Curable resin composition for hybrid bonding, and method for producing circuit connection body

Abstract

Provided is a curable resin composition for hybrid bonding, the composition comprising a maleimide compound having a maleimide group, and a reactive component different from the maleimide compound. The reactive component includes a styrene-based compound having a reactive group obtained by removing one or more hydrogen atoms bonded to a benzene ring from a compound represented by formula (I). R1 and R2 are each independently a hydrogen atom or a C1-C3 alkyl group.

Description

Curable resin composition for hybrid bonding and method for producing circuit connector

[0001] The present disclosure relates to a curable resin composition for hybrid bonding and a method for producing a circuit connection structure.

[0002] In the three-dimensional packaging of semiconductor chips, hybrid bonding, which bonds electrodes and insulating films, has been considered for miniaturization of wiring. It has also been proposed to form the insulating film for hybrid bonding using a resin material such as polyimide (Patent Document 1).

[0003] On the other hand, it is known that compositions containing maleimide compounds and allyl compounds are thermally cured by addition reactions including ene reactions and Diels-Alder reactions or radical polymerization (Non-Patent Document 1).

[0004] International Publication No. 2020 / 085183

[0005] Handbook of Thermoset Plastics, Third Edition, 2014, p. 459-510

[0006] An organic insulating film formed from a resin material is expected to be advantageous compared to an inorganic insulating film in terms of reducing the influence of particles, etc. The present disclosure relates to a curable resin composition containing a maleimide compound, which can form an insulating film for hybrid bonding by heating at a low temperature.

[0007] The present disclosure includes the following: [1] A compound comprising: a maleimide compound having a maleimide group; and a reactive component other than the maleimide compound, wherein the reactive component is represented by the following formula (I): and a styrene-based compound having a reactive group which is a group obtained by removing one or more hydrogen atoms bonded to a benzene ring from a compound represented by R １ and R ２ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. [2] The styrene-based compound is represented by the following formula (11) or (12): is a polymer containing a structural unit represented by R １ and R ２ is R in formula (1) １ and R ２ is defined similarly to L １ is a single bond or a divalent organic group, and R １１ is an alkyl group having 1 to 3 carbon atoms, p is an integer of 0 to 3, and L ２ is a single bond or a divalent organic group, and R １２

[0023] The curable resin composition for hybrid bonding according to [1], wherein is an alkyl group having 1 to 3 carbon atoms, and q is an integer of 0 to 4.

[0024]

[0025] The curable resin composition for hybrid bonding according to [1], wherein the polymer is a compound represented by the following formula (20): Further containing a structural unit represented by L ３ is a single bond or a divalent organic group, and R １３

[0013] The curable resin composition for hybrid bonding according to [2], wherein is an alkyl group having 1 to 3 carbon atoms, and r is an integer of 0 to 4. [4] The curable resin composition for hybrid bonding according to [2], comprising: a maleimide compound having a maleimide group; and a reactive component other than the maleimide compound, wherein the reactive component is a compound represented by the following formula (II): [5] A method for producing a circuit-connected structure comprising a first circuit member having a first electrode and a second circuit member having a second electrode, the method comprising: heating a first resin film including a portion provided around the first electrode to thereby form a first insulating film; and joining the first circuit member and the second circuit member having the second electrode and a second insulating film including a portion provided around the second electrode by hybrid bonding so that the first electrode and the second electrode are electrically connected, wherein the first resin film comprises the curable resin composition for hybrid bonding according to any one of [1] to [4]. [6] A method for manufacturing a circuit connection body comprising a first circuit member having a first electrode and a second circuit member having a second electrode, the method comprising: heating a first resin film including a portion provided around the first electrode, thereby forming a first insulating film; heating a second resin film including a portion provided around the second electrode, thereby forming a second insulating film; and joining the first circuit member and the second circuit member by hybrid bonding so that the first electrode and the second electrode are electrically connected, wherein the first resin film and the second resin film comprise the curable resin composition for hybrid bonding according to any one of [1] to [4].

[0008] A curable resin composition containing a maleimide compound is provided, which can form an insulating film for hybrid bonding by heating at a low temperature.

[0009] 1A and 1B are process diagrams showing an example of a method for manufacturing a circuit-connected body; 2A and 2B are process diagrams showing an example of a method for manufacturing a circuit-connected body; 3A and 3B are process diagrams showing an example of a method for manufacturing a circuit-connected body;

[0010] The present invention is not limited to the following examples.

[0011] 1, 2, and 3 are process diagrams illustrating an example of a method for manufacturing a circuit connection body. The method illustrated in FIGS. 1 to 3 includes preparing a first circuit member 10 having a first substrate 11, a first electrode 12, and a first insulating film 13; preparing a second circuit member 20 having a second substrate 21, a second electrode 22, and a second insulating film 23; and joining the first circuit member 10 and the second circuit member 20 by hybrid bonding so that the first electrode 12 and the second electrode 22 are electrically connected. This method forms a circuit connection body 1, which is a bonded assembly of the first circuit member 10 and the second circuit member 20. In hybrid bonding, for example, the first circuit member 10 and the second circuit member 20 are heated and pressurized, thereby bonding the first circuit member 10 and the second circuit member 20 so that the first insulating film 13 and the second insulating film 23 are bonded together and the first electrode 12 and the second electrode 22 are bonded together.

[0012] At least one of the first substrate 11 or the second substrate 21 may be a semiconductor substrate having a circuit surface. In this case, a semiconductor device is obtained as the circuit-connected body 1. Typically, an integrated circuit is provided on the circuit surface side of the semiconductor substrate. For example, the first substrate 11 may be a semiconductor wafer, and the second substrate 21 may be a semiconductor chip. A plurality of second circuit members 20 having semiconductor chips may be bonded to a single first circuit member 10 having a semiconductor wafer. In this case, the semiconductor wafer (first substrate 11) of the obtained circuit-connected body may be singulated into a plurality of semiconductor chips. The semiconductor substrate may be, for example, a silicon substrate. When the first circuit member 10 or the second circuit member 20 is not a semiconductor substrate, they may be various types of wiring substrates (e.g., interposers).

[0013] The first circuit member 10 has a plurality of first electrodes 12, and a first insulating film 13 is provided around the first electrodes 12 and includes a portion filling the gaps between the plurality of first electrodes 12. The first electrodes 12 and the first insulating film 13 are provided on a first substrate 11. When the first substrate 11 is a semiconductor substrate having a circuit surface, the first electrodes 12 and the first insulating film 13 are provided on the circuit surface. The first insulating film 13 forms a plurality of openings 13a which are through holes exposing the first substrate 11, and the first electrodes 12 are provided in the openings 13a.

[0014] The second circuit member 20 has a plurality of second electrodes 22, and the second insulating film 23 is provided around the second electrodes 22 and includes a portion that fills the gaps between the plurality of second electrodes 22. The second electrodes 22 and the second insulating film 23 are provided on a second substrate 21. When the second substrate 21 is a semiconductor substrate, the second electrodes 22 and the second insulating film 23 are provided on the circuit surface. The second insulating film 23 forms a plurality of openings 23a that are through holes that expose the second substrate 21, and the second electrodes 22 are provided in the openings 23a.

[0015] The first circuit member 10 is prepared by a method including providing a first electrode 12 on a main surface 11S of a first substrate as shown in FIG. 1(a), forming a first resin film 13A on the main surface 11S of the first substrate 11 facing the first electrode 12 as shown in FIG. 1(b), and forming a first insulating film 13 from the first resin film 13A by heating the first resin film 13A as shown in FIG. 1(c).

[0016] The first electrode 12 is made of a conductive material containing a metal such as copper. The first electrode 12 containing a metal can be formed by a common method such as plating.

[0017] The first resin film 13A is formed, for example, by applying a curable resin composition having fluidity. The curable resin composition having fluidity may contain a solvent. When a curable resin composition containing a solvent is used, the first resin film 13A can be formed by heating the applied curable resin composition to remove the solvent. The heating temperature for removing the solvent may be, for example, 60°C or higher and 150°C or lower. The first resin film 13A may be formed to cover the entire first electrodes 12 while filling the gaps between the multiple first electrodes 12. By heating the formed first resin film 13A, the first resin film 13A is cured or semi-cured, and the first insulating film 13 is formed.

[0018] The curable resin composition used to form the first resin film 13A may contain a maleimide compound having a maleimide group and a reactive component other than the maleimide compound. The reactive component is a compound involved in the curing reaction of the curable resin composition and may include a styrene-based compound, an allyl compound, or both. A curable resin composition containing a combination of a maleimide compound and a specific reactive component can be cured or semi-cured at a relatively low temperature to form an insulating film by the progress of a curing reaction involving the maleimide compound and the reactive component. The ability to cure at low temperatures is also advantageous in terms of reducing thermal damage to the first circuit board, etc. Furthermore, since the curing reaction is primarily an addition reaction such as radical polymerization and Diels-Alder reaction, it is less likely to generate volatile components due to elimination components. Details of the styrene-based compound and the allyl compound will be described later.

[0019] The surface of the first insulating film 13 formed from the curable resin composition containing the maleimide compound may contain many functional groups derived from maleimide groups, etc. Therefore, the first insulating film 13 may exhibit good bonding properties without necessarily requiring an activation treatment such as a plasma treatment. In addition, it may be possible to adjust the polishing rate of the first insulating film 13 based on the crosslink density, etc., of the first insulating film 13.

[0020] The temperature to which the first resin film 13A is heated before the first circuit member 10 and the second circuit member 20 are bonded may be, for example, 90° C. or higher and 250° C. or lower, or 90° C. or higher and 160° C. or lower. The heating time may be, for example, 10 minutes or higher and 150 minutes or lower. The heating conditions may be adjusted so that the first resin film 13A is semi-cured.

[0021] When the formed first insulating film 13 covers the first electrode 12 as shown in FIG. 1C , a portion of the first insulating film 13 is removed from the side opposite the first substrate 11, thereby forming an opening 13a in the first insulating film 13 that exposes the first electrode 12 as shown in FIG. 2D . The portion of the first insulating film 13 may be removed by polishing. A conventional polishing method, such as chemical mechanical polishing (CMP), may be used. The polishing may also remove a portion of the first electrode 12, thereby planarizing the tip surface of the first electrode 12 (the surface opposite the first substrate 11). Depending on the polishing rate, the height of the first electrode 12 may be greater than the thickness of the first insulating film 13 in the polished first circuit member 10. The difference between the height of the first electrode 12 and the thickness of the first insulating film 13 may be adjusted taking into account the difference in the linear thermal expansion coefficients of the first electrode 12 and the first insulating film 13, for example. The difference between the height of the first electrode 12 and the thickness of the first insulating film 13 may be, for example, 0.1 μm or more and 0.5 μm or less. The thickness of the first insulating film 13 may be, for example, not less than 1 μm and not more than 100 μm.

[0022] The second insulating film 23 of the second circuit member 20 can be an organic insulating film or an inorganic insulating film. When the second insulating film 23 is an organic insulating film, the second circuit member can be prepared using a curable resin composition in the same manner as the first circuit member 10. When both the first insulating film 13 and the second insulating film 23 are organic insulating films formed from a curable resin composition containing a maleimide compound, particularly good bonding properties are likely to be exhibited. The first insulating film 13 and the second insulating film 23 can be formed from a second resin film using the same or different curable resin compositions.

[0023] The shapes of the first electrode 12 and the second electrode 22 are not particularly limited, but some or all of these electrodes are arranged so that the first electrode 12 and the second electrode 22 face each other and are bonded to each other. The widths of the first electrode 12 and the second electrode 22 may be, for example, 1 μm or more or 100 μm or more, and 300 μm or less or 30 μm or less. Here, width refers to the maximum width of each electrode in a direction parallel to the main surface (circuit surface) of the first substrate 11 or the second substrate 21. The spacing between adjacent first electrodes 12 and adjacent second electrodes 22 may be, for example, 1 μm or more or 100 μm or more, and 300 μm or less or 30 μm or less. The heights of the first electrodes 12 and the second electrodes 22 may be, for example, 1 μm or more or 10 μm or more, and 100 μm or less or 10 μm or less. The height of the first electrode 12 may be the same as or different from the thickness of the first insulating film 13. The height of the second electrode 22 may be the same as or different from the thickness of the second insulating film 23.

[0024] From the viewpoint of bonding between electrodes, the surface of the tip of the first electrode 12 may have a surface roughness Ra of 1 nm or less. The surface of the tip of the second electrode 22 may also have a similar surface roughness Ra. The surface roughness Ra here is the arithmetic mean roughness (Ra) defined in JIS B 0601-2001.

[0025] 2(e), the prepared first circuit member 10 and second circuit member 20 are aligned so that the first electrode 12 and second electrode 22 to be bonded face each other. Then, as shown in FIG. 3, the first circuit member 10 and second circuit member 20 are heated and pressurized to bond the first electrode 12 and second electrode 22 and to bond the first insulating film 13 and second insulating film 23 together by hybrid bonding.

[0026] The bonding of the first electrode 12 and the second electrode 22 and the bonding of the first insulating film 13 and the second insulating film 23 may proceed simultaneously or sequentially. For example, after heating and pressurizing mainly for bonding the first insulating film 13 and the second insulating film 23, the first circuit member 10 and the second circuit member 20 may be further heated and pressurized to bond the first electrode 12 and the second electrode 22. The first insulating film 13 and / or the second insulating film 23 may be in a semi-cured state before bonding. In this case, the first insulating film 13 and / or the second insulating film 23 may be further cured during the heating and pressurizing for bonding the first circuit member 10 and the second circuit member 20. The first insulating film 13 and / or the second insulating film 23 may be further cured by heating after bonding.

[0027] The conditions for heating and pressing for bonding are adjusted so that the insulating film and the electrode are properly bonded. For example, the heating temperature for bonding may be 100° C. or higher and 250° C. or lower, and the pressure for bonding may be 1.0 MPa or higher and 5.0 MPa or lower. The heating and pressing time may be, for example, 10 seconds or higher and 1 hour or lower.

[0028] Curable Resin Composition The curable resin composition used to form the organic insulating film (first insulating film 13 and / or second insulating film 23) for hybrid bonding in the above-described production method can be a curable resin composition (curable maleimide resin composition) containing a maleimide compound having a maleimide group and a reactive component.

[0029] The maleimide compound is a compound having one or more maleimide groups. From the viewpoints of heat resistance and a reduced thermal expansion coefficient of the insulating film, the curable resin composition may contain a maleimide compound having two or more maleimide groups.

[0030] The maleimide compound may have a maleimide group containing a nitrogen atom directly bonded to a cyclic group (e.g., an aromatic group). For example, the maleimide compound in the curable resin composition may include a compound represented by the following formula (IIIa), (IIIb), or (IIIc):

[0031] In formula (IIIa), Q １ and Q ２each independently represents a cyclic group which may have a substituent, and L ５ is a divalent organic group or a single bond. １ and Q ２ may each independently be an aromatic group (e.g., a phenylene group) which may have a substituent (e.g., an alkyl group having 1 to 3 carbon atoms). ５ may be a group containing one or more cyclic groups (excluding a maleimide group) selected from a monocyclic ring, a fused ring, a non-fused bridged ring, and a spiro ring, which may have a substituent, an alkylene group having 1 to 5 carbon atoms which may have a substituent (for example, a methylene group, a propane-1,3-diyl group, or a propane-2,2-diyl group), or a single bond. ５ may have two or more cyclic groups and a single bond or a divalent organic group (for example, an optionally substituted methylene group, or an optionally substituted propane-2,2-diyl group) connecting the two or more cyclic groups. ５ is a cyclic group and Q １ or Q ２ and may further have a methylene group connecting L ５ However, L in formula (31) may have a cyclic group formed by removing one or more hydrogen atoms from benzene, 2,3-dihydro-1H-indene, or succinimide. Examples of the maleimide compound represented by formula (IIIa) include a compound represented by formula (31) below. ５ is L in formula (IIIa) ５ is defined in the same way as R ３１ is an alkyl group having 1 to 3 carbon atoms, and p and q are each independently an integer of 0 to 4. ３１ may be the same or different.

[0032] In formula (IIIb), Q ３ represents a cyclic group which may have a substituent. ３ may be an aromatic group (e.g., a phenylene group). ３ The cyclic group therein may have a substituent such as an alkyl group having 1 to 3 carbon atoms.

[0033] In formula (IIIc), Q ４ , Q ５ and Q ６are each independently a cyclic group which may have a substituent, and L ６ and L ７ are each independently a divalent organic group or a single bond, and n is an integer of 1 or more. ４ , Q ５ and Q ６ An example of this is Q １ and Q ２ This is similar to the example shown in L. ６ and L ７ An example of ５ Examples of the maleimide compound represented by formula (IIIc) include a compound represented by formula (32): ６ and L ７ represents L in formula (IIIa). ６ and L ７ where n is an integer of 1 or greater.

[0034] Specific examples of the maleimide compound include compounds represented by the following formulae 301, 302, 303, 304, and 305. In these formulae, n represents an integer of 1 or more.

[0035] Examples of commercially available maleimide compounds include NE-X-9470S (trade name, DIC), MIR-3000-70MT (trade name, Nippon Kayaku), BMI-1000 (trade name, Yamato Chemical Industries), BMI-2300 (trade name, Yamato Chemical Industries), BMI-5100 (trade name, Yamato Chemical Industries), BMI-80 (trade name, Yamato Chemical Industries), BMI (trade name, Yamato Chemical Industries), and SFR-2300MR-T (trade name, Resonac).

[0036] The curable resin composition may contain, as a reactive component other than the maleimide compound, a styrene-based compound having a reactive group obtained by removing one or more hydrogen atoms bonded to the benzene ring from a compound represented by the following formula (I): １ and R ２ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (for example, a methyl group). １is a hydrogen atom, and R ２ may be a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (for example, a methyl group).

[0037] The styrene-based compound may have a plurality of reactive groups. The reactive group of the styrene-based compound is represented, for example, by the following formula (Ia) or (Ib). R in formula (Ia) and (Ib) １ and R ２ is R in formula (I). １ and R ２ is defined in the same way as R １１ and R １２ is an alkyl group having 1 to 3 carbon atoms, p is an integer of 0 to 3, and q is an integer of 0 to 4. １１ and R １２ may be the same or different.

[0038] The styrene-based compound may be a polymer containing a structural unit represented by the following formula (11) or (12): １ and R ２ is R in formula (I) １ and R ２ In formula (11), L １ is a single bond or a divalent organic group, and R １１ is an alkyl group having 1 to 3 carbon atoms (for example, a methyl group), and p is an integer of 0 to 3. ２ is a single bond or a divalent organic group, and R １２ is an alkyl group having 1 to 3 carbon atoms (for example, a methyl group), and q is an integer of 0 to 4.

[0039] L １ or L ２ Examples of the divalent organic group as the aryl group include an oxy group (—O—), a —C(R １３ ) (R １４ )-, carbonyl group (-C(=O)-), carbonyloxy group (-C(=O)O-), amide group (-C(=O)NH-), carbonate group (-OC(=O)O-), sulfonyl group (-S(=O) ２-), and thio groups (-S-). １３ and R １４ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0040] The polymer as the styrene-based compound may further contain a structural unit represented by the following formula (20): ３ is a single bond or a divalent organic group, and R １３ is an alkyl group having 1 to 3 carbon atoms, and r is an integer of 0 to 4. ３ Examples of divalent organic groups as L １ and L ２ The examples of the divalent organic group are the same as those of the above.

[0041] The styrene-based compound may be a polymer containing a structural unit represented by the following formula (101) or a polymer represented by the following formula (102): １ , R ２ , L １ , L ２ , L ３ , R １１ , R １２ , R １３ , p, q and r are R in formula (11), (12) or (13). １ , R ２ , L １ , L ２ , L ３ , R １１ , R １２ , R １３ , p, q and r are defined in the same manner. １１ , L １２ and L １３ are each independently a single bond or a divalent organic group, and R １４ is an alkyl group having 1 to 3 carbon atoms (for example, a methyl group), s is an integer of 0 to 4, and m and n are each independently an integer of 1 or more. １１ , L １２ or L １３ Examples of divalent organic groups as L １ or L ２ The examples of divalent organic groups are the same as those of the above. １４may be the same or different.

[0042] The molecular weight of the styrene-based compound may be 234 or more and 300,000 or less. The weight average molecular weight and / or number average molecular weight of the styrene-based compound may be 234 or more and 300,000 or less. In this specification, the weight average molecular weight and number average molecular weight may be values ​​calculated as standard polystyrene measured by gel permeation chromatography.

[0043] The curable resin composition may contain, as a reactive component other than the maleimide compound, an allyl compound having a reactive group represented by the following formula (II) (hereinafter, sometimes referred to as an "allylamino compound"): The allylamino compound may have a plurality of reactive groups represented by formula (II).

[0044] The allylamino compound may be a compound represented by the following formula (20): ３ and R ４ are each independently a hydrogen atom or a monovalent organic group, and R ３ and R ４ may be bonded to each other to form a cyclic group.

[0045] R ３ or R ４ The monovalent organic group represented by R may be a hydrocarbon group (for example, an alkyl group having 1 to 6 carbon atoms) which may have a substituent. ３ and R ４ may be bonded to each other to form a cyclic group having 4 to 8 members. Specific examples of the allylamino compound include compounds represented by the following formula (21):

[0046] The content of the reactive component may be 10% by mass or more and 80% by mass or less, based on the total amount of the maleimide compound and the reactive component. The content of the reactive component may be 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more, based on the total amount of the maleimide compound and the reactive component, and may be 75% by mass or less, 70% by mass or less, 65% by mass or less, or 60% by mass or less. The total content of the styrene compound and the allylamino compound may be within these numerical ranges.

[0047] The reactive component may further include a compound other than the styrene-based compound and the allylamino compound. For example, the reactive component may include a compound having an allyl group and different from the allylamino compound having the reactive group represented by formula (II). The total content of the maleimide compound, the styrene-based compound, and the allylamino compound may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, or may be 100% by mass or less, based on the mass of the curable resin composition excluding the solvent.

[0048] The curable maleimide resin composition may further include a component that initiates or accelerates the reaction of the maleimide compound and the reactive component.

[0049] The curable resin composition may further contain a component that reduces the dielectric tangent of the cured product (insulating film) (hereinafter referred to as a "dielectric tangent adjuster"). The dielectric tangent adjuster includes, for example, an aromatic compound represented by the following formula (IVa), (IVb), or (IVc):

[0050] In formula (IVa), R ４１ , R ４４ and R ４５ each independently represents a hydrogen atom, a methyl group, or a t-butyl group; R ４２ and R ４３ each independently represents a hydrogen atom, a hydroxy group, or an organic group having 1 to 30 carbon atoms; Z １ represents an organic group having 7 to 80 carbon atoms and containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or an organic group having 2 to 15 carbon atoms and containing a carbonyl group.

[0051] In formula (VIb), R ４６ , R ４９ , R ５０ , R ５１ , R ５２ and R ５５ each independently represents a hydrogen atom, a methyl group, or a t-butyl group; R ４７ , R ４８ , R ５３ and R ５４ each independently represents a hydrogen atom, a hydroxy group, or an organic group having 1 to 30 carbon atoms; Z ２ represents a divalent organic group having 1 to 50 carbon atoms containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or a divalent organic group having 1 to 75 carbon atoms.

[0052] In formula (VIc), R ５６ , R ５９ , R ６０ , R ６１ , R ６４ , R ６５ , R ６６ , R ６７ and R ７０ each independently represents a hydrogen atom, a methyl group, or a t-butyl group; R ５７ , R ５８ , R ６２ , R ６３ , R ６８ and R ６９ each independently represents a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms; Z ３ represents a trivalent organic group having 1 to 50 carbon atoms containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or a trivalent organic group having 1 to 50 carbon atoms.

[0053] The content of the dielectric loss tangent adjuster may be 1% by mass or more and 50% by mass or less, based on the total amount of the maleimide compound and the reactive component, or the total amount of the maleimide compound, the styrene compound, and the allylamino compound. The content of the dielectric loss tangent adjuster may be 2% by mass or more or 5% by mass or more, and may be 50% by mass or less or 40% by mass or less, based on the total amount of the maleimide compound and the reactive component, or the total amount of the maleimide compound, the styrene compound, and the allylamino compound.

[0054] The curable resin composition may further contain a solvent that dissolves or disperses the maleimide compound and the reactive component. Examples of the solvent include γ-butyrolactone, cyclohexanone, cyclopentanone, mesitylene, N,N-dimethylformamide, propylene glycol monomethyl ether acetate, and ethyl lactate. The content of the solvent may be, for example, 10% by mass or more and 300% by mass or less based on the total amount of the maleimide compound and the reactive component, or the total amount of the maleimide compound, the styrene-based compound, and the allylamino compound.

[0055] The curable resin composition may further include an adhesion promoter, such as a silane coupling agent, an aluminum-based adhesion promoter, or a combination thereof.

[0056] Examples of the silane coupling agent include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-( 3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyltrimethoxysilane.

[0057] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0058] The content of the adhesive aid may be, for example, 0.5 mass % or more and 25 mass % or less based on the total amount of the maleimide compound and the reactive component, or the total amount of the maleimide compound, the styrene-based compound, and the allylamino compound.

[0059] The curable resin composition may further contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, 4-methoxyphenol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0060] The content of the polymerization inhibitor may be 0.005% by mass or more and 12% by mass or less based on the total amount of the maleimide compound and the reactive component, or the total amount of the maleimide compound, the styrene-based compound, and the allylamino compound.

[0061] The curable resin composition may further contain an azole compound. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]phenyl ...

[0033] benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

[0062] The content of the azole compound may be 0.1% by mass or more and 20% by mass or less, or 0.5% by mass or more and 5% by mass or less, based on the total amount of the maleimide compound and the reactive component, or the total amount of the maleimide compound, the styrene-based compound, and the allylamino compound.

[0063] The curable resin composition may contain a hindered phenol compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), and 4,4'-butylidene-bis(3-methyl-6-t-butylphenol). 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2 '-Methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5 H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3 ,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5 -tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)- Examples include 1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0064] The content of the hindered phenol compound may be 0.1% by mass or more and 20% by mass or less, or 0.5% by mass or more and 10% by mass or less, based on the total amount of the maleimide compound and the reactive component, or the total amount of the maleimide compound, the styrene-based compound, and the allylamino compound.

[0065] The curable resin composition may contain an organic titanium compound, such as a titanium chelate compound having two or more alkoxy groups, a tetraalkoxytitanium compound, a titanocene compound, a monoalkoxytitanium compound, a titanium oxide compound, a titanium tetraacetylacetonate compound, a titanate coupling agent, or a combination thereof.

[0066] Examples of titanium chelate compounds having two or more alkoxy groups include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate).

[0067] Examples of tetraalkoxytitanium compounds include titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, and titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}].

[0068] Examples of titanocene compounds include pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

[0069] Examples of monoalkoxytitanium compounds include titanium tris(dioctylphosphate) isopropoxide and titanium tris(dodecylbenzenesulfonate) isopropoxide.

[0070] Examples of titanium oxide compounds include titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), and phthalocyanine titanium oxide.

[0071] An example of a titanium tetraacetylacetonate compound is titanium tetraacetylacetonate.

[0072] An example of a titanate coupling agent is isopropyl tridodecylbenzenesulfonyl titanate.

[0073] The content of the organotitanium compound may be 0.05% by mass or more and 10% by mass or less, or 0.1% by mass or more and 2% by mass or less, based on the total amount of the maleimide compound and the reactive component, or the total amount of the maleimide compound, the styrene-based compound, and the allylamino compound.

[0074] [Example] 1. Synthesis of Styrenic Compound B2 2,2'-Diallylbisphenol A (Tokyo Chemical Industry Co., Ltd., 6.00 mmol, 1.85 g), 4,4'-difluorobenzophenone (Tokyo Chemical Industry Co., Ltd., 5.00 mmol, 1.09 g), and potassium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd., 30.0 mmol, 4.15 g) were placed in a three-necked flask. N-methylpyrrolidone (30 mL) and toluene (15 mL) were then added. A reflux condenser and a Dean-Stark receiver were attached to the three-necked flask, and a nitrogen atmosphere was created within the system. The reaction solution in the three-necked flask was heated while stirring. After the internal temperature reached 155°C, stirring was continued for an additional 30 minutes to allow the reaction to proceed. The reaction solution in the three-necked flask was then cooled to room temperature, and N-methylpyrrolidone (30 mL) was added thereto. The reaction solution was washed several times with water and ethanol, and then filtered to obtain a styrene-based compound B2 (white solid) (yield: 85%, weight average molecular weight: 28,000).１ The H-NMR spectrum confirmed that a 1-propenyl group was formed.

[0075] 2. Curable Resin Composition A resin varnish was obtained by mixing the components in the compounding ratio (parts by mass) shown in Table 1. The details of each component shown in Table 1 are as follows: (A) Maleimide Compound A1: Phenylmethanemaleimide (BMI-2300, Daiwa Chemical Industry Co., Ltd.) A2: 4,4'-diphenylmethane bismaleimide (BMI-1000, Daiwa Chemical Industry Co., Ltd.) A3: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (BMI-5100, Daiwa Chemical Industry Co., Ltd.) (B) Reactive component B1: Reaction product of polycondensate of 2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diol and 2,6-dimethylphenol with chloromethylstyrene (number average molecular weight: 1200, OPE-2St, Mitsubishi Gas Chemical Company, Inc.) B2: Synthetic product according to "1. Synthesis of styrene-based compound B2" B3: 1,3,4,6-tetraallyl glycoluril (TA-G, Shikoku Chemicals Corporation) B4: triallyl cyanurate B5: Aryl phenol resin (LVA01, Gun-ei Chemical Industry Co., Ltd.) (C) Silane coupling agent C1: 3-aminopropyltriethoxysilane (D) Azole compound D1: 1,2,3-benzotriazole (E) Solvent γ-butyrolactone (γ-BL)

[0076] 3. Cured Film (Insulating Film) Each resin varnish was dropped onto a glass substrate and formed by spin coating. The solvent was removed from the coating by heating at 110°C for 3 minutes to form a resin film. The resin film was then cured by heating at 250°C for 2 hours in a nitrogen atmosphere. The formed cured film was peeled off from the glass substrate and its thermal properties were evaluated. The cured film formed from the varnish of Example 3, 4, or 7 had high transparency. The cured film formed from the varnish of Example 5 or 6 was slightly cloudy. The cured film formed from the varnish of Example 1 or 2 was cloudy. A transparent cured film can be advantageous, for example, in terms of image recognition of alignment for alignment provided below the cured film.

[0077] 4. Curing characteristics The resin film sample before curing was analyzed by differential scanning calorimetry (DSC, heating rate: 10°C / min). From the obtained DSC thermogram, the onset temperature (T ｏｎｓｅｔ A low onset temperature of the exothermic peak corresponds to the ability to cure at a low temperature.

[0078] 5. Glass Transition Temperature (Tg) The Tg of the cured film was measured by dynamic mechanical analysis (DMA) under the following conditions. The temperature at which Tan δ showed a maximum value was recorded as Tg. Frequency: 10 Hz Heating rate: 5°C / min

[0079] 6. Coefficient of Linear Thermal Expansion (CTE) The coefficient of linear thermal expansion (CTE) of the cured film was measured by thermomechanical analysis. The CTE was determined in the temperature range of 50°C to 100°C.

[0080] 7. 1% Weight Loss Temperature (Td1) The 1% weight loss temperature (Td1) was determined by thermogravimetry of the cured film.

[0081]

[0082] The curable resin compositions of the examples containing a styrene-based compound or an allylamino compound as a reactive component exhibited an onset temperature, and it was confirmed that an insulating film could be formed by heating at a low temperature.

[0083] 1...circuit connector, 10...first circuit member, 11...first substrate, 12...first electrode, 13...first insulating film, 13a, 23a...opening, 13A...first resin film, 20...second circuit member, 21...second substrate, 22...second electrode, 23...second insulating film.

Claims

1. A compound comprising: a maleimide compound having a maleimide group; and a reactive component other than the maleimide compound, wherein the reactive component is represented by the following formula (I): and a styrene-based compound having a reactive group which is a group obtained by removing one or more hydrogen atoms bonded to a benzene ring from a compound represented by R １ and R ２ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

2. The styrene-based compound is represented by the following formula (11) or (12): is a polymer containing a structural unit represented by R １ and R ２ is R in formula (I) １ and R ２ is defined similarly to L １ is a single bond or a divalent organic group, and R １１ is an alkyl group having 1 to 3 carbon atoms, p is an integer of 0 to 3, and L ２ is a single bond or a divalent organic group, and R １２ 2. The curable resin composition for hybrid bonding according to claim 1, wherein is an alkyl group having 1 to 3 carbon atoms, and q is an integer of 0 to 4.

3. The polymer is represented by the following formula (20): Further containing a structural unit represented by L ３ is a single bond or a divalent organic group, and R １３ The curable resin composition for hybrid bonding according to claim 2, wherein is an alkyl group having 1 to 3 carbon atoms, and r is an integer of 0 to 4.

4. A compound comprising: a maleimide compound having a maleimide group; and a reactive component other than the maleimide compound, wherein the reactive component is represented by the following formula (II): A curable resin composition for hybrid bonding, comprising an allyl compound having a reactive group represented by the formula:

5. A method for manufacturing a circuit connection comprising a first circuit member having a first electrode and a second circuit member having a second electrode, the method comprising: heating a first resin film including a portion provided around the first electrode, thereby forming a first insulating film; and joining the first circuit member and the second circuit member having the second electrode and a second insulating film including a portion provided around the second electrode by hybrid bonding so that the first electrode and the second electrode are electrically connected, wherein the first resin film comprises the curable resin composition for hybrid bonding according to any one of claims 1 to 4.

6. A method for manufacturing a circuit connection comprising a first circuit member having a first electrode and a second circuit member having a second electrode, the method comprising: heating a first resin film including a portion provided around the first electrode, thereby forming a first insulating film; heating a second resin film including a portion provided around the second electrode, thereby forming a second insulating film; and joining the first circuit member and the second circuit member by hybrid bonding so that the first electrode and the second electrode are electrically connected, wherein the first resin film and the second resin film comprise the curable resin composition for hybrid bonding according to any one of claims 1 to 4.

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