KR-20260066086-A - Resin composition, cured product, prepreg, metal foil-clad laminate, resin composite sheet, printed circuit board, and semiconductor device

Abstract

Provides a resin composition, and, a cured product, prepreg, a metal foil-clad laminate, a resin composite sheet, a printed circuit board, and a semiconductor device. A resin composition comprising a resin (A) having a terminal group represented by formula (T1) and also having a terminal skeleton, and a maleimide compound (B), wherein the relative permittivity at a frequency of 10 GHz measured by the cavity resonator perturbation method of the cured maleimide compound (B) is 2.0 to 2.8. In formula (T1), Ma represents a hydrocarbon group having 1 to 12 carbon atoms that may each be independently substituted with a halogen atom, and x represents an integer from 0 to 4. * indicates a bonding position with other parts.

Inventors

• 이토 사야카
• 도쿠나가 나오야
• 야마모토 가츠야
• 하세베 게이이치

Assignees

• 미츠비시 가스 가가쿠 가부시키가이샤

Dates

Publication Date

20260512

Application Date

20240912

Priority Date

20230913

Claims (20)

1. A resin (A) having a terminal group represented by formula (T1) and also having a terminal skeleton, and It includes a maleimide compound (B), A cured product of the above maleimide compound (B) having a relative permittivity of 2.0 to 2.8 at a frequency of 10 GHz measured by the cavity resonator perturbation method, Resin composition. (In Equation (T1), Ma represents a hydrocarbon group having 1 to 12 carbon atoms that may each be independently substituted with a halogen atom, and x represents an integer from 0 to 4. * indicates a bonding position with other sites.)
2. In Article 1, A resin composition comprising the above resin (A), wherein the resin is represented by the formula (T1-1). (In Equation (T1-1), R is a group containing the constituent unit represented by Equation (Tx). Ma represents a hydrocarbon group having 1 to 12 carbon atoms that may each be independently substituted with a halogen atom. x is an integer from 0 to 4.) (In Equation (Tx), n, o, and p are the average number of repeating units, n represents a number greater than 0 and less than or equal to 20, o and p each independently represent numbers from 0 to 20, and 1.0 ≤ n + o + p ≤ 20.0. Ma each independently represents a hydrocarbon group having 1 to 12 carbon atoms that may be substituted with a halogen atom. x represents an integer from 0 to 4. Constituent units (a), (b), and (c) are each bonded to constituent units (a), (b), (c) or other groups in *, and each constituent unit may be bonded randomly.)
3. In Article 1, A resin composition having 1.1 ≤ n + o + p ≤ 20.0 in the constituent unit represented by the above formula (Tx).
4. In Article 1, Of the above resin (A) The parameter α calculated from equation (α) is between 0.55 and 1.00, and A parameter β calculated from equation (β) that is 0.20 or greater and 3.00 or less, Resin composition. (The values inside the parentheses in Equations (α) and (β) represent the integral between the corresponding chemical shift values in 1H -NMR.)
5. In Article 1, The above resin (A) comprises a resin represented by formula (T1-1), and Of the above resin (A) The parameter α calculated from equation (α) is between 0.55 and 1.00, and A parameter β calculated from equation (β) that is 0.20 or greater and 3.00 or less, Resin composition. (The values inside the parentheses in Equations (α) and (β) represent the integral between the corresponding chemical shift values in 1H -NMR.) (In Equation (T1-1), R is a group containing the constituent unit represented by Equation (Tx). Ma represents a hydrocarbon group having 1 to 12 carbon atoms that may each be independently substituted with a halogen atom. x is an integer from 0 to 4.) (In Equation (Tx), n, o, and p are the average number of repeating units, n represents a number greater than 0 and less than or equal to 20, o and p each independently represent numbers from 0 to 20, and 1.0 ≤ n + o + p ≤ 20.0. Ma each independently represents a hydrocarbon group having 1 to 12 carbon atoms that may be substituted with a halogen atom. x represents an integer from 0 to 4. Constituent units (a), (b), and (c) are each bonded to constituent units (a), (b), (c) or other groups in *, and each constituent unit may be bonded randomly.)
6. In Article 1 or Article 5, A resin composition having a number average molecular weight of the resin (A) of 400 to 3000 and a weight average molecular weight of the resin (A) of 500 to 6000.
7. In Article 1 or Article 5, A resin composition having a ratio of the weight-average molecular weight of the resin (A) to the number-average molecular weight of the resin (A), Mw/Mn, of 1.1 to 3.0.
8. In Article 1 or Article 5, A resin composition having a content of 5 to 90 parts by mass of the resin (A) relative to 100 parts by mass of the resin solid content in the resin composition.
9. In Article 1 or Article 5, A resin composition having a content of 5 to 90 parts by mass of the maleimide compound (B) per 100 parts by mass of the resin solid content in the resin composition.
10. In Article 1 or Article 5, A resin composition comprising one or more selected from the group consisting of the maleimide compound (B) represented by formula (M0), the compound represented by formula (M1), the compound represented by formula (M3), the compound represented by formula (M5), and the compound represented by formula (M7). (In formula (MO), R 51 each independently represents a hydrogen atom, a C1-C8 alkyl group, or a phenyl group, R 52 each independently represents a hydrogen atom or a methyl group, and n 1 represents an integer greater than or equal to 1.) (In formula (M1), RM1 , RM2 , RM3 , and RM4 each independently represent a hydrogen atom or an organic group. RM5 and RM6 each independently represent a hydrogen atom or an alkyl group. ArM represents a divalent aromatic group. A is a 4- to 6-membered ring alicyclic group. RM7 and RM8 each independently represent an alkyl group. mx is 1 or 2, and lx is 0 or 1. RM9 and RM10 each independently represent a hydrogen atom or an alkyl group. RM11 , RM12 , RM13 , and RM14 each independently represent a hydrogen atom or an organic group. RM15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms Represents an alkylthio group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group. px represents an integer from 0 to 3. nx represents an integer from 1 to 20.) (In formula (M3), R 55 each independently represents a hydrogen atom, a C1-C8 alkyl group, or a phenyl group, and n 5 represents an integer from 1 to 10.) (In formula (M5), R 58 each independently represents a hydrogen atom, a C1-C8 alkyl group, or a phenyl group, R 59 each independently represents a hydrogen atom or a methyl group, and n 6 represents an integer greater than or equal to 1.) (In the above formula (M7), R1 each independently represents an alkyl group having 1 to 10 carbon atoms, and R2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkylthio group; an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, R3 , R4 , R5 , and R6 each independently represent a hydrogen atom or a methyl group, and also one side of R3 and R4 is a hydrogen atom and the other is a methyl group, and one side of R5 and R6 is a hydrogen atom and the other is a methyl group, and X 1 is, the following expression (x): (In formula (x), R7 and R8 each independently represent a hydrogen atom or a methyl group, and one of R7 and R8 is a hydrogen atom and the other is a methyl group, and R9 each independently represents a C1- to C10 alkyl group, alkoxy group, or alkylthio group; a C6- to C10 aryl group, aryloxy group, or arylthio group; a C3- to C10 cycloalkyl group; a halogen atom; a hydroxyl group; or a mercapto group, and t represents an integer from 0 to 4.) It represents a substituent denoted by , where r is the average value of the number of X1 substituents per benzene ring to which X1 is attached, and represents a number from 0 to 4, p represents an integer from 1 to 3, q represents an integer from 0 to 4, and k represents an integer from 1 to 100.)
11. In Article 1 or Article 5, Additionally, a resin composition comprising a compound having two or more polymerizable carbon-carbon unsaturated double bonds.
12. In Article 11, A resin composition comprising at least one compound having two or more polymerizable carbon-carbon unsaturated double bonds selected from the group consisting of vinylaryl compounds, (meth)acrylate compounds, and (meth)allyl compounds.
13. In Article 12, A resin composition comprising at least one selected from the group consisting of a polymerizable compound having two or more carbon-carbon unsaturated double bonds, a polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds at the terminals, and a polymer having a structural unit represented by formula (V). (In Equation (V), Ar represents an aromatic hydrocarbon linker. * indicates a bonding position.)
14. In Article 1, The above resin (A) comprises a resin represented by formula (T1-1), and In the constituent unit represented by the above equation (Tx), 1.1 ≤ n + o + p ≤ 20.0, and Of the above resin (A) The parameter α calculated from equation (α) is between 0.55 and 1.00, and The parameter β calculated from equation (β) is between 0.20 and 3.00, and The number average molecular weight of the resin (A) is 400 to 3000, and the weight average molecular weight of the resin (A) is 500 to 6000, and The ratio of the weight-average molecular weight of the resin (A) to the number-average molecular weight of the resin (A), Mw/Mn, is 1.1 to 3.0, and The content of the resin (A) is 5 to 90 parts by mass per 100 parts by mass of the resin solid content in the resin composition, and The content of the maleimide compound (B) is 5 to 90 parts by mass per 100 parts by mass of resin solids in the resin composition, and A resin composition comprising one or more selected from the group consisting of the maleimide compound (B) represented by formula (M0), the compound represented by formula (M1), the compound represented by formula (M3), the compound represented by formula (M5), and the compound represented by formula (M7). (The values inside the parentheses in Equations (α) and (β) represent the integral between the corresponding chemical shift values in 1H -NMR.) (In Equation (T1-1), R is a group containing the constituent unit represented by Equation (Tx). Ma represents a hydrocarbon group having 1 to 12 carbon atoms that may each be independently substituted with a halogen atom. x is an integer from 0 to 4.) (In Equation (Tx), n, o, and p are the average number of repeating units, n represents a number greater than 0 and less than or equal to 20, o and p each independently represent numbers from 0 to 20, and 1.0 ≤ n + o + p ≤ 20.0. Ma each independently represents a hydrocarbon group having 1 to 12 carbon atoms that may be substituted with a halogen atom. x represents an integer from 0 to 4. Constituent units (a), (b), and (c) are each bonded to constituent units (a), (b), (c) or other groups in *, and each constituent unit may be bonded randomly.) (In formula (MO), R 51 each independently represents a hydrogen atom, a C1-C8 alkyl group, or a phenyl group, R 52 each independently represents a hydrogen atom or a methyl group, and n 1 represents an integer greater than or equal to 1.) (In formula (M1), RM1 , RM2 , RM3 , and RM4 each independently represent a hydrogen atom or an organic group. RM5 and RM6 each independently represent a hydrogen atom or an alkyl group. ArM represents a divalent aromatic group. A is a 4- to 6-membered ring alicyclic group. RM7 and RM8 each independently represent an alkyl group. mx is 1 or 2, and lx is 0 or 1. RM9 and RM10 each independently represent a hydrogen atom or an alkyl group. RM11 , RM12 , RM13 , and RM14 each independently represent a hydrogen atom or an organic group. RM15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms Represents an alkylthio group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group. px represents an integer from 0 to 3. nx represents an integer from 1 to 20.) (In formula (M3), R 55 each independently represents a hydrogen atom, a C1-C8 alkyl group, or a phenyl group, and n 5 represents an integer from 1 to 10.) (In formula (M5), R 58 each independently represents a hydrogen atom, a C1-C8 alkyl group, or a phenyl group, R 59 each independently represents a hydrogen atom or a methyl group, and n 6 represents an integer greater than or equal to 1.) (In the above formula (M7), R1 each independently represents an alkyl group having 1 to 10 carbon atoms, and R2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkylthio group; an aryl group having 6 to 10 carbon atoms, an aryloxy group or an arylthio group; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, R3 , R4 , R5 , and R6 each independently represent a hydrogen atom or a methyl group, and also one side of R3 and R4 is a hydrogen atom and the other is a methyl group, and one side of R5 and R6 is a hydrogen atom and the other is a methyl group, and X 1 is, the following expression (x): (In formula (x), R7 and R8 each independently represent a hydrogen atom or a methyl group, and one of R7 and R8 is a hydrogen atom and the other is a methyl group, and R9 each independently represents a C1- to C10 alkyl group, alkoxy group, or alkylthio group; a C6- to C10 aryl group, aryloxy group, or arylthio group; a C3- to C10 cycloalkyl group; a halogen atom; a hydroxyl group; or a mercapto group, and t represents an integer from 0 to 4.) It represents a substituent denoted by , where r is the average value of the number of X1 substituents per benzene ring to which X1 is attached, and represents a number from 0 to 4, p represents an integer from 1 to 3, q represents an integer from 0 to 4, and k represents an integer from 1 to 100.)
15. In Article 14, Additionally, a resin composition comprising a compound having two or more polymerizable carbon-carbon unsaturated double bonds.
16. In Article 15, A resin composition comprising at least one compound having two or more polymerizable carbon-carbon unsaturated double bonds selected from the group consisting of vinylaryl compounds, (meth)acrylate compounds, and (meth)allyl compounds.
17. In Article 16, A resin composition comprising at least one selected from the group consisting of a vinylaryl compound having two or more carbon-carbon unsaturated double bonds at the terminals, and a polymer having a structural unit represented by formula (V). (In Equation (V), Ar represents an aromatic hydrocarbon linker. * indicates a bonding position.)
18. In any one of Articles 1 to 5 and Articles 14 to 17, Additionally, a resin composition comprising a filler.
19. In Article 18, A resin composition comprising one or more fillers selected from the group consisting of silica, aluminum hydroxide, talc, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate.
20. In Article 18, A resin composition in which the content of the filler in the above resin composition is 1 to 1600 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

Description

Resin composition, cured product, prepreg, metal foil-clad laminate, resin composite sheet, printed circuit board, and semiconductor device The present invention relates to a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed circuit board, and a semiconductor device. Recently, the high integration and miniaturization of semiconductor devices used in mobile terminals, electronic devices, and communication equipment are accelerating. Along with this, technologies that enable high-density mounting of semiconductor devices are required, and improvements are also needed for printed circuit boards, which occupy a critical position in this process. Meanwhile, the applications of electronic devices and the like continue to diversify and expand. Consequently, the various characteristics required for printed circuit boards, the metal foil-clad laminates and prepregs used therein, and others are becoming more diverse and stringent. To obtain improved printed circuit boards while considering these required characteristics, various materials and processing methods have been proposed. One such example is the development of improved resin materials that constitute prepregs and resin composite sheets. Patent Document 1 discloses a resin having an isopropenphenyl group at the end and also having a terminal backbone, as a preferred material for semiconductor encapsulating materials and printed circuit boards. Figure 1 shows the 1H -NMR chart of the resin obtained in Synthesis Example 1. Hereinafter, a form for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Furthermore, the following present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment. Additionally, in this specification, "∼" is used to mean including the numerical values described before and after it as lower and upper limits. In this specification, various physical properties and characteristic values are defined as being at 23°C unless specifically described otherwise. In the notation of a group (atomic group) in this specification, notations that do not indicate substitution or non-substitution include groups (atomic groups) that have substituents, as well as groups (atomic groups) that do not have substituents. For example, "alkyl group" includes not only alkyl groups that do not have substituents (non-substituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups). In this specification, for notations that do not indicate substitution or non-substitution, it is preferable that they be non-substituted. In this specification, "(meth)allyl group" represents both allyl and metaallyl, or either; "(meth)acrylate" represents both acrylate and methacrylate, or either; "(meth)acryl" represents both acryl and methacryl, or either; and "(meth)acryloyl" represents both acryloyl and methacryloyl, or either. In this specification, the term "process" is used not only for independent processes but also for cases where the process cannot be clearly distinguished from other processes, provided that the intended function of the process is achieved. In cases where measurement methods, etc. described by the standards in this specification differ from year to year, unless specifically stated otherwise, they shall be based on the standards as of January 1, 2023. In the present specification, the term "resin solids" refers to components excluding fillers and solvents, and is intended to include resin (A), maleimide compound (B), and other components blended as needed, compounds having two or more polymerizable carbon-carbon unsaturated double bonds, and resin additive components (additives such as curing accelerators, flame retardants, etc.). In this specification, the terms dielectric constant and dielectric constant are used interchangeably. The resin composition of the present embodiment comprises a resin (A) having a terminal group represented by formula (T1) and also having a terminal skeleton (in this specification, it may be simply referred to as “resin (A)”) and a maleimide compound (B), and is characterized in that the relative permittivity at a frequency of 10 GHz measured by the cavity resonator perturbation method of the cured product of the maleimide compound (B) is 2.0 to 2.8. [Chemical Formula 26] (In Equation (T1), Ma represents a hydrocarbon group having 1 to 12 carbon atoms that may each be independently substituted with a halogen atom, and x represents an integer from 0 to 4. * indicates a bonding position with other sites.) By configuring it in this way, a resin composition is obtained that can provide a cured product with excellent low dielectric properties (Dk and Df) and also excellent heat resistance. The inventors have discovered the possibility that a resin (A) having an indan framework can provide a cured product