Maleimide resin composition, prepreg, resin film, laminate, printed wiring board and semiconductor package

Abstract

To provide a resin composition that exhibits low thermal expandability and high elasticity, along with small dielectric loss tangent (Df), and also provide a prepreg, a resin sheet, a laminate, a printed wiring board and a semiconductor package, produced using the resin composition.SOLUTION: A maleimide resin composition comprises (A) at least one selected from the group consisting of maleimide compounds with one or more N-substituted maleimide groups and its derivatives, (X) an aromatic ring-containing phosphorus oxide compound, and (Y) a halogen compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a maleimide resin composition, a prepreg, a resin film, a laminate, a printed wiring board, and a semiconductor package. [Background technology]

[0002] In recent years, with the advancement of higher wiring density and higher integration in printed wiring boards, particularly in semiconductor package substrate applications, "warping" caused by the difference in thermal expansion coefficient between the chip and the substrate during component mounting and package assembly has become a major issue. Warping is considered to be one of the factors that cause poor connections between semiconductor elements and printed wiring boards, and there is a demand for reducing warping. One of the factors that causes semiconductor packages to warp is the difference in the thermal expansion coefficient between the semiconductor element and the printed wiring board. Generally, the thermal expansion coefficient of the printed wiring board is greater than that of the semiconductor element, so stress is generated due to the thermal history applied when mounting the semiconductor element, which causes warping. Therefore, in order to suppress warping of semiconductor packages, it is necessary to reduce the thermal expansion coefficient of the printed wiring board and reduce the difference with the thermal expansion coefficient of the semiconductor element. Warping can also be suppressed by making the semiconductor package highly elastic.

[0003] In order to achieve low thermal expansion and high elasticity with the aim of reducing warping, high loading of inorganic filler and adoption of resins with low thermal expansion coefficients have been attempted (see, for example, Patent Document 1). However, high loading of inorganic filler can cause a decrease in insulation reliability, a decrease in adhesion between the resin and the wiring layer formed on its surface, and press molding defects during laminate manufacturing. Therefore, a substrate material that can achieve low thermal expansion and high elasticity without high loading of inorganic filler is desired.

[0004] Furthermore, in recent years, the speed and capacity of signals used has been increasing year by year in mobile communication devices such as mobile phones, their base station equipment, servers, routers and other network infrastructure devices, large computers, etc. Accordingly, the printed wiring boards mounted on these electronic devices must be compatible with higher frequencies, and there is a demand for board materials with excellent dielectric loss tangent (Df) in the high frequency band that enables the reduction of transmission loss. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2004-182851 A Summary of the Invention [Problem to be solved by the invention]

[0006] In view of the above circumstances, the present disclosure has an object to provide a resin composition having low thermal expansion, high elasticity, and a small dielectric loss tangent (Df), and further to provide a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor package produced using the resin composition. [Means for solving the problem]

[0007] As a result of investigations aimed at achieving the above object, the present inventors have found that the above object can be achieved by the present disclosure. The present disclosure includes the following embodiments [1] to

[13] . [1] (A) one or more compounds selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof; (X) an aromatic ring-containing phosphorus oxide compound; (Y) a halogen compound; 1. A maleimide resin composition comprising: [2] The maleimide resin composition according to the above [1], wherein the component (A) comprises at least one member selected from the group consisting of maleimide compounds having two or more N-substituted maleimide groups and derivatives thereof. [3] The maleimide resin composition according to the above [1] or [2], wherein the component (X) comprises at least one selected from the group consisting of (X1) a phosphate compound, (X2) a phosphine oxide compound, and (X3) a phosphaphenanthrene compound. [4] The maleimide resin composition according to any one of the above [1] to [3], wherein the component (X) has two or more phosphorus atoms in one molecule. [5] The maleimide resin composition according to any one of the above [1] to [4], wherein the component (Y) is a bromine compound. [6] The maleimide resin composition according to any one of the above [1] to [5], further comprising (B) a polymer having a hydrocarbon chain or a polyether chain. [7] The maleimide resin composition according to any one of the above [1] to [6], further comprising (C) an inorganic filler. [8] The maleimide resin composition according to any one of the above [1] to [7], further comprising (D) a curing accelerator. [9] A prepreg comprising the maleimide resin composition according to any one of the above [1] to [8] or a semi-cured product of the maleimide resin composition.

[10] A resin film comprising the maleimide resin composition according to any one of the above [1] to [8] or a semi-cured product of the maleimide resin composition.

[11] A laminate comprising a cured product of the maleimide resin composition according to any one of the above [1] to [8] or a cured product of the prepreg according to the above [9], and a metal foil.

[12] A printed wiring board comprising one or more members selected from the group consisting of a cured product of the maleimide resin composition according to any one of [1] to [8] above, a cured product of the prepreg according to [9] above, and the laminate according to

[11] above.

[13] A semiconductor package comprising the printed wiring board according to

[12] above and a semiconductor element. Effect of the Invention

[0008] According to the present disclosure, it is possible to provide a resin composition having low thermal expansion, high elasticity, and a small dielectric loss tangent (Df). It is also possible to provide a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor package using the resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] In the numerical ranges described in the present disclosure, the upper or lower limit of the numerical range may be replaced with the values ​​shown in the examples. In addition, the lower and upper limits of a numerical range may be arbitrarily combined with the lower or upper limit of another numerical range. In the expression of a numerical range "AA to BB", the numerical values ​​AA and BB at both ends are included in the numerical range as the lower and upper limits, respectively. In the present disclosure, for example, the description "10 or more" means 10 and a numerical value exceeding 10, and the same applies when the numerical values ​​are different. Also, for example, the description "10 or less" means 10 and a numerical value less than 10, and the same applies when the numerical values ​​are different. In addition, unless otherwise specified, each component and material exemplified in this disclosure may be used alone or in combination of two or more. In this disclosure, the content of each component in the resin composition means the total amount of the multiple substances present in the resin composition when multiple substances corresponding to each component (e.g., component (A)) are present in the resin composition, unless otherwise specified.

[0010] In the present disclosure, the term "resin component" is defined as all components among the solid contents constituting the resin composition, excluding inorganic compounds such as (C) inorganic filler, which will be described later. In the present disclosure, the term "solid content" refers to components in a resin composition other than the organic solvent described below. In other words, the solid content includes not only those that are solid at room temperature around 25° C., but also those that are liquid, syrup-like, or wax-like at room temperature around 25° C. The expression "containing XX" described in the present disclosure includes both the meaning of containing XX in a reacted state when XX is capable of reacting, and the meaning of simply containing XX. Any combination of the descriptions in this disclosure is also included in this disclosure and this embodiment.

[0011] [Maleimide resin composition] The maleimide resin composition of the present embodiment (hereinafter, may be simply referred to as a resin composition) is as follows. (A) one or more maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof (hereinafter, sometimes simply referred to as maleimide compound (A) or component (A)), (X) an aromatic ring-containing phosphorus oxide compound (hereinafter, sometimes simply referred to as phosphorus oxide compound (X) or (X) component), (Y) a halogen compound (hereinafter, sometimes referred to as halogen compound (Y) or sometimes simply referred to as component (Y)), 1. A maleimide resin composition comprising:

[0012] The reason why the use of the maleimide resin composition of the present embodiment exhibits low thermal expansion and high elasticity while also reducing the dielectric loss tangent (Df) is not clear, but is presumed to be as follows. It is believed that the aromatic rings in the phosphorus oxide compound (X) cause stacking between the phosphorus oxide compounds (X) and between the maleimide compound (A) and the phosphorus oxide compound (X), and as a result, the intermolecular forces of the aromatic rings make it difficult for the molecules themselves to move, imparting rigidity and resulting in high elasticity and low thermal expansion. Furthermore, the presence of the phosphorus oxide compound (X) between the stacked maleimide compounds (A) increases the free volume, improving the dielectric loss tangent (Df), and in addition, the presence of the halogen compound (Y) around the maleimide compound (A) and throughout the resin composition provides a synergistic effect in improving the dielectric loss tangent (Df). Hereinafter, each component contained in the resin composition of the present embodiment will be described in detail.

[0013] (Maleimide compound (A)) The maleimide compound preferably contains at least one selected from the group consisting of maleimide compounds (a1) having two or more N-substituted maleimide groups [hereinafter, may be simply referred to as "maleimide compound (a1)" or "(a1) component"] and derivatives thereof. In other words, the (A) component preferably contains at least one selected from the group consisting of maleimide compounds having two or more N-substituted maleimide groups and derivatives thereof. In addition, examples of the above-mentioned "derivative" include an addition reaction product between a maleimide compound (a1) having two or more N-substituted maleimide groups and an amine compound such as a diamine compound (see examples of amine compound (a2)) described later.

[0014] The maleimide compound (a1) is not particularly limited as long as it is a maleimide compound having two or more N-substituted maleimide groups.Specific examples of the maleimide compound (a1) include aromatic maleimide compounds such as bis(4-maleimidophenyl)methane, polyphenylmethane maleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and biphenylaralkyl type bismaleimide; and aliphatic maleimide compounds such as 1,6-bismaleimido-(2,2,4-trimethyl)hexane and pyrrolidine acid binder type long chain alkyl bismaleimide. Among these, from the viewpoints of adhesion to metal foil and mechanical properties, the maleimide compound (a1) is preferably an aromatic maleimide compound, more preferably an aromatic bismaleimide compound, further preferably 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, or a biphenylaralkyl-type bismaleimide, and particularly preferably 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide or a biphenylaralkyl-type bismaleimide. As the maleimide compound having a biphenylaralkyl skeleton, a maleimide compound represented by the following general formula (a1-1) is preferably mentioned.

[0015] [ka] (m is an integer from 1 to 5.)

[0016] In addition, the maleimide compound (a1) is also preferably a compound represented by the following general formula (A1-1). [ka] (In the formula, X a1 represents a divalent organic group.

[0017] X in the above general formula (A1-1) a1 Examples of the divalent organic group represented by the formula include groups represented by the following general formula (A1-2), (A1-3), (A1-4) or (A1-5).

[0018] [ka] (In the formula, R a1 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a1 represents an integer of 0 to 4. * represents a bonding position.)

[0019] R a1 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable. n a1 represents an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 is more preferable. a1If is an integer equal to or greater than 2, multiple R a1 They may be the same or different.

[0020] [ka] (In the formula, R a2 and R a3 Each of X independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, -S-, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent group represented by the following general formula (A1-3-1): a2 and n a3 Each independently represents an integer of 0 to 4. * indicates a bonding position.)

[0021] R a2 and R a3 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a1 This is the same as the explanation for the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by the formula (1). X a2 Examples of the alkylene group having 1 to 5 carbon atoms include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc. As the alkylene group, an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group is more preferable. X a2 Examples of the alkylidene group having 2 to 5 carbon atoms include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, etc. As the alkylidene group, an isopropylidene group is preferable. n a2 and n a3 represents an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 or 2 is more preferable. a2 If is an integer equal to or greater than 2, multiple R a2may be the same or different. a3 If is an integer equal to or greater than 2, multiple R a3 They may be the same or different from each other. X a2 The divalent group represented by the general formula (A1-3-1) is as follows.

[0022] [ka] (In the formula, R a4 and R a5 Each of X independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a3 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, -S-, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. a4 and n a5 Each independently represents an integer of 0 to 4. * indicates a bonding position.)

[0023] R a4 and R a5 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a1 This is the same as the explanation for the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by the formula (1). X a3 The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by the formula (A1-3) above are preferably represented by the formula (A1-4). a2 Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms are shown below. Among these, an isopropylidene group is preferred from the viewpoints of adhesion to metal foil, solder heat resistance and thermal expansion coefficient. X a3 Among the groups represented by the formula (I), an alkylidene group having 2 to 5 carbon atoms is preferred, and an isopropylidene group is more preferred. n a4 and n a5 represents an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 is more preferable. a4If is an integer equal to or greater than 2, multiple R a4 may be the same or different. a5 If is an integer equal to or greater than 2, multiple R a5 They may be the same or different from each other.

[0024] [ka] (In the formula, n a6 represents an integer from 1 to 10. * represents a bonding position.)

[0025] n a6 From the viewpoint of availability, an integer of 1 to 5 is preferable, and an integer of 1 to 3 is more preferable.

[0026] [ka] (In the formula, R a6 and R a7 Each of n independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. a7 represents an integer of 1 to 8. * represents a bonding position.)

[0027] R a6 and R a7 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a1 This is the same as the explanation for the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by the formula (1). n a7 represents an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1. n a7 If is an integer equal to or greater than 2, multiple R a6 may be the same or different, and multiple R a7 They may be the same or different from each other.

[0028] X in the above general formula (A1-1) a1From the viewpoint of dielectric loss tangent (Df), the following formula (X a1 -1)~(X a1 -3), and is preferably a divalent group represented by the following formula (X a1 -3) is more preferable.

[0029] [ka] (In the formula, * indicates the bonding position with the nitrogen atom in the maleimide group.)

[0030] As the maleimide compound, from the viewpoints of solubility in organic solvents, compatibility, adhesion to metal foil, and dielectric loss tangent (Df), a derivative of the maleimide compound (a1) is preferred. The derivative of the maleimide compound (a1) may be a modified maleimide compound having a structural unit derived from the maleimide compound (a1) and a structural unit derived from an amine compound (a2) having a primary amino group [hereinafter, sometimes abbreviated as "amine compound (a2)" or "component (a2)".]. The modified maleimide compound is preferably a compound obtained by addition reaction between a maleimide group in the component (a1) and a primary amino group in the component (a2).

[0031] The amine compound (a2) is preferably a compound having two or more amino groups, and more preferably a diamine compound having two amino groups. Examples of the amine compound (a2) include 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(3-aminophenoxy)benzene, 1,3 -Bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 1,4-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, 4,4'-[ Examples of diamine compounds include aromatic diamine compounds such as 1,4-phenylenebis(1-methylethylidene)]bisaniline, 3,3'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, and 9,9-bis(4-aminophenyl)fluorene; and amine-modified siloxane compounds having a primary amino group.

[0032] (Content of component (A)) The content of component (A) in the resin composition of this embodiment is not particularly limited, but is preferably 5 to 60 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 10 to 35 parts by mass, relative to 100 parts by mass of the total solid content. If the content of component (A) is equal to or more than the lower limit, sufficient adhesive strength with the metal foil and high solder heat resistance tend to be obtained, and if it is equal to or less than the upper limit, the elastic modulus tends to be prevented from becoming too high.

[0033] (Phosphorus oxide compound (X)) The resin composition of the present embodiment contains an aromatic ring-containing phosphorus oxide compound as component (X) and does not contain halogen atoms in order to avoid overlap with component (Y). Here, the "phosphorus oxide compound" refers to a compound having the following phosphorus oxide structure. [ka] (* indicates the bond position.)

[0034] The aromatic ring contained in the (X) component is preferably an aromatic ring having 6 to 18 ring carbon atoms, and examples thereof include a benzene ring, a naphthalene ring, and an anthracene ring. The aromatic ring is preferably a benzene ring. The aromatic ring may or may not have a substituent. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group; and an alkoxy group, such as a methoxy group, an ethoxy group, and an isopropoxy group. The substituent is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.

[0035] The (X) component preferably has 2 or more aromatic rings in one molecule, more preferably 2 to 10, even more preferably 2 to 6, particularly preferably 4 to 6, and most preferably 5. When the (X) component has 2 or more aromatic rings in one molecule, the multiple aromatic rings may be the same or different, but are preferably the same. In the (X) component, the aromatic ring may be bonded directly to the phosphorus atom, may be bonded to the phosphorus atom via an oxygen atom, or may be bonded to the phosphorus atom via an alkylene group such as a methylene group. From the viewpoints of low thermal expansion, high elasticity, and dielectric tangent (Df), the (X) component preferably has two or more phosphorus atoms in one molecule, more preferably has 2 to 4 phosphorus atoms in one molecule, and even more preferably has 2 phosphorus atoms in one molecule.

[0036] From the viewpoints of low thermal expansion, high elasticity and dielectric loss tangent (Df), the (X) component preferably contains at least one selected from the group consisting of (X1) a phosphate compound [hereinafter, also referred to as a phosphate compound (X1) or simply referred to as a (X1) component], (X2) a phosphine oxide compound [hereinafter, also referred to as a phosphine oxide compound (X2) or simply referred to as a (X2) component] and (X3) a phosphaphenanthrene compound [hereinafter, also referred to as a phosphaphenanthrene compound (X3) or simply referred to as a (X3) component], more preferably contains at least one selected from the group consisting of a phosphate compound (X1) and a phosphine oxide compound (X2), and even more preferably contains a phosphine oxide compound (X2). The components (X1) to (X3) will be described in detail below.

[0037] (Phosphate compound (X1)) The phosphate compound (X1) may be used alone or in combination of two or more. Commercially available phosphate compounds may be used. The phosphate compound (X1) preferably has two or more phosphate groups in the molecule, and more preferably has two phosphate groups in the molecule. Here, the phosphate group is a group represented by the following formula. [ka] (* indicates the bond position.)

[0038] The phosphate compound having two or more phosphate groups in the molecule preferably has a linking group that links two or more phosphate groups. The linking group is not particularly limited, but may be a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, a methylene group, an ethylene group, or the like. From the viewpoint of the (X1) component having a high melting point, the linking group preferably contains at least one selected from the group consisting of a phenylene group, a xylylene group, a biphenylene group, and a naphthylene group, and more preferably contains a phenylene group.

[0039] From the viewpoints of low thermal expansion, high elasticity and dielectric loss tangent (Df), the oxygen atom of the phosphate group may be substituted on the aromatic ring. From the viewpoint of improving the adhesive strength to the metal foil and the solder heat resistance while maintaining a low thermal expansion property, the phosphate compound (X1) is preferably a compound represented by the following general formula (X-1).

[0040] [ka] (In the formula, R x1 ~R x4 Each of Z independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. x1 represents a divalent group represented by the following general formula (X-2) or a divalent condensed polycyclic aromatic hydrocarbon group. x1 ~n x4 Each independently represents an integer of 0 to 5, c5 represents an integer from 0 to 5.)

[0041] [ka] (In the formula, R x5 and R x6 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. x2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, -S-, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. x6 and n x7 Each independently represents an integer of 0 to 4. x8 represents an integer from 1 to 3.)

[0042] R in the general formula (X-1) x1 ~R x4 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable. n x1 ~n x4 represents an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 2, and even more preferably 2. x1 ~n x4 If is an integer equal to or greater than 2, multiple R x1 Fellow, R x2 Fellow, R x3 R x4 They may be the same or different. n x5 represents an integer of 0 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1. x5 If is an integer equal to or greater than 2, multiple Z x1 n x4 They may be the same or different.

[0043] The definitions of each group in the general formula (X-2) are as described above.

[0044] Z in the general formula (X-1) x1 Examples of the divalent condensed polycyclic aromatic hydrocarbon group represented by the formula (I) include a divalent group obtained by removing two hydrogen atoms from a condensed polycyclic aromatic hydrocarbon such as naphthalene, anthracene, or pyrene. The condensed polycyclic aromatic hydrocarbon group may be substituted or unsubstituted by a substituent. Examples of the substituent of the condensed polycyclic aromatic hydrocarbon group include aliphatic hydrocarbon groups having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, or an n-pentyl group; and halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0045] Specific examples of the phosphate compound (X1) include 1,3-phenylene-bis(di-2,6-dimethylphenyl phosphate), 1,3-phenylene-bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), 1,4-phenylene-bis(di-2,6-dimethylphenyl phosphate), 4,4'-biphenylene-bis(di-2,6-dimethylphenyl phosphate), bisphenol A polyphenyl phosphate, 4,4'-biphenol-polycresyl phosphate, bisphenol A polycresyl phosphate, 4,4'-biphenol-poly(2,6-xylenyl phosphate), bisphenol A poly(2,6-xylenyl phosphate), and the like. In addition, "poly" in the above specific examples of the phosphate compound means a compound having 2 or more structural units composed of a structure derived from a divalent phenol compound and a structure derived from phosphoric acid that constitute the phosphate compound, and may also mean a compound containing the compound such that the average number of the structural units exceeds 1. Here, the "structural unit" refers to, for example, the structural unit in parentheses in the general formula (X-1).

[0046] (Phosphine oxide compound (X2)) The phosphine oxide compound may be used alone or in combination of two or more kinds. Commercially available phosphine oxide compounds can be used. The phosphine oxide compound preferably has two or more diphenylphosphine oxide groups in the molecule, and more preferably has two diphenylphosphine oxide groups in the molecule. Here, the diphenylphosphine oxide group is a group represented by the following formula. [ka] (* indicates the bond position.)

[0047] The melting point of the phosphine oxide compound is preferably 280° C. or higher, more preferably 310° C. or higher, from the viewpoint of the dielectric loss tangent (Df). The melting point of the phosphine oxide compound is limited to about 450° C., from the viewpoint of the decomposition temperature of organic matter. For this reason, the melting point of the phosphine oxide compound is preferably 280 to 450° C., more preferably 310 to 450° C. The melting point can be measured using a thermogravimetry / differential thermal analyzer (TG / DTA).

[0048] The phosphine oxide compound having two or more diphenylphosphine oxide groups in the molecule preferably has a linking group that links two or more diphenylphosphine oxide groups. The linking group is not particularly limited, but examples thereof include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, a methylene group, and an ethylene group. From the viewpoint of the (X2) component having a high melting point, the linking group preferably contains at least one selected from the group consisting of a phenylene group, a xylylene group, a biphenylene group, and a naphthylene group, and more preferably contains a phenylene group.

[0049] Specific examples of the phosphine oxide compound (X2) include the following compounds. [ka]

[0050] (Phosphaphenanthrene compound (X3)) The phosphaphenanthrene compound may be used alone or in combination of two or more kinds. As the phosphaphenanthrene compound, a commercially available product may be used. Examples of the phosphaphenanthrene compound include compounds represented by the following formula (X-3). [ka] (In the formula, R x10 and R x11 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. b and c are each independently an integer of 0 to 4. A is a hydrogen atom or a group represented by any one of the following formulas (X-4) to (X-6). [ka] (* indicates the bond position.) [ka] (* indicates the bond position.) [ka] (* indicates the bond position.)

[0051] Examples of the phosphaphenanthrene compound include 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, 9,10-dihydro-10-(2,5-dihydroxyphenyl)-9-oxa-10-phosphaphenanthrene 10-oxide, and the like.

[0052] (Halogen compounds (Y)) The resin composition of the present embodiment contains a halogen compound as the (Y) component. The halogen compound may be a low molecular weight compound or a high molecular weight compound. The molecular weight of the low molecular weight compound is not particularly limited, but is preferably 1,500 or less, more preferably 200 to 1,500, even more preferably 500 to 1,300, even more preferably 700 to 1,200, particularly preferably 800 to 1,100, and most preferably 900 to 1,100. The molecular weight of the high molecular weight compound is not particularly limited, but is preferably more than 1,500, more preferably more than 1,500 to 30,000, even more preferably 2,000 to 20,000, and particularly preferably 2,000 to 15,000.

[0053] Examples of the halogen compound (Y) include chlorine compounds, bromine compounds, etc. Among these, the halogen compound (Y) is preferably a bromine compound. Examples of the chlorine compound include chain aliphatic chlorine compounds, cyclic aliphatic chlorine compounds, etc. Here, the chain aliphatic chlorine compound is a compound having a site where a chlorine atom is directly bonded to a chain aliphatic hydrocarbon group, and the cyclic aliphatic chlorine compound is a compound having a site where a chlorine atom is directly bonded to a cyclic aliphatic hydrocarbon group. Examples of the bromine compound include linear aliphatic bromine compounds, cyclic aliphatic bromine compounds, and aromatic bromine compounds. Here, the linear aliphatic chlorine compound is a compound having a portion where a bromine atom is directly bonded to a linear aliphatic hydrocarbon group, and the cyclic aliphatic chlorine compound is a compound having a portion where a bromine atom is directly bonded to a cyclic aliphatic hydrocarbon group. In addition, the aromatic bromine compound is a compound having a portion where a bromine atom is bonded to an aromatic ring, but does not include a compound having a portion where a bromine atom is also bonded to an aliphatic hydrocarbon group. Among these, the aromatic bromine compound is preferable from the viewpoint of low thermal expansion, high elasticity, and dielectric loss tangent (Df). Specific examples of the bromine compound include the following compounds.

[0054] [ka]

[0055] [ka]

[0056] (Content of (X) component and (Y) component) The contents of the (X) component and the (Y) component in the resin composition of this embodiment are not particularly limited, but are preferably 0.5 to 10 parts by mass of the (X) component and 0.5 to 7 parts by mass of the (Y) component relative to 100 parts by mass of the total amount of solids, more preferably 1.0 to 7 parts by mass of the (X) component and 1.5 to 7 parts by mass of the (Y) component, even more preferably 1.5 to 5 parts by mass of the (X) component and 2.5 to 6.0 parts by mass of the (Y) component, and particularly preferably 2.0 to 5 parts by mass of the (X) component and 3.5 to 5.5 parts by mass of the (Y) component. If the contents of the (X) component and the (Y) component are within the above numerical ranges, the thermal expansion and elasticity are low, and the dielectric loss tangent (Df) can be reduced.

[0057] ((B) Polymers Having Hydrocarbon Chains or Polyether Chains) The resin composition of the present embodiment may further contain a polymer having a hydrocarbon chain or a polyether chain as component (B). The polymer having a hydrocarbon chain or a polyether chain is preferably a polymer having a hydrocarbon chain or a polyether chain in the main chain. Here, in the present disclosure, the "main chain" refers to the relatively longest bond chain in the polymer molecule, and the "side chain" refers to an atomic group branched off from the main chain. When the resin composition of the present embodiment contains the component (B), the dielectric loss tangent (Df) tends to be further improved. In the component (B), the term "hydrocarbon chain" refers to a structure in which carbon atoms bonded to hydrogen atoms are linked in a chain, and the term "polyether chain" refers to a structure in which units containing polyether bonds are linked in a chain. The component (B) may be used alone or in combination of two or more types.

[0058] Examples of polymers having a hydrocarbon chain include conjugated diene polymers, styrene-based elastomers, and modified products thereof. Examples of polymers having a polyether chain include polyphenylene ether and modified products of polyphenylene ether. Among these, from the viewpoints of compatibility with other resins, dielectric loss tangent (Df) and heat resistance, polymers having a hydrocarbon chain are preferred, and conjugated diene polymers and styrene-based elastomers are more preferred. From the same viewpoint, conjugated diene polymers having vinyl groups in their side chains are preferred. Hereinafter, the conjugated diene polymer having a vinyl group in its side chain may be referred to as "conjugated diene polymer (B1)" or "component (B1)", and the styrene-based elastomer may be referred to as "styrene-based elastomer (B2)" or "component (B2)".

[0059] (Conjugated diene polymer (B1)) As described above, the component (B1) is a conjugated diene polymer having a vinyl group in the side chain. By using the component (B1) as the component (B), the dielectric loss tangent (Df) of the cured product of the obtained resin composition tends to be even better. The component (B1) may be used alone or in combination of two or more types.

[0060] The (B1) component is preferably a conjugated diene polymer having multiple vinyl groups in the side chains. The number of vinyl groups that the (B1) component has in one molecule is not particularly limited, but from the viewpoints of dielectric loss tangent (Df) and heat resistance, it is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more.

[0061] In the present disclosure, a conjugated diene polymer means a polymer of a conjugated diene compound. Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene. The conjugated diene polymer may be a polymer of one kind of conjugated diene compound, or may be a polymer of two or more kinds of conjugated diene compounds. The conjugated diene polymer may be a copolymer of one or more conjugated diene compounds and one or more monomers other than the conjugated diene compounds. In this case, the polymerization method is not particularly limited and may be any of random polymerization, block polymerization, and graft polymerization.

[0062] Specific examples of the (B1) component include polybutadiene having a 1,2-vinyl group, butadiene-styrene copolymer having a 1,2-vinyl group, polyisoprene having a 1,2-vinyl group, etc. Among these, from the viewpoint of dielectric loss tangent (Df) and heat resistance, polybutadiene having a 1,2-vinyl group and butadiene-styrene copolymer having a 1,2-vinyl group are preferred, and polybutadiene having a 1,2-vinyl group is more preferred. As the polybutadiene having a 1,2-vinyl group, butadiene homopolymer having a 1,2-vinyl group is preferred. The butadiene-derived 1,2-vinyl group contained in the component (B1) is a vinyl group contained in a structural unit derived from butadiene represented by the following formula (b1-1).

[0063] [ka]

[0064] When the (B1) component is a polybutadiene having a 1,2-vinyl group, the content of the structural unit having a 1,2-vinyl group with respect to all structural units derived from butadiene constituting the polybutadiene [hereinafter, sometimes referred to as "vinyl group content"] is not particularly limited, but from the viewpoints of compatibility with other resins, dielectric loss tangent (Df), low thermal expansion and heat resistance, it is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 85 mol% or more. There is no particular limit to the upper limit of the vinyl group content, and it may be 100 mol% or less, 97 mol% or less, or 95 mol% or less. As the structural unit having a 1,2-vinyl group, a structural unit derived from butadiene represented by the above formula (b1-1) is preferable. From the same viewpoint, the polybutadiene having a 1,2-vinyl group is preferably a 1,2-polybutadiene homopolymer.

[0065] The number average molecular weight of the (B1) component is not particularly limited, but from the standpoints of compatibility with other resins, dielectric tangent (Df), low thermal expansion, and heat resistance, it is preferably 400 to 4,000, more preferably 500 to 3,000, even more preferably 600 to 2,000, and particularly preferably 700 to 1,500.

[0066] (Styrene-based elastomer (B2)) There are no particular limitations on the component (B2) as long as it is an elastomer having a structural unit derived from a styrene-based compound. The component (B2) may be used alone or in combination of two or more types.

[0067] The component (B2) is preferably one having a structural unit derived from styrene and represented by the following general formula (b2-1).

[0068] [ka] (In the formula, R b5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R b6is an alkyl group having 1 to 5 carbon atoms. k is an integer of 0 to 5.

[0069] R b5 and R b6 Examples of the alkyl group having 1 to 5 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, etc. Among these, an alkyl group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 or 2 carbon atoms is more preferred, and a methyl group is even more preferred. k is preferably an integer of 0 to 2, more preferably 0 or 1, and further preferably 0.

[0070] Examples of structural units contained in the component (B2) other than those derived from styrene-based compounds include structural units derived from butadiene, structural units derived from isoprene, structural units derived from maleic acid, and structural units derived from maleic anhydride. The butadiene-derived structural unit and the isoprene-derived structural unit may be hydrogenated. When hydrogenated, the butadiene-derived structural unit is a structural unit having a mixture of ethylene units and butylene units, and the isoprene-derived structural unit is a structural unit having a mixture of ethylene units and propylene units.

[0071] As the (B2) component, from the viewpoints of dielectric tangent (Df), adhesion to a conductor, heat resistance, and low thermal expansion, one or more types selected from the group consisting of hydrogenated styrene-butadiene-styrene block copolymers (SEBS, SBBS), hydrogenated styrene-isoprene-styrene block copolymers (SEPS), and styrene-maleic anhydride copolymers (SMA) are preferred, one or more types selected from the group consisting of hydrogenated styrene-butadiene-styrene block copolymers (SEBS) and hydrogenated styrene-isoprene-styrene block copolymers (SEPS) are more preferred, and hydrogenated styrene-butadiene-styrene block copolymers (SEBS) are even more preferred.

[0072] In the above SEBS, the content of structural units derived from styrene [hereinafter may be referred to as "styrene content"] is not particularly limited, but from the viewpoints of low thermal expansion, dielectric loss tangent (Df), adhesion to a conductor, and heat resistance, it is preferably 5 to 80 mass%, more preferably 10 to 75 mass%, even more preferably 15 to 70 mass%, still more preferably 20 to 50 mass%, and particularly preferably 35 to 50 mass%.

[0073] The melt flow rate (MFR) of SEBS is not particularly limited, but is preferably 0.1 to 20 g / 10 min, more preferably 0.3 to 17 g / 10 min, and even more preferably 0.5 to 15 g / 10 min, measured under conditions of 230° C. and a load of 2.16 kgf (21.2 N).

[0074] Examples of commercially available SEBS products include the Tuftec (registered trademark) H series and M series manufactured by Asahi Kasei Corporation, the Septon (registered trademark) series manufactured by Kuraray Co., Ltd., and the Kraton (registered trademark) G Polymer series manufactured by Kraton Polymer Japan, Ltd.

[0075] The weight average molecular weight (Mw) of the (B2) component is not particularly limited, but is preferably 12,000 to 1,000,000, more preferably 30,000 to 500,000, even more preferably 50,000 to 120,000, and particularly preferably 70,000 to 100,000. The weight average molecular weight (Mw) is measured in terms of polystyrene by gel permeation chromatography (GPC), and more specifically, is a value measured by the measurement method described in the Examples.

[0076] [Content ratio of conjugated diene polymer (B1) and styrene-based elastomer (B2)] In the resin composition of the present embodiment, when the (B1) component and the (B2) component are used in combination, the content ratio of the (B1) component to the (B2) component [(B1) / (B2)] is not particularly limited, but from the viewpoints of moldability, compatibility with other resins, and dielectric loss tangent (Df), it is preferably 5 / 95 to 70 / 30, more preferably 10 / 90 to 60 / 40, even more preferably 15 / 85 to 50 / 50, and particularly preferably 20 / 80 to 40 / 60, on a mass basis.

[0077] (B) Component Content When the resin composition of the present embodiment contains the thermoplastic resin (B), the content of the thermoplastic resin (B) is not particularly limited, but is preferably 3 to 35 parts by mass, more preferably 5 to 30 parts by mass, even more preferably 10 to 30 parts by mass, and particularly preferably 15 to 30 parts by mass, relative to 100 parts by mass of the total solid content in the resin composition. If the content of the thermoplastic resin (B) is 3 parts by mass or more relative to 100 parts by mass of the total solid content in the resin composition, the dielectric loss tangent (Df) tends to be further improved, and if it is 35 parts by mass or less, the heat resistance and flame retardancy tend to be maintained well.

[0078] ((C) Inorganic filler) The resin composition of the present embodiment contains an inorganic filler as component (C) [hereinafter, may be referred to as inorganic filler (C)], and thus tends to have further improved low thermal expansion properties, elastic modulus, heat resistance, and flame retardancy. The inorganic filler (C) may be used alone or in combination of two or more kinds.

[0079] Examples of the inorganic filler (C) include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (calcined clay, etc.), molybdic acid compounds such as zinc molybdate, talc, aluminum borate, silicon carbide, etc. Among these, from the viewpoints of low thermal expansion, elastic modulus, heat resistance, and flame retardancy, silica, alumina, mica, and talc are preferred, silica and alumina are more preferred, and silica is even more preferred. Examples of silica include crushed silica, fumed silica, fused silica, and the like.

[0080] The particle size of the inorganic filler (C) is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, even more preferably 0.2 to 1 μm, and particularly preferably 0.3 to 0.8 μm. Here, the particle size of the inorganic filler (C) refers to the average particle size, and is the particle size at the point corresponding to 50% volume when the cumulative frequency distribution curve of the particle size is calculated with the total volume of the particles being 100%. The particle size of the inorganic filler (C) can be measured by a particle size distribution measuring device using a laser diffraction scattering method. The shape of the inorganic filler (C) may be spherical, crushed, or the like, with the spherical shape being preferred.

[0081] ((C) Component Content) When the resin composition of the present embodiment contains an inorganic filler (C), the content of the inorganic filler (C) in the resin composition is not particularly limited, but from the viewpoints of low thermal expansion, elastic modulus, and heat resistance, it is preferably 5 to 70 parts by mass, more preferably 15 to 65 parts by mass, even more preferably 20 to 60 parts by mass, particularly preferably 30 to 55 parts by mass, and most preferably 40 to 55 parts by mass, relative to 100 parts by mass of the total solid content.

[0082] When the resin composition of the present embodiment contains an inorganic filler (C), a coupling agent may be used to improve the dispersibility of the inorganic filler (C) and the adhesion to the organic component. The coupling agent is preferably a silane coupling agent. Examples of the silane coupling agent include aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, and silicone oligomer coupling agents. The coupling agents may be used alone or in combination of two or more. When a coupling agent is used, the surface treatment method of the inorganic filler (C) may be an integral blend treatment method in which the inorganic filler (C) is blended in the resin composition and then the coupling agent is added, or a method in which the inorganic filler (C) is previously surface-treated with the coupling agent in a dry or wet manner. Among these, the method in which the inorganic filler (C) is previously surface-treated with the coupling agent in a dry or wet manner is preferred from the viewpoint of more effectively expressing the characteristics of the inorganic filler (C). For the purpose of improving dispersibility in the resin composition, the inorganic filler (C) may be dispersed in an organic solvent in advance to form a slurry, which may then be mixed with the other components.

[0083] ((D) Curing Accelerator) The resin composition of the present embodiment contains a curing accelerator as component (D) [hereinafter, may be referred to as curing accelerator (D)], which tends to improve the curability, elastic modulus, dielectric loss tangent (Df), heat resistance, and adhesion to a conductor. The curing accelerator (D) may be used alone or in combination of two or more kinds.

[0084] Examples of the curing accelerator (D) include acid catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine, and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; isocyanate mask imidazole compounds such as an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; organic peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, and α,α'-bis(t-butylperoxy)diisopropylbenzene; and carboxylates such as manganese, cobalt, and zinc. Among these, from the viewpoints of heat resistance and storage stability, imidazole compounds, isocyanate-masked imidazole compounds, organic peroxides, and carboxylates are preferred, organic peroxides are more preferred, and α,α'-bis(t-butylperoxy)diisopropylbenzene is even more preferred.

[0085] ((D) Component Content) When the resin composition of the present embodiment contains a curing accelerator (D), the content of the curing accelerator (D) is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, even more preferably 0.1 to 6 parts by mass, and particularly preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the total of the resin components in the resin composition. When the content of the curing accelerator (D) is equal to or more than the lower limit, the elastic modulus, the dielectric loss tangent (Df), the heat resistance, and the adhesion to the conductor tend to be better. In addition, when the content of the curing accelerator (D) is equal to or less than the upper limit, the storage stability of the resin composition tends to be better.

[0086] (Other Ingredients) The resin composition of the present embodiment may further contain one or more selected from the group consisting of resin materials other than the above-mentioned components, antioxidants, flame retardants, flame retardant assistants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and other additives, as necessary. Each of these may be used alone or in combination of two or more. The amount of these used is not particularly limited, and may be used as necessary within a range that does not impair the effects of the present embodiment.

[0087] The resin composition of the present embodiment may be in a state of being dissolved or dispersed in an organic solvent, that is, in a state of a so-called “resin varnish.” Hereinafter, a resin composition containing an organic solvent may be referred to as a resin varnish. Examples of the organic solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon-based solvents such as toluene and xylene; ester-based solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, and ethyl acetate; amide-based solvents such as N-methylpyrrolidone, formamide, N-methylformamide, and N,N-dimethylacetamide; and alcohol-based solvents such as methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, and dipropylene glycol monopropyl ether. The organic solvent may be used alone or in combination of two or more. The solid content concentration in the resin varnish is preferably from 10 to 70 mass %, more preferably from 20 to 60 mass %, and even more preferably from 35 to 60 mass %.

[0088] [Prepreg] The prepreg of the present embodiment is a prepreg containing the maleimide resin composition of the present embodiment or a semi-cured product of the maleimide resin composition. The prepreg of the present embodiment contains, for example, the maleimide resin composition of the present embodiment or a semi-cured product of the maleimide resin composition and a sheet-like fiber substrate. The prepreg is formed using the maleimide resin composition or resin sheet of the present embodiment and a sheet-like fiber substrate, and can be obtained, for example, by impregnating or coating the maleimide resin composition or resin sheet of the present embodiment into a sheet-like fiber substrate, drying, and semi-curing (B-stage) as necessary. More specifically, the prepreg of the present embodiment can be produced, for example, by heating and drying in a drying oven at a temperature of 80 to 200° C. for 1 to 30 minutes to semi-cure (B-stage). Here, in the present disclosure, B-stage refers to bringing into a B-stage state as defined in JIS K6900 (1994). The amount of the maleimide resin composition used can be appropriately determined so that the solid content concentration derived from the maleimide resin composition in the prepreg after drying is 30 to 90 mass %. By setting the solid content concentration in the above range, better moldability tends to be obtained when the laminate is made.

[0089] As the sheet-like fiber substrate for the prepreg, a known one used in various laminates for electrical insulating materials is used. The sheet-like fiber substrate is not particularly limited, but is preferably a sheet-like fiber reinforcement substrate used for the purpose of reinforcing the prepreg. Examples of the material of the sheet-like fiber substrate include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet-like fiber substrates have shapes such as woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat. The thickness of the sheet-like fiber base material is not particularly limited, but may be, for example, 0.02 to 0.5 mm. In addition, the sheet-like fiber substrate may be surface-treated with a coupling agent or the like, or mechanically opened, from the viewpoints of impregnation with the maleimide resin composition, heat resistance, moisture absorption resistance, and processability when formed into a laminate.

[0090] As a method for impregnating or coating the maleimide resin composition on a sheet-like fiber substrate, the following hot melt method or solvent method can be used. The hot melt method is a method in which the maleimide resin composition does not contain an organic solvent, and (1) the maleimide resin composition is first coated onto a coated paper having good peelability from the maleimide resin composition, and then the coated paper is laminated onto a sheet-like fiber substrate, or (2) the maleimide resin composition is coated onto a sheet-like fiber substrate by a die coater. On the other hand, the solvent method is a method in which an organic solvent is added to a maleimide resin composition, and a sheet-shaped fiber substrate is immersed in the obtained maleimide resin composition to impregnate the maleimide resin composition into the sheet-shaped fiber substrate, and then the substrate is dried.

[0091] [Resin film] The resin film of the present embodiment is a resin film containing the maleimide resin composition of the present embodiment or a semi-cured product of the maleimide resin composition. The resin film of the present embodiment can be produced, for example, by applying a maleimide resin composition containing an organic solvent, i.e., a resin varnish, to a support, drying by heating, and semi-curing (B-staging) as necessary. Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride; polyester films such as polyethylene terephthalate (hereinafter also referred to as "PET") and polyethylene naphthalate; and various plastic films such as polycarbonate films and polyimide films. Metal foils such as copper foil and aluminum foil, and release paper may also be used as the support. The support may be subjected to a surface treatment such as a matte treatment or a corona treatment. The support may also be subjected to a release treatment using a silicone resin-based release agent, an alkyd resin-based release agent, a fluororesin-based release agent, or the like. The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, and more preferably 25 to 50 μm.

[0092] The method of applying the resin varnish to the support is not particularly limited, and any coating device known to those skilled in the art, such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, a die coater, etc., can be used. These coating devices may be appropriately selected depending on the film thickness. The drying temperature and drying time may be appropriately determined depending on the amount of organic solvent used and the boiling point of the organic solvent used, but for example, in the case of a resin varnish containing about 40 to 60 mass % of organic solvent, a resin film can be suitably formed by drying at 50 to 150°C for about 3 to 10 minutes.

[0093] [Laminate] The laminate of the present embodiment is a laminate having a cured product of the maleimide resin composition of the present embodiment or a cured product of the prepreg, and a metal foil. The laminate of the present embodiment can be produced, for example, by disposing a metal foil on one or both sides of a single prepreg of the present embodiment, or by disposing a metal foil on one or both sides of a prepreg obtained by stacking two or more prepregs of the present embodiment, and then by hot pressing. In the laminate obtained by this production method, the prepreg of the present embodiment is C-staged. In this disclosure, C-stage refers to bringing the prepreg into the C-stage state defined by JIS K6900 (1994). Note that a laminate having a metal foil is sometimes called a metal-clad laminate.

[0094] The metal of the metal foil is not particularly limited, but from the viewpoint of electrical conductivity, it may be copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing one or more of these metal elements, with copper and aluminum being preferred, and copper being more preferred. The conditions for hot and pressure molding are not particularly limited, but may be, for example, a temperature of 100 to 300° C., a pressure of 0.2 to 10 MPa, and a time of 0.1 to 5 hours. In addition, the hot and pressure molding may be performed using a vacuum press or the like to maintain a vacuum state for 0.5 to 5 hours.

[0095] [Printed wiring board] The printed wiring board of this embodiment has one or more selected from the group consisting of the cured product of the maleimide resin composition of this embodiment, the cured product of the prepreg, and the laminate of this embodiment. The printed wiring board of this embodiment can be manufactured by performing a circuit formation process by drilling, metal plating, etching of metal foil, etc. 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, and a multilayer printed wiring board can be manufactured by further performing a multilayer adhesion process as necessary. In the printed wiring board of this embodiment, the prepreg of this embodiment or the resin film of this embodiment is C-staged.

[0096] [Semiconductor package] The semiconductor package of the present embodiment is a semiconductor package having a printed wiring board and a semiconductor element. The semiconductor package of the present embodiment can be manufactured by mounting a semiconductor element such as a semiconductor chip or memory at a predetermined position on the printed wiring board of the present embodiment and sealing the semiconductor element with a sealing resin or the like.

[0097] The resin composition, prepreg, resin film, laminate, printed wiring board, and semiconductor package of the present embodiment can be suitably used in electronic devices that handle high-frequency signals of 10 GHz or more. In particular, the printed wiring board is useful as a printed wiring board for millimeter-wave radar. EXAMPLES

[0098] The present embodiment will be specifically described below with reference to examples, although the present embodiment is not limited to the following examples.

[0099] In each example, the number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by the following procedure. (Method of measuring number average molecular weight (Mn) and weight average molecular weight (Mw)) The number average molecular weight and weight average molecular weight were calculated by gel permeation chromatography (GPC) from a calibration curve using standard polystyrene. The calibration curve was approximated by a third-order equation using standard polystyrene: TSKstandard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, product name]. The measurement conditions for GPC are shown below. Equipment: High-speed GPC equipment HLC-8320GPC Detector: UV-8320 ultraviolet absorption detector [manufactured by Tosoh Corporation] Column: Guard column: TSK Guardcolumn SuperHZ-L + Column: TSKgel SuperHZM-N + TSKgel SuperHZM-M + TSKgel SuperH-RC (all product names manufactured by Tosoh Corporation) Column size: 4.6 x 20 mm (guard column), 4.6 x 150 mm (column), 6.0 x 150 mm (reference column) Eluent: Tetrahydrofuran Sample concentration: 10mg / 5mL Injection volume: 25μL Flow rate: 1.00mL / min Measurement temperature: 40℃

[0100] Examples 1 to 2, Comparative Examples 1 to 4 (Preparation of Maleimide Resin Composition and Resin Varnish) Each component shown in Table 1 was blended in the amount shown in Table 1 (the amount shown in Table 1 is the mass part of the solid content) and mixed in methyl ethyl ketone to obtain a resin composition (resin varnish) with a non-volatile content (solid content concentration) of 50 mass %. In Table 1, the unit of the blending amount of each component is parts by mass, and in the case of a solution or dispersion, it means parts by mass converted into solid content. (Preparation of prepregs) The resin varnish prepared in each example was impregnated into a glass cloth (Nitto Boseki Co., Ltd., #2116 type, E glass), and then heated and dried at 120°C for 5 minutes to obtain a prepreg with a resin composition content of 46 mass%. (Preparation of double-sided copper-clad laminates) A 12 μm thick electrolytic copper foil "3EC-M3-VLP-18" (product name, manufactured by Mitsui Mining & Smelting Co., Ltd.) was placed on both sides of the four layers of prepreg so that the adhesive surface was aligned with the prepreg, and the foil was heated and pressed at 230°C for 80 minutes under vacuum press conditions of 3 MPa to produce a double-sided copper-clad laminate. The double-sided copper-clad laminate thus obtained was subjected to various measurements according to the following measurement methods. The results are shown in Table 1.

[0101] [Measurement method] (1) Measurement method for thermal expansion coefficient The double-sided copper-clad laminate obtained in each example was immersed in a 10% by mass solution of ammonium persulfate, a copper etching solution, to remove the copper foil, and a 5 mm square evaluation board was prepared from the evaluation board. The evaluation board was subjected to a thermomechanical analysis by compression method using a thermomechanical measurement apparatus (TMA) [Model Q400, manufactured by TA Instruments Japan, Inc.]. After mounting the evaluation substrate in the X-direction on the device, measurements were performed twice under the measurement conditions of a load of 5 g and a temperature rise rate of 10°C / min. The average thermal expansion coefficient (average of linear thermal expansion coefficients in the plane direction) from 30°C to 100°C in the second measurement was calculated, and this was used as the thermal expansion coefficient (linear thermal expansion coefficient). The second measurement result was used in order to improve measurement accuracy.

[0102] (2) Elasticity measurement method The double-sided copper-clad laminate obtained in each example was immersed in a 10% by mass solution of ammonium persulfate, which is a copper etching solution, to remove the copper foil, and a 5 mm x 30 mm evaluation board was produced from the evaluation board. The storage modulus of the evaluation board at 25°C was measured using a dynamic viscoelasticity measuring device (manufactured by UBM Co., Ltd.). If the storage modulus at 25°C is 8.2 GPa or more, the effect of reducing warpage is good, which is preferable.

[0103] (3) Measurement method of dielectric tangent (Df) The double-sided copper-clad laminate obtained in each example was immersed in a 10 mass % solution of ammonium persulfate, which is a copper etching solution, to remove the copper foil, and then a 2 mm x 50 mm evaluation board was produced from the removed copper foil. The dielectric loss tangent (Df) of the evaluation substrate was measured in the 10 GHz band at an ambient temperature of 25° C. according to the cavity resonator perturbation method.

[0104] [Table 1]

[0105] The details of the components in each table are as follows: [Component (A)] Maleimide compound A-1: ​​Maleimide compound having a biphenylaralkyl skeleton "MIR-3000" (manufactured by Nippon Kayaku Co., Ltd., product name) Maleimide compound A-2: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide

[0106] [(X) component] Aromatic ring-containing phosphorus oxide compound X-1: A phosphorus oxide compound having the following structure [ka]

[0107] [(X') component] ·Non-aromatic ring-containing phosphorus oxide compound X'-2: Aluminum diethylphosphinate (see the structural formula below) [ka]

[0108] [(Y) component] Halogen compound: Decabromodiphenylethane (see the structural formula below) [ka]

[0109] [(B) Component] Conjugated diene polymer B1-1: 1,2-polybutadiene homopolymer, number average molecular weight = 3,200, vinyl group content = 90% or more Styrene-based elastomer B2-1: Hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene content = 42% by mass, weight average molecular weight 95,000

[0110] [(C) component] Inorganic filler C-1: Fused spherical silica treated with silane coupling, average particle size 0.5 μm [(D) component] Curing accelerator D-1: α,α'-bis(t-butylperoxy)diisopropylbenzene

[0111] As is clear from Table 1, the copper-clad laminates obtained in each Example had low thermal expansion, high elasticity, and a small dielectric dissipation factor (Df). On the other hand, in Comparative Example 1 and Comparative Example 4, which do not contain the (Y) component and instead increase the content of the (X) component, it is found that the low thermal expansion is insufficient, the elastic modulus is low, and the dielectric loss tangent (Df) is significantly worse than in Example 1 and Example 2, respectively. In Comparative Example 2, which does not contain the (X) component and instead increases the content of the (Y) component, it is found that the low thermal expansion is significantly insufficient and the elastic modulus is significantly lower than in Example 1. And, in Comparative Example 3, which uses a phosphorus oxide compound (aluminum diethylphosphinate) not containing an aromatic ring as the (X') component instead of the (X) component, it is found that the low thermal expansion is significantly insufficient, the elastic modulus is significantly lower, and the dielectric loss tangent (Df) is also significantly worse than in Example 1.

Claims

1. (A) one or more compounds selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof; (X) an aromatic ring-containing phosphorus oxide compound; (Y) a halogen compound; 1. A maleimide resin composition comprising:

2. 2. The maleimide resin composition according to claim 1, wherein the component (A) comprises at least one member selected from the group consisting of maleimide compounds having two or more N-substituted maleimide groups and derivatives thereof.

3. 2. The maleimide resin composition according to claim 1, wherein the component (X) comprises at least one selected from the group consisting of (X1) a phosphate compound, (X2) a phosphine oxide compound, and (X3) a phosphaphenanthrene compound.

4. 2. The maleimide resin composition according to claim 1, wherein the component (X) has two or more phosphorus atoms in one molecule.

5. 2. The maleimide resin composition according to claim 1, wherein the component (Y) is a bromine compound.

6. 2. The maleimide resin composition according to claim 1, further comprising (B) a polymer having a hydrocarbon chain or a polyether chain.

7. 2. The maleimide resin composition according to claim 1, further comprising (C) an inorganic filler.

8. 2. The maleimide resin composition according to claim 1, further comprising (D) a curing accelerator.

9. A prepreg comprising the maleimide resin composition according to claim 1 or a semi-cured product of the maleimide resin composition.

10. A resin film comprising the maleimide resin composition according to claim 1 or a semi-cured product of the maleimide resin composition.

11. A laminate comprising the cured product of the maleimide resin composition according to claim 1 and a metal foil.

12. A printed wiring board having a cured product of the maleimide resin composition according to claim 1.

13. A semiconductor package comprising the printed wiring board according to claim 12 and a semiconductor element.

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