JP2023168111A - Thermosetting resin composition, prepreg, laminate, metal-clad laminate, printed wiring board, antenna device, antenna module and communication device - Google Patents

Abstract

To provide a thermosetting resin composition that can express high relative dielectric constant (high Dk) and low dielectric loss tangent (low Df), and a prepreg, a laminate, a metal-clad laminate, a printed wiring board, an antenna device, an antenna module and a communication device, each including the composition.SOLUTION: A thermosetting resin composition includes (a) a maleimide compound having at least one N-substituted maleimide group, (b) a compound that is represented by the formula (1) and is not reactive with the maleimide group included in the component (a), and (c) at least one high-dielectric-constant inorganic filler selected from the group consisting of titanium-based inorganic fillers and zircon-based inorganic fillers. (Xb1 denotes a single bond or a C1-5 aliphatic hydrocarbon group, Rb1 and Rb2 each denote a C1-10 aliphatic hydrocarbon group, an aromatic hydrocarbon group with 6-18 ring-forming carbon atoms, and a heterocyclic aromatic hydrocarbon group with 5-20 ring-forming atoms, an oxygen atom-containing group, and a group consisting of a combination of them, and m and n each denote an integer of 0-5).SELECTED DRAWING: None

Description

The present disclosure relates to a thermosetting resin composition, a prepreg, a laminate, a metal-clad laminate, a printed wiring board, an antenna device, an antenna module, and a communication device.

In recent years, as mobile terminals such as smartphones have become widespread, and technological innovations such as IoT (Internet of Things) have progressed, the number of home appliances and electronic devices having wireless communication functions is increasing. There are concerns that this will increase the communication traffic of wireless networks and reduce communication speed and communication quality.
In order to solve this problem, a fifth generation mobile communication system (hereinafter sometimes referred to as "5G") is being developed and is already being used. In 5G, multiple antenna elements are used to perform advanced beamforming and spatial multiplexing, and in addition to the conventionally used 6GHz band signals, higher frequency millimeter wave bands of several tens of GHz will be used. use the signal. This is expected to increase communication speed and improve communication quality. Hereinafter, frequencies of 10 GHz and above will be referred to as high frequencies.

In this way, in 5G, antenna modules need to be able to handle high-frequency signals, and for this purpose, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the laminate in the high frequency band are low, and in particular, the dielectric A low tangent (Df) is required.
Since high-frequency radio waves have high linearity, signals carried on high-frequency radio waves tend to be easily blocked by obstacles such as buildings. Therefore, in order to avoid this interruption, a plurality of antenna devices are mounted on the antenna module. The antenna device can be made smaller by increasing the dielectric constant (Dk) of the substrate material, so increasing the dielectric constant (Dk) is effective for mounting multiple antenna devices, and also reduces the size of the antenna module. This also leads to downsizing of communication devices. Therefore, a laminate used in an antenna module capable of handling high-frequency signals is required to have a relative permittivity (Dk) of a predetermined height and a low dielectric loss tangent (Df).

Here, one method of increasing the dielectric constant (Dk) of the substrate material is to use a high dielectric constant material (for example, see Patent Document 1). The small antenna described in Patent Document 1 is manufactured by laminating and sandwiching a first dielectric layer made of a low dielectric constant material with second and third dielectric layers made of a high dielectric constant material. .

International Publication No. 2005/101574

However, in general, when trying to achieve a high dielectric constant (high Dk), a low dielectric loss tangent (low Df) tends to worsen. There is a need for the development of substrate materials that have the following properties.

In view of these current circumstances, an object of the present disclosure is to provide a thermosetting resin composition that can exhibit a high dielectric constant (high Dk) and a low dielectric loss tangent (low Df), and to An object of the present invention is to provide prepregs, laminates, metal-clad laminates, printed wiring boards, antenna devices, antenna modules, and communication devices using the same materials.

As a result of extensive research in order to achieve the above object, the present inventors have discovered that by blending a compound with a specific structure into a thermosetting resin composition containing a high dielectric constant inorganic filler and a specific maleimide compound. It has been found that the above object can be achieved.
The present disclosure includes the embodiments [1] to [24] below.

[1] (a) A maleimide compound having at least one N-substituted maleimide group,
(b) a compound represented by the following general formula (1) and showing no reactivity with the maleimide group contained in the component (a); and (c) a titanium-based inorganic filler and a zircon-based inorganic filler. at least one high dielectric constant inorganic filler selected from the group consisting of;
A thermosetting resin composition comprising:

(In general formula (1), X ^b1 represents a single bond or a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 5 carbon atoms. R ^b1 and R ^b2 each independently represent a substituted or unsubstituted Aliphatic hydrocarbon group having 1 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring-forming carbon atoms, substituted or unsubstituted heterocyclic aromatic hydrocarbon group having 5 to 20 ring-forming atoms Represents a hydrogen group, an oxygen atom-containing group, or a group consisting of a combination thereof. m and n are each independently an integer of 0 to 5.)
[2] The thermosetting resin composition according to [1] above, wherein the component (a) contains (a1) a maleimide compound having at least two N-substituted maleimide groups.
[3] Component (a) is a group consisting of (a1) a maleimide compound having at least two N-substituted maleimide groups, (a2) a monoamine compound, and (a3) an amine compound having at least two amino groups. The thermosetting resin composition according to [1] or [2] above, which contains a reactant with at least one selected from.
[4] The component (a1) has an aliphatic hydrocarbon group between the nitrogen atoms of any two N-substituted maleimide groups among the plurality of N-substituted maleimide groups (however, an aromatic hydrocarbon group or a maleimide compound having an aromatic hydrocarbon group between the nitrogen atoms of any two N-substituted maleimide groups among the plurality of N-substituted maleimide groups, The thermosetting resin composition according to [2] or [3].
[5] The above component (a) contains a reaction product of (a1) a maleimide compound having at least two N-substituted maleimide groups and (a3') a silicone compound having at least two amino groups. The thermosetting resin composition according to [1], [2] or [4].
[6] The component (a) is an amine compound having the component (a1), the component (a3'), and (a3) at least two amino groups (excluding the component (a3'). ), the thermosetting resin composition according to the above [5].
[7] The thermosetting resin composition according to any one of [1] to [6] above, wherein the component (b) is represented by the following general formula (1').

(In general formula (1'), R ^b1 , R ^b2 , m and n are the same as in general formula (1) above.)
[8] The thermosetting resin composition according to any one of [1] to [7] above, wherein the component (b) has a boiling point of 260° C. or higher at one atmospheric pressure (101.325 kPa).
[9] The thermosetting resin composition according to any one of [1] to [8] above, wherein the component (b) is at least one selected from the group consisting of diethylbiphenyl and benzylbiphenyl.
[10] The thermosetting resin composition according to any one of [1] to [6] above, wherein in the general formula (1), R ^b1 and R ^b2 are oxygen atom-containing groups.
[11] The thermosetting according to any one of [1] to [10] above, wherein the content of the component (b) is 0.001 to 1.0 mol per 1 mol of the component (a). resin composition.
[12] The thermosetting resin composition according to any one of [1] to [11] above, further comprising (c') an inorganic filler other than the component (c).
[13] The thermosetting resin composition according to any one of [1] to [12] above, further comprising (d) a thermosetting resin.
[14] The thermosetting resin composition according to any one of [1] to [13] above, further comprising (e) a curing accelerator.
[15] The thermosetting resin composition according to any one of [1] to [14] above, further comprising (f) a monoamine compound.
[16] The thermosetting resin composition according to any one of [1] to [15] above, further comprising (g) an amine compound having at least two amino groups.
[17] The thermosetting resin composition according to any one of [1] to [16] above, further comprising (g') a silicone compound having at least two amino groups.
[18] A prepreg containing a semi-cured product of the thermosetting resin composition according to any one of [1] to [17] above.
[19] A laminate comprising a cured prepreg according to [18] above.
[20] A metal-clad laminate in which metal foil is arranged on one or both sides of the laminate according to [19] above.
[21] The cured product of the thermosetting resin composition according to any one of [1] to [17] above, the cured product of the prepreg according to [18] above, the laminate according to [19] above, and the above A printed wiring board comprising at least one selected from the group consisting of metal-clad laminates according to [20].
[22] An antenna device comprising the laminate according to [19] above or the metal-clad laminate according to [20] above.
[23] An antenna module comprising a power feeding circuit and the antenna device according to [22] above.
[24] A communication device comprising a baseband signal processing circuit and the antenna module according to [23] above.

According to the present disclosure, a thermosetting resin composition capable of exhibiting a high dielectric constant (high Dk) and a low dielectric loss tangent (low Df), a prepreg, a laminate, a metal-clad laminate, and a printed wiring board using the same , an antenna device, an antenna module, and a communication device.

In the numerical ranges described in this disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples. Further, the lower limit value and upper limit value of the numerical range can be arbitrarily combined with the lower limit value or upper limit value of other numerical ranges, respectively.
In this disclosure, for example, the description "10 or more" means 10 and a numerical value exceeding 10, and this applies even if the numerical values are different. Further, for example, the description "10 or less" means a numerical value of 10 and less than 10, and this applies even if the numerical values are different.
Moreover, each component and material illustrated in this disclosure may be used alone, or two or more types may be used in combination, unless otherwise specified. In the present disclosure, if there are multiple substances corresponding to each component in the composition, unless otherwise specified, the content of each component in the composition refers to the total amount of the multiple substances present in the composition. means.
In the present disclosure, "resin component" refers to component (a) and component (b) described below, as well as component (d), component (f), component (g), and (g') used as necessary. ) components and other optionally used resins, (c) at least one high dielectric constant inorganic filler selected from the group consisting of titanium-based inorganic fillers and zircon-based inorganic fillers, (c' ) Inorganic fillers other than the component (c), curing accelerators and additives (e) are not included. Moreover, "solid content" means the remainder after excluding volatile components from the components constituting the thermosetting resin composition.
In this disclosure, a high frequency band refers to a band of 10 GHz or higher.
This embodiment also includes aspects in which the items described in this disclosure are arbitrarily combined.

[Thermosetting resin composition]
The thermosetting resin composition of one aspect of the present embodiment (hereinafter sometimes referred to as "aspect 1") is
(a) A maleimide compound having at least one N-substituted maleimide group [sometimes referred to as component (a). ],
(b) A compound represented by the following general formula (1) and showing no reactivity with the maleimide group contained in component (a) [sometimes referred to as component (b)]. ], and (c) at least one high dielectric constant inorganic filler selected from the group consisting of titanium-based inorganic fillers and zircon-based inorganic fillers [sometimes referred to as component (c). ],
A thermosetting resin composition comprising:
(The definitions of each group in general formula (1) are as described below.)
Here, in this disclosure, the expressions "thermosetting resin composition containing ..." and "thermosetting resin composition comprising ..." refer to the expressions described in .... It includes both a thermosetting resin composition containing the components as they are, and a thermosetting resin composition obtained by reacting at least a part of the components described in .

By blending the component (b) having the specific structure with the components (a) and (c), a heat source that can exhibit a high dielectric constant (high Dk) and a low dielectric loss tangent (low Df). A curable resin composition could be obtained. Although the exact reason why such results were obtained is unknown, the present inventors speculate as follows. The component (a) is easily oriented in the thermosetting resin composition, and due to the orientation, the dipole moments of the respective molecules overlap, forming a large dipole moment for the oriented molecules. For this reason, it was thought that the ability to follow changes in the external electric field deteriorated, resulting in poor dielectric properties. On the other hand, by inhibiting the orientation of the component (a) with the component (b), the number of molecules of the component (a) that are oriented can be reduced, and thus the overlapping dipole moment can be reduced. As a result, it is presumed that the followability to changes in the external electric field became better and the dielectric loss tangent (Df) became lower. In addition, the component (c) ensured a high dielectric constant (high Dk), and it was possible to achieve both a high dielectric constant (high Dk) and a low dielectric loss tangent (low Df). However, whether the inference is correct or not does not affect the scope of the present disclosure.

The thermosetting resin composition of another aspect of the present embodiment (hereinafter sometimes referred to as "aspect 2") is
(a) a maleimide compound having at least one N-substituted maleimide group [component (a)],
(b) a compound represented by the following general formula (1) and showing no reactivity with the maleimide group contained in the component (a) [component (b)], and (c) a titanium-based inorganic filler and at least one high dielectric constant inorganic filler selected from the group consisting of zircon-based inorganic fillers [component (c)],
Component (a) is a thermosetting resin composition comprising (a1) a maleimide compound having at least two N-substituted maleimide groups [hereinafter sometimes referred to as component (a1)]. . ] and (a3') a silicone compound having at least two amino groups [hereinafter sometimes referred to as (a3') component. ] [Hereinafter, the reaction product may be referred to as silicone-modified maleimide resin (X). ] It is a thermosetting resin composition containing.
(The definitions of each group in general formula (1) are as described below.)
The thermosetting resin composition of aspect 2 can exhibit a high dielectric constant (high Dk) and a low dielectric loss tangent (low Df), and has a low elastic modulus, so it tends to have excellent low warpage properties. In particular, the mechanism by which the thermosetting resin composition was obtained that can exhibit high dielectric constant (high Dk) and low dielectric loss tangent (low Df) is explained in the same manner as in Embodiment 1.
In addition, in aspect 2, the component (a) includes the component (a1), the component (a3'), and (a3) an amine compound having at least two amino groups [hereinafter referred to as component (a3)]. Sometimes. ] may be a reaction product. However, the (a3) component does not include the (a3') component, and the (a3) component and the (a3') component are different.

The thermosetting resin composition of yet another aspect of the present embodiment (hereinafter sometimes referred to as "aspect 3") is:
(a) a maleimide compound having at least one N-substituted maleimide group [component (a)],
(b) a compound represented by the following general formula (1) and showing no reactivity with the maleimide group contained in the component (a) [component (b)],
(c) at least one high dielectric constant inorganic filler selected from the group consisting of titanium-based inorganic fillers and zircon-based inorganic fillers [component (c)]; and (g') at least two amino groups. silicone compound [hereinafter sometimes referred to as component (g')]. ],
A thermosetting resin composition comprising:
The thermosetting resin composition of aspect 3 can exhibit a high dielectric constant (high Dk) and a low dielectric loss tangent (low Df), and has a low elastic modulus, so it tends to have excellent low warpage properties. In particular, the mechanism by which a thermosetting resin composition capable of exhibiting a high dielectric constant (high Dk) and a low dielectric loss tangent (low Df) is obtained is explained in the same manner as in Aspect 1.

(The definitions of each group in general formula (1) are as described below.)
Each component contained in the thermosetting resin composition of this embodiment will be described in detail below. The following description is common to all of Aspects 1 to 3, unless otherwise specified.

<(a) Maleimide compound having at least one N-substituted maleimide group>
By containing component (a), the thermosetting resin composition of this embodiment can have excellent heat resistance and low thermal expansion. Note that the above-mentioned effects of the component (b) are significantly exhibited by the presence of the component (a).
In Embodiment 1, component (a) is (a1) a maleimide compound having at least two N-substituted maleimide groups [hereinafter sometimes referred to as component (a1)] from the viewpoint of heat resistance and low thermal expansion. ], it is more preferable to contain the component (a1) at 50% by mass or more, it is even more preferable to contain the component (a1) at 80% by mass or more, and the component (a1) is at least 90% by mass. It is particularly preferable to do so, and component (a) may be component (a1) itself.
In addition, in Aspect 1, the component (a) is composed of the component (a1) and the monoamine compound (a2) [hereinafter, component (a2)] from the viewpoint of heat resistance, low thermal expansion, and adhesiveness to metal foil. It is sometimes called. ] and (a3) a reaction product with at least one selected from the group consisting of amine compounds having at least two amino groups [hereinafter sometimes referred to as modified maleimide resin (A)]. ] It is also preferable to contain. Component (a) preferably contains the modified maleimide resin (A) in an amount of 50% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and (a) The component may be the modified maleimide resin (A) itself.
Furthermore, in the above embodiment 1, an embodiment in which the component (a) contains the component (a1) and the modified maleimide resin (A) is also preferable. In this case, the total content of the component (a1) and the modified maleimide resin (A) in component (a) is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more. , particularly preferably substantially 100% by weight.

In Aspects 2 and 3, component (a) more preferably contains the silicone-modified maleimide resin (X) in an amount of 50% by mass or more, even more preferably 80% by mass or more, and 90% by mass or more. It is particularly preferable to contain the silicone-modified maleimide resin (X), and component (a) may be the silicone-modified maleimide resin (X) itself.
Furthermore, in Aspects 2 and 3, it is also preferable that the component (a) contains the component (a1) and the silicone-modified maleimide resin (X). In this case, the total content of the component (a1) and the silicone-modified maleimide resin (X) in component (a) is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more. , particularly preferably substantially 100% by weight.

((a1) Maleimide compound having at least two N-substituted maleimide groups)
The component (a1) has an aliphatic hydrocarbon group between the nitrogen atoms of any two N-substituted maleimide groups among the plurality of N-substituted maleimide groups (however, an aromatic hydrocarbon group is not present). or a maleimide compound [hereinafter referred to as an aliphatic hydrocarbon group-containing maleimide compound], or an aromatic compound between the nitrogen atoms of any two N-substituted maleimide groups among a plurality of N-substituted maleimide groups. Examples include maleimide compounds having a group hydrocarbon group [hereinafter referred to as aromatic hydrocarbon group-containing maleimide compounds]. Among these, aromatic hydrocarbon group-containing maleimide compounds are preferred from the viewpoints of high heat resistance, dielectric loss tangent (Df), high metal foil adhesion, high glass transition temperature, low thermal expansion, and moldability. The aromatic hydrocarbon group-containing maleimide compound may contain an aromatic hydrocarbon group between any of two arbitrarily selected combinations of maleimide groups; It may have a hydrogen group.
As the component (a1), from the viewpoint of high heat resistance, dielectric loss tangent (Df), high metal foil adhesion, high glass transition temperature, low thermal expansion property, and moldability, 2 to 5 N atoms per molecule are selected. A maleimide compound having a -substituted maleimide group is preferred, and a maleimide compound having two N-substituted maleimide groups in one molecule is more preferred.
In addition, from the viewpoint of high heat resistance, dielectric loss tangent (Df), high metal foil adhesion, high glass transition temperature, low thermal expansion property, and moldability, the component (a1) is expressed by the following general formula (a1-1). More preferred are the maleimide compounds shown.

(In the formula, X ^a1 is a group represented by the following general formula (a1-2), (a1-3), (a1-4) or (a1-5).)

(In the formula, R ^a1 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p1 is an integer of 0 to 4.)

(In the formula, R ^a2 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X ^a2 is an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms. , an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a group represented by the following general formula (a1-3'). q1 is each independently an integer of 0 to 4. be.)

(In the formula, R ^a3 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X ^a3 is an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms. , an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. r1 is each independently an integer of 0 to 4.)

(In the formula, n1 is an integer from 1 to 15.)

(In the formula, R ^a4 is each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u1 is an integer of 1 to 8.)

Each group in each of the above general formulas will be explained below.
In the general formula (a1-2), the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^a1 includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, Examples include t-butyl group and n-pentyl group. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
R ^a1 is preferably an aliphatic hydrocarbon group.
p1 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 from the viewpoint of availability. When p1 is an integer of 2 or more, the plurality of R ^a1s may be the same or different.

In the general formula (a1-3), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^a2 include the same ones as those represented by R ^a1 . The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably an ethyl group.
R ^a2 is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^a2 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, etc. It will be done. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^a2 include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like. Among these, isopropylidene group is preferred.
Among the above options, X ^a2 is preferably an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, or a group represented by general formula (a1-3');') is more preferable.
q1 is each independently an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 2 from the viewpoint of availability. When q1 is an integer of 2 or more, the plurality of ^Ra2 's may be the same or different.

In the general formula (a1-3'), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^a3 include the same ones as those represented by R ^a2 .
The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^a3 include the same ones as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^a2. It will be done.
Among the above options, X ^a3 is preferably an alkylidene group having 2 to 5 carbon atoms, more preferably an isopropylidene group.
r1 is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability. When r1 is an integer of 2 or more, the plurality of ^Ra3s may be the same or different.

In the general formula (a1-4), n1 represents the number of repeating structural units enclosed in parentheses, and is specifically an integer of 1 to 10, preferably 1 from the viewpoint of availability. It is an integer of ˜5, more preferably an integer of 1-3.
In the general formula (a1-5), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^a4 are the same as those represented by R ^a1 in the general formula (a1-2). The preferred aliphatic hydrocarbon group having 1 to 5 carbon atoms and halogen atom for R ^a4 are also the same as for R ^a1 . R ^a4 's bonded to the same carbon atom may be the same or different.
u1 represents the number of repeating structural units enclosed in parentheses, and is specifically an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1. When u1 is an integer of 2 or more, the plurality of R ^a4s may be the same or different.

X ^a1 in the group represented by general formula (a1-1) is selected from the viewpoints of high heat resistance, dielectric loss tangent (Df), high metal foil adhesion, high glass transition temperature, low thermal expansion property, and formability. , is preferably a group represented by any of the following formulas.

As the component (a1), a maleimide compound in which X ^a1 in the general formula (a1-1) is a group represented by the general formula (a1-3) is more preferable; X ^a1 is a group represented by the general formula (a1-3), and X ^a2 in the general formula (a1-3) is a group represented by the general formula (a1-3'). Certain compounds are even more preferred.

Component (a1) includes N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-[1,3 -(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4- maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bis(4-maleimidophenyl) ether, Bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)ketone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1 ,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, bis[4 -(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,1-bis[4 -(4-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane, 2,2 -Bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane , 2,2-bis[4-(4-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoro Propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4'-bis(3-maleimidophenoxy)biphenyl, 4 , 4'-bis(4-maleimidophenoxy)biphenyl, biphenylaralkyl maleimide, bis[4-(3-maleimidophenoxy)phenyl]ketone, bis[4-(4-maleimidophenoxy)phenyl]ketone, 2,2' -Bis(4-maleimidophenyl)disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimidophenoxy)phenyl] Sulfoxide, bis[4-(4-maleimidophenoxy)phenyl]sulfoxide, bis[4-(3-maleimidophenoxy)phenyl]sulfone, bis[4-(4-maleimidophenoxy)phenyl]sulfone, bis[4-(3-maleimidophenoxy)phenyl]sulfone -maleimidophenoxy)phenyl]ether, bis[4-(4-maleimidophenoxy)phenyl]ether, 1,4-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3- Bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[ 4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1, 3-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α , α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, polyphenylmethanemaleimide (e.g., Daiwa Kasei Co., Ltd.) (product name: BMI-2300, etc.). Component (a1) may be used alone or in combination of two or more.

Among these, as component (a1), bis(4-maleimidophenyl)methane, bis(4-maleimidophenyl)sulfone, 3,3'-dimethyl -5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane are preferred, and 2,2-bis[4-(4-maleimidophenoxy) ) phenyl]propane is more preferred. In addition, from the viewpoint of solubility in organic solvents, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bis(4-maleimidophenyl)methane, and polyphenylmethane maleimide are Bis(4-maleimidophenyl)methane is preferred from the viewpoint of being preferred and inexpensive.

((a2) Monoamine compound)
By reacting the component (a1) with the component (a2), heat resistance, low thermal expansion, etc. can be further improved.
The component (a2) is not particularly limited as long as it is a compound having one amino group, but it has high heat resistance, dielectric loss tangent (Df), high metal foil adhesion, high glass transition temperature, low thermal expansion, and moldability. From the viewpoint of properties, monoamine compounds having an acidic substituent are preferred, and compounds represented by the following general formula (a2-1) are more preferred.
(In the formula, R ^a5 is each independently an acidic substituent, such as a hydroxyl group, a carboxy group, or a sulfonic acid group, and each R ^a6 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen It is an atom. x2 is an integer from 1 to 5, y2 is an integer from 0 to 4, and satisfies 1≦x2+y2≦5.)

In the formula (a2-1), the acidic substituent represented by R ^a5 is preferably a hydroxyl group or a carboxy group from the viewpoint of solubility and reactivity, and more preferably a hydroxyl group from the viewpoint of heat resistance.
x2 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and more Preferably it is 1.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^a6 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, etc. . The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the halogen atom represented by R ^a6 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
y2 is an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, from the viewpoint of high heat resistance, low dielectric constant, high glass transition temperature, low thermal expansion, and moldability. , more preferably 0 or 1, particularly preferably 0.
In addition, when x2 is an integer of 2 or more, a plurality of R ^a5 may be the same or different. Further, when y2 is an integer of 2 or more, the plurality of R ^a6s may be the same or different.

Ingredients (a2) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzoic acid, Examples include benzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline. Among these, from the viewpoint of solubility and synthesis yield, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferred; From the viewpoint of heat resistance, m-aminophenol and p-aminophenol are more preferred, and from the viewpoint of low thermal expansion, p-aminophenol is even more preferred.
The monoamine compound (a2) may be used alone or in combination of two or more.

((a3) Amine compound having at least two amino groups)
As component (a3), an amine compound having an amino group at at least one end of the molecule is preferable, and an amine compound having amino groups at both ends of the molecule is more preferable. Furthermore, it may be an amine compound having an amino group in a side chain, or an amine compound having an amino group in a side chain and at least one molecule end. The component (a3) may contain a siloxane skeleton or may not contain a siloxane skeleton. Examples of compounds containing a siloxane skeleton include (a3') silicone compounds having at least two amino groups. (a3') The silicone compound having at least two amino groups is a compound used in the above embodiment 2, and will be described later.
All of the above amino groups are preferably primary amino groups.
Among these, amine compounds having amino groups at both ends of the molecule are preferred, and such amine compounds have high heat resistance, dielectric loss tangent (Df), high metal foil adhesion, high glass transition temperature, low thermal expansion, and From the viewpoint of moldability, diamine compounds represented by the following general formula (a3-1) are preferred.

(In the general formula (a3-1), X ^a4 is a group represented by the following general formula (a3-2), (a3-3) or (a3-4).)

(In general formula (a3-2), R ^a7 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p3 is an integer of 0 to 4.)

(In general formula (a3-3), R ^a8 and R ^a9 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X ^a5 is an alkylene group having 1 to 5 carbon atoms. , an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, a group represented by the following general formula (a3-3-1) or the following general formula (a3 -3-2). q3 and r3 are each independently an integer of 0 to 4.)
(In the general formula (a3-3-1), R ^a10 and R ^a11 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or ^a halogen atom. It is an alkylene group, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. s3 and t3 are each independently an integer of 0 to 4. )
(In general formula (a3-3-2), R ^a12 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X ^a7 and X ^a8 each independently have 1 to 5 carbon atoms. It is an alkylene group, an alkylidene group having 2 to 5 carbon atoms, an ether group, or a single bond. u3 is an integer of 0 to 4.)

(In general formula (a3-4), R ^a13 to R ^a16 each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. X ^a9 and X ^a10 each independently represent 2 Represents a valent organic group.v3 is an integer from 1 to 100.)

In the general formula (a3-2), the aliphatic hydrocarbon group represented by R ^a7 includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n -pentyl group, etc. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
Among the above, R ^a7 is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p3 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 2 from the viewpoint of availability. When p3 is an integer of 2 or more, the plurality of ^Ra7 's may be the same or different.

In the general formula (a3-3), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^a8 and R ^a9 include the same ones as in the case of R ^a7 . The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^a5 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, etc. It will be done. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group, from the viewpoint of heat resistance and low thermal expansion.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^a5 include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like. Among these, isopropylidene group is preferred from the viewpoint of heat resistance and low thermal expansion.
Among the above options, as X ^a5 , an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms are preferable. More preferred ones are as described above.
q3 and r3 are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 2. When q3 or r3 is an integer of 2 or more, the plurality of R ^a8s or R ^a9s may be the same or different.

In the general formula (a3-3-1), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^a10 and R ^a11 include the same ones as in the case of R ^a8 and R ^a9 . , and preferred embodiments are also the same.
The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^a6 are the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^a5 above. Can be mentioned.
Among the above options, X ^a6 is preferably an alkylidene group having 2 to 5 carbon atoms, more preferably an isopropylidene group.
s3 and t3 are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0. When s3 or t3 is an integer of 2 or more, the plurality of R ^a10s or R ^a11s may be the same or different.

In the general formula (a3-3-2), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^a12 are the same as those for R ^a10 and R ^a11 , and preferred embodiments are also included. It's the same.
The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^a7 and X ^a8 include the same ones as in the case of X ^a6 , and the preferred embodiments are also the same. u3 is an integer of 0 to 4, and from the viewpoint of availability, is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. When u3 is an integer of 2 or more, the plurality of R ^a12s may be the same or different.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^a13 to R ^a16 in the general formula (a3-4) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, Examples include t-butyl group and n-pentyl group. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
In the substituted phenyl group represented by R ^a13 to R ^a16 , examples of the substituent on the phenyl group include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, etc. It will be done. Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, and the like. Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group and an allyl group. Examples of the alkynyl group having 2 to 5 carbon atoms include ethynyl group and propargyl group.
Each of R ^a13 to R ^a16 is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group.
Examples of the divalent organic group represented by X ^a9 and X ^a10 include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, or a divalent linking group consisting of a combination thereof. Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group, and propylene group. Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms. Examples of the alkynylene group include alkynylene groups having 2 to 10 carbon atoms. Examples of the arylene group include arylene groups having 6 to 20 carbon atoms such as phenylene group and naphthylene group.
v3 represents the number of repeating units of the structural unit enclosed in square brackets, and specifically is an integer from 1 to 100, may be an integer from 2 to 100, or may be an integer from 5 to 100. It may be an integer from 10 to 100, an integer from 15 to 70, or an integer from 20 to 50.

As component (a3), a diamine compound in which X ^a4 in the general formula (a3-1) is a group represented by the general formula (a3-3) is preferable; X ^a4 is a group represented by the general formula (a3-3), and X ^a5 in the general formula (a3-3) is a group represented by the general formula (a3-3-2); Certain diamine compounds are more preferred.

Specific examples of component (a3) include 4,4'-(1,3-phenylene diisopropylidene) bisaniline, diaminobenzidine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenylsulfone, 4,4'-methylene-bis(2 -chloroaniline), 1,3'-bis(4-aminophenoxy)benzene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl] Sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4'-bis(4-aminophenoxy)benzene , 4,4'-diaminodiphenyl sulfide, 4,4'-diamino-3,3'-biphenyldiol, 9,9'-bis(4-aminophenyl)fluorene, o-tolidine sulfone, and the like.
Although not particularly limited, among these, 4,4'-(1,3-phenylene diisopropylidene) bisaniline is preferred.

((a3') Silicone compound having at least two amino groups)
Component (a3') is not particularly limited as long as it is a silicone compound having at least two amino groups, but it is preferably a silicone compound having two amino groups in one molecule. A silicone compound having 5 primary amino groups is preferred.
The component (a3') only needs to have an amino group (preferably a primary amino group) in either or both the side chain or the terminal of the siloxane skeleton, and from the viewpoint of easy availability and low warpage. , preferably at the ends, and more preferably at both ends. Hereinafter, a silicone compound having an amino group (preferably a primary amino group) at both ends is also referred to as a "both ends amino-modified silicone compound." From the same viewpoint, the component (a3') is preferably represented by the following general formula (a3'-1).

(In the general formula (a3'-1), R ^a13 to R ^a16 , X ^a9 , X ^a10 and v3 are the same as those in the general formula (a3-4), and their preferred embodiments are also the same.)

As the component (a3'), commercially available products can be used. For example, as the component (a3') having a methyl group in the side chain, "KF-8010" (functional group equivalent of amino group 430 g/mol), " X-22-161A” (functional group equivalent of amino group 800 g/mol), “X-22-161B” (functional group equivalent of amino group 1,500 g/mol), “KF-8012” (functional group equivalent of amino group 800 g/mol), "KF-8008" (functional group equivalent of amino group 5,700 g/mol), "X-22-9409" (functional group equivalent of amino group 700 g/mol) (Shin-Etsu Chemical (manufactured by Kogyo Co., Ltd.), etc. In addition, as the (a3') component having a phenyl group in the side chain, "X-22-1660B-3" (functional group equivalent of amino group 2,200 g/mol) (manufactured by Shin-Etsu Chemical Co., Ltd.), "BY -16-853U" (functional group equivalent of amino group 460 g/mol), "BY-16-853" (functional group equivalent of amino group 650 g/mol), "BY-16-853B" (functional group equivalent of amino group 2,200 g/mol) (manufactured by Dow Corning Toray Co., Ltd.). These may be used alone or in combination of two or more.
Among these, from the viewpoint of low water absorption, commercially available products containing component (a3') include "X-22-161A", "X-22-161B", "KF-8012", "KF-8008", "X-22-1660B-3" and "BY-16-853B" are preferred, and from the viewpoint of low thermal expansion, "X-22-161A", "X-22-161B", "KF-8012", "X-22-1660B-3'' is more preferred.

The functional group equivalent of the amino group possessed by the component (a3') is preferably 300 to 3,000 g/mol, more preferably 400 to 2,500 g/mol, and even more preferably 600 to 2,300 g/mol.

(Production method of modified maleimide resin (A) and silicone modified maleimide resin (X))
In aspect 1, by containing the modified maleimide resin (A) as the component (a), it becomes easier to control the molecular weight of the resin in the thermosetting resin composition, and it becomes easier to improve low thermal expansion and elastic modulus. There is a tendency.
In aspects 2 and 3, by containing silicone-modified maleimide resin (X) as component (a), the molecular weight of the resin in the thermosetting resin composition can be easily controlled, and low thermal expansion and low warping properties are achieved. It tends to be easier to improve.

There are no particular restrictions on the method for producing the modified maleimide resin (A), but the amino group of the component (a2) and the component (a3) may be bonded to the carbon-carbon double bond of the maleimide group of the component (a1). The modified maleimide resin (A) can be produced by subjecting at least one of the amino groups possessed to an addition reaction.
Although there are no particular limitations on the method for producing the silicone-modified maleimide resin (X), the amino group (and any necessary The silicone-modified maleimide resin (X) can be produced by addition-reacting the amino group of the component (a3) [however, the component (a3') is excluded from the component (a3)] according to the can.
The production of the modified maleimide resin (A) and the production of the silicone-modified maleimide resin (X) are preferably carried out in an organic solvent while being heated and kept warm. The reaction temperature is not particularly limited, but is preferably 70 to 200°C, more preferably 70 to 150°C, even more preferably 100 to 130°C. The reaction time is not particularly limited, but is preferably 0.1 to 10 hours, more preferably 1 to 6 hours.

Moreover, a reaction catalyst can be used if necessary in the production of the modified maleimide resin (A) and the production of the silicone-modified maleimide resin (X). The reaction catalyst is not particularly limited, but examples thereof include amine compounds such as triethylamine, pyridine, and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; and phosphorus catalysts such as triphenylphosphine. These may be used alone or in combination of two or more.

In the production of modified maleimide resin (A), the number of maleimide groups in component (a1) [amount of component (a1) used (g)/functional group equivalent of maleimide groups in component (a1) (g/eq)] is particularly limited. However, the number of amino groups in component (a2) [amount of component (a2) used (g)/functional group equivalent of amino groups in component (a2) (g/eq)] and the number of amino groups in component (a3) It is preferably 0.1 to 10 times, and 1 to 9 times the total number of bases [amount used of component (a3) (g)/functional group equivalent of amino group of component (a3) (g/eq)]. It is more preferably 1.1 to 9 times, even more preferably 2 to 8 times. When it is above the lower limit, especially twice or more, gelation tends to be suppressed and the heat resistance tends to be good, and when it is below the above upper limit, the solubility in organic solvents and the heat resistance tend to be good. There is a tendency to
Similarly, in the production of silicone-modified maleimide resin (X), the number of maleimide groups in component (a1) [amount of component (a1) used (g)/functional group equivalent of maleimide groups in component (a1) (g/eq)] is not particularly limited, but the number of amino groups in component (a3') [amount of component (a3') used (g)/functional group equivalent of amino groups in component (a3') (g/eq)] and (a3) component [however, (a3') component is excluded. The number of amino groups [amount of component (a3) used (g)/functional group equivalent of amino group of component (a3) (g/eq)] is preferably 0.1 to 10 times, preferably 1 to It is more preferably 9 times, even more preferably 1.1 to 9 times, and particularly preferably 2 to 8 times. When it is above the lower limit, especially twice or more, gelation tends to be suppressed and the heat resistance tends to be good, and when it is below the above upper limit, the solubility in organic solvents and the heat resistance tend to be good. There is a tendency to

The production of the modified maleimide resin (A) and the production of the silicone-modified maleimide resin (X) are preferably carried out in the presence of an organic solvent. There are no particular restrictions on the organic solvent, but alcoholic solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and ether solvents such as tetrahydrofuran. Solvents; aromatic solvents such as toluene, xylene, mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; and sulfur atom-containing solvents such as dimethyl sulfoxide. One type of organic solvent may be used alone, or two or more types may be used in combination. Among these, cyclohexanone, propylene glycol monomethyl ether, and methyl cellosolve are preferred from the viewpoint of solubility, and cyclohexanone and propylene glycol monomethyl ether are more preferred from the viewpoint of low toxicity; they are highly volatile and do not remain as a residual solvent during prepreg production. Since propylene glycol monomethyl ether is difficult to use, propylene glycol monomethyl ether is more preferred.

(Content of component (a))
The content of component (a) in the thermosetting resin composition of Aspect 1 is not particularly limited, but is 30 to 99 parts by mass based on 100 parts by mass of the resin component in the thermosetting resin composition. is preferably 35 to 90 parts by weight, more preferably 40 to 85 parts by weight, particularly preferably 45 to 80 parts by weight, and most preferably 55 to 80 parts by weight.
The content of component (a) in the thermosetting resin compositions of aspects 2 and 3 is not particularly limited, but is 2 to 99 parts by mass based on 100 parts by mass of the resin component in the thermosetting resin composition. It is preferably 30 to 99 parts by weight, more preferably 35 to 90 parts by weight, even more preferably 40 to 85 parts by weight, particularly preferably 45 to 80 parts by weight, and most preferably 55 to 80 parts by weight.

<(b) Compound represented by general formula (1) and showing no reactivity with the maleimide group contained in component (a)>
As mentioned above, by blending the component (b) with the component (a), the dielectric loss tangent (Df) of the thermosetting resin composition can be lowered.
Component (b) is represented by the following general formula (1), provided that it does not show reactivity with the maleimide group contained in component (a). That is, the substituents that each group in general formula (1) may have are limited to substituents that do not show reactivity with the maleimide group contained in component (a). Here, "not showing reactivity" means not reacting at temperatures below 200°C.
In addition, examples of substituents that are reactive with the maleimide group contained in component (a) include an amino group, an epoxy group (including a glycidyl group), and a maleimide group.
Component (b) may be used alone or in combination of two or more.

In the general formula (1), X ^b1 represents a single bond or a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 5 carbon atoms. R ^b1 and R ^b2 each independently represent a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring carbon atoms; Represents a substituted heterocyclic aromatic hydrocarbon group having 5 to 20 ring atoms, an oxygen atom-containing group, or a group consisting of a combination thereof. m and n are each independently an integer of 0 to 5.

The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by X ^b1 includes alkylene groups having 1 to 5 carbon atoms such as methylene group, dimethylene group, trimethylene group, pentamethylene group; 2 to 5 carbon atoms such as isopropylidene group; 5 alkylidene groups are mentioned. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methylene group or an isopropylidene group.
The aliphatic hydrocarbon group may have a substituent or may be unsubstituted. The substituent is not particularly limited as long as it is a substituent that does not show reactivity with the maleimide group contained in component (a), but includes halogen atoms, hydroxyl groups, nitro groups, cyano groups, etc. (hereinafter referred to as " substituent A).
Among the above options, a single bond is preferable as X ^b1 from the viewpoint of low dielectric loss tangent (low Df).

Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ^b1 and R ^b2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n- Examples include pentyl group and n-octyl group. Among these, aliphatic hydrocarbon groups having 1 to 5 carbon atoms are preferred, aliphatic hydrocarbon groups having 2 or 3 carbon atoms are more preferred, and ethyl groups are even more preferred.
The aliphatic hydrocarbon group may have a substituent or may be unsubstituted. Examples of the substituent include the above-mentioned substituent A.

Examples of the aromatic hydrocarbon group having 6 to 18 ring carbon atoms represented by R ^b1 and R ^b2 include a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group, and the like. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, and more preferably a phenyl group or a biphenylyl group.
The aromatic hydrocarbon group may have a substituent or may be unsubstituted. Examples of the substituent include, in addition to the above substituent A, an aliphatic hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms).

Examples of the heterocyclic aromatic hydrocarbon group having 5 to 20 ring atoms represented by R ^b1 and R ^b2 include triazinyl group, oxazolyl group, pyridinyl group, and thiophenyl group. The heterocyclic aromatic hydrocarbon group is preferably a heterocyclic aromatic hydrocarbon group having 5 to 12 ring atoms.
The heterocyclic aromatic hydrocarbon group may have a substituent or may be unsubstituted. Examples of the substituent include, in addition to the substituent A, an aliphatic hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms).

The oxygen atom-containing groups represented by R ^b1 and R ^b2 include -OR ^b3 (R ^b3 is a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 10 carbon atoms; a substituted or unsubstituted aliphatic hydrocarbon group having 6 to 10 ring carbon atoms; ), keto group, -OP(=O)(-OR ^b4 )(-OR ^b5 ) [R ^b4 and R ^b5 each independently represent a substituted or unsubstituted Represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring carbon atoms. ] etc. The oxygen atom-containing group is preferably a keto group, -OP(=O)(-OR ^b4 )(-OR ^b5 ).
The aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ^b3 , R ^b4 and R ^b5 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group. group, n-pentyl group, n-octyl group, etc. Among these, aliphatic hydrocarbon groups having 1 to 10 carbon atoms are preferred, and aliphatic hydrocarbon groups having 1 to 5 carbon atoms are more preferred. The aliphatic hydrocarbon group may have a substituent or may be unsubstituted. Examples of the substituent include the substituent A described above.
Examples of the aromatic hydrocarbon group having 6 to 18 ring carbon atoms represented by R ^b3 , R ^b4 and R ^b5 include phenyl group, naphthyl group, anthryl group, biphenylyl group and the like. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, and more preferably a phenyl group. The aromatic hydrocarbon group may have a substituent or may be unsubstituted. Examples of the substituent include, in addition to the substituent A, an aliphatic hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, still more preferably 1 carbon number), etc. can be mentioned.

R ^b1 and R ^b2 are an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 18 ring atoms, a heterocyclic aromatic hydrocarbon group having 5 to 20 ring atoms, and an oxygen atom-containing group. Such combinations include "aliphatic hydrocarbon group having 1 to 10 carbon atoms - aromatic hydrocarbon group having 6 to 18 ring forming atoms", "aliphatic hydrocarbon group having 1 to 10 carbon atoms - number of ring forming atoms""Heterocyclic aromatic hydrocarbon group having 5 to 20 carbon atoms", "Aromatic hydrocarbon group having 6 to 18 ring carbon atoms - Aliphatic hydrocarbon group having 1 to 10 carbon atoms - Aromatic having 6 to 18 ring carbon atoms""Heterocyclic aromatic hydrocarbon group having 5 to 20 ring atoms - Aliphatic hydrocarbon group having 1 to 10 carbon atoms - Aromatic hydrocarbon group having 6 to 18 ring atoms" , "Aliphatic hydrocarbon group having 1 to 10 carbon atoms - oxygen atom-containing group", "Aromatic hydrocarbon group having 6 to 18 ring-forming carbon atoms - oxygen atom-containing group", "Oxygen atom-containing group - ring-forming carbon group" 6 to 18 aromatic hydrocarbon groups. Note that in these combinations, the first group in the square brackets is bonded to the benzene ring shown in the general formula (1).
Among these, combinations include "aliphatic hydrocarbon group having 1 to 10 carbon atoms - aromatic hydrocarbon group having 6 to 18 ring carbon atoms" and "oxygen atom-containing group - ring forming carbon group 6 to 18 carbon atoms". Aromatic hydrocarbon group" is preferable, aralkyl group such as benzyl group, "keto group - aromatic hydrocarbon group having 6 to 18 ring carbon atoms" is preferable, and benzyl group and "keto group - phenyl group" are more preferable. . Note that the "keto group-phenyl group" is a group represented by the following structural formula.
(* indicates a bonding site to another structure (specifically, a benzene ring).)

m and n are each independently an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1, and may be 0 or 1. It is also preferable that m is 0 and n is 1, and it is preferable that m is 1 and n is also 1.
Note that when m is an integer of 2 to 5, multiple R ^b1 's may be the same or different. When n is an integer of 2 to 5, the plurality of R ^b2 's may be the same or different.

Preferred embodiments of the general formula (1) are the following general formula (1-1) and the following general formula (1-2).

(In general formula (1-1), X ^b1 , R ^b1 and R ^b2 are the same as those in general formula (1) above, and their preferred embodiments are also the same.)

(In general formula (1-2), X ^b1 and R ^b2 are the same as those in general formula (1) above, and their preferred embodiments are also the same.)

The component (b) is preferably a compound represented by the following general formula (1'). Needless to say, the premise is that this compound also exhibits no reactivity with the maleimide group contained in component (a).
(In general formula (1'), R ^b1 , R ^b2 , m and n are the same as those in general formula (1) above, and their preferred embodiments are also the same.)

Preferred embodiments of the general formula (1') are the following general formula (1'-1) and the following general formula (1'-2).

(In general formula (1'-1), R ^b1 and R ^b2 are the same as those in general formula (1') above, and their preferred embodiments are also the same.)

(In general formula (1'-2), R ^b2 is the same as in general formula (1') above, and the preferred embodiments are also the same.)

Component (b) preferably has a boiling point of 260°C or higher under one atmospheric pressure (101.325 kPa), and preferably 280°C or higher, from the viewpoint of avoiding voids from occurring in the reflow process of printed wiring boards. More preferably, the temperature may be 300°C or higher. There is no particular restriction on the upper limit of the boiling point, and the boiling point of component (b) under one atmospheric pressure (101.325 kPa) may be, for example, 500°C or lower, 450°C or lower, or 400°C. The temperature may be below or 350°C or below.
From the above viewpoint, the component (b) is preferably at least one selected from the group consisting of diethylbiphenyl and benzylbiphenyl, and preferably selected from the group consisting of 4,4'-diethylbiphenyl and 4-benzylbiphenyl. It is more preferable that at least one kind is used.

(Content of component (b))
The content of component (b) is not particularly limited, but is preferably 0.001 to 1.0 mol, more preferably 0.01 to 0.95 mol, per 1 mol of component (a). mol, more preferably 0.01 to 0.90 mol, particularly preferably 0.05 to 0.90 mol, particularly in embodiment 1 it may be 0.15 to 0.90 mol, or 0.01 to 0.90 mol. It may be 15 to 0.70 mol. In Aspects 2 and 3, the content of component (b) may be 0.001 to 0.5 mol, or 0.01 to 0.5 mol, per 1 mol of component (a). The amount may be mol, 0.04 to 0.3 mol, or 0.04 to 0.2 mol. If the content of the component (b) is equal to or higher than the lower limit, the effect of reducing the dielectric loss tangent (Df) in a high frequency band tends to be more likely to occur. Note that the content of component (b) may exceed the above upper limit, but since the effect of reducing dielectric loss tangent (Df) in high frequency bands tends to reach a plateau, from the viewpoint of reducing manufacturing costs, It is preferable to set it below the said upper limit value.

<(c) At least one high dielectric constant inorganic filler selected from the group consisting of titanium-based inorganic fillers and zircon-based inorganic fillers>
From the viewpoint of achieving a high dielectric constant (high Dk), the thermosetting resin composition of the present embodiment further includes (c) at least one type selected from the group consisting of a titanium-based inorganic filler and a zircon-based inorganic filler. It contains a high dielectric constant inorganic filler.
The titanium-based inorganic filler is preferably at least one selected from the group consisting of titanium dioxide and metal titanate from the viewpoint of achieving a high dielectric constant (high Dk). As the metal titanate, from the viewpoint of high dielectric constant (high Dk), alkali metal titanate such as potassium titanate; alkaline earth titanate such as barium titanate, calcium titanate, strontium titanate, etc. Metal salts; examples include aluminum titanate and lead titanate. The titanate metal salt is preferably at least one selected from these examples. In particular, from the viewpoint of achieving a high dielectric constant (high Dk), alkaline earth metal titanates are more preferred, and calcium titanate, strontium titanate, and aluminum titanate are even more preferred. Moreover, aluminum titanate is preferable from the viewpoint of having a relatively high dielectric constant (high Dk) and a low dielectric loss tangent (low Df).
The zircon-based inorganic filler is preferably an alkali metal zirconate salt from the viewpoint of achieving a high dielectric constant (high Dk). The alkali metal zirconate salt is preferably at least one selected from the group consisting of calcium zirconate and strontium zirconate from the viewpoint of achieving a high dielectric constant (high Dk).
As component (c), titanium-based inorganic fillers are preferred from the viewpoint of high dielectric constant (high Dk) and specific gravity, and more preferred ones are as described above.

The average particle diameter of component (c) is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.4 μm or more, and from the viewpoint of heat resistance, 1.0 μm or more. It is more preferable that it is, and it is especially preferable that it is 1.5 μm or more. The upper limit of the average particle diameter of component (c) is preferably 4.5 μm or less, more preferably 4.0 μm or less, from the viewpoint of eliminating coarse particles that may cause insulation defects; More preferably, it is .5 μm or less.
From the above, the average particle diameter of component (c) is preferably 0.1 to 4.5 μm, and the lower limit and upper limit in this numerical range can be changed based on the above description.
Here, in the present disclosure, the average particle diameter refers to the average primary particle diameter.
Note that in the present disclosure, the average particle diameter is the d50 value (median diameter of volume distribution) obtained by analyzing the particle size distribution using a particle size distribution measuring device. The method and conditions for analyzing particle size distribution may be in accordance with the methods described in Examples.
There is no particular restriction on the shape of component (c), but since industrially available high dielectric constant inorganic fillers are generally irregular in shape, it may be irregular in shape, but it may be spherical, etc. Other shapes are also possible.

(Content of component (c))
The content of component (c) in the thermosetting resin composition of the present embodiment is not particularly limited, but from the viewpoint of dielectric constant (Dk), the content of the solid content in the thermosetting resin composition is It is preferably 1 to 60 volume%, more preferably 5 to 50 volume%, may be 15 to 45 volume%, or even 25 to 40 volume%, based on the total amount. It may be 30 to 40% by volume.
If the content of component (c) in the thermosetting resin composition of the present embodiment is at least the lower limit, the dielectric constant (Dk) tends to be sufficiently increased; For example, it tends to be possible to suppress the dielectric loss tangent (Df) from increasing too much.

<(c') Inorganic filler other than component (c)>
From the viewpoint of low thermal expansion, the thermosetting resin composition of the present embodiment further contains (c') an inorganic filler other than the component (c) [hereinafter sometimes referred to as component (c')]. ] may be contained.
Component (c') is not particularly limited, but includes silica, alumina, mica, beryllia, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate. , silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide, quartz powder, short glass fibers, fine glass powder, hollow glass, etc., and at least one selected from the group consisting of these. is preferred. Preferable examples of the glass include E glass, T glass, and D glass. Component (c') may be used alone or in combination of two or more.
Among these, silica is preferred from the viewpoint of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include precipitated silica with a high water content produced by a wet process, and dry process silica containing almost no bound water or the like produced by a dry process. Dry process silica is further classified into crushed silica, fumed silica, fused spherical silica, etc. depending on the manufacturing method. Among these, fused spherical silica is preferred from the viewpoint of low thermal expansion and fluidity when filled in a resin.

Component (c') may be surface-treated with a coupling agent. The method of surface treatment using a coupling agent may be a dry or wet surface treatment method for the inorganic filler before blending, or a surface treatment method in which the surface-untreated inorganic filler is blended with other components. A so-called integral blend processing method may be used, in which a coupling agent is added to the composition after it is made into a product.
Examples of the coupling agent include silane coupling agents, titanate coupling agents, silicone oligomers, and the like. Among these, silane coupling agents are preferred. Examples of the silane coupling agent include epoxysilane coupling agent, aminosilane coupling agent, vinylsilane coupling agent, phenylsilane coupling agent, alkylsilane coupling agent, alkenylsilane coupling agent, and alkynyl silane coupling agent. Silane coupling agents, haloalkylsilane coupling agents, siloxane coupling agents, hydrosilane coupling agents, silazane coupling agents, alkoxysilane coupling agents, chlorosilane coupling agents, (meth)acrylic silanes Examples include coupling agents, isocyanurate silane coupling agents, ureido silane coupling agents, mercaptosilane coupling agents, sulfide silane coupling agents, isocyanate silane coupling agents, and the like. Among these, aminosilane coupling agents are more preferred.

The average particle diameter of component (c') is not particularly limited, but is preferably 0.01 to 30 μm, more preferably 0.05 to 20 μm, even more preferably 0.1 to 10 μm, and particularly preferably 0. .2 to 5 μm, may be 0.2 to 2 μm, or may be 0.1 to 1 μm.
By setting the average particle diameter of the component (c') to be equal to or larger than the lower limit value, there is a tendency to maintain good fluidity when the thermosetting resin composition is highly filled with the component (c'). By setting the average particle diameter of the component (c') to be equal to or less than the upper limit value, it tends to be possible to suppress an increase in surface roughness of the insulating layer.

(Content of (c') component)
When the thermosetting resin composition of the present embodiment contains component (c'), the content is not particularly limited, but the solid content in the thermosetting resin composition , preferably 5 to 65 volume %, more preferably 10 to 60 volume %, even more preferably 15 to 60 volume %, particularly preferably 20 to 55 volume %, even if it is 20 to 50 volume %. It may be 20 to 40 volume %, or it may be 25 to 40 volume %.
If the content of component (c') is at least the lower limit, it tends to have good low thermal expansion properties, and when it is at least the upper limit, it tends to prevent fading in the prepreg.

<(d) Thermosetting resin>
The thermosetting resin composition of the present embodiment further includes (d) a thermosetting resin [hereinafter sometimes referred to as component (d). ] may be contained. When the thermosetting resin composition of this embodiment contains the component (d), it is possible to particularly improve the adhesiveness with metal foils such as copper foils. However, the thermosetting resin composition of this embodiment does not need to contain the (d) thermosetting resin.
Note that the component (d) does not include the component (a).

Component (d) includes epoxy resin, phenol resin, unsaturated imide resin (excluding component (a) above), cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, and unsaturated polyester resin. , allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, etc., and at least one selected from the group consisting of these is preferable. Among these, epoxy resin is preferred from the viewpoint of moldability and electrical insulation, and from the viewpoint of improving adhesiveness with metal foil.
In addition, from the viewpoint of moldability, the thermosetting resin (d) has an ICI viscosity at 150° C. of preferably 1.0 Pa·s or less, more preferably 0.5 Pa·s or less, and even more preferably 0.3 Pa. - It is preferable to select a thermosetting resin having a temperature of 0.2 Pa·s or less, particularly preferably 0.2 Pa·s or less. Here, ICI viscosity is a viscosity measured with a cone-plate viscometer, which measures a high shear rate known as an ICI viscometer.

(Content of component (d))
When the thermosetting resin composition of the present embodiment contains (d) a thermosetting resin, the content is determined from the viewpoints of heat resistance, low thermal expansion, and adhesion to metal foil. It is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, and even more preferably 15 to 40 parts by weight, based on 100 parts by weight of the resin component of the thermosetting resin composition.

<(e) Curing accelerator>
The thermosetting resin composition of the present embodiment further contains (e) a curing accelerator [hereinafter sometimes referred to as component (e). ] may be contained. When the thermosetting resin composition contains component (e), heat resistance, flame retardance, adhesion to metal foil, etc. tend to improve.
Component (e) includes imidazole compounds and derivatives thereof; organic phosphorus compounds such as phosphine compounds, phosphonium salts, and adducts of tertiary phosphine and quinone compounds; secondary amines, tertiary amines, and Examples include quaternary ammonium salts. Component (e) may be used alone or in combination of two or more.

((e) Content of component)
When the thermosetting resin composition contains component (e), the content thereof is preferably 0.1 to 10 parts by mass, and 0.1 to 5 parts by mass, based on 100 parts by mass of the resin component. Parts by mass are more preferred, and 0.1 to 2 parts by mass are even more preferred. When the amount is 0.1 parts by mass or more, excellent heat resistance, flame retardancy, and adhesion with metal foil tend to be obtained, and when the amount is 10 parts by mass or less, heat resistance and stability over time tend to be obtained. The properties and press formability tend to be less likely to decrease.

<(f) Monoamine compound>
The thermosetting resin composition of the present embodiment further includes (f) a monoamine compound [hereinafter sometimes referred to as component (f). ] may or may not be contained. By containing component (f) in the thermosetting resin composition of this embodiment, heat resistance and low thermal expansion can be further improved.
As the component (f), the same monoamine compound as the monoamine compound (a2) can be used, and the preferred embodiments are also the same.

(Content of (f) component)
When the thermosetting resin composition of the present embodiment contains component (f), the content is determined from the viewpoint of reducing the coefficient of thermal expansion while maintaining heat resistance. It is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the resin component of the composition.

<(g) Amine compound having at least two amino groups>
The thermosetting resin composition of the present embodiment further includes (g) an amine compound having at least two amino groups [hereinafter sometimes referred to as component (g). ] may or may not be contained. By containing component (g) in the thermosetting resin composition of this embodiment, heat resistance and low thermal expansion can be further improved.
The amino group is preferably a primary amino group.
As component (g), the same amine compound as the above-mentioned (a3) amine compound having at least two amino groups can be used, and the preferred embodiments are also the same.

((g) Component content)
When the thermosetting resin composition of the present embodiment contains component (g), the content is determined from the viewpoint of reducing the coefficient of thermal expansion while maintaining heat resistance. It is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the resin component of the composition.

<(g') Silicone compound having at least two amino groups>
In particular, the thermosetting resin composition of Embodiment 3 further contains (g') a silicone compound having at least two amino groups. Note that only when the thermosetting resin composition of the present embodiment contains the component (g'), the component (g) is defined as not containing the component (g').
As the component (g'), the same silicone compound as the above-mentioned (a3') silicone compound having at least two amino groups can be used, and the preferred embodiments are also the same.

(Content of (g') component)
When the thermosetting resin composition of the present embodiment contains component (g'), the content is determined from the viewpoint of reducing the coefficient of thermal expansion while maintaining heat resistance. It is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the resin component of the resin composition.

<Other ingredients>
The thermosetting resin composition of the present embodiment may optionally contain a known thermoplastic resin, an organic filler, a flame retardant, a flame retardant aid, an ultraviolet absorber, and a peroxide to the extent that the thermosetting properties are not impaired. , an antioxidant, a photopolymerization initiator, a fluorescent brightener, an adhesion improver, and the like.

Thermoplastic resins include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, and polyether ether. Examples include ketone resin, silicone resin, and tetrafluoroethylene resin.

Examples of the organic filler include resin fillers made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, and resin fillers with a core-shell structure.
Examples of flame retardants include aromatic phosphate ester compounds, phosphazene compounds, phosphinic esters, metal salts of phosphinic acid compounds, red phosphorus, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and its like. Examples include phosphorus-based flame retardants such as derivatives; nitrogen-based flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate; and halogen-containing flame retardants containing bromine, chlorine, and the like.
Examples of flame retardant aids include inorganic flame retardants such as antimony trioxide, sodium antimonate, zinc sulfide, zinc borate, zinc stannate, and zinc molybdate. These may be supported on a carrier such as talc, if necessary.
Note that substances that function as flame retardants and substances that function as flame retardant aids are not classified as component (c'), but as flame retardants or flame retardant aids, even if they are inorganic compounds.

Examples of the ultraviolet absorber include benzotriazole ultraviolet absorbers.
Examples of peroxides include organic peroxides such as α,α'-bis(t-butylperoxyisopropyl)benzene.
Examples of the antioxidant include hindered phenol antioxidants and hindered amine antioxidants.
Examples of the photopolymerization initiator include benzophenone photopolymerization initiators, benzyl ketal photopolymerization initiators, thioxanthone photopolymerization initiators, and the like.
Examples of the fluorescent brightener include stilbene derivative fluorescent brighteners.
Examples of the adhesion improver include urea compounds such as urea silane, and the aforementioned coupling agents.

(varnish)
The thermosetting resin composition of this embodiment may be in the form of a varnish in which each component is dissolved or dispersed in an organic solvent in order to be used for manufacturing prepregs and the like. That is, varnish is also included in the thermosetting resin composition of this embodiment.
Organic solvents used for varnish include alcoholic solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; butyl acetate, propylene Ester solvents such as glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; dimethyl sulfoxide, etc. Examples include sulfur atom-containing solvents. One type of organic solvent may be used alone, or two or more types may be used in combination.
Among these, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferred from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferred from the viewpoint of low toxicity.
The solid content concentration of the varnish is preferably 40 to 90% by mass, more preferably 50 to 80% by mass. When the solid content concentration of the varnish is within the above range, good coating properties can be maintained and a prepreg with an appropriate amount of resin composition deposited can be obtained.

The thermosetting resin composition of the present embodiment can be produced by mixing components (a) to (c) and the aforementioned components that can be used as necessary by a known method. At this time, each component may be dissolved or dispersed in the organic solvent while stirring. Conditions such as mixing order, temperature, time, etc. are not particularly limited and can be set arbitrarily.
The thermosetting resin composition of this embodiment can exhibit a high dielectric constant (Dk) and a low dielectric loss tangent (Df), so it is suitable for use in antenna modules, especially small-sized ones compatible with fifth generation mobile communication systems (5G). It is useful for use as an integrated antenna module.

[Prepreg]
The prepreg of this embodiment contains a semi-cured product of the thermosetting resin composition of this embodiment.
The prepreg of this embodiment can be produced, for example, by impregnating a fiber base material with the thermosetting resin composition of this embodiment and B-staged by heating or the like. Here, in the present disclosure, B-staging refers to bringing the material into a B-stage state as defined in JIS K6900 (1994), and is also referred to as semi-curing. In other words, the semi-cured product of a thermosetting resin composition is a B-staged thermosetting resin composition.
As the fiber base material, well-known materials used in various laminates for electrically insulating materials can be used. Examples of the material include inorganic fibers such as E glass, S glass, low dielectric glass, and Q glass; organic fibers such as low dielectric glass polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. In particular, from the viewpoint of obtaining a base material with excellent dielectric properties, low dielectric glass and Q glass are preferred.

These fiber base materials have shapes such as woven fabrics, nonwoven fabrics, raw binders, chopped strand mats, and surfacing mats. The material and shape of the fiber base material are appropriately selected depending on the intended use and performance of the molded product, and a single material and a single shape may be used, or two may be used as necessary. It is also possible to combine two or more types of materials or two or more types of shapes. The thickness of the fiber base material can be, for example, about 0.01 to 0.5 mm. These fiber base materials are preferably those that have been surface-treated with a silane coupling agent or the like, or those that have been subjected to mechanical opening treatment, in terms of heat resistance, moisture resistance, processability, and the like.

In the prepreg of this embodiment, for example, the amount of adhesion of the thermosetting resin composition to the fiber base material (solid content of the thermosetting resin composition in the prepreg) is preferably 20 to 90% by mass. As a step, a fiber base material is impregnated with a thermosetting resin composition. Thereafter, a prepreg can be obtained by heating and drying, for example, at a temperature of 100 to 200° C. for 1 to 30 minutes to form a B-stage.
The thickness of the prepreg of this embodiment is not particularly limited, and may be 10 to 300 μm, 10 to 200 μm, or 10 to 70 μm. The thickness is the thickness of the prepreg after heating and drying.

The prepreg of this embodiment can exhibit a high dielectric constant (Dk) and a low dielectric loss tangent (Df), and is therefore useful for antenna modules, particularly for miniaturized antenna modules compatible with 5G.

[Laminated board, metal-clad laminate]
The laminate of this embodiment is a laminate containing a cured product of the prepreg of this embodiment.
The laminate of this embodiment is obtained by laminating and molding the prepreg of this embodiment. Specifically, one sheet of prepreg of this embodiment or a stack of 2 to 20 sheets of prepreg is prepared, and a metal foil such as copper, aluminum, etc. is arranged on one or both sides of the prepreg, and then laminated molding is performed. It can be manufactured by A laminate having an insulating layer formed using the prepreg of the present embodiment by the manufacturing method (the insulating layer is C-staged) and a metal foil disposed on one or both sides of the insulating layer. is obtained. The metal foil is not particularly limited as long as it is used as an electrically insulating material. Note that the laminate of this embodiment in which metal foil is arranged on one or both sides of the laminate is particularly referred to as a metal-clad laminate. Furthermore, in the present disclosure, C-staging refers to bringing the device into a C-stage state as defined in JIS K6900 (1994).
As for the forming conditions when manufacturing laminates and metal-clad laminates, for example, methods for producing laminates and multilayer boards for electrical insulating materials can be applied, and multistage presses, multistage vacuum presses, continuous molding, autoclave molding machines, etc. can be used. It can be molded at a temperature of 100 to 300°C, a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours. Moreover, the prepreg of this embodiment and the wiring board for inner layers can be combined and laminated to form a laminate to produce a laminate.

The laminate of this embodiment has a high dielectric constant (Dk) and a low dielectric loss tangent (Df), and is therefore useful for antenna modules, particularly for miniaturized antenna modules compatible with 5G.

Considering that the laminate of this embodiment is used as an antenna module, it is preferable that the laminate has conductor patterns such as a power feeding conductor pattern, a grounding conductor pattern, and a shorting conductor. The short-circuiting conductor is a conductor that short-circuits the power feeding conductor pattern and the grounding conductor pattern, and is provided at a via hole portion to be described later.
The conductor pattern is preferably formed of a metal whose main component is copper, aluminum, gold, silver, or an alloy thereof.

It is preferable that the laminate of this embodiment has a via hole. The via hole enables formation of the short-circuiting conductor, and enables conduction between the power feeding conductor pattern and the grounding conductor pattern.
There are no particular limitations on the method for forming via holes, and methods such as laser, plasma, or a combination thereof can be used. As the laser, a carbon dioxide laser, a YAG laser, a UV laser, an excimer laser, etc. can be used.
Further, after forming the via hole, desmear treatment may be performed using an oxidizing agent. As the oxidizing agent, permanganates such as potassium permanganate and sodium permanganate; dichromates; ozone; hydrogen peroxide-sulfuric acid; nitric acid are preferred, permanganates are more preferred; More preferred is an aqueous solution of sodium hydroxide, a so-called aqueous alkaline permanganate solution.
The laminate of this embodiment can be manufactured by forming shorting conductors in the via holes after forming the via holes. The conductor used here is preferably formed of the same metal as the metal forming the conductor pattern.

[Printed wiring board]
The printed wiring board of this embodiment has a cured product of the thermosetting resin composition of this embodiment. The printed wiring board of this embodiment is selected from the group consisting of the cured product of the thermosetting resin composition of this embodiment, the cured product of prepreg, the laminate of this embodiment, and the metal-clad laminate of this embodiment. It can also be said that it has one or more types.
The printed wiring board of this embodiment is formed by drilling holes by a known method using one or more selected from the group consisting of the prepreg of this embodiment, the resin film of this embodiment, and the laminate of this embodiment. It can be manufactured by performing circuit formation processing such as metal plating or etching of metal foil. Moreover, a multilayer printed wiring board can be manufactured by further performing a multilayer adhesive process as required. In the printed wiring board of this embodiment, the prepreg of this embodiment or the resin film of this embodiment is C-staged.

[Antenna device]
The present disclosure also provides an antenna device having the laminate of this embodiment. The antenna device may be one in which one of the above laminates is installed, or may be one in which a plurality of the above laminates are installed. Although there is no particular restriction on how to install the plurality of antenna elements, it is preferable, for example, to arrange them in a two-dimensional array. The configuration of the antenna device is not particularly limited, and for example, Japanese Patent No. 6777273 can be referred to.

[Antenna module]
The present disclosure also provides an antenna module that includes a power feeding circuit and the antenna device of this embodiment. The power supply circuit is not particularly limited, but an RFIC (Radio Frequency Integrated Circuit) or the like can be used. The RFIC includes a switch, a power amplifier, a low noise amplifier, an attenuator, a phase shifter, a signal combiner/brancher, a mixer, an amplifier circuit, and the like.
The high frequency signal supplied from the RFIC is transmitted to the power feeding point of the power feeding conductor via a shorting conductor formed in a via of the antenna module laminate.
The configuration of the antenna module is not particularly limited, and for example, Japanese Patent No. 6777273 can be referred to.

[Communication device]
Furthermore, the present disclosure also provides a communication device including a baseband signal processing circuit and the antenna module of this embodiment.
The communication device of this embodiment up-converts the signal transmitted from the baseband signal processing circuit to the antenna module to a high-frequency signal and radiates it from the antenna device, and down-converts the high-frequency signal received by the antenna device to the baseband signal. The signal can be processed in a band signal processing circuit.

Next, the present embodiment will be described in more detail with reference to the following examples, but these examples do not limit the present disclosure.
Note that the dielectric constant (Dk) and dielectric loss tangent (Df) of the copper-coated resin plates obtained in each example were measured by the following methods.

[1. Measuring method of dielectric constant (Dk) and dielectric loss tangent (Df) in high frequency band]
A 2 mm x 50 mm evaluation resin sample was prepared from a sample in which the copper foil was removed by immersing the copper-coated resin plate obtained in each example in a 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a copper etching solution. Created.
Using the evaluation resin sample, the dielectric constant (Dk) and dielectric loss tangent (Df) in the 10 GHz band were calculated from the resonance frequency and the no-load Q value obtained by the cavity resonator method. The measuring instruments used were vector network analyzer E8364B manufactured by Agilent Technologies, CP531 (10 GHz resonator) and CPMA-V2 (program) manufactured by Kanto Electronics Applied Development Co., Ltd. at an ambient temperature of 25°C. went.

[Examples 1 to 4, Comparative Examples 1 to 3]
A resin powder of a thermosetting resin composition was prepared by mixing each component and each blending amount listed in Table 1, and then crushing and stirring in a mortar for 10 minutes.
Next, a partially hollowed out Teflon (registered trademark) plate (thickness: 1 mm) was placed on the copper foil, and the resin powder was poured into the hollowed out part of the Teflon plate, and the temperature was increased under a pressure of 3.0 MPa. After increasing the temperature to 240°C at a rate of 4.0°C/min and holding it for 85 minutes, the resin powder was made into a C-stage, and after releasing the pressure, it was cooled for 30 minutes to produce a copper-coated resin plate. . Using the obtained resin plate with copper, the dielectric constant (Dk) and dielectric loss tangent (Df) were measured according to the method described above. The results are shown in Table 1.

Each component listed in Table 1 is shown below.
[(a) Component]
・2,2-bis[4-(4-maleimidophenoxy)phenyl]propane [see structural formula below]

[(b) Component]
・4,4'-diethylbiphenyl [see structural formula below]; boiling point 315°C (1 atm)
・Biphenyl skeleton-containing compound 1 [see structural formula below]; melting point 185°C

[(c) Component]
・Strontium titanate (average particle size: 3 μm)
・Aluminum titanate (average particle size: 3 μm)
[(c') component]
・Silica (average particle size; 0.5 μm)
The particle size distribution was measured using a particle size distribution measuring device "Microtrac MT3000" (manufactured by Microtrac Bell Co., Ltd.), and the average particle size (d50) was determined. Note that water (containing 0.1% by mass of sodium hexametaphosphate) was used as the measurement solvent, the measurement mode was set to transmission, and the measurement time was 30 seconds.

[(g) Component]
・4,4'-(1,3-phenylenediisopropylidene)bisaniline [See structural formula below]

[(g') component]
・Silicone compound with two amino groups: KF-8012 (manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent: 2,200 g/eq)

[Other ingredients: peroxide]
・α,α-bis(t-butylperoxy-m-isopropyl)benzene [see structural formula below]

From Table 1, in Examples 1 to 4, high relative dielectric constant (high Dk) and low dielectric loss tangent (low Df) were achieved. On the other hand, in Comparative Example 1 in which component (b) was not used, a low dielectric loss tangent (low Df) could not be achieved. Further, in Comparative Examples 1 and 2 in which silica as the component (c') was used instead of the component (c), a high dielectric constant (high Dk) could not be achieved.

Claims (24)

(a) a maleimide compound having at least one N-substituted maleimide group;
(b) a compound represented by the following general formula (1) and showing no reactivity with the maleimide group contained in the component (a); and (c) a titanium-based inorganic filler and a zircon-based inorganic filler. at least one high dielectric constant inorganic filler selected from the group consisting of;
A thermosetting resin composition comprising:
(In general formula (1), X ^b1 represents a single bond or a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 5 carbon atoms. R ^b1 and R ^b2 each independently represent a substituted or unsubstituted Aliphatic hydrocarbon group having 1 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring-forming carbon atoms, substituted or unsubstituted heterocyclic aromatic hydrocarbon group having 5 to 20 ring-forming atoms Represents a hydrogen group, an oxygen atom-containing group, or a group consisting of a combination thereof. m and n are each independently an integer of 0 to 5.) The thermosetting resin composition according to claim 1, wherein the component (a) contains (a1) a maleimide compound having at least two N-substituted maleimide groups. Component (a) is selected from the group consisting of (a1) a maleimide compound having at least two N-substituted maleimide groups, (a2) a monoamine compound, and (a3) an amine compound having at least two amino groups. The thermosetting resin composition according to claim 1, containing a reactant with at least one type of. The component (a1) has an aliphatic hydrocarbon group between the nitrogen atoms of any two N-substituted maleimide groups among the plurality of N-substituted maleimide groups (however, no aromatic hydrocarbon group is present). ) maleimide compound, or a maleimide compound having an aromatic hydrocarbon group between the nitrogen atoms of any two N-substituted maleimide groups among the plurality of N-substituted maleimide groups. The thermosetting resin composition described. 2. The method according to claim 1, wherein the component (a) contains a reaction product of (a1) a maleimide compound having at least two N-substituted maleimide groups and (a3') a silicone compound having at least two amino groups. The thermosetting resin composition described. The component (a) comprises the component (a1), the component (a3'), and (a3) an amine compound having at least two amino groups (excluding the component (a3')). The thermosetting resin composition according to claim 5, which is a reactant. The thermosetting resin composition according to claim 1, wherein the component (b) is represented by the following general formula (1').
(In general formula (1'), R ^b1 , R ^b2 , m and n are the same as in general formula (1) above.) The thermosetting resin composition according to claim 1, wherein the boiling point of the component (b) under one atmospheric pressure (101.325 kPa) is 260°C or higher. The thermosetting resin composition according to claim 1, wherein the component (b) is at least one selected from the group consisting of diethylbiphenyl and benzylbiphenyl. The thermosetting resin composition according to claim 1, wherein in the general formula (1), R ^b1 and R ^b2 are oxygen atom-containing groups. The thermosetting resin composition according to claim 1, wherein the content of the component (b) is 0.001 to 1.0 mol per 1 mol of the component (a). The thermosetting resin composition according to claim 1, further comprising (c') an inorganic filler other than the component (c). The thermosetting resin composition according to claim 1, further comprising (d) a thermosetting resin. The thermosetting resin composition according to claim 1, further comprising (e) a curing accelerator. The thermosetting resin composition according to claim 1, further comprising (f) a monoamine compound. The thermosetting resin composition according to claim 1, further comprising (g) an amine compound having at least two amino groups. The thermosetting resin composition according to claim 1, further comprising (g') a silicone compound having at least two amino groups. A prepreg comprising a semi-cured product of the thermosetting resin composition according to any one of claims 1 to 17. A laminate comprising a cured prepreg according to claim 18. A metal-clad laminate comprising a metal foil arranged on one or both sides of the laminate according to claim 19. A printed wiring board comprising a cured product of the thermosetting resin composition according to any one of claims 1 to 17. An antenna device comprising the laminate according to claim 19 or the metal-clad laminate according to claim 20. An antenna module comprising a power feeding circuit and the antenna device according to claim 22. A communication device comprising a baseband signal processing circuit and the antenna module according to claim 23.