Curable maleimide resin composition, adhesive, primer, chip coating agent, and semiconductor device

Abstract

Provided is a curable maleimide resin composition which can be cured under low-temperature conditions without using a solvent having defects such as a high boiling point and toxicity, such as NMP, among aprotic polar solvents, and which can impart a cured product having excellent adhesiveness to a semiconductor element material. The curable maleimide resin composition contains (A) a maleimide compound having a number average molecular weight of 5,000-50,000, (B) a reaction initiator, (C) a silane coupling agent having one or more epoxy groups in one molecule, and (D) an imidazole having a diaminotriazine ring.

Description

Technical Field

[0001] The present invention relates to a curable maleimide resin composition, an adhesive, a primer, a chip coating agent and a semiconductor device. Background Art

[0002] Si (silicon) semiconductors or SiC (silicon carbide) semiconductors are used for elements built into power semiconductor modules.

[0003] On the other hand, SiN (silicon nitride) semiconductors are also mostly used in high-performance logic circuits or memories.

[0004] In the past, curable epoxy resin compositions or curable cyanate resin compositions have been widely used as encapsulants for protecting semiconductor elements (Patent Documents 1 and 2). However, when a semiconductor device is operated under high temperature conditions, since the linear expansion coefficients of the semiconductor element, substrate, and encapsulation material are different, when repeatedly exposed to high-temperature-low-temperature environmental conditions, there is a problem that stress is applied to the periphery of the semiconductor device due to temperature changes, resulting in the problem of easy peeling of the encapsulation material.

[0005] In addition, the cured resin component used in the packaging material has low moisture resistance and high hardness of the cured resin. Therefore, since the sealing material does not adhere to the semiconductor element in the sealing process of the semiconductor element or peels off in the subsequent process, there is a problem of reduced reliability of the packaging.

[0006] In order to solve these problems, people have proposed the scheme (patent documentation 3 and patent documentation 4) of forming primer layer on semiconductor element or metal lead frame.As primer layer, mainly use polyimide resin.Because polyimide resin is excellent in heat resistance, flame retardancy, mechanical characteristics and electrical insulation, it is widely used as the varnish of interlayer insulation film or surface protection film of semiconductor.After polyimide resin is directly or across insulating film applied to semiconductor element etc. with varnish state, it is solidified and forms the protective film that comprises polyimide resin, and the scheme of further encapsulating with encapsulation materials such as epoxy resin has been proposed (patent documentation 5 and patent documentation 6).

[0007] The varnish of the polyimide resin generally uses N-methyl-2-pyrrolidone (NMP) as a solvent. NMP has been widely used as an aprotic polar solvent since the beginning, but it is difficult to remove due to its high boiling point, and it is easy to leak and toxic. Therefore, the restrictions centered on Europe have become strict. In addition, the polyimide resin needs to be cured under very high temperature conditions such as above 250°C, and the polyimide resin itself is also easily affected by moisture absorption, so there are problems such as popcorn cracks and unstable quality, so there is a desire for alternative materials.

[0008] In order to solve these problems, people have proposed using a composition containing a thermosetting maleimide compound as a primer (Patent Document 7). In addition, in recent years, there has been a tendency to use unplated copper or copper wire for lead frames. In order to ensure the adhesion of the primer to copper, people have also proposed using a nitrogen atmosphere or an organic peroxide with a low half-life temperature. However, in order to improve the reliability of the primer, it is important to have adhesion not only to metals but also to semiconductor elements, and high adhesion is also required for packaging materials and metals, and further for semiconductor elements.

[0009] Prior art literature

[0010] Patent Literature

[0011] [Patent Document 1]: Japanese Patent Application Publication No. 2015-48434

[0012] [Patent Document 2]: Japanese Patent Application Publication No. 2015-93971

[0013] [Patent Document 3]: Japanese Patent Application Publication No. 2019-176085

[0014] [Patent Document 4]: Japanese Patent Application Publication No. 2022-148684

[0015] [Patent Document 5]: Japanese Patent Application Publication No. 2007-8977

[0016] [Patent Document 6]: Japanese Patent Application Publication No. 2010-70645

[0017] [Patent Document 7]: Japanese Patent Application Publication No. 2021-25031 Summary of the invention

[0018] Problem that the invention aims to solve

[0019] Therefore, the object of the present invention is to provide a curable maleimide resin composition, which can avoid the use of solvents such as NMP in aprotic polar solvents that have disadvantages such as high boiling point or toxicity, and can be cured under low temperature conditions, and in particular can provide a cured product with excellent adhesion to semiconductor element materials such as Si or SiN, SiC. In addition, the object of the present invention is also to provide an adhesive, substrate material, primer, coating material using the maleimide resin composition, and a semiconductor device having a cured product of the composition.

[0020] Solutions to the problem

[0021] The present inventors have conducted intensive studies to solve the above problems and have found that the following curable maleimide resin composition can achieve the above objects, thereby completing the present invention.

[0022] <1>

[0023] A curable maleimide resin composition comprises (A) a maleimide compound, (B) a reaction initiator and (C) a silane coupling agent, wherein the silane coupling agent of the component (C) has one or more epoxy groups in one molecule.

[0024] The maleimide compound (A) is represented by the following formula (1) and has a number average molecular weight of 5,000 to 50,000.

[0025] [Chemical formula 1]

[0026]

[0027] (In formula (1), Q 1 are independently a divalent group represented by the following formula,

[0028] [Chemical formula 2]

[0029]

[0030] In the above formula, X 1 are independently divalent groups selected from the following formulae.

[0031] [Chemical formula 3]

[0032]

[0033] In addition, a is a number from 0 to 50, b is a number from 1 to 50, A 1 and A 2 are each independently a group represented by the following formula (2) or the following formula (3),

[0034] [Chemical formula 4]

[0035]

[0036] (In formula (2) and formula (3), X 2 is a divalent group selected from the following formulas,

[0037] [Chemical formula 5]

[0038]

[0039] In formula (2), R 1 are independently a hydrogen atom, a chlorine atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms.

[0040] <2>

[0041] The curable maleimide resin composition as described in <1>, further comprising (D) an imidazole having a diaminotriazine ring.

[0042] <3>

[0043] The curable maleimide resin composition as described in <1> or <2> further comprises (E) an organic solvent, but does not comprise N-methylpyrrolidone (NMP).

[0044] <4>

[0045] The curable maleimide resin composition according to any one of <1> to <3>, wherein the reaction initiator (B) is an organic peroxide having a 1-hour half-life temperature of 150° C. or less.

[0046] <5>

[0047] An adhesive comprising the curable maleimide resin composition according to any one of <1> to <4>.

[0048] <6>

[0049] A primer comprising the curable maleimide resin composition according to any one of <1> to <4>.

[0050] <7>

[0051] A chip coating agent comprising the curable maleimide resin composition according to any one of <1> to <4>.

[0052] <8>

[0053] A semiconductor device comprising a cured product of the curable maleimide resin composition according to any one of <1> to <4>.

[0054] Effects of the Invention

[0055] The curable maleimide resin composition of the present invention can avoid the use of solvents such as NMP among aprotic polar solvents that have disadvantages such as high boiling point or toxicity, and can be cured under low temperature conditions, and can particularly provide a cured product with excellent adhesion to Si or to SiN and SiC. Therefore, the curable maleimide resin composition of the present invention can be suitably used as an adhesive, a primer, a coating material, and a semiconductor device having a cured product of the composition. DETAILED DESCRIPTION

[0056] Hereinafter, the present invention will be described in more detail.

[0057] (A) Maleimide compounds

[0058] The component (A) is a maleimide compound represented by the following formula (1) and having a number average molecular weight of 5,000 to 50,000.

[0059] [Chemical formula 6]

[0060]

[0061] (In formula (1), Q 1 are independently a divalent group represented by the following formula,

[0062] [Chemical formula 7]

[0063]

[0064] In the above formula, X 1 are independently divalent groups selected from the following formulae.

[0065] [Chemical formula 8]

[0066]

[0067] In addition, a is a number from 0 to 50, b is a number from 1 to 50, A 1 and A 2 Each is independently represented by the following formula (2) or the following formula (3).

[0068] [Chemical formula 9]

[0069]

[0070] (In formula (2) and formula (3), X 2 is a divalent group selected from the following formulas,

[0071] [Chemical formula 10]

[0072]

[0073] In formula (2), R 1 are independently a hydrogen atom, a chlorine atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms.

[0074] From the viewpoint of easy availability of raw materials, X in formula (1) 1 , preferably -CH2-, -C(CH3)2-.

[0075] In formula (1), a is a number of 0-50, preferably a number of 1-40.

[0076] In formula (1), b is a number of 1-50, preferably a number of 1-40.

[0077] In formula (1), A 1 and A 2 Each independently represents a group represented by the above formula (2) or the above formula (3).

[0078] From the viewpoint of easy availability of raw materials, X in formula (2) and formula (3) is 2 , preferably -CH2-, -C(CH3)2-.

[0079] In formula (2), R 1 They are independently a hydrogen atom, a chlorine atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms.

[0080] As R in formula (2) 1 The unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms as shown in the figure may be methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, etc., and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as F, Cl, Br, etc., such as trifluoromethyl, etc. From the viewpoint of easy availability of raw materials, R 1 , preferably a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 3 carbon atoms.

[0081] In the maleimide compound represented by formula (1), A 1 and A 2 Preferably, they are different groups. For example, in formula (1), preferably, in A 1 In the case of a group represented by the formula (2), A 2 is a group represented by the formula (3), and for example, in A 1 In the case of a group represented by the formula (3), A 2 It should be noted that in the maleimide compound represented by formula (1), A 1 and A 2 They cannot be formula (2) at the same time.

[0082] The bonding form of the unit with repeating unit number a and the unit with repeating unit number b in the maleimide compound represented by formula (1) may be random or block, but is preferably block from the viewpoint of mechanical strength of the cured product.

[0083] (A) component is a component having a bisphenol structure in one molecule, as shown in the above formula (1), which is soluble in solvents other than NMP and is a component with excellent solvent solubility. In addition, from the viewpoint of easy access to raw materials, maleimide compounds having a bisphenol structure are also preferred. As the bisphenol structure possessed by the (A) component, bisphenol A, bisphenol F, bisphenol E, bisphenol AF, etc. can be cited, and there is no particular limitation on them, preferably bisphenol A and bisphenol F. In addition, since a and b are respectively within the above ranges, the maleimide compound shown in the above formula (1) is a compound with good balance between solubility and film-forming properties in solvents when uncured and the toughness and heat resistance of the obtained cured product.

[0084] The number average molecular weight of the maleimide compound of the component (A) is 5000 to 50000, preferably 7000 to 40000, and more preferably 8000 to 20000. If the number average molecular weight of the maleimide compound of the component (A) is within this range, the maleimide compound of the component (A) can stably dissolve in the solvent, can ensure wettability to the substrate, and the film before curing is unlikely to crack, thereby becoming a good compound.

[0085] It should be noted that the number average molecular weight referred to in this specification refers to the number average molecular weight measured by gel permeation chromatography (GPC) under the following conditions using polystyrene as a standard substance.

[0086] [GPC measurement conditions]

[0087] Elution solvent: tetrahydrofuran

[0088] Flow rate: 0.35mL / min

[0089] Detector: Refractive Index Detector (RI)

[0090] Column: TSK-GEL H type (manufactured by TOSOH CORPORATION)

[0091] Column temperature: 40°C

[0092] Sample injection volume: 5 μL (0.2 mass % THF solution)

[0093] The maleimide compound represented by the formula (1) as the component (A) can be produced by the method described in, for example, JP-A-2021-017485.

[0094] (A) The maleimide compound of the component may be used alone or in combination of two or more.

[0095] In addition, in the curable maleimide resin composition of the present invention (wherein, in the case of containing the (E) organic solvent described later, it is a curable maleimide resin composition that does not contain the (E) organic solvent), the (A) component is preferably contained in an amount of 70 to 99.9% by mass, more preferably 80 to 99.5% by mass, and even more preferably 85 to 99.0% by mass.

[0096] (B) Reaction initiator

[0097] The reaction initiator of the component (B) is a component added for initiating and accelerating the crosslinking reaction of the maleimide compound of the component (A) or the reaction between the maleimide group in the component (A) and a reactive group capable of reacting therewith.

[0098] As component (B), there is no particular limitation as long as it is a component that promotes the crosslinking reaction. In order to improve productivity, it is preferably a thermal free radical polymerization initiator and / or a photopolymerization initiator that can be easily cured in a short time. When a thermal free radical polymerization initiator is used as component (B), the curable maleimide resin composition of the present invention is cured at a relatively low temperature (e.g., a temperature below 220°C). When a photopolymerization initiator is used as component (B), the curable maleimide resin composition of the present invention is cured by light irradiation. It should be noted that component (B) does not contain the imidazole having a diaminotriazine ring (D) described later.

[0099] Representative examples of thermal radical polymerization initiators include organic peroxides such as dicumyl peroxide, tert-butyl perbenzoate, tert-amyl perbenzoate, dibenzoyl peroxide, dilauroyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,1-di(tert-butylperoxy)cyclohexane, di-tert-butyl peroxide, dibenzoyl peroxide, and 1,6-bis(tert-butylperoxycarbonyloxy)hexane.

[0100] The photopolymerization initiator is not particularly limited as long as it is an initiator that initiates the reaction by light. Examples of the photopolymerization initiator include aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholino-1-propanone, 2,4-diethylthioxanthone, 2-ethylanthraquinone and phenanthrenequinone; and Benzyl derivatives such as dimethyl ketal; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-phenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)- )-5-phenylimidazole dimer and 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer and other 2,4,5-triaryl imidazole dimers; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; bisacyl phosphine oxide such as bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide Phosphine oxide; alkyl ketone compounds such as 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone; acyl phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; benzophenone compounds, etc.

[0101] Relative to 100 parts by mass of component (A), the reaction initiator is preferably mixed with 0.05 to 10 parts by mass, and more preferably mixed with 0.1 to 5 parts by mass. In addition, when other thermosetting resins described later are mixed in the composition, the reaction initiator is preferably mixed in the range of 0.05 to 10 parts by mass, and particularly preferably mixed in the range of 0.1 to 5 parts by mass, relative to 100 parts by mass of the sum of component (A) and other thermosetting resin components. If the reaction initiator is not in the range of 0.05 to 10 parts by mass relative to 100 parts by mass of the above-mentioned component (A), curing may become very slow or accelerated during molding, so it is not preferred. In addition, the balance of heat resistance and moisture resistance of the obtained cured product may also deteriorate.

[0102] The reaction initiator may be used alone or in combination of two or more.

[0103] (C) Silane coupling agent

[0104] The silane coupling agent of the component (C) is a silane coupling agent having one or more epoxy groups in one molecule, and is preferably a silane coupling agent represented by the following general formula (4).

[0105] R 2 d Si(OR 3 ) 4-d (4)

[0106] (In formula (4), R 2 are independently selected from monovalent hydrocarbon groups having an epoxy group or alkyl groups having 1 to 6 carbon atoms, wherein at least one R 2 is a monovalent hydrocarbon group having an epoxy group. 3 are independently an alkyl group having 1 to 6 carbon atoms, and d is 1, 2 or 3).

[0107] The monovalent hydrocarbon group having an epoxy group is preferably a monovalent hydrocarbon group having an epoxy group having 3 to 20 carbon atoms, and more preferably a group selected from 3-glycidoxypropyl, 8-glycidoxyoctyl and 2-(3,4-epoxycyclohexyl)ethyl.

[0108] Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group, and methyl group and ethyl group are preferred.

[0109] The silane coupling agent as the component (C) can improve the adhesiveness to the semiconductor element such as Si, SiN, SiC, etc. by having one or more epoxy groups in one molecule.

[0110] In addition, R 3 The alkyl groups are independently alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl and hexyl. Specific examples include methyl, ethyl, propyl and butyl, and methyl and ethyl are particularly preferred. d is 1, 2 or 3, and 1 is particularly preferred.

[0111] Specific examples of the component (C) include KBM-403, KBE-403, KBM-303, KBM-4803, and KBM-402 (all manufactured by Shin-Etsu Chemical Co., Ltd.) or hydrolyzates thereof.

[0112] The amount of component (C) is preferably 0.2 to 4.5 parts by mass, particularly preferably 0.5 to 2.5 parts by mass, relative to 100 parts by mass of component (A). If the amount of component (C) is less than 0.2 parts by mass, sufficient adhesive force cannot be exerted; if the amount of component (C) is greater than 4.5 parts by mass, not only voids are easily generated during molding of the composition, but also the strength of the molded product is easily reduced.

[0113] The composition of the present invention may further contain the following components as necessary.

[0114] (D) Imidazole with a diaminotriazine ring

[0115] In the present invention, an imidazole having a diaminotriazine ring as component (D) may also be used. The diaminotriazine ring has an effect of improving the adhesive force on metals, especially copper. In addition, since it contains imidazole, it also promotes the polymerization of maleimide and is also effective in imparting heat resistance. As component (D), any imidazole having a diaminotriazine ring is not particularly limited.

[0116] Specific examples of the component (D) include 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine (trade name 2MZ-A, manufactured by Shikoku Chemicals Holdings Co., Ltd.), 2,4-diamino-6-[2-(2-undecyl-1-imidazolyl)ethyl]-1,3,5-triazine (trade name C11Z-A, manufactured by Shikoku Chemicals Holdings Co., Ltd.), 2,4-diamino-6-[2-(4-methyl-1-imidazolyl)ethyl]-1,3,5-triazine (trade name 2E4MZ-A, manufactured by Shikoku Chemicals Holdings Co., Ltd.), and 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine isocyanuric acid adduct (trade name 2MA-OK, manufactured by Shikoku Chemicals Holdings Co., Ltd.).

[0117] The amount of component (D) is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of component (A). If the amount of component (D) is 0.05 to 5 parts by mass relative to 100 parts by mass of component (A), the effect of improving the adhesive force can be obtained, and the dispersibility is good, and neither the appearance is poor nor the reliability is reduced.

[0118] (E) Organic solvents

[0119] The composition of the present invention may also contain an organic solvent as component (E). If it is an organic solvent that can dissolve component (A), its type is not limited, but from the perspective of environmental burden, N-methyl-2-pyrrolidone (NMP) is excluded from the object. At this time, the so-called "the (E) component can dissolve the above-mentioned (A) component" means that when component (E) is used as a solvent to prepare a 25% by mass solution of component (A), no dissolved residue of component (A) is visually confirmed at 25°C. By combining with an organic solvent, it can be suitably used as a varnish or primer.

[0120] As the component (E), for example, common organic solvents such as methyl ethyl ketone (MEK), cyclohexanone, ethyl acetate, tetrahydrofuran (THF), isopropyl alcohol (IPA), xylene, toluene, and anisole can be used. These organic solvents can be used alone or in combination of two or more.

[0121] When the composition of the present invention is used as a primer, the organic solvent as the component (E) is preferably cyclohexanone, xylene, anisole, or the like.

[0122] From the viewpoint of solubility of the above-mentioned (A) component, the organic solvent of the (E) component is preferably anisole, xylene, toluene, cyclohexanone and the like. On the other hand, from the viewpoints of high boiling point and toxicity, it is preferred not to use the above-mentioned NMP or dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and the like among the aprotic polar solvents. Different from the conventional compositions containing polyimide compounds that are only soluble in aprotic polar solvents, the composition of the present invention has the advantage that these aprotic polar solvents can be used without using them.

[0123] The amount of the component (E) to be added is preferably 100 to 800 parts by mass, more preferably 150 to 700 parts by mass, based on 100 parts by mass of the component (A).

[0124] Other additives

[0125] In the scope of not damaging the effect of the present invention, various additives can be coordinated in the curable maleimide resin composition of the present invention. For example, in order to improve the resin properties, it is also possible to coordinate the adhesive aids other than thermosetting resins such as acrylic resins, organopolysiloxanes, silicone oils, thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, light stabilizers, polymerization inhibitors, flame retardants, pigments, dyes and silane coupling agents, etc. In addition, in order to improve electrical properties, it is also possible to coordinate ion trapping agents, etc. And then, in order to improve dielectric properties, it is also possible to coordinate fluorine-containing materials, etc. In order to adjust the coefficient of thermal expansion (CTE), it is also possible to add inorganic fillers such as silicon dioxide.

[0126] The curable maleimide resin composition of the present invention can be prepared by mixing the components (A), (B), (C), and (D), as well as the component (E) and other additives.

[0127] The curable maleimide resin composition of the present invention can be used as an adhesive, a primer, a chip coating agent, a coating material for a semiconductor device, a buffer coating, a rewiring layer, etc. There is no particular limitation on the method and form of use.

[0128] The following are examples of use, but the present invention is not limited thereto.

[0129] For example, after applying a curable maleimide resin composition containing component (A), component (B), component (C), and component (D) and / or component (E) to a substrate (e.g., a metal lead frame such as a lead frame plated with silver, a copper lead frame, etc.), the organic solvent is removed by heating the substrate at a temperature of usually 80° C. or more, preferably 100° C. or more for 0.5 to 5 hours. In addition, if the maleimide resin composition is a thermosetting type, the substrate is heated at a temperature of 130° C. or more, preferably 150° C. or more for 0.5 to 10 hours; if the maleimide resin composition is a photocurable type, a maleimide film having a flat surface and being strong can be formed by irradiating the substrate with 365 nm UV light.

[0130] In the case of a conventional polyimide, it is necessary to dry at 150°C or above and to heat cure at 220°C or above, but the curable maleimide resin composition of the present invention does not require such high temperature conditions. Specifically, the removal of the organic solvent can be carried out at 150°C or below, and the heat curing (film formation) can be carried out at 200°C or below.

[0131] In order to effectively remove the organic solvent in the composition and effectively promote the reaction of the resin, according to the situation, the curing temperature can be increased in stages, and heating can be performed for the purpose of completely ending the curing after photocuring. The cured product (film) obtained by curing the composition of the present invention has excellent mechanical properties, heat resistance, relative dielectric constant, dielectric loss tangent, moisture resistance and adhesion. Therefore, the cured product of the present invention can also be used as, for example, an adhesive for semiconductor elements and lead frames; a primer for semiconductor sealing materials and lead frames; a chip coating agent (passivation film) on the surface of semiconductor elements; a bonding protective film for the joints of diodes, transistors, etc.; an α-ray shielding film for VLSI; an interlayer insulating film; and a conformal coating for printed circuit boards.

[0132] Examples of the coating method include methods using a spin coater, a slit coater, a spray coater, a dip coater, and a bar coater, but are not particularly limited.

[0133] By forming the epoxy resin molding material for semiconductor packaging on the cured product (film) after forming the cured product (film), the adhesion between the epoxy resin molding material for semiconductor packaging and the semiconductor element or substrate can be improved. The semiconductor device obtained in this way has high reliability because no cracks are observed in the epoxy resin molding material for semiconductor packaging and no peeling of the molding material from the substrate during reflow soldering after moisture absorption.

[0134] In this case, as the semiconductor encapsulation epoxy resin molding material, a known semiconductor encapsulation epoxy resin composition can be used, or a commercially available product can be used. The known semiconductor encapsulation epoxy resin molding material includes a curing agent for epoxy resins such as epoxy resins, phenolic resins, and acid anhydrides having two or more epoxy groups in one molecule, and / or an inorganic filler.

[0135] [Example]

[0136] The present invention will be described in detail below by showing examples and comparative examples, but the present invention is not limited to the following examples. In the examples and comparative examples, "room temperature" means 25°C.

[0137] The components used in Examples and Comparative Examples are shown below. The number average molecular weight (Mn) in the following is a value obtained by using polystyrene as a standard substance measured by gel permeation chromatography (GPC) under the following measurement conditions.

[0138] [GPC measurement conditions]

[0139] Elution solvent: tetrahydrofuran

[0140] Flow rate: 0.35mL / min

[0141] Detector: Refractive Index Detector (RI)

[0142] Column: TSK-GEL H type (manufactured by TOSOH CORPORATION)

[0143] Column temperature: 40°C

[0144] Sample injection volume: 5 μL (0.2 mass % THF solution)

[0145] (A) Maleimide compounds

[0146] [Synthesis example 1]

[0147] 65.06 g (0.125 mol) of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride, 61.59 g (0.150 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 250 g of anisole were added to a 1 L glass four-necked flask equipped with a stirrer, a Dean-Stark tube, a cooling condenser and a thermometer, and stirred at 80° C. for 3 hours to synthesize an amic acid. Then, the temperature was directly raised to 150° C. and stirred for 2 hours while distilling off the by-produced water, thereby producing a diamine at both ends.

[0148] After cooling the flask containing the obtained two-terminal diamine solution to room temperature, 4.39 g (0.055 mol) of maleic anhydride was added, and the mixture was stirred at 80° C. for 3 hours to synthesize maleic acid. Then, it was directly heated to 150° C. and stirred for 2 hours while distilling off the by-product water, thereby obtaining a varnish of an aromatic bismaleimide compound represented by the following formula (A-1). The number average molecular weight (Mn) of the aromatic bismaleimide compound is 12000. Anisole was added to make the non-volatile component of the varnish 17% by mass.

[0149] [Chemical formula 11]

[0150]

[0151] (In formula (A-1), P and Q are independently divalent groups represented by the following formula.)

[0152] [Chemical formula 12]

[0153]

[0154] [Synthesis example 2]

[0155] 65.06 g (0.125 mol) of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride, 35.26 g (0.115 mol) of 4,4-methylenebis(2,6-diethylaniline) and 250 g of anisole were added to a 1L glass four-necked flask equipped with a stirrer, a Dean-Stark tube, a cooling condenser and a thermometer, and stirred at 80° C. for 3 hours to synthesize amic acid. Then, the mixture was heated to 150° C. and stirred for 2 hours while distilling off the by-produced water to synthesize a copolymer.

[0156] Then, 7.05 g (0.015 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane was added to the flask containing the copolymer solution cooled to room temperature, and stirred at 80° C. for 3 hours to synthesize an amic acid. Then, the temperature was directly raised to 150° C. and stirred for 2 hours while distilling off the by-produced water, thereby synthesizing a diamine at both ends.

[0157] After cooling the flask containing the obtained two-terminal diamine solution to room temperature, 1.45g (0.015 mol) of maleic anhydride was added, and the mixture was stirred at 80°C for 3 hours to synthesize maleamic acid. Then, it was directly heated to 150°C and stirred for 2 hours while distilling off the by-product water, thereby obtaining a varnish of an aromatic bismaleimide compound shown in the following formula (A-2). The number average molecular weight (Mn) of the aromatic bismaleimide compound is 15500. Anisole was added to make the non-volatile component of the varnish 17% by mass.

[0158] [Chemical formula 13]

[0159]

[0160] Other maleimide compounds (for comparative examples)

[0161] (A-3): A bismaleimide compound represented by the following formula (trade name: BMI-5000, Mn: 8000, manufactured by Designer Molecules Inc.)

[0162] [Chemical formula 14]

[0163]

[0164] -C 36 H 70 - represents a hydrocarbon group derived from the dimer acid skeleton.

[0165] n≈8 (average)

[0166] (A-4): 4,4'-diphenylmethanebismaleimide (BMI-1000, Mn: 410, manufactured by Yamato Chemical Industry Co., Ltd.)

[0167] (B) Reaction initiator

[0168] (B-1): Dicumyl peroxide (trade name: PERKADOX BC-FF, manufactured by Nippon Kayaku Nouryon Co., Ltd., 1-hour half-life temperature 132°C)

[0169] (B-2): 1,6-bis(tert-butylperoxycarbonyloxy)hexane (trade name: KAYALENE 6-70, manufactured by Nippon Kayaku Nouryon Co., Ltd., 1-hour half-life temperature 117°C)

[0170] (C) Silane coupling agent

[0171] (C-1): 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (trade name: KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0172] (C-2): 3-Glycidoxypropyltriethoxysilane (trade name: KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0173] (C-3): Hydrolyzate of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (component C-1): component (component (C-1): water = 4:1 (mass ratio), hydrolyzate mixed at 25°C for 12 hours)

[0174] (C-4): N-phenyl-3-aminopropyltrimethoxysilane (trade name: KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd. (for comparative example)

[0175] (C-5): 3-methacryloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) (for comparative example)

[0176] (D) Imidazole with a diaminotriazine ring

[0177] (D-1): 2,4-diamino-6-[2-(4-methyl-1-imidazolyl)ethyl]-1,3,5-triazine (trade name: 2E4MZ-A, manufactured by Shikoku Chemical Holdings Co., Ltd.)

[0178] Comparative Example Polyimide

[0179] Polyamic acid varnish (KJR-655, manufactured by Shin-Etsu Chemical Co., Ltd., NMP varnish, non-volatile content 15% by mass) was used directly.

[0180] (Formulation Examples 1 to 16, Examples 1 to 8, Comparative Examples 1 to 13)

[0181] A varnish of a curable maleimide resin composition was prepared by mixing the components in the formulation shown in Table 1. In all formulations, anisole was added so that the component (A) was 16.7% by mass, and the component (A) was completely dissolved.

[0182] <Adhesion and failure mode>

[0183] The varnish of the composition obtained in the above-mentioned Formulation Examples 1 to 16 was applied by spraying to Si, SiN or SiC cut into 20 mm×20 mm, and cured according to the curing conditions described in Table 2 or Table 3 to form a cured film (primer).

[0184] Under the conditions of pressure 6.9 MPa and temperature 175°C, semiconductor sealing epoxy resin molding material KMC-2284 (manufactured by Shin-Etsu Chemical Co., Ltd.) was cured on the cured film for 120 seconds to form a bottom area of ​​10 mm 2 , a cylindrical shape with a height of 3 mm. Then, using a universal adhesion tester (DAGE SERIES 4000: manufactured by Nordson DAGE), the adhesion at 25°C was measured at a speed of 0.2 mm / sec for the test piece post-cured at 180°C for 4 hours. The evaluation criteria of ○, △ and × for the failure mode after the adhesion measurement are as follows, and the goodness of the failure mode results is ○>△>×.

[0185] ○: Semiconductor device damage

[0186] △: Cohesive failure of packaging materials on semiconductor components

[0187] ×: The packaging material peels off from the interface of the semiconductor element

[0188] These measurement results are shown in Tables 2 and 3. In addition, the details of the curing conditions A to C are as follows.

[0189] Curing conditions A: 110℃ 30 minutes + 180℃ 2 hours

[0190] Curing condition B: 110℃ for 30 minutes + 220℃ for 2 hours

[0191] Curing conditions C: 150℃ for 1 hour + 200℃ for 1 hour + 250℃ for 4 hours

[0192] In addition, Comparative Example 1 is the result of measuring the adhesive force under the condition that no primer (clear varnish of the composition) is used. Therefore, the column of curing conditions is not described.

[0193] [Table 1]

[0194]

[0195] [Table 2]

[0196]

[0197] [Table 3]

[0198]

Claims

1. A curable maleimide resin composition comprising (A) a maleimide compound, (B) a reaction initiator and (C) a silane coupling agent, wherein: The silane coupling agent of the component (C) has one or more epoxy groups in one molecule. The maleimide compound (A) is represented by the following formula (1) and has a number average molecular weight of 5,000 to 50,000. [Chemical formula 1] In formula (1), Q 1 are independently a divalent group represented by the following formula, [Chemical formula 2] Q 1 In the above formula, X 1 are independently divalent groups selected from the following formulas, [Chemical formula 3] In addition, a is a number from 0 to 50, b is a number from 1 to 50, A 1 and A 2 are each independently a group represented by the following formula (2) or the following formula (3), [Chemical formula 4] In formula (2) and formula (3), X 2 is a divalent group selected from the following formulas, [Chemical formula 5] In formula (2), R 1 They are independently a hydrogen atom, a chlorine atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms. 2 . The curable maleimide resin composition according to claim 1 , further comprising (D) an imidazole having a diaminotriazine ring. 3 . The curable maleimide resin composition according to claim 1 , further comprising (E) an organic solvent, but excluding N-methylpyrrolidone (NMP).

4. The curable maleimide resin composition according to claim 1, wherein (B) The reaction initiator is an organic peroxide having a one-hour half-life temperature of 150°C or less. 5 . An adhesive comprising the curable maleimide resin composition according to claim 1 . 6 . A primer comprising the curable maleimide resin composition according to claim 1 . 7 . A chip coating agent comprising the curable maleimide resin composition according to claim 1 . 8 . A semiconductor device comprising a cured product of the curable maleimide resin composition according to claim 1 .

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