JP7069618B2 - Maleimide compounds, and compositions and cured products using them. - Google Patents

Description

The present invention relates to a maleimide compound, and a composition and a cured product using the maleimide compound.

In recent years, fiber reinforced plastics (FRP), in which reinforcing fibers such as glass fibers are added to a matrix resin to improve the strength, have been attracting attention because they are lightweight and have a high elastic modulus. The heat resistance of FRP is determined by the matrix resin. At present, the application of FRP to high-temperature members is limited, and there is a demand for a matrix resin having heat resistance that enables application to high-temperature members.

Further, power semiconductors using silicon carbide (SiC) or gallium nitride (GaN) are attracting attention because they can reduce the waste of electricity. The power semiconductor can operate at a high temperature of 200 ° C. or higher as compared with the conventional silicon (Si) element that operates at 125 to 150 ° C. Therefore, high heat resistance is also required for semiconductor encapsulants and the like constituting power devices.

As described above, especially for advanced material applications, there is a demand for materials having higher physical properties such as heat resistance as compared with conventional materials.

By the way, as a compound having heat resistance, an aromatic bismaleimide compound in which a cured product has a rigid structure is known. As the aromatic bismaleimide compound, for example, 4,4'-diphenylmethane bismaleimide, 4,4'-biphenylene type bismaleimide compound described in Patent Document 1 and the like are known.

For example, in Patent Document 1, the 4,4'-biphenylene type bismaleimide compound and the like are described in a highly heat-resistant substrate material, a flexible substrate material compatible with a high-temperature process, a material for a highly heat-resistant CFRP, a sealing material for an automotive SiC power device, and the like. It is described that it can be suitably used for a material having extremely high heat resistance.

Japanese Unexamined Patent Publication No. 2015-193628

Although the conventional aromatic maleimide compound gives a cured product having a certain heat resistance, it has a high melting point by itself, and it has been found that suitable applications are limited. For example, 4,4'-diphenylmethanebismaleimide does not melt at a low temperature, and it is difficult to pour it into a mold to form it.

Therefore, an object of the present invention is to provide a maleimide compound having a low melting point, which exhibits high heat resistance as a physical characteristic of a cured product.

The present inventors have conducted diligent research to solve the above problems. As a result, they have found that the above-mentioned problems can be solved by a maleimide compound having a predetermined structure, and have completed the present invention.

That is, the present invention relates to a maleimide compound represented by the following formula (1).

At this time, in the above formula (1), R ¹ independently represents a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms and a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms. , R ² are independently hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 10 carbon atoms, and substituted or unsubstituted carbon atoms. The numbers 2 to 10 represent an alkoxyalkyl group, A represents a substituted or unsubstituted aromatic-containing group, and n and m each independently represent an integer of 1 to 5.

According to the present invention, there is provided a maleimide compound having a low melting point, which exhibits high heat resistance as a physical property of a cured product.

Hereinafter, embodiments for carrying out the present invention will be described in detail.

<Maleimide compound>
The maleimide compound according to the present invention has a structure represented by the above formula (1).

The maleimide compound described above has a low melting point. Since the maleimide compound can be poured into a mold in a molten state and cured, it can be suitably applied to FRP, advanced materials for power semiconductor encapsulation materials, and the like. The reason why the maleimide compound according to the present invention has a low melting point is not necessarily clear, but it is presumed to be due to the following mechanism. That is, since the maleimide group originally has a planar structure of the maleimide group, the maleimide compound tends to overlap between molecules due to π-π stacking. As a result, maleimide compounds tend to have a higher melting point. On the other hand, the maleimide compound according to the present invention has a substituent of an alkenyl group and an alkynyl group in the aromatic ring. As a result, it is considered that π-π stacking is prevented or suppressed, and the degree of intramolecular overlap is relatively small, so that the maleimide compound has a low melting point.

Further, in one embodiment, the maleimide compound according to the present invention has a low melt viscosity. As a result, since it is easy to flow, it is easy to pour it at the time of molding, and a uniform cured product can be obtained. The reason why such an effect is obtained is not clear, but it is presumed that it is due to the prevention or suppression of π-π stacking by the substituents of the alkenyl group and the alkynyl group of the aromatic ring, as described above.

Further, in one embodiment, the cured product of the maleimide compound according to the present invention has excellent heat resistance. More specifically, the conventional maleimide compound is known to have high heat resistance, but the maleimide compound according to the present invention may have even higher heat resistance. As a result, it can be suitably applied to advanced material applications such as FRP and power semiconductor encapsulants. For example, the following mechanism can be considered as the reason why such an effect can be obtained. That is, the maleimide compound according to the present invention has a substituent of an alkenyl group and an alkynyl group in the aromatic ring. Therefore, excellent heat resistance can be obtained because not only the cross-linking based on the maleimide group but also the cross-linking by the alkenyl group and the alkynyl group occur at the time of curing.

Further, in one embodiment, the cured product of the maleimide compound according to the present invention has a low dielectric loss tangent. Therefore, it can be particularly preferably applied to electronic members, circuit board materials, insulating films, semiconductor encapsulants and the like. For example, the following mechanism can be considered as the reason why such an effect can be obtained. That is, in general, the dielectric loss tangent is affected by the concentration of polar functional groups and the rigidity of the molecule. The maleimide group contained in the maleimide compound has high rigidity, and even after the maleimide group is polymerized and cured, it forms a succinimide structure, and the rigidity is maintained and a strong crosslinked form is formed. There is. On the other hand, the imide group that the maleimide compound has as a partial structure can be called a polar functional group because polarization can occur, and contributes to a higher dielectric loss tangent. According to the maleimide compound according to the present invention, since the aromatic ring has a substituent of an alkenyl group and an alkynyl group, the concentration of the polar functional group as a whole of the maleimide compound is lowered. Then, the maleimide compound according to the present invention may have a lower dielectric loss tangent. Since the substituents of the alkenyl group and the alkynyl group are directly bonded to the aromatic ring, the Claisen rearrangement does not proceed or hardly progresses at the time of curing, in a high temperature environment, in a high humidity environment, etc. There is a tendency that the increase in dielectric loss tangent due to the formation of polar groups is unlikely to occur.

In the above formula (1), R ¹ independently represents a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms and a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms.

The alkenyl group having 2 to 10 carbon atoms is not particularly limited, but is not particularly limited, but is a vinyl group, a 1-propenyl group, an isopropenyl group, an allyl group, a methallyl group (methallyl group), a 1-butenyl group, a 2-butenyl group, 3 -Butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-octenyl group, 2-octenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, 1,3-Butadienyl group, 1,4-Butadienyl group, 2,4-Butadienyl group, Hexa-1,3-dienyl group, Hexa-2,5-dienyl group, Hexa-1,3,5-trienyl group, etc. Can be mentioned.

The alkynyl group having 2 to 10 carbon atoms is not particularly limited, but is ethynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1, Examples thereof include a 3-butadynyl group.

The alkenyl group having 2 to 10 carbon atoms and the alkynyl group having 2 to 10 carbon atoms may have a substituent. The "substituent of R ¹ " is not particularly limited, and examples thereof include an alkoxy group having 1 to 10 carbon atoms, a halogen atom, and the like.

The alkoxy group having 1 to 10 carbon atoms is not particularly limited, but is limited to a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group and an octyloxy group. , Nonyloxy group and the like.

The halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The above-mentioned substituent of R ¹ may be contained alone or in combination of two or more.

Of these, R ¹ is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, an isopropenyl group, an allyl group, a metalyl group, and the like. It is more preferably a 2-butenyl group, a 3-butenyl group, a cyclohexenyl group or a 2,4-butadienyl group, and an isopropenyl group, an allyl group, a metalyl group, a 2-butenyl group or a 3-butenyl group. It is particularly preferable, and most preferably an allyl group.

R ² is independently a hydrogen atom, an alkyl group having 1 to 10 substituted or unsubstituted carbon atoms, an alkoxy group having 1 to 10 substituted or unsubstituted carbon atoms, and a substituted or unsubstituted carbon atom number. Represents 2-10 alkoxyalkyl groups.

The alkyl group having 1 to 10 carbon atoms is not particularly limited, but is limited to a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. Group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, n-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group , Cyclooctyl group, cyclononyl group and the like.

The alkoxy group having 1 to 10 carbon atoms is not particularly limited, but is limited to a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group and an octyloxy group. , Nonyloxy group and the like.

The alkoxyalkyl group having 2 to 10 carbon atoms is not particularly limited, but is limited to a methyloxymethyl group, an ethyloxymethyl group, a propyloxymethyl group, a butyloxymethyl group, a methyloxyethyl group, an ethyloxyethyl group, and a propyloxy group. Ethyl group, butyloxyethyl group, methyloxypropyl group, ethyloxypropyl group, propyloxypropyl group, butyloxypropyl group, methyloxybutyl group, ethyloxybutyl group, propyloxybutyl group, butyloxybutyl group and the like. Be done.

An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkoxyalkyl group having 2 to 10 carbon atoms may have a substituent. The "substituent of R ² " is not particularly limited, and examples thereof include halogen atoms.

The halogen atom is not particularly limited, but the halogen atom described above can be used as the substituent of ^R1 .

Of these, ^R2 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a hydrogen atom or methyl. It is more preferably a group, an ethyl group, a propyl group or an isopropyl group, particularly preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

A represents a substituted or unsubstituted aromatic-containing group. In addition, in this specification, an "aromatic-containing group" means a group having at least one aromatic ring.

The aromatic-containing group is not particularly limited, but is a group having one aromatic ring such as benzene, thiophene, imidazole, oxazole, thiazole, pyrrol, furan, pyran, pyrazolone, pyridine, pyridazine, pyrimidine, pyrrol and the like; naphthalene and benzo. Groups with two aromatic rings, such as imidazole, benzoxazole, indol, quinoline, isoquinoline, benzothiophene, carbazole, a group to which two aromatic rings are attached by a linking group; anthracene, benzo [a] fluorene, acrydin, a linking group. A group having three aromatic rings such as a group to which three aromatic rings are bonded; benz [a] anthracene, pyrene, chrysen, fluoranthen, pyrene, tetracene, triphenylene, a group to which four aromatic rings are bonded by a linking group, etc. Examples thereof include a group having two aromatic rings.

At this time, examples of the linking group include a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an amide group, a carbamate group, a carbonate group, a substituted or unsubstituted alkylene having 1 to 10 carbon atoms, and the like. ..

The alkylene having 1 to 10 carbon atoms is not particularly limited, and examples thereof include methylene, ethylene, propylene, isopropylene, butylene, 1-methylpropylene, 2-methylpropylene, and pentylene. At this time, the alkylene having 1 to 10 carbon atoms may form a ring between two aromatic rings.

The alkylene having 1 to 10 carbon atoms may have a substituent. The "substituent of the linking group" is not particularly limited, and examples thereof include a halogen atom and an alkoxy group having 1 to 10 carbon atoms.

The halogen atom is not particularly limited, but the halogen atom described above can be used as the substituent of ^R1 .
The alkoxy group having 1 to 10 carbon atoms is not particularly limited, but the above-mentioned ^R2 can be used.

These linking groups may have the above-mentioned substituents alone or in combination of two or more.

Examples of the group to which the two aromatic rings are bonded by the linking group include biphenyl, phenylpyridine, phenylthiophene, bithiophene, diphenyl ether, diphenyl sulfide, diphenyl sulfone, fluorene, diphenylmethane, 1,2-diphenyl ethane and 1,1-diphenyl. Examples thereof include ethane, 1,3-diphenylpropane and the like.

The groups to which the three aromatic rings are bonded by the linking group include terphenyl, 1-phenylnaphthalene, 2-phenylnaphthalene, diphenylthiophene, triphenylmethane, 1,1,1-triphenylethane, 1,1, and so on. Examples thereof include 2-triphenylethane and 1,1,3-triphenylpropane.

The aromatic-containing group may have a substituent. In other words, the hydrogen atom of the aromatic ring may be substituted with a substituent. The "substituted group of the aromatic-containing group" is not particularly limited, but is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and a halogen atom. And so on.

The alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, and the alkoxyalkyl group having 2 to 10 carbon atoms are not particularly limited, but are the same as those described in ^R2 above. Things can be mentioned.

Moreover, as a halogen atom, the above-mentioned thing as a substituent of R ¹ can be mentioned.

The substituents of these aromatic-containing groups may be contained alone or in combination of two or more.

In one preferred embodiment, A is represented by the following formulas (2-1) to (2-13).

In the above formulas (2-1) to (2-13), X is independently a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an amide group, a carbamate group, a carbonate group, a substituted or non-substituted group. Represents a substituted alkylene having 1 to 10 carbon atoms.

Specific examples of X are the same as those of the above-mentioned linking group.

Y represents a nitrogen atom, CR ³ . At this time, the R ³ is a hydrogen atom or an substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

The alkyl group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include the same as those described in ^R2 above.

At this time, the alkyl group having 1 to 10 carbon atoms may have a substituent. The "substituent of R ³ " is not particularly limited, and examples thereof include halogen atoms.

The halogen atom is not particularly limited, but the halogen atom described above can be used as the substituent of ^R1 .

The hydrogen atom constituting the aromatic ring represented by the above formulas (2-1) to (2-13) may be substituted with a substituent. The substituent at this time is the same as the above-mentioned "substituent of the aromatic-containing group".

The above-mentioned R ¹ and maleimide group are each directly bonded to the aromatic ring. That is, it has a structure in which the hydrogen atoms constituting the aromatic ring of the aromatic-containing group are substituted with ^R1 by the number of n and the maleimide groups by the number of m.

In one embodiment, A preferably has two or three aromatic rings, more preferably has two aromatic rings, and has a structure represented by the formulas (2-1) and (2-2). It is more preferable, and it is particularly preferable to have a structure represented by the formula (2-2). When the number of aromatic rings is two or three, preferably two, the overlap between molecules due to the π-π stacking of the maleimide compound is less likely to occur, and the melt viscosity of the maleimide compound is less than that in the case where the number of aromatic rings is larger than this. Is preferable because it can decrease.

Further, in one embodiment, A is preferably formulas (2-1) to (2-7) and (2-13), and is preferably formulas (2-1) to (2-7). More preferably, the formulas (2-1) to (2-4), (2-6) and (2-7) are further preferable, and the formula (2-2) is particularly preferable. When the aromatic ring has a high flatness, the obtained cured product tends to have an overlap between molecules due to π-π stacking, and the molecules are regularly arranged at the time of curing, so that the cured product of the maleimide compound is prepared. It is preferable because the heat resistance is high and the coefficient of thermal expansion can be small.

Further, in one embodiment, A is preferably formulas (2-1) to (2-7) and (2-13), and is preferably formulas (2-1) to (2-7). More preferably, the formulas (2-1) to (2-4), (2-6) and (2-7) are further preferable, and the formula (2-2) is particularly preferable. Compared with those having carbon atoms and nitrogen atoms bonded to three or more aromatic rings, the stability of the compound decomposed by radicals is relatively low, so that decomposition is less likely to occur, and the heat resistance of the cured product of the maleimide compound. It is preferable because the properties are high, and in particular, the heat-resistant decomposition temperature can be high.

Further, in one embodiment, A preferably has three or more aromatic rings, more preferably has three to five aromatic rings, and has formulas (2-3) to (2-13). Is more preferable, and (2-8) is particularly preferable. Since A has a large number of aromatic rings, the concentration of the polar functional group of the imide group as a whole of the molecule of the imide group which the maleimide compound has as a partial structure can be lowered, and the dielectric adjacency of the cured product of the maleimide compound can be lowered. preferable.

According to a preferred embodiment, A has an excellent balance of melt viscosity, heat resistance, and dielectric loss tangent, and thus A is represented by the formulas (2-1) to (2-4), (2-6) to (2-8). , (2-2), (2-8), and (2-9) are more preferable, and (2-2) and (2-8) are even more preferable.

Further, n and m are independently integers of 1 to 5.

The n is preferably 1 to 4, more preferably 1 to 2, and even more preferably 2.

Further, the m is preferably 1 to 4, more preferably 1 to 2, and further preferably 2.

The ratio of m to n (m: n) is preferably 1: 5 to 5: 1, more preferably 1: 2 to 2: 1, and further preferably 1: 1. preferable. When the ratio of m and n is in the above range, heat resistance and a low melting point can be compatible with each other, which is preferable.

Specific structures of the maleimide compound according to the present invention include compounds represented by the following formulas (3-1) to (3-49).

Of the above, from the viewpoint of excellent melt viscosity of the maleimide compound, the formulas (3-1) to (3-37) are preferable, and the formulas (3-5) to (3-19), (3-24). , (3-37) is more preferable, and the formulas (3-9) to (3-19) are further preferable.

Further, from the viewpoint of reducing the coefficient of thermal expansion of the cured product of the maleimide compound, the formulas (3-4) to (3-49) are preferable, and the formulas (3-4) to (3-25) and the formula (3-25) are used. 3-49) is more preferable.

Further, from the viewpoint of increasing the heat-resistant decomposition temperature of the cured product of the maleimide compound, the formulas (3-1) to (3-25) and the formulas (3-49) are preferable, and the formulas (3-1) to (3-1) to ( 3-5), formulas (3-9) to (3-25), and formula (3-49) are more preferable.

Further, from the viewpoint of lowering the dielectric loss tangent of the cured product of the maleimide compound, the formulas (3-4) to (3-49) are preferable, and the formulas (3-20) to (3-49) are preferable. More preferred.

From the viewpoint of excellent balance of melt viscosity, heat resistance, and dielectric loss tangent, the formulas (3-9) to (3-19) and the formulas (3-27) to (3-44) are preferable, and the formulas (3-9) to (3-19) are preferable. 3-9) to (3-19), formulas (3-27) to (3-37) are more preferable, and formulas (3-9) to (3-19) are even more preferable.

The above-mentioned maleimide compound may be used alone or in combination of two or more.

<Composition>
According to one embodiment of the invention, a composition comprising the maleimide compound described above is provided.

Since the above-mentioned maleimide compound has a low melting point, the composition can also be poured into a mold in a molten state and cured. Therefore, it can be suitably applied to FRP, advanced materials for power semiconductor encapsulation materials, and the like.

Further, in one embodiment, the above-mentioned maleimide compound has a low melt viscosity. Therefore, since the composition is easy to flow, it is easy to pour it at the time of molding, and a uniform cured product can be obtained.

Further, in one embodiment, the cured product of the above-mentioned maleimide compound has excellent heat resistance. Therefore, the cured product obtained by curing the composition containing the same can be suitably used for heat-resistant members and electronic members.

Further, in one embodiment, the cured product of the above-mentioned maleimide compound has a low dielectric loss tangent. Therefore, the cured product obtained by curing the composition containing the same can be suitably used for electronic members, circuit board materials, insulating films, semiconductor encapsulants and the like.

In one embodiment, the composition comprises the maleimide compound described above. In addition, if necessary, a reactive compound, a filler, a fibrous substrate, a dispersion medium, a resin, a curing agent, a curing accelerator, other formulations and the like may be further contained.

[Reactive compound]
The composition of the present invention may contain a reactive compound other than the maleimide compound of the present invention. By containing the reactive compound, it is possible to impart various characteristics such as reactivity, heat resistance, and handleability to the composition.

The reactive compound referred to here is a compound having a reactive group, and may be a monomer, an oligomer, or a polymer.

The reactive group may be a functional group that does not react with the maleimide compound of the present invention or a functional group that reacts, but in order to further improve the heat resistance, it may be a functional group that reacts with the maleimide compound of the present invention. preferable.

Examples of the functional group that reacts with the maleimide compound of the present invention include an epoxy group, a cyanato group, a maleimide group, a phenolic hydroxyl group, an oxazine ring, an amino group, and a group having a carbon-carbon double bond.

Examples of the compound having an epoxy group include an epoxy resin and a phenoxy resin.

Examples of the compound having a cyanate group include cyanate ester resin.

Examples of the compound having a maleimide group include a maleimide resin and a bismaleimide resin.

Examples of the compound having a phenolic hydroxyl group include phenol novolac resin, cresol novolak resin, dicyclopentadiene-modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, and biphenyl aralkyl resin.

Examples of the compound having an oxazine ring include benzoxazine obtained by reacting a phenol compound and an aromatic amino compound with formaldehyde. These phenol compounds and aromatic amino compounds may have a reactive functional group in the structure.

Compounds having an amino group include DDM (4,4'-diaminodiphenylmethane), DDE (4,4'-diaminodiphenyl ether), 3,4'-diaminodiphenyl ether, and 2,2- {bis4- (4-aminophenoxy). ) Phenyl} Propane, 4,4'-bis (4-aminophenoxy) Biphenyl and other aromatic amino compounds can be mentioned.

Examples of the compound having a group having a carbon-carbon double bond include other maleimide compounds, vinyl compounds, (meth) allyl compounds and the like. In the present specification, the term "other maleimide compound" means a maleimide compound other than the maleimide compound according to the present invention.

The above-mentioned reactive compound may have only one type of reactive group, may have a plurality of types, and may have one or a plurality of functional groups. Moreover, you may use a plurality of kinds at the same time.

Preferred reactive compounds include epoxy resins, phenoxy resins, cyanate ester resins, maleimide compounds, vinyl compounds, aromatic amino compounds and the like.

Among them, other maleimide compounds, cyanate ester resins, epoxy resins, and aromatic amino compounds are particularly preferable.

The cross-linking density of the other maleimide compound is improved by the self-addition reaction between the maleimide group, the substituted or unsubstituted alkenyl group, the substituted or unsubstituted alkynyl group, and the enreaction of the maleimide group with the maleimide compound of the present invention. As a result, heat resistance, especially the glass transition temperature, is improved.

Usually, a maleimide compound is used, and in order to obtain a uniform cured product, high temperature and long-term curing conditions are required. Therefore, in many cases, a peroxide catalyst is used in combination to promote the reaction. However, even when the maleimide compound of the present invention does not use a catalyst, the curing reaction proceeds and a uniform cured product can be obtained. The use of a peroxide-based catalyst has problems such as an increase in the viscosity of the composition, a decrease in pot life, and a decrease in physical properties due to a trace amount of peroxide remaining in the cured product. Since it is not necessary to use a peroxide-based curing agent for the maleimide compound of No. 1, these problems can be solved.

The cured product of the cyanate ester resin and the maleimide compound of the present invention exhibits excellent dielectric properties.

When the epoxy resin is used in combination with the maleimide compound of the present invention, toughness and metal adhesion can be imparted to the cured product.

The crosslink density of the aromatic amino compound is improved by the Michael addition reaction between the amino group and the maleimide group, and the heat-resistant decomposition temperature and the glass transition temperature are improved.

The epoxy resin is not particularly limited as long as it has an epoxy group. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol sulfide type epoxy resin, etc. Phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin , Tetraphenyl ethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol Examples thereof include co-condensed novolak type epoxy resin, naphthylene ether type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, biphenyl modified novolak type epoxy resin, anthracene type epoxy resin and the like. These may be used alone or in combination of two or more.

The phenoxy resin is a high molecular weight thermoplastic polyether resin based on diphenol and epichlorohydrin such as epichlorohydrin, and the weight average molecular weight is preferably 20,000 to 100,000. The structure of the phenoxy resin includes, for example, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, and adamantan skeleton. Examples thereof include those having one or more skeletons selected from a terpene skeleton and a trimethylcyclohexane skeleton.

Examples of the cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, and phenylene ether type cyanate ester resin. Naftylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac type cyanate ester resin, triphenylmethane type cyanate ester. Resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolak type Examples thereof include cyanate ester resin, naphthol-cresol co-condensed novolak type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate ester resin, biphenyl modified novolak type cyanate ester resin, anthracene type cyanate ester resin and the like. These may be used alone or in combination of two or more.

Among these cyanate ester resins, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, and polyhydroxynaphthalene type cyanate ester resin are particularly excellent in heat resistance. , Naftylene ether type cyanate ester resin and novolak type cyanate ester resin are preferably used, and dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable in that a cured product having excellent dielectric properties can be obtained.

Examples of other maleimide compounds include various compounds represented by any of the following structural formulas (i) to (iii).

In formula (i), R is an s-valent organic group, α and β are any of a hydrogen atom, a halogen atom, an alkyl group and an aryl group, respectively, and s is an integer of 1 or more.

In formula (ii), R is any of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, s is an integer of 1 to 3, and t is an average of 0 to 10 in repeating units. Is.

In the formula (iii), R is any of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, s is an integer of 1 to 3, and t is an average of 0 to 0 to a repeating unit. It is 10.

These other maleimide compounds may be used alone or in combination of two or more.

The oxazine compound is not particularly limited, and is, for example, a reaction product of bisphenol F, formalin and aniline (FA type benzoxazine resin), or a reaction product of 4,4'-diaminodiphenylmethane, formalin and phenol (P). -D-type benzoxazine resin), bisphenol A and formalin and aniline reaction products, dihydroxydiphenyl ether and formalin and aniline reaction products, diaminodiphenyl ether and formalin and phenol reaction products, dicyclopentadiene-phenol-added resin Examples thereof include reaction products of formalin and aniline, reaction products of phenolphthaline and formalin and aniline, and reaction products of dihydroxydiphenylsulfide and formalin and aniline. These may be used alone or in combination of two or more.

Examples of vinyl compounds include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth) acrylate, 2 -Alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms such as ethylhexyl (meth) acrylate and lauryl (meth) acrylate; aralkyl such as benzyl (meth) acrylate and 2-phenylethyl (meth) acrylate. (Meta) acrylates; Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; ω-alkoxyalkyl such as 2-methoxyethyl (meth) acrylate and 4-methoxybutyl (meth) acrylate. (Meta) Acrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate; Alkyl esters of crotonic acid such as methyl crotonate and ethyl crotonate; dimethylmalate, di- Dialkyl esters of unsaturated dibasic acids such as n-butylmalate, dimethylfumarate, and dimethylitaconate; α-olefins such as ethylene and propylene; vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, etc. Fluoroolefins; Alkyl vinyl ethers such as ethyl vinyl ether and n-butyl vinyl ether; Cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- Examples thereof include tertiary amide group-containing monomers such as (meth) acryloylpyrrolidine and N-vinylpyrrolidone.

Examples of the (meth) allyl compound include allyl esters such as allyl acetate, allyl chloride, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate. Allyloxyalcohols such as allyloxymethanol and allyloxyethanol;, diallyl phthalate, diallyl isophthalate, diallyl cyanurate, diallyl isocyanurate, pentaerythritol diallyl ether, trimethylolpropane diallyl ether, glycerin diallyl ether, bisphenol A diallyl ether, A compound containing two allyl groups such as bisphenol F diallyl ether, ethylene glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, propylene glycol diallyl ether, dipropylene glycol diallyl ether, and tripropylene glycol diallyl ether; triallyl isothia. Examples thereof include compounds containing three or more allyl groups such as nurate, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, and trimethylolpropanetriallyl ether; or metaallyl forms of these compounds.

[Filler]
The composition of the present invention may further contain a filler. Examples of the filler include an inorganic filler and an organic filler.

Examples of the inorganic filler include inorganic fine particles.

As the inorganic fine particles, for example, those having excellent heat resistance include alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, silicon dioxide, fused silica, crystalline silica, ultrafine powder amorphous). Silica, etc.); Examples of excellent thermal conductivity include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond, etc .; Metal fillers and / or metal-coated fillers using (eg, iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); Minerals such as talc, zeolite, wollastonite, smectite, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; high refractive index Barium titanate, zirconia oxide, titanium oxide, etc .; as photocatalytic properties, titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, terium, nickel, iron, cobalt, etc. Photocatalyst metals such as silver, molybdenum, strontium, chromium, barium, and lead, composites of the above metals, oxides thereof, etc .; Their composites and oxides; metals such as silver and copper, tin oxide, indium oxide, etc. as having excellent conductivity; silica, etc. as having excellent insulating properties; Titanium oxide, zinc oxide, etc.

These inorganic fine particles may be selected in a timely manner depending on the intended use, and may be used alone or in combination of two or more. Further, since the inorganic fine particles have various properties other than the properties mentioned in the examples, they may be selected according to the timely application.

For example, when silica is used as the inorganic fine particles, there is no particular limitation, and known silica fine particles such as powdered silica and colloidal silica can be used. Examples of commercially available powdered silica fine particles include Aerosil 50, 200 manufactured by Nippon Aerosil Co., Ltd., Syldex H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., and E220A manufactured by Nippon Silysia Chemical Ltd. , E220, SYLYSIA470 manufactured by Fuji Silysia Chemical Ltd., SG flakes manufactured by Nippon Ita Glass Co., Ltd. and the like.

Examples of commercially available colloidal silica include metalnol silica sol manufactured by Nissan Chemical Industry Co., Ltd., IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, and the like. Examples thereof include ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like.

Surface-modified silica fine particles may be used. For example, the silica fine particles are surface-treated with a reactive silane coupling agent having a hydrophobic group, or modified with a compound having a (meth) acryloyl group. can give. Commercially available powdered silica modified with a compound having a (meth) acryloyl group includes Aerosil RM50, R711 manufactured by Nippon Aerosil Co., Ltd., and commercially available colloidal silica modified with a compound having a (meth) acryloyl group. Examples include MIBK-SD manufactured by Nissan Chemical Industry Co., Ltd.

The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or indefinite shapes can be used. The primary particle diameter is preferably in the range of 5 to 200 nm. When it is 5 nm or more, the inorganic fine particles are preferably dispersed in the dispersion, and when it is 200 nm or less, a decrease in the strength of the cured product can be prevented.

As the titanium oxide fine particles, not only the extender pigment but also an ultraviolet light-responsive photocatalyst can be used, and for example, anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide and the like can be used. Further, particles designed to be doped with different elements in the crystal structure of titanium oxide to respond to visible light can also be used. As the element to be doped in titanium oxide, anionic elements such as nitrogen, sulfur, carbon, fluorine and phosphorus, and cationic elements such as chromium, iron, cobalt and manganese are preferably used. Further, as a form, a powder, a sol or a slurry dispersed in an organic solvent or water can be used. Examples of commercially available powdered titanium oxide fine particles include Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd., ATM-100 manufactured by TAYCA Corporation, and the like. Examples of commercially available slurry-shaped titanium oxide fine particles include TAYCA Corporation TKD-701.

[Fibrous substrate]
The composition of the present invention may further contain a fibrous substrate. The fibrous substrate of the present invention is not particularly limited, but is preferably one used for a fiber reinforced resin, and examples thereof include inorganic fibers and organic fibers.

Examples of the inorganic fiber include carbon fiber, glass fiber, boron fiber, alumina fiber, silicon carbide fiber and other inorganic fibers, as well as carbon fiber, activated carbon fiber, graphite fiber, glass fiber, tungsten carbide fiber and silicon carbide fiber (silicon carbide fiber). ), Ceramic fiber, alumina fiber, natural fiber, mineral fiber such as genbuiwa, boron fiber, boron nitride fiber, boron carbide fiber, metal fiber and the like. Examples of the metal fiber include aluminum fiber, copper fiber, brass fiber, stainless fiber, and steel fiber.

Examples of organic fibers include synthetic fibers made of resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate, and cellulose and pulp. Examples thereof include natural fibers such as cotton, wool and silk, and regenerated fibers such as proteins, polypeptides and alginic acid.

Among them, carbon fiber and glass fiber are preferable because they have a wide range of industrial use. Of these, only one type may be used, or a plurality of types may be used at the same time.

The fibrous substrate described above may be an aggregate of fibers, may be continuous or discontinuous, and may be woven or non-woven. Further, a fiber bundle in which fibers are arranged in one direction may be used, or a sheet in which the fiber bundles are arranged may be used. Further, the aggregate of fibers may have a three-dimensional shape having a thickness.

[Dispersion medium]
In the composition of the present invention, a dispersion medium may be used for the purpose of adjusting the solid content and viscosity of the composition. The dispersion medium is not particularly limited as long as it is a liquid medium that does not impair the effects of the present invention, and examples thereof include various organic solvents and liquid organic polymers.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), cyclic ethers such as tetrahydrofuran (THF) and dioxolan, and esters such as methyl acetate, ethyl acetate and butyl acetate. , Aromatic substances such as toluene and xylene, and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether. These can be used alone or in combination, but among them, methyl ethyl ketone is preferable from the viewpoint of volatility at the time of coating and solvent recovery.

The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and is, for example, a carboxyl group-containing polymer modified product (Floren G-900, NC-500: Kyoeisha), an acrylic polymer (Floren WK-20: Kyoeisha). , Amine salt of special modified phosphoric acid ester (HIPLAAD ED-251: Kusumoto Kasei), modified acrylic block copolymer (DISPERBYK2000; Big Chemie) and the like.

[resin]
Further, the composition of the present invention may have a resin other than the maleimide compound of the present invention. As the resin, a known and commonly used resin may be blended as long as the effect of the present invention is not impaired, and for example, a thermosetting resin or a thermoplastic resin can be used.

The thermosetting resin is a resin having a property of being substantially insoluble and insoluble when cured by means such as heating or radiation or a catalyst. Specific examples thereof include phenol resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, diallyl terephthalate resin, epoxy resin, silicone resin, urethane resin, furan resin, ketone resin, and xylene. Examples thereof include resins, thermosetting polyimide resins, benzoxazine resins, active ester resins, aniline resins, cyanate ester resins, styrene / maleic anhydride (SMA) resins, and maleimide resins other than the maleimide compounds of the present invention. These thermosetting resins can be used alone or in combination of two or more.

The thermoplastic resin is a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethylmethacrylate resin, acrylic resin, and polyvinyl chloride resin. Polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate Resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyether sulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyether ether ketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, Shinji Examples thereof include tactical polystyrene resin and cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more.

In addition, an allyl group-containing resin typified by diallyl bisphenol or triallyl isocyanurate, a polyphosphoric acid ester, a phosphoric acid ester-carbonate copolymer, or the like may be contained. These can be used alone or in combination of two or more.

[Curing agent]
The composition of the present invention may further contain a curing agent. Examples of the curing agent include amine-based curing agents, amide-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, active ester-based curing agents, carboxyl group-containing curing agents, and thiol-based curing agents.

Examples of amine-based curing agents include diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylether, diaminodiphenylsulfone, orthophenylenediamine, metaphenylenediamine, paraphenylenediamine, metaxylenedamine, paraxylenedamine, diethyltoluenediamine, diethylenetriamine, and triethylenetetramine. Examples thereof include isophorone diamine, imidazole, BF3-amine complex, guanidine derivative, guanamine derivative and the like.

Examples of the amide-based curing agent include a polyamide resin synthesized from a dimer of dicyandiamide and linolenic acid and ethylenediamine.

Examples of the acid anhydride-based curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexa. Examples include hydrophthalic anhydride.

Examples of the phenolic curing agent include bisphenol A, bisphenol F, bisphenol S, resorcin, catechol, hydroquinone, fluorene bisphenol, 4,4'-biphenol, 4,4', 4 "-trihydroxytriphenylmethane, naphthalenediol, 1 , 1,2,2-Tetrakis (4-hydroxyphenyl) ethane, calixarene, phenol novolac resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadienephenol addition type resin, phenol aralkyl resin (Zylock) Resin), polyhydric phenol novolak resin synthesized from polyhydric hydroxy compounds typified by resorcin novolak resin and formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensation. Novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenolic resin (polyvalent phenolic compound in which phenol nuclei are linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenolic nuclei are linked by bismethylene group) , Aminotriazine-modified phenolic resin (polyvalent phenolic compound in which phenolic nuclei are linked with melamine, benzoguanamine, etc.) and alkoxy group-containing aromatic ring-modified novolak resin (polyvalent phenol in which phenolic nuclei and alkoxy group-containing aromatic rings are linked with formaldehyde). Compounds) and other polyhydric phenolic compounds can be mentioned.

These curing agents may be used alone or in combination of two or more.

[Curing accelerator]
The composition of the present invention may further contain a curing accelerator. The curing accelerator may be used alone or in combination with the above-mentioned curing agent.

As the curing accelerator, various compounds that promote the curing reaction of the curable resin can be used. Specific examples of the effect promoter include phosphorus compounds, tertiary amine compounds, imidazole compounds, organic acid metal salts, Lewis acids, amine complex salts and the like. Among these, imidazole compounds, phosphorus compounds, and tertiary amine compounds are preferably used, and particularly when used as semiconductor encapsulant materials, they are excellent in curability, heat resistance, electrical properties, moisture resistance reliability, and the like. , Triphenylphosphine and tetraphenylphosphonium tetra-p-tolylbolate are preferable for phosphorus compounds, and 1,8-diazabicyclo- [5.4.0] -undecene (DBU) is preferable for tertiary amines.

[Other formulations]
The composition of the present invention may have other formulations. Examples of the other formulations include catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow modifiers, coupling agents, dyes, leveling agents, and the like. Examples thereof include a rheology control agent, an ultraviolet absorber, an antioxidant, a flame retardant, and a plasticizer.

These other formulations may be used alone or in combination of two or more.

<Cured maleimide>
According to one embodiment of the present invention, there is provided a cured product (maleimide cured product) obtained by curing the above-mentioned maleimide compound. The above-mentioned maleimide compound can be homopolymerized, and a cured maleimide can be obtained.

The cured product may contain the above-mentioned curing agent, curing accelerator, or the like, if necessary.

<Curing product>
Since the cured product obtained by curing the composition of the present invention has excellent heat resistance, it can be suitably used for heat-resistant members and electronic members. Further, since the dielectric loss tangent is low, it can be suitably used for circuit board materials, insulating films, and semiconductor encapsulants.

The method for molding the cured product is not particularly limited, and the composition may be molded alone or may be laminated with a base material to form a laminated body.

When the composition of the present invention is cured, it may be thermally cured. Although a known and commonly used curing catalyst may be used for thermal curing, the composition of the present invention can be cured by the reaction of a maleimide group with an alkenyl group and an alkynyl group without using a curing catalyst. Is.

When thermosetting is performed, it may be cured by one heating or may be cured through a multi-step heating step.

When a curing catalyst is used, for example, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate and acetic acid; inorganic bases such as sodium hydroxide or potassium hydroxide; tetra. Titanium esters such as isopropyl titanate and tetrabutyl titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonen-5 (DBN) , 1,4-diazabicyclo [2.2.2] Octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole and other compounds containing various basic nitrogen atoms. Kind; Various quaternary ammonium salts such as tetramethylammonium salt, tetrabutylammonium salt, dilauryldimethylammonium salt, etc., quaternary ammonium salts having chloride, bromide, carboxylate, hydroxyoxide, etc. as counter anions; Tin carboxylates such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diacetylacetonate, tin octylate or tin stearate; benzoyl peroxide, cumenehydroperoxide, dicumyl peroxide, lauroyl peroxide. , Di-t-butyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, t-butyl perbenzoate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, etc. Organic peroxides and the like can be used. The catalyst may be used alone or in combination of two or more.

Further, since the maleimide compound of the present invention has a carbon-carbon double bond, active energy ray curing can also be used in combination. When performing active energy ray curing, a photopolymerization initiator may be added to the composition. As the photopolymerization initiator, a known one may be used, and for example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used. Examples of the acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 4 -(2-Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and the like can be mentioned. Examples of the benzyl ketals include 1-hydroxycyclohexyl-phenylketone, benzyl dimethyl ketal and the like. Examples of the benzophenones include benzophenone, methyl o-benzoylbenzoate and the like. Examples of the benzoins include benzoin, benzoin methyl ether, benzoin isopropyl ether and the like. The photopolymerization initiator may be used alone or in combination of two or more.

When thermosetting and active energy ray curing are used in combination, heating and active energy ray irradiation may be performed at the same time or separately. For example, heat curing may be performed after irradiation with active energy rays, or active energy ray curing may be performed after heat curing. Further, each curing method may be combined twice or more, and the curing method may be appropriately selected according to the intended use.

<Laminated body>
The cured product of the present invention can be laminated with a base material to form a laminated body.

The base material of the laminate may be an inorganic material such as metal or glass, or an organic material such as plastic or wood, and may be used in a timely manner depending on the application. The shape of the laminate may be a flat plate, a sheet, or a three-dimensional structure. It does not matter whether it is possessed or three-dimensional. It may have any shape depending on the purpose, such as one having a curvature on the entire surface or a part thereof. Further, there are no restrictions on the hardness, thickness, etc. of the base material. Further, the cured product of the present invention may be used as a base material, and the cured product of the present invention may be further laminated.

In the case of applications such as circuit boards and semiconductor package substrates, it is preferable to laminate metal foils, and examples of the metal foils include copper foils, aluminum foils, gold foils, silver foils, etc., and copper foils are used because of their good workability. Is preferable.

In the laminated body of the present invention, the cured product layer may be formed by directly coating or molding on the base material, or may be laminated with an already molded product. In the case of direct coating, the coating method is not particularly limited, and the spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, etc. Examples include a screen printing method and an inkjet method. In the case of direct molding, in-mold molding, insert molding, vacuum forming, extrusion laminating molding, press molding and the like can be mentioned.

When laminating the molded composition, the uncured or semi-cured composition layer may be laminated and then cured, or the cured composition layer in which the composition is completely cured may be laminated on the substrate. good.

Further, the cured product of the present invention may be laminated by applying a precursor that can be a base material and curing the cured product, and the precursor that can be a base material or the composition of the present invention is uncured or semi-cured. It may be cured after adhering in the state of. The precursor that can be a base material is not particularly limited, and examples thereof include various curable resin compositions.

<Fiber reinforced plastic>
When the composition of the present invention has a fibrous substrate and the fibrous substrate is a reinforcing fiber, the composition containing the fibrous substrate can be used as a fiber-reinforced resin.

The method for incorporating the fibrous substrate into the composition is not particularly limited as long as the effect of the present invention is not impaired, and the fibrous substrate and the composition are kneaded, coated, impregnated, injected, pressure-bonded, etc. There is a method of compounding by a method. At this time, it can be selected in a timely manner depending on the form of the fiber and the use of the fiber reinforced resin.

The method for molding the fiber-reinforced resin of the present invention is not particularly limited. If a plate-shaped product is to be manufactured, the extrusion molding method is common, but a flat press can also be used. In addition, an extrusion molding method, a blow molding method, a compression molding method, a vacuum forming method, an injection molding method and the like can be used. If a film-shaped product is to be manufactured, a solution casting method can be used in addition to the melt extrusion method. When the melt molding method is used, inflation film molding, cast molding, extrusion lamination molding, calendar molding, and sheet molding can be used. , Fiber molding, blow molding, injection molding, rotary molding, coating molding and the like. Further, in the case of a resin that is cured by an active energy ray, a cured product can be produced by using various curing methods using the active energy ray. In particular, when a thermosetting resin is used as the main component of the matrix resin, a molding method in which the molding material is made into a prepreg and heated under pressure by a press or an autoclave can be mentioned. In addition, RTM (Resin Transfer Molding) molding, Examples thereof include VaRTM (Vaccum Assist Resin Transfer Molding) molding, laminated molding, hand lay-up molding and the like.

<Prepreg>
The fiber-reinforced resin of the present invention can form a state called an uncured or semi-cured prepreg. After the product is distributed in the state of prepreg, the final curing may be performed to form a cured product. In the case of forming a laminated body, it is preferable to form a prepreg, then stack other layers, and then perform final curing, because a laminated body in which each layer is in close contact can be formed.

The mass ratio of the composition to be used at this time and the fibrous substrate is not particularly limited, but it is usually preferable to adjust the resin content in the prepreg to be 20 to 60% by mass.

<Heat-resistant materials and electronic materials>
The maleimide compound of the present invention can be suitably used for heat-resistant members and electronic members because the cured product has a low linear expansion and is excellent in heat-resistant decomposition. In particular, it can be suitably used for semiconductor encapsulants, circuit boards, build-up films, build-up boards, etc., adhesives and resist materials. Further, it can be suitably used for a matrix resin of a fiber reinforced resin, and is particularly suitable as a prepreg having high heat resistance. In addition, it can be made into a paint because it is soluble in various solvents, and it can be cured at a low temperature compared to the conventional heat-resistant paint that requires high-temperature baking at 300 ° C or higher, so it is for heat-resistant paint. It can also be suitably used as a resin. The heat-resistant members and electronic members thus obtained can be suitably used for various purposes, for example, industrial mechanical parts, general mechanical parts, automobile / railway / vehicle parts, space / aviation-related parts, electronic / electrical parts, and the like. Examples include, but are not limited to, building materials, containers / packaging materials, daily necessities, sports / leisure products, housing materials for wind power generation, and the like.

Hereinafter, typical products will be described with examples.

1. 1. Semiconductor encapsulation material As a method for obtaining a semiconductor encapsulation material from the composition of the present invention, an extruder, a feeder, a b -There is a method of sufficiently melting and mixing until it becomes uniform using a compound or the like. At that time, fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, and silicon nitride having higher thermal conductivity than fused silica are used. It is preferable to increase the filling of silicon or the like, or to use fused silica, crystalline silica, alumina, silicon nitride or the like. It is preferable to use an inorganic filler in the range of 30 to 95% by mass per 100 parts by mass of the curable resin composition, and above all, improvement of flame retardancy, moisture resistance and solder crack resistance, and a coefficient of linear expansion. 70 parts by mass or more is more preferable, and 80 parts by mass or more is further preferable.

2. 2. Semiconductor device For semiconductor package molding to obtain a semiconductor device from the curable resin composition of the present invention, the semiconductor encapsulation material is cast or molded using a transfer molding machine, an injection molding machine, or the like, and further, 50 to 250 ° C. A method of heating for 2 to 10 hours can be mentioned.

3. 3. Printed circuit board As a method for obtaining a printed circuit board from the composition of the present invention, the above prepregs are laminated by a conventional method, copper foils are appropriately laminated, and a pressure of 1 to 10 MPa is applied at 170 to 300 ° C. for 10 minutes. A method of heat-bonding for 3 hours can be mentioned.

4. Build-up substrate A method for obtaining a build-up substrate from the composition of the present invention includes, for example, the following steps. First, a step of applying the above composition, which is appropriately mixed with rubber, a filler, etc., to a circuit board on which a circuit is formed by using a spray coating method, a curtain coating method, or the like, and then curing the composition (step 1). After that, if necessary, a predetermined through-hole portion or the like is drilled, treated with a roughening agent, and the surface thereof is washed with hot water to form irregularities, and a metal such as copper is plated (step). 2). A step (step 3) in which such an operation is sequentially repeated as desired to alternately build up and form a resin insulating layer and a conductor layer having a predetermined circuit pattern. The through-hole portion is drilled after the outermost resin insulating layer is formed. Further, the build-up substrate of the present invention is coarsely formed by heat-pressing a copper foil with a resin, which is a semi-cured resin composition on a copper foil, onto a wiring board on which a circuit is formed at 170 to 300 ° C. It is also possible to produce a build-up substrate by omitting the steps of forming a chemical surface and plating.

5. Build-up film As a method of obtaining a build-up film from the composition of the present invention, the above composition is applied to the surface of the support film (Y) which is a base material, and an organic solvent is further applied by heating or blowing hot air. It can be produced by drying to form a layer (X) of the composition.

Examples of the organic solvent used here include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol. Carbitols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used, and the non-volatile content is 30 to 60% by mass. preferable.

The thickness of the formed layer (X) is usually equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm. The layer (X) of the above composition in the present invention may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches.

The support film and protective film described above include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples include metal foils such as patterns, copper foils, and aluminum foils. The support film and the protective film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably used in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

The above-mentioned support film (Y) is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the curable resin composition layer constituting the build-up film is heat-cured, it is possible to prevent the adhesion of dust and the like in the curing step. When peeling after curing, the support film is usually subjected to a mold release treatment in advance.

A multilayer printed circuit board can be manufactured using the build-up film obtained as described above. For example, when the layer (X) is protected by a protective film, the layer (X) is peeled off and then laminated on one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. If necessary, the build-up film and the circuit board may be heated (preheated) as necessary before laminating. As for the laminating conditions, the crimping temperature (laminating temperature) is preferably 70 to 140 ° C., and the crimping pressure is 1 to 11 kgf / cm ² (9.8 × 10 ⁴ to 107.9 × 10 ⁴ N / m ² ). It is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less.

6. Conductive Paste As a method for obtaining a conductive paste from the composition of the present invention, for example, a method of dispersing conductive particles in the composition can be mentioned. The conductive paste can be a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of the conductive particles used.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the description of the examples. Although the display of "parts" is used in the examples, it indicates "parts by mass" unless otherwise specified.

<Synthesis of maleimide compound>
[Example 1]
76.17 g (0.45 mol) of 2-allylaniline hydrochloride was placed in a 200 mL flask equipped with a temperature system, a cooling tube and a stirrer, and heated to 100 ° C. with stirring. 6.76 g (0.23 mol) of paraformaldehyde was added, and the mixture was reacted at 100 ° C. for 5 hours and then air-cooled at 70 ° C. The reaction mixture was neutralized with 20% aqueous sodium hydroxide solution, and the product was extracted with ethyl acetate. After washing with ion-exchanged water, adding sodium sulfate and drying, the mixture was concentrated under reduced pressure to synthesize 47.86 g (yield: 76%) of the diamino compound represented by the following formula.

37.07 g (0.38 mol) of maleic anhydride and 0.7 L of toluene were charged in a 2 L flask equipped with a thermometer, a cooling tube, a Dean Stark trap, and a stirrer, and the mixture was stirred at room temperature. Then, a mixed solution of 47.86 g (0.17 mol) of the diamino compound obtained above and 80 mL of dimethylformamide (DMF) prepared separately was added dropwise to the 2 L flask over 1 hour.

After completion of the dropping, the reaction was carried out at room temperature for another 2 hours. After adding 3.92 g of p-toluenesulfonic acid monohydrate, heating the reaction solution, cooling and separating the azeotropic water and toluene under reflux, only toluene is returned to the system and the dehydration reaction is carried out for 8 hours. gone. After air cooling to room temperature, the brown solution obtained by concentration under reduced pressure was dissolved in 320 mL of ethyl acetate. Then, it was washed 3 times with 120 mL of ion-exchanged water and 3 times with 120 mL of a 2% aqueous sodium hydrogen carbonate solution. After adding sodium sulfate and drying, the mixture was concentrated under reduced pressure, and the obtained reaction product was vacuum dried at 80 ° C. for 4 hours to produce a maleimide compound represented by the following formula.

The molecular weight of the obtained maleimide compound was measured by electric field desorption mass spectrometry (FD-MS). Specifically, JMS-T100GC AccuTOF (manufactured by JEOL Ltd.) was used as the apparatus. The measurement range (m / z) is 50.00 to 2000.00, the rate of change is 25.6 mA / min, the final current value is 40 mA, and the cathode voltage is −10 kV. As a result, a peak of M ⁺ = 438 was confirmed in the FD-MS spectrum.

[Example 2]
Diamino compound 54 represented by the following formula in the same manner as in Example 1 except that 23.88 g (0.23 mol) of benzaldehyde was used instead of 6.76 g (0.23 mol) of paraformaldehyde. .08 g (yield: 68%) was synthesized.

32.95 g (0.34 mol) of maleic anhydride and 0.7 L of toluene were charged in a 2 L flask equipped with a thermometer, a cooling tube, a Dean Stark trap, and a stirrer, and the mixture was stirred at room temperature. Then, a mixed solution of 54.08 g (0.15 mol) of the diamino compound obtained above and 70 mL of dimethylformamide (DMF) prepared separately was added dropwise to the 2 L flask over 1 hour.

After completion of the dropping, the reaction was carried out at room temperature for another 2 hours. 3.49 g of p-toluenesulfonic acid monohydrate is added, the reaction solution is heated, water and toluene that azeotrope under reflux are cooled and separated, and then only toluene is returned to the system and the dehydration reaction is carried out for 8 hours. gone. After air cooling to room temperature, the brown solution obtained by concentration under reduced pressure was dissolved in 285 mL of ethyl acetate. Then, it was washed 3 times with 100 mL of ion-exchanged water and 3 times with 100 mL of a 2% aqueous sodium hydrogen carbonate solution. After adding sodium sulfate and drying, the mixture was concentrated under reduced pressure, and the obtained reaction product was vacuum dried at 80 ° C. for 4 hours to produce a maleimide compound represented by the following formula.

When the molecular weight was measured by the same method as in Example 1, a peak of M ⁺ = 514 was confirmed in the FD-MS spectrum.

[Example 3]
It is represented by the following formula in the same manner as in Example 1 except that 35.88 g (0.23 mol) of 2-naphthaldehyde was used instead of 6.76 g (0.23 mol) of paraformaldehyde. 60.40 g (yield: 65%) of the diamino compound was synthesized.

Example 2 and Example 2 except that 60.40 g (0.15 mol) of the compound synthesized above was used as the diamino compound and the amount of p-toluenesulfonic acid monohydrate to be added was changed to 3.51 g. A maleimide compound represented by the following formula was produced by the same method.

When the molecular weight was measured by the same method as in Example 1, a peak of M ⁺ = 564 was confirmed in the FD-MS spectrum.

[Comparative Example 1]
A commercially available maleimide compound BMI-1000 (4,4'-diphenylmethanebismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.) represented by the following formula was used.

<Evaluation of maleimide compound>
Various performances were evaluated using the maleimide compounds of Examples 1 to 3 and Comparative Example 1.

[Melting viscosity]
The melt viscosity at 150 ° C. was measured. At this time, a cone plate type measuring machine was used to measure the melt viscosity. The obtained results are shown in Table 1 below.

From the results in Table 1, it can be seen that the maleimide compounds of Examples 1 to 3 melt at 150 ° C. and have a low melt viscosity.

<Evaluation of cured product>
Various performances were evaluated using the cured products of the maleimide compounds of Examples 1 and 2 and Comparative Example 1.

[Manufacturing of cured product]
A cured product of the maleimide compound was cast by casting 10 g of the maleimide compound so that the plate thickness after molding was 2.4 mm, and then heating at 170 ° C. for 2 hours, then at 200 ° C. for 2 hours, and further at 250 ° C. for 2 hours. Manufactured.

[Glass-transition temperature]
The produced cured product (thickness: 2.4 mm) was cut into a size of 5 mm in width and 54 mm in length, and the glass transition temperature was measured using this as a test piece.

For the measurement, DMS7100 (DMA, manufactured by Hitachi High-Tech Science Co., Ltd.) is used as a viscoelasticity measuring device, and the measurement conditions are that the deformation mode is lifted with both hands, the measurement mode is sinusoidal vibration, the frequency is 1 Hz, and the temperature rise temperature is 3. The temperature was set to ° C./min. Then, the temperature at which the elastic modulus change was maximum (tanδ change rate was the largest) was evaluated as the glass transition temperature.

The obtained results are shown in Table 2 below.

[Thermal expandability]
The produced cured product (thickness: 2.4 mm) was cut into a size having a width of 5 mm and a length of 5 mm, and the thermal expandability was measured using this as a test piece.

Specifically, TMA / SS7100 (manufactured by SII Nanotechnology Co., Ltd.) was used as a pyrolytic device. The measurement conditions were a heating rate of 3 ° C./min. The coefficient of expansion of the test piece in the range of 25 to 250 ° C. was evaluated as thermal expandability.

The obtained results are shown in Table 2 below.

[Heat-resistant decomposition temperature (5% weight loss temperature (Td5))]
The produced cured product (thickness: 2.4 mm) was cut into small pieces, and the heat-resistant decomposition temperature was evaluated using this as a test piece.

Specifically, TG / TA6200 (manufactured by SII Nanotechnology Co., Ltd.) was used as a weight analyzer. The measurement conditions were a temperature rise temperature of 5 ° C./min and a measurement environment under a nitrogen atmosphere. The 5% weight loss temperature (Td5) at which the weight of the test piece was reduced by 5% was evaluated as the heat-resistant decomposition temperature.

The obtained results are shown in Table 2 below.

[Dissipation factor]
A cured product produced by casting 10 g of a maleimide compound so that the plate thickness after molding was 2.0 mm and heating at 170 ° C. for 2 hours, then at 200 ° C. for 2 hours, and further at 250 ° C. for 2 hours was obtained. It was cut into a size having a width of 1 mm and a length of 100 mm, and the dielectric loss tangent was measured using this as a test piece.

Specifically, a network analyzer E8632C (manufactured by Agilent Technologies Co., Ltd.) was used as an apparatus. The measurement was performed by the cavity resonance method according to JIS C 6481. More specifically, the dielectric loss tangent of the test piece after being stored in a room at 23 ° C. and 50% humidity after absolute drying for 24 hours was measured at 1 GHz.

The obtained results are shown in Table 2 below.

From the results in Table 2, it can be seen that Examples 1 and 2 are excellent in heat resistance. It can also be seen that the dielectric loss tangent is also low.

Claims (20)

The following formula (1):

(In the above formula (1), R ¹ independently represents an alkenyl group having 2 to 10 substituted or unsubstituted carbon atoms and an alkynyl group having 2 to 10 substituted or unsubstituted carbon atoms, respectively, and R ² each independently has a hydrogen atom, an alkyl group having 1 to 10 substituted or unsubstituted carbon atoms, an alkoxy group having 1 to 10 substituted or unsubstituted carbon atoms, and 2 substituted or unsubstituted carbon atoms. Represents 10 to 10 alkoxyalkyl groups, where n and m are independently represented by 2 or 3 integers).
In the above formula (1), A is the following formulas (2-1) to (2-13):

( In the above formulas (2-1) to (2-13),
X is independently a single bond, a sulfur atom, a sulfonyl group, a carbonyl group, an amide group, a carbamate group, a carbonate group, a substituted or unsubstituted alkylene having 1 to 10 carbon atoms (1 to 10 carbon atoms). The alkylene is any one selected from the group consisting of (may form a ring between two aromatic rings).
Y represents a nitrogen atom, CR ³ , where R ³ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
At this time, the hydrogen atom constituting the aromatic ring may be substituted with a substituent. )
A maleimide compound represented by any one selected from the group consisting of. The maleimide compound according to claim 1, wherein A has 2 or 3 aromatic rings. The R ¹ , Vinyl group, 1-propenyl group, isopropenyl group, allyl group, methallyl group (methallyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-hexenyl group, 2-hexenyl group, 3 -Hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-octenyl group, 2-octenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, 1,3-butadienyl group, 1,4-butadienyl group, 2 , 4-Butadienyl group, Hexa-1,3-dienyl group, Hexa-2,5-dienyl group, Hexa-1,3,5-trienyl group, Ethynyl group, Propargyl group, 1-butynyl group, 2-Butynyl group The maleimide compound according to claim 1 or 2, wherein the maleimide compound is at least one selected from the group consisting of a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group and a 1,3-butadiynyl group. The R ¹ The maleimide compound according to claim 1 or 2, wherein the maleimide compound is any one selected from the group consisting of an allyl group, a 3-butenyl group, and a 1,3-butadiynyl group. A cured maleimide compound obtained by curing the maleimide compound according to any one of claims 1 to 4 . A composition comprising the maleimide compound according to any one of claims 1 to 4 . The composition according to claim 6 , further comprising a reactive compound. The composition according to claim 6 or 7 , further comprising a filler. The composition according to any one of claims 6 to 8 , further comprising a fibrous substrate. A cured product obtained by curing the composition according to any one of claims 6 to 9 . A laminate having a base material and a layer containing the cured product according to claim 10 . A composition for a heat-resistant material, which comprises the composition according to any one of claims 6 to 9 . A heat-resistant member containing the cured product according to claim 10 . An electronic composition comprising the composition according to any one of claims 6 to 9 . An electronic member comprising the cured product according to claim 10 . A semiconductor encapsulant comprising the composition according to any one of claims 6 to 9 . A prepreg comprising the composition of claim 9 . A circuit board comprising the prepreg according to claim 17 and a copper foil layer. The laminate according to claim 11 , which is a build-up film. A build-up substrate comprising the build-up film according to claim 19 .