Curable resin composition, method for producing resin cured body, and method for producing circuit connector

Abstract

A curable resin composition comprising: a blocked maleimide compound having a maleimide group blocked by a blocking agent that dissociates by heating; and a reactive component that is a compound having a reactive group that reacts with a maleimide group, or a compound that generates a reactive group by heating. The sealing agent may be a compound that dissociates from the maleimide group by heating at 220 DEG C or less and has a boiling point of 250 DEG C or less.

Description

TECHNICAL FIELD

[0002] The present disclosure relates to a curable resin composition, a method for producing a resin hardened body, and a method for producing a circuit connecting body. BACKGROUND

[0004] In three-dimensional packaging of semiconductor chips, in order to miniaturize wiring, mixed bonding that bonds an insulating film together with bonding of electrodes is being studied. It has also been proposed to form an insulating film for mixed bonding using a resin material such as polyimide (Patent Literature 1).

[0005] On the other hand, it is known that a composition containing a maleimide compound and an allyl compound is heat-hardened by an addition reaction including Ene reaction and Diels-Alder reaction or radical polymerization (Non-Patent Literature 1).

[0006] [Related Art Documents]

[0007] [Patent Literature]

[0008] Patent Literature 1: International Publication No. 2020 / 085183

[0009] [Non-Patent Literature]

[0010] Non-Patent Literature 1: Handbook of Thermoset Plastics, Third Edition 2014, p. 459-510 SUMMARY

[0012] [Problems to be Solved by the Invention]

[0013] By hardening a resin film containing a curable resin composition containing a maleimide compound, an insulating film can be formed. With regard to the curable resin composition, in order to suppress tackification caused by progress of hardening reaction in storage, refrigerated storage is sometimes required. An aspect of the present disclosure relates to a curable resin composition containing a maleimide compound, which has improved viscosity stability at room temperature.

[0014] [Technical Means for Solving the Problems]

[0015] The present disclosure contains the following. [1]

[0017] A curable resin composition containing:

[0018] a blocked maleimide compound having a maleimide group blocked with a blocking agent that is dissociated by heating; and

[0019] a reactive component that is a compound having a reactive group that reacts with a maleimide group, or a compound that generates the reactive group by heating. [2]

[0021] The curable resin composition according to [1], wherein the blocking agent is a compound that is dissociated from the maleimide group by heating at 230°C or lower and has a boiling point of 250°C or lower. [3]

[0023] The curable resin composition according to [1] or [2], wherein the blocking agent comprises a diene compound having a diene group. [4]

[0025] The curable resin composition according to [3], wherein the diene compound is a compound having a furan group. [5]

[0027] The curable resin composition according to any one of [1] to [6], wherein the reactive component comprises an allyl compound having an allyl group represented by the following formula (III):

[0028] [Chemical Formula 1]

[0029]

[0030] a styrene compound in which one or more hydrogen atoms bonded to a benzene ring are removed from the compound represented by the following formula (I): 22 and R 23 are each independently a hydrogen atom or an alkyl group having a carbon number of 1 to 3. [6]

[0032] The curable resin composition according to any one of [1] to [5], wherein the reactive component comprises an allyl compound having an allyl group. [7]

[0034] The curable resin composition according to any one of [1] to [7], wherein the reactive component comprises an amine compound having an amino group. [8]

[0036] The curable resin composition according to any one of [1] to [7], wherein the reactive component comprises a thiol compound having a thiol group. [9]

[0038] The curable resin composition according to any one of [1] to [8], wherein the reactive component contains a phenol compound having a phenolic hydroxyl group.

[10]

[0040] The curable resin composition according to any one of [1] to [9], wherein the reactive component contains a benzoxazine compound having a benzoxazine group.

[11]

[0042] The curable resin composition according to any one of [1] to

[10] , further containing a solvent.

[12]

[0044] A method of manufacturing a resin hardened body, comprising:

[0045] forming a heat-hardenable intermediate molded body by the curable resin composition according to any one of [1] to

[11] ; and

[0046] allowing hardening of the intermediate molded body by heat treatment, thereby forming a resin hardened body,

[0047] the intermediate molded body is formed in such a manner that a maleimide compound having a maleimide group is generated in the intermediate molded body by dissociation of the blocking agent from the blocked maleimide compound.

[13]

[0049] The method according to

[12] , further comprising storing the curable resin composition at an environment of 20°C or higher and 35°C or lower.

[14]

[0051] A method of manufacturing a circuit connecting body, wherein the circuit connecting body includes a first circuit member having a first electrode, and a second circuit member having a second electrode,

[0052] the method includes:

[0053] forming a heat-hardenable first resin film containing a portion disposed around the first electrode;

[0054] allowing hardening of the first resin film by heat treatment, thereby forming a first insulating film from the first resin film; and

[0055] for the first circuit member having the first electrode and the first insulating film, and the second circuit member having the second electrode and a second insulating film containing a portion disposed around the second electrode, joining by mixed bonding in such a manner that the first electrode and the second electrode are electrically connected,

[0056] The first resin film is formed from the curable resin composition according to any one of [1] to

[11] ,

[0057] The first resin film is formed in a manner that a maleimide compound having a maleimide group is generated in the first resin film by dissociating the blocking agent from the blocked maleimide compound.

[15]

[0059] A method of manufacturing a circuit connecting body, wherein the circuit connecting body includes a first circuit member having a first electrode, and a second circuit member having a second electrode,

[0060] The method includes:

[0061] forming a first resin film containing a portion provided around the first electrode, which is thermally curable;

[0062] hardening of the first resin film is performed by heat treatment, thereby forming a first insulating film from the first resin film;

[0063] forming a second resin film containing a portion provided around the second electrode, which is thermally curable;

[0064] hardening of the second resin film is performed by heat treatment, thereby forming a second insulating film from the second resin film; and

[0065] the first circuit member having the first electrode and the first insulating film, and the second circuit member having the second electrode and the second insulating film are joined by mixed bonding in a manner that the first electrode and the second electrode are electrically connected,

[0066] The first resin film and the second resin film are formed from the curable resin composition according to any one of [1] to

[11] ,

[0067] The first resin film and the second resin film are formed in a manner that a maleimide compound having a maleimide group is generated in the first resin film and the second resin film by dissociating the blocking agent from the blocked maleimide compound.

[0068] [Effects of the Invention]

[0069] The viscosity stability at normal temperature of the curable resin composition containing a maleimide compound can be improved. The curable resin composition can have excellent storage stability. BRIEF DESCRIPTION OF DRAWINGS

[0071] FIG. 1 is a process diagram showing an example of a method of manufacturing a semiconductor device.

[0072] Fig. 2 is a process chart showing an example of a method of manufacturing a semiconductor device.

[0073] Fig. 3 is a process chart showing an example of a method of manufacturing a semiconductor device. DETAILED DESCRIPTION

[0075] The present application is not limited to the following examples.

[0076] Curable resin composition

[0077] An example of a curable resin composition includes a blocked maleimide compound having a maleimide group blocked by a blocking agent, and a reactive component. The reactive component can be a compound having a reactive group that reacts with the maleimide group, or a compound that generates a reactive group by heating. The maleimide group is blocked by the blocking agent, whereby the hardening of the reaction between the maleimide compound and the reactive component is inhibited at ordinary temperature (for example, 20°C to 35°C). Therefore, even if the reactive component has high reactivity, the curable resin composition can have high viscosity stability at ordinary temperature. Various resin hardened bodies such as a resin film can be formed using the curable resin composition.

[0078] The blocking agent can be a compound that is dissociated from the maleimide group by heating at 230°C or lower. The blocking agent can also be a compound that is dissociated from the maleimide group by heating at 40°C or higher and 230°C or lower.

[0079] If the blocking agent is a compound having a low boiling point, the blocking agent dissociated from the maleimide group can be easily volatilized from a resin film containing the curable resin composition. The amount of the blocking agent remaining in the resin film after hardening is small, which can be advantageous for inhibiting defects of the resin film such as voids. From the viewpoint, the blocking agent can be a compound having a boiling point of 250°C or lower or 230°C or lower. The compound used as the blocking agent can have a boiling point of 40°C or higher. The boiling point herein refers to the boiling point at one atmosphere.

[0080] The blocking agent can also include a diene compound having a dienyl group. The diene compound as the blocking agent can be a compound capable of reacting with the maleimide group by a Diels-Alder reaction, examples of which include a compound represented by the following Formula 2. In Formula 2, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom or a monovalent organic group. R 1 , R 2 , R 3 , R4 , R 5 , and R 6 Two of the groups in R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 may be bonded to form a cyclic group. The maleimide group 1 and the diene compound 2 rapidly react through a Diels-Alder reaction to form a blocked maleimide group 1A. The diene compound 2 is easily dissociated from the blocked maleimide group 1A by heating.

[0081] [Chemical Formula 2]

[0082]

[0083] R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 may be independently alkyl (-R) which can have a substituent, alkoxycarbonyl (-C(=0)OR) which can have a substituent, or alkanoyl (-C(=0)R) which can have a substituent, respectively. Examples of the substituent which the alkyl, alkoxycarbonyl, and alkanoyl can have include hydroxy, alkanoyloxy (-0(C=0)R), alkoxycarbonyl, alkanoyl, aryl, and furanyl. As R 1 , R 2 , R 3 , R 4 , R 5 , or R 6 , the carbon number of the organic group can be 1 to 10. R 2 and R 6 may be bonded to form a cyclic group which can contain a hetero atom.

[0084] The diene compound can be a compound having a furanyl group. The compound having a furanyl group is represented by, for example, the following formula (20).

[0085] [Chemical Formula 3]

[0086]

[0087] In formula (20), R 1 , R 3 , R 4 , and R 5 are defined in the same manner as R 1 , R 3 , R 4 , and R 5 in formula 2. For example, R 1 may be a monovalent organic group, R 3 , R 4 , and R 5is a hydrogen atom. Examples of the compound represented by formula (20) include a compound represented by formula (20A), formula (20B), formula (20C), or formula (20D) below. In these formulas, R 20 is an alkanediyl group having 1 to 3 carbons (e.g., methylene), R 21 is an alkyl group having 1 to 6 carbons (e.g., methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl).

[0088] [Chemical 4]

[0089]

[0090] Specific examples of the compound represented by formula (20) include furfuryl alcohol (boiling point: 170°C), 2-furan carboxylic acid n-propyl ester (boiling point: 211°C), 2-acetylfuran (boiling point: 173°C), 2-furan carboxylic acid methyl ester (boiling point: 181°C), furfuryl acetate (boiling point: 177°C), 2-furan carboxylic acid ethyl ester (boiling point: 196°C), and furfuryl propionate (boiling point: 196°C).

[0091] The blocked maleimide compound is a compound derived from a maleimide compound having one or more maleimide groups by reaction with a blocking agent. The curable resin composition can include a blocked maleimide compound derived from a maleimide compound having two or more maleimide groups in terms of reduction in heat resistance and coefficient of thermal expansion of a resin hardened body formed from the curable resin composition.

[0092] The maleimide compound from which the blocked maleimide compound is derived can have a maleimide group including a nitrogen atom directly bonded to a cyclic group (e.g., an aromatic group). For example, the maleimide compound can include a compound represented by formula (la), formula (lb), or formula (lc) below.

[0093] [Chemical 5]

[0094]

[0095] In formula (la), Q 1 and Q 2 are each independently a cyclic group which can have a substituent, L 5 is a divalent organic group or a single bond. Q 1 and Q 2 may be an aromatic group (e.g., phenylene group) which can each independently have a substituent (e.g., an alkyl group having 1 to 3 carbons). L 5It can be a group selected from monocyclic, condensed, non-condensed crosslinked, and spirocyclic rings, containing one or more cyclic groups (excluding maleimide groups) that may have substituents, alkylene groups having 1 to 5 carbon atoms (e.g., methylene, propane-1,3-diyl, propane-2,2-diyl), or a single bond. L 5 It may have two or more cyclic groups, and single bonds or divalent organic groups linking two or more cyclic groups (e.g., methylene groups may have substituents, propane-2,2-diyl groups may have substituents). L 5 It can also combine cyclic groups with Q 1 Or Q 2 Linked methylene group. L 5 It may also have a cyclic group formed by removing one or more hydrogen atoms from benzene, 2,3-dihydro-1H-indene, or succinimide. Examples of maleimide compounds represented by formula (Ia) include compounds represented by formula (11) below. L in formula (11) 5 With L in equation (Ia) 5 Similarly, R is defined. 31 It is an alkyl group having 1 to 3 carbon atoms, where p and q are independent integers from 0 to 4. Multiple R groups in the same molecule 31 They can be the same or different.

[0096] [Chemistry 6]

[0097]

[0098] In equation (Ib), Q 3 This indicates a cyclic group that can have substituents. Q 3 It can also be an aromatic group (e.g., phenylene). Q 3 The cyclic group in it may have substituents such as alkyl groups having 1 to 3 carbon atoms.

[0099] In equation (Ic), Q 4 Q 5 and Q 6 Each is an independent cyclic group that can have substituents, L 6 and L 7 Each can be an independent divalent organic group or a single bond, where n is an integer greater than or equal to 1. Q 4 Q 5 and Q 6 Examples and Q 1 and Q 2 The example is the same. L 6 and L 7 Examples and L 5 The examples are the same. Examples of maleimide compounds represented by formula (Ic) include compounds represented by formula (12) below. In formula (12), L 6 and L 7With L in equation (Ia) 6 and L 7 Similarly, n is defined as an integer greater than or equal to 1.

[0100] [Chemistry 7]

[0101]

[0102] Specific examples of maleimide compounds include those represented by formulas 101, 102, 103, 104, or 105 below. In these formulas, n represents an integer greater than 1.

[0103] [Chemistry 8]

[0104]

[0105] [Chemistry 9]

[0106]

[0107] [Chemistry 10]

[0108]

[0109] [Chemistry 11]

[0110]

[0111] [Chemistry 12]

[0112]

[0113] Examples of commercially available maleimide compounds include: NE-X-9470S (trade name, DIC), MIR-3000-70MT (trade name, Nippon Gunpowder), 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).

[0114] The reactive component may include at least one compound selected from the group consisting of styrene compounds, allyl compounds, amine compounds, thiols, phenols, and benzoxazine compounds. The reactive component may include styrene compounds and allyl compounds.

[0115] Styrene compounds are compounds having a reactive group formed by removing one or more hydrogen atoms bonded to a benzene ring from the compound represented by formula (IV) below. In formula (IV), R22 and R 23 Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (e.g., methyl). R is also acceptable. 22 It is a hydrogen atom and R 23 It is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (e.g., methyl). Styrene compounds tend to react with maleimide compounds at lower temperatures. However, because the maleimide group of maleimide compounds is blocked, the curable resin composition can have high viscosity stability at room temperature.

[0116] [Chemistry 13]

[0117]

[0118] Styrene compounds can have multiple reactive groups. The reactive groups of styrene compounds are represented, for example, by the following formula (IVa) or formula (IVb). The R in formulas (IVa) and (IVb) 22 and R 23 With R in equation (IV) 22 and R 23 Similarly, R is defined. 11 and R 12 It is an alkyl group with 1 to 3 carbon atoms, where p is an integer from 0 to 3 and q is an integer from 0 to 4. Multiple Rs in the same molecule 11 and R 12 They can be the same or different.

[0119] [Chemistry 14]

[0120]

[0121] Styrene compounds can be polymers comprising the structural units represented by formula (41) or formula (42). R in formulas (41) and (42) 22 and R 23 With R in equation (IV) 22 and R 23 Similarly, L is defined. In equation (41), L 1 R is a single bond or a divalent organic group. 11 It is an alkyl group having 1 to 3 carbon atoms (e.g., methyl), and p is an integer from 0 to 3. In formula (42), L 2 R is a single bond or a divalent organic group. 12 It is an alkyl group having 1 to 3 carbon atoms (e.g., methyl), and q is an integer from 0 to 4.

[0122] [Chemistry 15]

[0123]

[0124] [Chemistry 16]

[0125]

[0126] As L 1 or L 2 Examples of divalent organogroups include oxygen (-O-), -C(R-) 16 (R) 17 -, carbonyl (-C(=O)-), carbonyloxy (-C(=O)O-), amide (-C(=O)NH-), carbonate (-OC(=O)O-), sulfonyl (-S(=O)2-), and thio (-S-). R 16 and R 17 Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0127] Polymers that are styrene compounds may also contain structural units represented by the following formula (43). In formula (43), L 3 R is a single bond or a divalent organic group. 13 It is an alkyl group having 1 to 3 carbon atoms, and r is an integer from 0 to 4. As L 3 Examples of divalent organogroups and L 1 and L 2 The examples of related divalent organic groups are the same.

[0128] [Chemistry 17]

[0129]

[0130] Styrene compounds may be polymers comprising the structural unit represented by formula (401) or the polymer represented by formula (402). In formulas (401) and (402), R 21 R 22 L 1 L 2 L 3 R 11 R 12 R 13 p, q and r are related to R in equation (41), equation (42) or equation (43). 21 R 22 L 1 L 2 L 3 R 11 R 12 R 13 p, q, and r are defined similarly. In equation (402), L 11 L 12 and L 13 Each is an independent single bond or a divalent organic group, R 14It is an alkyl group having 1 to 3 carbon atoms (e.g., methyl), s is an integer from 0 to 4, and m and n are each independently an integer greater than 1. As L 11 L 12 or L 13 Examples of divalent organogroups and L 1 or L 2 The examples of related divalent organic groups are the same. Multiple R groups in the same molecule... 14 They can be the same or different.

[0131] [Chemistry 18]

[0132]

[0133] [Chemistry 19]

[0134]

[0135] The molecular weight of styrene compounds can be greater than 200 and less than 100,000. The weight-average molecular weight and / or number-average molecular weight of styrene compounds can be greater than 500 and less than 100,000. In this specification, the weight-average molecular weight and number-average molecular weight can be values ​​converted from standard polystyrene determined by gel permeation chromatography.

[0136] The reactive component may include allyl compounds having an allyl group as a reactive group. An allyl compound is a compound having one or more allyl groups (2-propenyl, -CH2CH=CH2). In terms of the heat resistance and reduction of the coefficient of thermal expansion of the cured resin, the curable resin composition may include allyl compounds having two or more allyl groups.

[0137] Allyl compounds may include compounds having a cyclic group and an allyl or allyloxy group directly bonded to the cyclic group. For example, the allyl compounds in a curable maleimide resin composition may include compounds represented by formula (Va), (Vb), (Vc), or (Vd).

[0138] [Chemistry 20]

[0139]

[0140] In equations (Va) and (Vb), Q 7 and Q 8 Each independently represents a cyclic group that can have substituents, L 8 This indicates a divalent organic group or a single bond. Q 7 and Q 8 Each group can be independently formed by removing one or more hydrogen atoms from benzene, isocyanuric acid, or nadimide. 8It can be a group selected from monocyclic, condensed, non-condensed crosslinked, and spirocyclic rings containing one or more cyclic groups (excluding maleimide groups) that may have substituents, straight-chain alkylene groups that may have substituents (e.g., methylene, propane-1,3-diyl), propane-2,2-diyl that may have substituents, or a single bond. L 8 It may have two or more cyclic groups, and single bonds or divalent organic groups linking two or more cyclic groups (e.g., methylene groups may have substituents, propane-2,2-diyl groups may have substituents). L 8 It can also combine cyclic groups with Q 7 Or Q 8 Linked methylene group. L 8 The cyclic group in it can be substituted, for example, with a substituent selected from methyl, hydroxy, and allyl groups. 8 It may also have phenylene compounds that can have substituents.

[0141] In equations (Vc) and (Vd), Q 9 This indicates a cyclic group that can have substituents. Q 9 It can also be an aromatic group (e.g., phenylene) or a group formed by removing one or more hydrogen atoms from isocyanuric acid. Q 9 The cyclic group in it can be substituted with methyl or allyl groups, for example.

[0142] Specific examples of allyl compounds include compounds represented by the following formulas 501, 502, 503, 504, 505, 506, 507, 508, or 509. In these formulas, n represents an integer greater than 1.

[0143] [Chemistry 21]

[0144]

[0145] [Chemistry 22]

[0146]

[0147] [Chemistry 23]

[0148]

[0149] [Chemistry 24]

[0150]

[0151] [Chemistry 25]

[0152]

[0153] [Chemistry 26]

[0154]

[0155] [Chemistry 27]

[0156]

[0157] [Chemistry 28]

[0158]

[0159] [Chemistry 29]

[0160]

[0161] Examples of commercially available allyl compounds include: DABPA (trade name, Kanto Chemical), DA-BPF (trade name, Yokkaichi Synthetic), LVA01 (trade name, Gunei Chemical Industry), BPA-AE (trade name, Konishi Chemical Industry), BANI-X (trade name, Maruzen Petrochemical), BANI-M (trade name, Maruzen Petrochemical), FATC-809 (trade name, Gunei Chemical Industry), FATC-809AP (trade name, Gunei Chemical Industry), DAIC (trade name, Shikoku Chemical Industry), and DD-1 (trade name, Shikoku Chemical Industry).

[0162] The curable resin composition may contain an allyl compound (hereinafter sometimes referred to as "allyl amino compound") having a reactive group represented by formula (5). The allyl amino compound may have multiple reactive groups represented by formula (5). The allyl amino compound tends to react with bismaleimide compounds at lower temperatures. However, because the maleimide group is blocked, the curable resin composition may have high viscosity stability at room temperature.

[0163] [Chemistry 30]

[0164]

[0165] Allylamino compounds can be compounds represented by the following formula (50). In formula (50), R 24 and R 25 Each can be independently a hydrogen atom or a monovalent organic group, R 24 and R 25 They can bond with each other to form cyclic groups.

[0166] [Chemistry 31]

[0167]

[0168] As R 24 or R 25 The monovalent organogroup can be a hydrocarbon group that can have substituents (e.g., an alkyl group having 1 to 6 carbon atoms). R 24 and R25 They can bond with each other to form cyclic groups of 4- to 8-membered rings. Specific examples of allylamino compounds include compounds represented by the following formula 510.

[0169] [Chemistry 32]

[0170]

[0171] Amine compounds are compounds having an amino group as the reactive group. Amine compounds can be aliphatic amines, aromatic amines, or combinations thereof. Examples of aliphatic amines include cyclohexylamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]-undecane. Examples of aromatic amines include aniline, toluene, naphthylamine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and 4,4'-diaminodiphenylmethane (BAPP). methane (MDA), m-phenylenediamine (MPD), 4,4'-diaminodiphenyl ether, 2'-methoxy-4,4'-diaminobenzoyl aniline, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'- Diaminobiphenyl, 4,4'-diaminobenzoyl aniline, bis-aniline fluorene, 2,2-bis-[4-(3-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)]biphenyl, bis[4-(3-aminophenoxy)]biphenyl, bis[1-(4-aminophenoxy)]biphenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[4-(4-aminophenoxy)phenyl]methane, bis [4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)]benzophenone, bis[4-(3-aminophenoxy)]benzophenone, bis[4,4'-(4-aminophenoxy)]benzoyl aniline, bis[4,4'-(3-aminophenoxy)]benzoyl aniline, 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene, 9,9-bis[4-(3-aminophenoxy)phenyl]fluorene [phenoxy)phenyl]fluorene, 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis-[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-dimethylaniline, 4,4'-methylene-2,6-diethylaniline, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 3,3'-Diaminodiphenylmethane, 4,4'-Diaminodiphenyl sulfide, 3,3'-Diaminodiphenyl sulfide, 4,4'-Diaminodiphenyl sulfone, 3,3'-Diaminodiphenyl sulfone, 3,3-Diaminodiphenyl ether, 3,4'-Diaminodiphenyl ether, benzidine, 3,3'-Diaminobiphenyl, 3,3'-Dimethyl-4,4'-Diaminobiphenyl, 3,3'-Dimethoxybenzidine, 4,4''-Diamino-p-terphenyl, 3,3''-Diamino-p-terphenyl, p-phenylenediamine, 2,6-Diaminopyridine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(1-methylethylene)] Bisaniline, 4,4'-[1,3-phenylenebis(1-methylethylene)]bisaniline, bis(p-aminocyclohexyl)methane, bis(p-β-amino-tert-butylphenyl) ether, bis(p-β-methyl-δ-aminopentyl)benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis(β-amino-tert-butyl)toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-phenylenediamine, p-phenylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, and 2,5-diamino-1,3,4-oxadiazole.

[0172] Thiols are compounds that have a thiol group as a reactive group. Thiols can be dithiols with two thiol groups, examples of which include 1,2-ethanethiol, 1,3-dimercaptopropane, 1,4-dimercaptobutane, bis(2-mercaptoethyl) ether, bis(2-mercaptoethyl) sulfide, and bis(2-mercaptoethyl) sulfone.

[0173] Phenolic compounds are compounds with a phenolic hydroxyl group as a reactive group. Benzoxazine compounds are compounds with a benzoxazine group. Benzoxazine compounds can generate a phenolic hydroxyl group as a reactive group through heating.

[0174] The content of reactive components, based on the total amount of the blocked maleimide compound and the reactive components, can be 10% by mass or more and 80% by mass or less. The content of reactive components, based on the total amount of the blocked maleimide compound and the reactive components, can be 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more, or 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 blocked maleimide compound and the reactive components, based on the total amount of the components in the curable resin composition after solvent removal, can be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, or 100% by mass or less.

[0175] The curable resin composition may further comprise a solvent that dissolves or disperses the blocked maleimide compound and the reactive component. Examples of solvents include: γ-butyrolactone, cyclohexanone, cyclopentanone, 1,3,5-trimethylbenzene, N,N-dimethylformamide, propylene glycol monomethyl ether acetate, and ethyl lactate. The solvent content is based on the total amount of the blocked maleimide compound and the reactive component, and may be, for example, 10% by mass or more and 300% by mass or less.

[0176] The curing resin composition may also contain components that initiate or promote the reaction of maleimide compounds and reactive components.

[0177] The curable resin composition may further contain an ingredient that reduces the dielectric loss tangent of the cured resin body (insulating film) (hereinafter referred to as "dielectric loss tangent modifier"). The dielectric loss tangent modifier may, for example, contain an aromatic compound represented by formula (VIa), (VIb) or (VIc).

[0178] [Chemistry 33]

[0179]

[0180] In formula (VIa), R 41 R 44 and R 45 Each can independently represent a hydrogen atom, a methyl group, or a tert-butyl group, R 42 and R 43 Z represents, independently, a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms. 1 It refers to an organogroup with 7 to 80 carbon atoms containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen and nitrogen, or an organogroup with 2 to 15 carbon atoms containing a carbonyl group.

[0181] In equation (VIb), R 46 R 49 R 50 R 51 R 52 and R 55 Each can independently represent a hydrogen atom, a methyl group, or a tert-butyl group, R 47 R 48 R 53 and R 54 Z represents, independently, a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms. 2 It refers to a divalent organometallic group with 1 to 50 carbon atoms, or a divalent organometallic group with 1 to 75 carbon atoms, containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen and nitrogen.

[0182] In formula (VIc), R 56 R59 R 60 R 61 R 64 R 65 R 66 R 67 and R 70 Each can independently represent a hydrogen atom, a methyl group, or a tert-butyl group, R 57 R 58 R 62 R 63 R 68 and R 69 Z represents, independently, a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms. 3 It refers to a trivalent organometallic group having 1 to 50 carbon atoms, containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen and nitrogen.

[0183] The content of dielectric loss tangent modifier, based on the total amount of blocked maleimide compound and reactive component, can be 1% or more by mass and 50% or less by mass. The content of electrical loss tangent modifier, based on the total amount of blocked maleimide compound and reactive component, can be 2% or more by mass or 5% or more by mass, and can be 50% or less by mass or 40% or less by mass.

[0184] The curable resin composition may also contain adhesive aids. Adhesive aids may include, for example, silane coupling agents, aluminum-based adhesive aids, or combinations thereof.

[0185] Examples of silane coupling agents include: γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyl dimethoxysilane, γ-glycidoxypropylmethyl dimethoxysilane, γ-mercaptopropylmethyl dimethoxysilane, 3-methacryloyloxypropyl dimethoxymethylsilane, 3-methacryloyloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, and diethoxy-3-glycidoxypropylmethyl Silane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, and N-phenylaminopropyltrimethoxysilane.

[0186] Examples of aluminum-based adhesive additives include: tri(ethyl acetoacetate)aluminum, tri(acetylacetonate)aluminum, and ethyl acetoacetate diisopropoxide aluminum.

[0187] The content of the adhesive additive, for example based on the total amount of the blocked maleimide compound and the reactive component, may be more than 0.5% by mass and less than 25% by mass.

[0188] The curable resin composition may further contain a polymerization inhibitor. Examples of polymerization inhibitors 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-phenylhydroxyamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxyamine ammonium salt.

[0189] The content of polymerization inhibitor, based on the total amount of blocked maleimide compound and reactive component, can be above 0.005% by mass and below 12% by mass.

[0190] The curable resin composition may further comprise an azole compound. Examples of azole compounds include: 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tert-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]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-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.

[0191] The content of azole compounds is based on the total amount of blocked maleimide compounds and reactive components, and can be 0.1% by mass or more and 20% by mass or more and 0.5% by mass or less and 5% by mass.

[0192] The curable resin composition may contain a hindered phenolic compound. Examples of hindered phenolic compounds include: 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydroquinone, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], and 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. 2,2-Thio-diethylidene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) 1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-sec-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-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-Triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4- tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0193] The content of the hindered phenolic compound is based on the total amount of the blocked maleimide compound and the reactive component, and can be 0.1% by mass or more and 20% by mass or more and 0.5% by mass or more and 10% by mass.

[0194] The curable resin composition may contain an organotitanium compound. The organotitanium compound may be, for example, a titanium chelate compound having two or more alkoxy groups, a tetraalkoxy titanium compound, a cyclopentadiene titanium compound, a monoalkoxy titanium compound, a titanium oxide compound, a tetraacetylacetone titanium compound, a titanate coupling agent, or a combination thereof.

[0195] Examples of titanium chelate compounds having two or more alkoxy groups include: bis(triethanolamine)diisopropoxide titanium, bis(n-butanol)bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, diisopropoxide bis(tetramethylheptanedione) titanium and diisopropoxide bis(ethylacetoacetic acid) titanium.

[0196] Examples of tetraalkoxy titanium compounds include: tetra(n-butanol)titanium, tetraethanol titanium, tetra(2-ethylhexanol)titanium, tetraisobutanol titanium, tetraisopropanol titanium, tetramethanol titanium, tetramethoxypropanol titanium, tetramethylphenol titanium, tetra(n-nonanol)titanium, tetra(n-propanol)titanium, tetrastearyl titanium, and tetra[bis{2,2-(allyloxymethyl)butanol}]titanium.

[0197] Examples of cyclopentadienyl titanium compounds include: pentamethylcyclopentadienyltrimethylethanol titanium, 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-pyrrole-1-yl)phenyl) titanium.

[0198] Examples of monoalkoxy titanium compounds include tris(dioctyl phosphate) isopropoxide titanium and tris(dodecylbenzenesulfonate) isopropoxide titanium.

[0199] Examples of titanium oxide compounds include bis(pentanedione)titanium oxide, bis(tetramethylheptanone)titanium oxide, and titanium phthalocyanine.

[0200] As an example of a tetraacetylacetone titanium compound, tetraacetylacetone titanium can be cited.

[0201] Examples of titanate coupling agents include isopropyltri-dodecylbenzenesulfonyl titanate.

[0202] The content of organotitanium compounds is based on the total amount of blocked maleimide compounds and reactive components, and can be 0.05% by mass or more and 10% by mass or more and 0.1% by mass or less and 2% by mass.

[0203] The curable resin composition may further comprise a tertiary amine. Examples of tertiary amines include: N,N-bis(3-dimethylaminopropyl)N-isopropanolamine, N,N-dimethylaminoethyl-N'-methylethanolamine (DABCO (trademark) T, Air Products and Chemicals, Inc. of Allentown, PA), N,N,N'-trimethylaminopropylethanolamine (POLYCAT (trademark) 17 from Air Products and Chemicals, Inc.), N,N-dimethylethanolamine (DABCO (trademark) DMEA), N,N-dimethyl-N',N'-2-hydroxy(propyl)-1,3-propanediamine, and dimethylaminopropylamine. amine (DMAPA), (N,N-dimethylaminoethoxy)ethanol, methyl-hydroxy-ethyl-piperazine, bis(N,N-dimethyl-3-aminopropyl)amine (POLYCAT (trademark) 15), N,N-dimethylaminopropylurea (DABCO (trademark) NE 1060, DABCO (trademark) NE 1070), N,N'-bis(3-dimethylaminopropyl)urea (DABCO (trademark) NE 1060, DABCO (trademark) NE 1070), bis(dimethylamino)-2-propanol, 6-dimethylamino-1-hexanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole and N-(2-hydroxyethyl)imidazole.

[0204] The content of tertiary amines is based on the total amount of blocked maleimide compounds and reactive components, and can be above 0.1% by mass and below 15% by mass.

[0205] The curable resin composition can be manufactured by a method comprising reacting the maleimide compound with the blocking agent in a solution containing a maleimide compound, a blocking agent, a reactive component, and a solvent to generate a blocked maleimide compound. The reaction of the maleimide compound with the blocking agent is mostly carried out rapidly at temperatures, for example, above 20°C and below 40°C.

[0206] Method for manufacturing resin-cured bodies and circuit connectors

[0207] Various resin-cured bodies, such as resin films, can be formed using the curable resin compositions exemplified above. Methods for forming resin-cured bodies include, for example, forming an intermediate molded body using a curable resin composition; and curing the intermediate molded body by heat treatment, thereby forming the resin-cured body.

[0208] An intermediate molded body is a molded body containing a curable resin composition before curing, such as a resin film. When the curable resin composition contains a solvent, the intermediate molded body is formed by removing the solvent from the curable resin composition of a predetermined shape. The intermediate molded body is formed by dissociating the blocking agent from the blocking maleimide compound, thereby generating a maleimide compound having maleimide groups within the intermediate molded body. Curing of the curable resin composition forming the intermediate molded body is achieved through heat treatment of the thermosetting intermediate molded body containing the maleimide compound. By heating the curable resin composition containing the solvent, the solvent can be removed, and the blocking agent can be dissociated from the blocking maleimide compound. By heating the curable resin composition, the blocking agent can be dissociated from the blocking maleimide compound, and the blocking agent can be removed. The heating temperature for dissociating and removing the blocking agent, and, if necessary, removing the solvent, can be, for example, 60°C or higher and 150°C or lower, or 90°C or higher and 120°C or lower.

[0209] The curable resin composition can be stored before being used to form a cured resin body. The curable resin composition exhibits high viscosity stability at room temperature, therefore refrigeration is not always necessary. For example, it can be stored at temperatures above 20°C and below 35°C. The storage period can be, for example, more than one hour and less than one year.

[0210] A resin-cured body comprising a cured or semi-cured curable resin composition can be formed by heat treatment of the intermediate molded body. Further curing can also be achieved by reheating the resin-cured body comprising a semi-cured curable resin composition after grinding, bonding with other components, or other processing. The heating temperature used to form the resin-cured body comprising a cured or semi-cured curable resin composition can be, for example, 100°C or higher and 300°C or lower.

[0211] The curable resin composition can be used to form a resin-cured body that serves as a resin film or insulating film, acting as a circuit connector. For example, the curable resin composition can be used to manufacture a circuit connector by co-bonding.

[0212] Figures 1, 2, and 3 are process diagrams illustrating an example of a method for manufacturing a circuit connector. The method shown in Figures 1-3 includes: preparing a first circuit component 10 having a first substrate 11, a first electrode 12, and a first insulating film 13; preparing a second circuit component 20 having a second substrate 21, a second electrode 22, and a second insulating film 23; and bonding the first circuit component 10 and the second circuit component 20 by hybrid bonding in a manner that electrically connects the first electrode 12 and the second electrode 22. By this method, a circuit connector 1 is formed as a junction of the first circuit component 10 and the second circuit component 20. In hybrid bonding, for example, the first circuit component 10 and the second circuit component 20 are heated and pressurized, thereby bonding the first insulating film 13 to the second insulating film 23 and the first electrode 12 to the second electrode 22.

[0213] At least one of the first substrate 11 or the second substrate 21 may be a semiconductor substrate with a circuit surface. In this case, a semiconductor device can be obtained as a circuit interconnect 1. Typically, an integrated circuit is disposed 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 components 20 having semiconductor chips may be bonded to a first circuit component 10 having a semiconductor wafer. In this case, the semiconductor wafer (first substrate 11) of the obtained circuit interconnect can be monolithically divided into a plurality of semiconductor chips. The semiconductor substrate may also be a silicon substrate, for example. When the first circuit component 10 or the second circuit component 20 is not a semiconductor substrate, they may also be various wiring substrates (e.g., interposers).

[0214] The first circuit component 10 has a plurality of first electrodes 12, and the first insulating film 13 includes a portion disposed around the first electrodes 12 and filling the gaps between the plurality of first electrodes 12. The first electrodes 12 and the first insulating film 13 are disposed 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 disposed on the circuit surface. The first insulating film 13 forms a plurality of openings 13a as through holes exposed on the first substrate 11, and the first electrodes 12 are disposed in the openings 13a.

[0215] The second circuit component 20 has a plurality of second electrodes 22, and the second insulating film 23 includes portions disposed around the second electrodes 22 and filling the gaps between the plurality of second electrodes 22. The second electrodes 22 and the second insulating film 23 are disposed on the second substrate 21. When the second substrate 21 is a semiconductor substrate, the second electrodes 22 and the second insulating film 23 are disposed on the circuit surface. The second insulating film 23 forms a plurality of openings 23a as through holes exposed on the second substrate 21, and the second electrodes 22 are disposed within the openings 23a.

[0216] The first circuit component 10 is prepared by the following method, which includes: setting a first electrode 12 on the main surface 11S of the first substrate as shown in FIG1(a); forming a first resin film 13A on the main surface 11S on the side of the first electrode 12 of the first substrate 11 as shown in FIG1(b); and forming a first insulating film 13 by heat treatment of the first resin film 13A as shown in FIG1(c).

[0217] The first electrode 12 is formed of a conductive material containing metals such as copper. The first electrode 12 containing metal can be formed by conventional methods such as plating.

[0218] The first resin film 13A is formed, for example, by coating a flowable curable resin composition. The flowable curable resin composition may contain a solvent. When using a curable resin composition containing a solvent, the first resin film 13A can be formed by heating the coated curable resin composition and removing the solvent. Heating for solvent removal can cause the sealing agent to dissociate from the maleimide compound, and may further cause the sealing agent to evaporate. A sealing agent may remain in the first resin film 13A. The heating temperature for solvent removal and sealing agent dissociation can be, for example, 60°C or higher and 150°C or lower, or 90°C or higher and 120°C or lower. The first resin film 13A can be formed in such a way that it fills the gaps between a plurality of first electrodes 12 while covering the entire first electrode 12. By heating the formed first resin film 13A, the first resin film 13A hardens or semi-hardens, forming a first insulating film 13. The first insulating film 13 contains a hardened or semi-hardened curable resin composition. In the case where the first insulating film 13 comprises a semi-cured curable resin composition, this can be confirmed, for example, by observing the heat generated during curing in a differential scanning calorimetry (DSC) thermogram obtained by differential scanning calorimetry of a sample of the first insulating film 13. In the case of a cured curable resin composition, heat generated during curing is substantially not observed.

[0219] The curable resin composition can be cured or semi-cured at a relatively low temperature to form an insulating film through a curing reaction involving maleimide compounds and reactive components. Advantages include the ability to cure at low temperatures, reducing thermal damage to the first circuit board and the like. Furthermore, the curing reaction is primarily an addition reaction such as free radical polymerization and Diels-Alder reaction, thus minimizing the generation of volatile components caused by the release of other components.

[0220] The surface of the first insulating film 13, formed from a curable resin composition containing a maleimide compound, may contain a large number of functional groups derived from maleimide groups, etc. Therefore, activation treatments such as plasma treatment are not necessarily required, and the first insulating film 13 can exhibit good adhesion. Furthermore, it is possible to adjust the polishing speed of the first insulating film 13 based on the crosslinking density, etc., in the first insulating film 13.

[0221] The temperature for heat treatment of the first resin film 13A used to form the first insulating film 13 can be, for example, 100°C or higher and 150°C or lower, or 150°C or higher and 300°C or lower. The heat treatment time can be, for example, 5 minutes or higher and 120 minutes or lower. The heat treatment conditions can also be adjusted to allow the first resin film 13A to partially harden. The thickness of the first insulating film 13 can be 1 μm or higher, or 10 μm or higher, or 100 μm or lower.

[0222] When the first insulating film 13, as shown in FIG1(c), covers the first electrode 12, a portion of the first insulating film 13 is removed from the side opposite to the first substrate 11, thereby forming an opening 13a of the first insulating film 13 exposing the first electrode 12, as shown in FIG2(d). A portion of the first insulating film 13 can also be removed by grinding. As a grinding method, conventional methods such as Chemical Mechanical Polishing (CMP) can be used. Grinding can also remove a portion of the first electrode 12, thereby planarizing the surface of the front end of the first electrode 12 (the surface opposite to the first substrate 11). Depending on the grinding speed, the height of the first electrode 12 in the ground first circuit component 10 can be greater than the thickness of the first insulating film 13. The difference between the height of the first electrode 12 and the thickness of the first insulating film 13 can also be adjusted, taking into account the difference in the coefficients of linear thermal expansion of the first electrode 12 and the first insulating film 13. The difference between the height of the first electrode 12 and the thickness of the first insulating film 13 can, for example, be 0.1 μm or more and 0.5 μm or less.

[0223] The second insulating film 23 of the second circuit component 20 can be an organic or inorganic insulating film. When the second insulating film 23 is an organic insulating film, the second circuit component can be prepared using the same method as the first circuit component 10, which includes heat-treating the second resin film containing a curable resin composition. If 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, they tend to exhibit particularly good adhesion. The first insulating film 13 and the second insulating film 23 can be formed using the same or different curable resin compositions.

[0224] 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 in a manner where the first electrode 12 and the second electrode 22 are face-to-face. The width of the first electrode 12 and the second electrode 22 may be, for example, more than 1 μm or more than 100 μm, and may be less than 300 μm or less than 30 μm. Here, the 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, more than 1 μm or more than 100 μm, and may be less than 300 μm or less than 30 μm. The height of the first electrode 12 and the second electrode 22 may be, for example, more than 1 μm or more than 10 μm, and may be less than 100 μm or less than 10 μm. 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.

[0225] Regarding the inter-electrode bonding, the surface of the tip of the first electrode 12 may have a surface roughness Ra of less than 1 nm. The surface of the tip of the second electrode 22 may also have the same surface roughness Ra. The surface roughness Ra here is the arithmetic mean roughness (Ra) specified in Japanese Industrial Standards (JIS) B 0601-2001.

[0226] As shown in Figure 2(e), the prepared first circuit component 10 and second circuit component 20 are aligned with the first electrode 12 and the second electrode 22 facing each other. Next, as shown in Figure 3, the first circuit component 10 and the second circuit component 20 are bonded by hybrid bonding through heating and pressurizing, so that the first electrode 12 and the second electrode 22 are bonded, and the first insulating film 13 and the second insulating film 23 are bonded.

[0227] The joining of the first electrode 12 and the second electrode 22, and the joining of the first insulating film 13 and the second insulating film 23, can be performed simultaneously or sequentially. For example, after heating and pressurizing primarily for joining the first insulating film 13 and the second insulating film 23, the first circuit component 10 and the second circuit component 20 can be further heated and pressurized to join 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-hardened state before joining. In this case, the first insulating film 13 and / or the second insulating film 23 may be further hardened during the heating and pressurizing process for joining the first circuit component 10 and the second circuit component 20. The first insulating film 13 and / or the second insulating film 23 may also be further hardened by heating after joining.

[0228] The heating and pressurizing conditions used for bonding are adjusted to ensure proper bonding of the insulating film and the electrode. For example, the heating temperature used for bonding can be 150°C or higher and 250°C or lower, and the pressure used for bonding can be 1.0 MPa or higher and 5.0 MPa or lower. The heating and pressurizing time can be, for example, 10 seconds or higher and 1 hour or lower.

[0229] [Example]

[0230] The present invention is not limited to the following embodiments.

[0231] 1. Prepare the following ingredients.

[0232] (A) Maleimide compound A1

[0233] Phenylmethane maleimide (BMI-2300, Daiwa Chemical Industries, Ltd.)

[0234] [Chemistry 34]

[0235]

[0236] (B) Styrene compounds B1

[0237] 2,2'-Dialylbisphenol A (Tokyo Chemical Industries, Ltd., 6.00 mmol, 1.85 g), 4,4'-Difluorobenzophenone (Tokyo Chemical Industries, Ltd., 5.00 mmol, 1.09 g), and potassium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd., 30.0 mmol, 4.15 g) were added to a three-necked flask. N-methylpyrrolidone (30 mL) and toluene (15 mL) were then added. A reflux duct and a Dean-Stark container were attached to the three-necked flask, and the system was placed under a nitrogen atmosphere. The reaction mixture in the three-necked flask was heated while being stirred. After the internal temperature reached 155°C, stirring was continued for 30 minutes to allow the reaction to proceed. Then, the reaction mixture in the three flasks was cooled to room temperature, and N-methylpyrrolidone (30 mL) was added. After washing the reaction solution several times with water and ethanol, styrene compound B1 (white solid) was obtained by filtration (yield 50%, weight average molecular weight 1500). Based on the obtained styrene compound B1... 1 H-nuclear magnetic resonance (NMR) spectroscopy confirmed the formation of 1-propenyl groups.

[0238] [Chemistry 35]

[0239]

[0240] (C) Sealant

[0241] Furfuryl alcohol (the compound represented by formula (20A))

[0242] (D) Solvent

[0243] Propylene glycol monomethyl ether acetate (MPA)

[0244] 2. Curing resin composition (varnish)

[0245] A solution containing maleimide compound A1 and MPA was prepared. Furfuryl alcohol was added to the solution, and the solution was heated to 65°C–75°C while stirring for 1 hour. After the solution temperature dropped to room temperature, a solution of MPA containing styrene compound B1 was added to the solution, and the mixture was stirred at room temperature for 30 minutes to obtain a varnish of a curable resin composition. Varnishes of Examples 1–4 containing each component in the proportions (parts by mass) shown in Table 1 were prepared. Varnishes of Comparative Example 1 or Comparative Example 2 containing each component in the proportions shown in Table 1 were also prepared in the same manner, except that furfuryl alcohol was not added.

[0246] 3. Stability

[0247] The viscosity (initial viscosity η0) of the freshly prepared varnish was measured. The viscosity η1 of the varnish was measured after standing at room temperature for 1 hour. Table 1 shows the viscosity measurement results and the viscosity ratio η1 / η0. The varnish of the example incorporating furfuryl alcohol showed a stable viscosity. This is believed to be because the maleimide compound was blocked by furfuryl alcohol.

[0248] [Table 1]

[0249]

[0250] Explanation of icon numbers

[0251] 1: Circuit connector

[0252] 10: First circuit component

[0253] 11: First substrate

[0254] 12: First electrode

[0255] 13: First insulating film

[0256] 13a, 23a: Opening

[0257] 13A: First resin film

[0258] 20: Second circuit component

[0259] 21: Second substrate

[0260] 22: Second electrode

[0261] 23: Second insulating film

Claims

1. A curable resin composition comprising: Blocked maleimide compounds having maleimide groups blocked by a blocking agent that dissociates upon heating; and The reactive component is a compound having a reactive group that reacts with a maleimide group, or a compound that generates the reactive group by heating.

2. The curable resin composition according to claim 1, wherein, The blocking agent is a compound that dissociates from the maleimide group by heating to below 230°C and has a boiling point to below 250°C.

3. The curable resin composition according to claim 1, wherein, The sealing agent comprises a diene compound having a diene group.

4. The curable resin composition according to claim 3, wherein, The diene compound is a compound having a furan group.

5. The curable resin composition according to claim 1, wherein, The reactive component comprises having the following formula (IV): [Chemistry 1] The compound represented is a styrene-based compound formed by removing one or more hydrogen atoms bonded to the benzene ring, R 22 and R 23 Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

6. The curable resin composition according to claim 1, wherein, The reactive component comprises an allyl compound having an allyl group.

7. The curable resin composition according to claim 1, wherein, The reactive component comprises an amine compound having an amino group.

8. The curable resin composition according to claim 1, wherein, The reactive component comprises a thiol compound having a thiol group.

9. The curable resin composition according to claim 1, wherein, The reactive component comprises phenolic compounds having phenolic hydroxyl groups.

10. The curable resin composition according to claim 1, wherein, The reactive component comprises a benzoxazine compound having a benzoxazine group.

11. The curable resin composition according to claim 1, further comprising a solvent.

12. A method for manufacturing a resin-cured body, comprising: A thermosetting intermediate molded body is formed by means of the curable resin composition according to any one of claims 1 to 11; as well as The intermediate molded body is hardened by heat treatment, thereby forming a resin-cured body. The intermediate molded body is formed by dissociating the blocking agent from the blocked maleimide compound to generate a maleimide compound having a maleimide group in the intermediate molded body.

13. The method of claim 11, further comprising storing the curable resin composition in an environment above 20°C and below 35°C.

14. A method for manufacturing a circuit connector, wherein, The circuit connector includes: a first circuit component having a first electrode, and a second circuit component having a second electrode. The method includes: A thermosetting first resin film is formed, comprising a portion disposed around the first electrode; The first resin film is hardened by heat treatment, thereby forming a first insulating film from the first resin film; and For the first circuit component having the first electrode and the first insulating film, and the second circuit component having the second electrode and a second insulating film including a portion disposed around the second electrode, the first electrode and the second electrode are joined by hybrid bonding in a manner that electrically connects them. The first resin film is formed from the curable resin composition according to any one of claims 1 to 11. The first resin film is formed by dissociating the blocking agent from the blocking maleimide compound to generate a maleimide compound having maleimide groups in the first resin film.

15. A method for manufacturing a circuit connector, wherein, The circuit connector includes: a first circuit component having a first electrode, and a second circuit component having a second electrode. The method includes: A thermosetting first resin film is formed, comprising a portion disposed around the first electrode; The first resin film is hardened by heat treatment, thereby forming a first insulating film from the first resin film; A thermosetting second resin film is formed, comprising a portion disposed around the second electrode; The second resin film is hardened by heat treatment, thereby forming a second insulating film from the second resin film; and For the first circuit component having the first electrode and the first insulating film, and the second circuit component having the second electrode and the second insulating film, the first electrode and the second electrode are joined by hybrid bonding in a manner that electrically connects them. The first resin film and the second resin film are formed from the curable resin composition according to any one of claims 1 to 11. The first resin film and the second resin film are formed by dissociating the blocking agent from the blocking maleimide compound to generate maleimide compounds having maleimide groups in the first resin film and the second resin film.

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