydroxyl group-containing compound, a polyfunctional aromatic cyanate compound and a benzoxazine ring-containing compound. The solvent-free thermosetting composition according to claim 1, wherein the hydroxyl group of the hydroxyl group-containing compound is phenolic. The solvent-free thermosetting composition according to claim 1, wherein the hydroxyl group of the hydroxyl group-containing compound is alcoholic. The solvent-free thermosetting composition according to claim 1, wherein 0.0001 to 0.3 mol of the reaction product is present with respect to 1 mol of the polyfunctional aromatic cyanate compound. The solvent-free thermosetting composition according to claim 1, wherein the benzoxazine ring-containing compound is present in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the polyfunctional aromatic cyanate compound. The solvent-free thermosetting composition according to claim 1, further comprising a polyfunctional maleimide compound incompatible with each other. The solvent-free thermosetting composition according to claim 6, wherein the polyfunctional maleimide compound is present in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the polyfunctional cyanate compound. A frozen product obtained by freezing the room temperature liquid solvent-free thermosetting composition according to any one of claims 1 to 7. A benzoxazine ring-containing compound that is solid at room temperature is added to a mixed solution of a melt that is obtained by heating and melting a polyfunctional aromatic cyanate compound that is solid at room temperature and a hydroxyl group-containing compound that is liquid at room temperature. The method for producing a room temperature liquid solvent-free thermosetting composition according to claim 1, wherein the oxadin ring-containing compound is melted and then cooled to room temperature. A benzoxazine ring-containing compound that is solid at room temperature in a mixture of a melt obtained by heating and melting both a polyfunctional aromatic cyanate compound that is solid at room temperature and a polyfunctional maleimide compound that is solid at room temperature and a hydroxyl group-containing compound that is liquid at room temperature. The method for producing a room temperature liquid solvent-free thermosetting composition according to claim 6, wherein the benzoxazine ring-containing compound is melted in the mixed solution and then cooled to room temperature. The room temperature liquid according to claim 9 or 10, wherein the mixed solution is prepared so that the hydroxyl group of the hydroxyl group-containing compound has a ratio of 0.00005 to 0.1 mol with respect to 1 mol of the cyanate group of the polyfunctional aromatic cyanate compound. A method for producing a solvent-free thermosetting composition.