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

Abstract

To provide a curable maleimide resin composition capable of avoiding use of a solvent having such draw back as high boiling point, or toxicity such as NMP in an aprotonic polar solvent, and curing at a low temperature, and giving a cured product excellent in adhesiveness to a semiconductor element material.SOLUTION: A curable maleimide resin composition includes: (A) a maleimide compound having a number average molecular weight of 5,000-50,000; (B) a reaction initiator; and (C) a silane coupling agent having one or more epoxy groups in one molecule. A curable maleimide resin composition further includes (D) an imidazole having a diaminotriazine ring.SELECTED DRAWING: None

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 technology]

[0002] The elements built into power semiconductor modules use Si (silicon) semiconductors and SiC (silicon carbide) semiconductors.

[0003] On the other hand, SiN (silicon nitride) semiconductors are also widely used for high-performance logic and memory.

[0004] Conventionally, curable epoxy resin compositions and curable cyanate resin compositions have been widely used as sealants for protecting semiconductor elements (Patent Documents 1 and 2). However, when a semiconductor device is operated at high temperatures, the linear expansion coefficients of the semiconductor element, the base material, and the sealant are different from one another, and therefore, when the device is repeatedly exposed to high and low temperature environments, stress is applied to the periphery of the semiconductor device due to temperature changes, which can easily cause peeling of the sealant. Furthermore, the cured resin components used in the encapsulant have low moisture resistance and the hardness of the cured resin is high. As a result, the encapsulant does not adhere to the semiconductor element during the encapsulation process or peels off in a later process, causing a problem of reduced package reliability.

[0005] In order to solve these problems, it has been proposed to form a primer layer on the semiconductor element or metal lead frame (Patent Documents 3 and 4). Polyimide resin is mainly used as the primer layer. Polyimide resin is widely used as a varnish for interlayer insulating films or surface protective films of semiconductors because of its excellent heat resistance, flame retardancy, mechanical properties, and electrical insulation properties. It has been proposed to apply polyimide resin in a varnish state directly to a semiconductor element or the like or via an insulating film, and then harden the varnish to form a protective film made of polyimide resin, which is then sealed with a sealing material such as epoxy resin (Patent Documents 5 and 6).

[0006] Polyimide resin varnishes generally use N-methyl-2-pyrrolidone (NMP) as a solvent. NMP has long been widely used as an aprotic polar solvent, but because it has a high boiling point and is difficult to remove, and is easily exposed to and toxic, regulations on it are becoming stricter, especially in Europe. In addition, polyimide resins need to be cured at extremely high temperatures of over 250°C, and polyimide resins themselves are susceptible to moisture absorption, causing issues such as popcorn cracks and unstable quality, so alternative materials are desired.

[0007] To solve these problems, it has been proposed to use a composition containing a thermosetting maleimide compound as a primer (Patent Document 7). Furthermore, in recent years, there has been a trend toward using unplated copper or copper wire for lead frames, and the use of a nitrogen atmosphere or an organic peroxide with a low half-life temperature has been proposed to ensure adhesion to copper. However, in order to improve the reliability of the primer, adhesion to not only metals but also semiconductor elements is important, and high adhesion to encapsulants, metals, and semiconductor elements is required. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2015-48434 A [Patent Document 2] JP 2015-93971 A [Patent Document 3] JP 2019-176085 A [Patent Document 4] JP 2022-148684 A [Patent Document 5] JP 2007-8977 A [Patent Document 6] JP 2010-70645 A [Patent Document 7] Patent Publication No. 2021-25031 Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, an object of the present invention is to provide a curable maleimide resin composition which can avoid the use of aprotic polar solvents such as NMP, which have drawbacks such as a high boiling point and toxicity, can be cured at low temperatures, and gives a cured product which has excellent adhesion, particularly to semiconductor element materials such as Si, SiN, and SiC.It is also an object of the present invention to provide an adhesive, a substrate material, a primer, a coating material which uses this maleimide resin composition, and a semiconductor device which has a cured product of the composition. [Means for solving the problem]

[0010] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems, and as a result have found that the following curable maleimide resin composition can achieve the above object, thereby completing the present invention.

[0011] [1] (A) a maleimide compound represented by the following formula (1) and having a number average molecular weight of 5,000 to 50,000: (B) a reaction initiator, and (C) Silane coupling agent wherein the silane coupling agent of component (C) has one or more epoxy groups in one molecule. [ka] (In formula (2), Q 1 are independently expressed by the following formula: [ka] In the above formula, X 1 are independently expressed by the following formula: [ka] In addition, a is a number from 0 to 50, b is a number from 1 to 50, and A1 and A 2 are each independently represented by the following formula (2) or the following formula (3): [ka] (In formula (3) and formula (4), X 2 is expressed as follows: [ka] 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. [2] The curable maleimide resin composition according to [1], further comprising (D) an imidazole having a diaminotriazine ring. [3] The curable maleimide resin composition according to [1] or [2], further comprising (E) an organic solvent (excluding N-methylpyrrolidone (NMP)). [4] (B) The curable maleimide resin composition according to any one of [1] to [3], wherein the reaction initiator is an organic peroxide having a one-hour half-life temperature of 150° C. or lower. [5] An adhesive comprising the curable maleimide resin composition according to any one of [1] to [4]. [6] A primer comprising the curable maleimide resin composition according to any one of [1] to [4]. [7] A chip coating agent comprising the curable maleimide resin composition according to any one of [1] to [4]. [8] A semiconductor device comprising a cured product of the curable maleimide resin composition according to any one of [1] to [4]. Effect of the Invention

[0012] The curable maleimide resin composition of the present invention can avoid the use of aprotic polar solvents such as NMP, which have drawbacks such as a high boiling point and toxicity, can be cured at low temperatures, and can give a cured product that has excellent adhesion, particularly to Si and SiN. Thus, the curable maleimide resin composition of the present invention is useful as an adhesive, a primer, a coating material, and a semiconductor device having a cured product of the composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will now be described in more detail.

[0014] (A) Maleimide compound The component (A) is a maleimide compound represented by the following formula (1) and has a number average molecular weight of 5,000 to 50,000. [ka] (In formula (1), Q 1 are independently expressed by the following formula: [ka] In the above formula, X 1 are independently expressed by the following formula: [ka] In addition, a is a number from 0 to 50, b is a number from 1 to 50, and A 1 and A 2 are each independently represented by the following formula (2) or the following formula (3): [ka] (In formula (2) and formula (3), X 2 is expressed as follows: [ka] In formula (2), R 1are independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms.

[0015] X in formula (1) 1 From the viewpoint of availability of raw materials, -CH2- and -C(CH3)2- are preferred. In the formula (1), a is a number from 0 to 50, and preferably a number from 1 to 40. In formula (1), b is a number from 1 to 50, and preferably a number from 1 to 40. In formula (1), A 1 and A 2 are each independently a group represented by the following formula (2) or (3):

[0016] X in formula (2) and formula (3) 2 From the viewpoint of availability of raw materials, -CH2- and -C(CH3)2- are preferred. 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. R in Equation (2) 1 Examples of the unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a cyclohexyl group, and the like, and also include groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as F, Cl, Br, and the like, such as a trifluoromethyl group. 1 From the viewpoint of availability of raw materials, it is preferable that the alkyl group is a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 3 carbon atoms.

[0017] In addition, in the maleimide compound represented by formula (1), A 1 and A 2 For example, in the formula (1), A 1 When A is a group represented by the formula (2), 2 is a group represented by the above formula (3), and for example, A 1When A is a group represented by the formula (3), 2 is preferably a group represented by the formula (2). 1 and A 2 However, this does not simultaneously result in equation (2). The bonding pattern of the repeating units a and the repeating units b in the maleimide compound represented by formula (1) may be a random type or a block type, but is preferably a block type from the viewpoint of the mechanical strength of the cured product.

[0018] As shown in the above formula (1), component (A) has a bisphenol structure in one molecule, is soluble in solvents other than NMP, and has excellent solvent solubility. In addition, maleimide compounds having a bisphenol structure are suitable from the viewpoint of ease of obtaining raw materials. Examples of the bisphenol structure of component (A) include bisphenol A, bisphenol F, bisphenol E, and bisphenol AF, and are not particularly limited, but bisphenol A and bisphenol F are preferred. In addition, the maleimide compound shown in the above formula (1) has a and b in the above ranges, respectively, so that the balance between the solubility in solvents and film-forming ability when uncured and the toughness and heat resistance of the obtained cured product is good.

[0019] The number average molecular weight of the maleimide compound of component (A) is 5,000 to 50,000, preferably 7,000 to 40,000, and more preferably 8,000 to 20,000. When the number average molecular weight is within this range, the maleimide compound of component (A) dissolves stably in a solvent, wettability with respect to the substrate can be ensured, and the coating before curing is less likely to crack and is of good quality. 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. [GPC measurement conditions] Developing solvent: Tetrahydrofuran Flow rate: 0.35mL / min Detector: Refractive index detector (RI) Column: TSK-GEL H type (Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 5 μL (0.2% by mass in THF solution)

[0020] The maleimide compound represented by formula (1) of component (A) can be produced, for example, by the method described in JP-A-2021-017485. The maleimide compound of the component (A) may use one type alone, or two or more types in combination. Furthermore, the curable maleimide resin composition of the present invention (however, in the case where the curable maleimide resin composition contains an organic solvent (E) described below, the curable maleimide resin composition excluding the organic solvent (E)) preferably contains 70 to 99.9 mass %, more preferably 80 to 99.5 mass %, and even more preferably 85 to 99.0 mass % of the component (A).

[0021] (B) Reaction initiator The reaction initiator, component (B), is added to initiate and promote the crosslinking reaction of the maleimide compound, component (A), and the reaction between the maleimide group in component (A) and a reactive group that can react with the maleimide group. The (B) component is not particularly limited as long as it accelerates the crosslinking reaction, but a thermal radical polymerization initiator and / or a photopolymerization initiator that can be easily cured in a short time is preferred to improve productivity. When a thermal radical polymerization initiator is used in the (B) component, the curable maleimide resin composition of the present invention is cured at a relatively low temperature (for example, a temperature below 220°C), whereas when a photopolymerization initiator is used in the (B) component, the composition is cured by light irradiation. Note that the (B) component does not contain imidazole having a diaminotriazine ring (D) described below.

[0022] Representative examples of the thermal radical polymerization initiator include organic peroxides, such as dicumyl peroxide, t-butyl peroxybenzoate, t-amyl peroxybenzoate, dibenzoyl peroxide, diuraloyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,1-di(t-butylperoxy)cyclohexane, di-t-butyl peroxide, dibenzoyl peroxide, and 1,6-bis(t-butylperoxycarbonyloxy)hexane.

[0023] The photopolymerization initiator is not particularly limited as long as it initiates a 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; benzyl dimethyl ketal, etc. Benzyl derivatives of 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 2,4,5-triarylimidazole dimers such as 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; bisacylphosphine oxides such as bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Sides include alkylphenone 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-morpholinyl)phenyl]-1-butanone, acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and benzophenone compounds.

[0024] The reaction initiator is preferably blended in an amount of 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the component (A). When other thermosetting resins described later are blended in the composition, it is preferable to blend them in an amount of 0.05 to 10 parts by mass, particularly 0.1 to 5 parts by mass, per 100 parts by mass of the total of the component (A) and other thermosetting resin components. If the amount is outside the range of 0.05 to 10 parts by mass per 100 parts by mass of the component (A), curing may become very slow or fast during molding, which is not preferable. In addition, the balance of heat resistance and moisture resistance of the obtained cured product may be poor. The reaction initiator may be used alone or in combination of two or more kinds.

[0025] (C) Silane coupling agent The silane coupling agent of the component (C) has one or more epoxy groups in one molecule, and is preferably represented by the following general formula (4). R 2 d Si(OR 3 ) 4-d (4) (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, provided that R 2 At least one of R 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).

[0026] 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 a 3-glycidoxypropyl group, an 8-glycidoxyoctyl group, and a 2-(3,4-epoxycyclohexyl)ethyl group. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and preferably a methyl group or an ethyl group.

[0027] The silane coupling agent, component (C), has one or more epoxy groups in each molecule, which improves adhesion to semiconductor elements such as Si, SiN, and SiC.

[0028] Also, R 3 are independently an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group, with a methyl group and an ethyl group being particularly preferred. d is 1, 2, or 3, and is particularly preferably 1.

[0029] Specific examples of the component (C) include KBM-403, KBE-403, KBM-303, KBM-4803, KBM-402 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and hydrolysates thereof.

[0030] The amount of component (C) is preferably 0.2 to 4.5 parts by mass, and particularly preferably 0.5 to 2.5 parts by mass, per 100 parts by mass of component (A). If the amount of component (C) is less than 0.2 parts by mass, sufficient adhesive strength is not exhibited, whereas if it is more than 4.5 parts by mass, not only is voids likely to occur during molding of the composition, but the strength of the molded product is also likely to decrease.

[0031] The composition of the present invention may further contain the following ingredients, if necessary.

[0032] (D) Imidazole having a diaminotriazine ring In the present invention, an imidazole having a diaminotriazine ring can be further blended as component (D). The diaminotriazine ring is particularly effective in improving adhesion to metals such as copper. In addition, since it has an imidazole, it also promotes the polymerization of maleimide and is effective in imparting heat resistance. The component (D) is not particularly limited as long as it is an imidazole having a diaminotriazine ring.

[0033] Specific examples include 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine (trade name 2MZ-A, manufactured by Shikoku Kasei Holdings Co., Ltd.), 2,4-diamino-6-[2-(2-undecyl-1-imidazolyl)ethyl]-1,3,5-triazine (trade name C11Z-A, manufactured by Shikoku Kasei Holdings Co., Ltd.), 2,4-diamino-6-[2-(4-methyl-1-imidazolyl)ethyl]-1,3,5-triazine (trade name 2E4MZ-A, manufactured by Shikoku Kasei 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 Kasei Holdings Co., Ltd.).

[0034] The blend amount of component (D) is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of component (A). When the blend amount of component (D) is 0.05 to 5 parts by mass per 100 parts by mass of component (A), the adhesive strength is improved, dispersibility is good, and there is no poor appearance or reduced reliability.

[0035] (E) Organic solvent The composition of the present invention may further contain an organic solvent as component (E). There is no limitation on the type of organic solvent as long as it is capable of dissolving component (A), but N-methyl-2-pyrrolidone (NMP) is excluded from the scope in terms of environmental impact. In this case, "component (E) can dissolve component (A)" refers to a state in which when a 25% by mass solution of component (A) is prepared using component (E) as a solvent, no residual component (A) is visually observed at 25°C. By adding an organic solvent, the composition can be suitably used as a varnish or primer.

[0036] As the component (E), for example, a general organic solvent such as methyl ethyl ketone (MEK), cyclohexanone, ethyl acetate, tetrahydrofuran (THF), isopropanol (IPA), xylene, toluene, anisole, etc. These may be used alone or in combination of two or more. When the composition of the present invention is used as a primer, the organic solvent of component (E) is preferably cyclohexanone, xylene, anisole, or the like. From the viewpoint of the solubility of the above-mentioned component (A), the organic solvent of the component (E) is preferably an organic solvent such as anisole, xylene, toluene, or cyclohexanone. On the other hand, from the viewpoint of high boiling point and toxicity, it is preferable not to use the above-mentioned NMP, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), or the like among the aprotic polar solvents. Unlike conventional compositions containing polyimide compounds that are soluble only in aprotic polar solvents, the composition of the present invention has the advantage that it is not necessary to use these aprotic polar solvents.

[0037] The blend amount of the component (E) is preferably 100 to 800 parts by mass, and more preferably 150 to 700 parts by mass, per 100 parts by mass of the component (A).

[0038] Other Additives The curable maleimide resin composition of the present invention may contain various additives within a range that does not impair the effects of the present invention. For example, in order to improve the resin properties, a thermosetting resin such as an acrylic resin, an organopolysiloxane, a silicone oil, a thermoplastic resin, a thermoplastic elastomer, an organic synthetic rubber, a light stabilizer, a polymerization inhibitor, a flame retardant, a pigment, a dye, an adhesive assistant other than silane coupling, and the like may be added. In addition, in order to improve the electrical properties, an ion trapping agent and the like may be added. Furthermore, in order to improve the dielectric properties, a fluorine-containing material and the like may be added. Inorganic fillers such as silica may be added to adjust the coefficient of thermal expansion (CTE).

[0039] The curable maleimide resin composition of the present invention can be produced by mixing the components (A), (B), (C), and (D) as well as the component (E) and other additives. 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 semiconductor devices, a buffer coat, a rewiring layer, etc. There are no particular limitations on the method and form of use. Examples of use are given below, but are not limited to these.

[0040] For example, a curable maleimide resin composition containing components (A), (B), and (C), and further components (D) and (E), is applied to a substrate (e.g., a metal lead frame such as a silver-plated lead frame or a copper lead frame), and then the organic solvent is removed by heating for 0.5 to 5 hours at a temperature of usually 80° C. or higher, preferably 100° C. or higher. Furthermore, if the substrate is a thermosetting type, a strong maleimide coating having a flat surface can be formed by heating the substrate for 0.5 to 10 hours at a temperature of 130° C. or higher, preferably 150° C. or higher, or if the substrate is a photocurable type, by irradiating the substrate with 365 nm UV light. Generally, polyimides require drying at 150°C or higher and thermal curing at 220°C or higher, but the curable maleimide resin composition of the present invention does not require such high temperature conditions. Specifically, the organic solvent can be removed at 150°C or lower, and thermal curing (film formation) can be performed at 200°C or lower. In order to efficiently remove the organic solvent in the composition and to effectively promote the reaction of the resin, the curing temperature may be raised stepwise in some cases, or heating may be performed to completely complete the curing after photocuring. The cured product (film) obtained by curing the composition of the present invention has excellent mechanical properties, heat resistance, dielectric constant, dielectric loss tangent, moisture resistance, and adhesiveness. Therefore, the cured product of the present invention can be used as, for example, an adhesive between a semiconductor element and a lead frame; a primer used between a semiconductor encapsulant and a lead frame; a chip coating agent (passivation film) on the surface of a semiconductor element; a junction protection film for the junction of a diode, a transistor, etc.; an alpha-ray shielding film for VLSI; an interlayer insulating film; and a conformal coating for a printed circuit board.

[0041] Examples of the application method include, but are not limited to, a spin coater, a slit coater, a spray, a dip coater, a bar coater, and the like.

[0042] After forming the cured product (film), the epoxy resin molding material for semiconductor encapsulation is molded onto the cured product (film), thereby improving the adhesion between the epoxy resin molding material for semiconductor encapsulation and the semiconductor element or substrate. The semiconductor device obtained in this manner is highly reliable, since no cracks or peeling from the substrate are observed in the epoxy resin molding material for semiconductor encapsulation during solder reflow after moisture absorption.

[0043] In this case, as the epoxy resin molding material for semiconductor encapsulation, a known epoxy resin composition for semiconductor encapsulation containing an epoxy resin having two or more epoxy groups in one molecule; a phenolic resin; an epoxy resin curing agent such as an acid anhydride; and / or an inorganic filler, etc., can be used, and a commercially available product can also be used. EXAMPLES

[0044] The present invention will be described in detail below with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In the examples and comparative examples, "room temperature" means 25°C.

[0045] The components used in the examples and comparative examples are shown below. In the following, the number average molecular weight (Mn) is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard substance, measured under the following measurement conditions. [GPC measurement conditions] Developing solvent: Tetrahydrofuran Flow rate: 0.35mL / min Detector: Refractive index detector (RI) Column: TSK-GEL H type (Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 5 μL (0.2% by mass in THF solution)

[0046] (A) Maleimide compound [Synthesis Example 1] 65.06g (0.125 mol) of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride, 61.59g (0.150 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 250g of anisole were added to a 1L glass four-neck flask equipped with a stirrer, a Dean-Stark tube, a cooling condenser, and a thermometer, and an amic acid was synthesized by stirring at 80°C for 3 hours. Thereafter, the temperature was raised to 150°C and stirred for 2 hours while distilling off the by-product water, producing a diamine at both ends. The flask containing the obtained solution of diamines at both ends was cooled to room temperature, and then 4.39 g (0.055 mol) of maleic anhydride was added and stirred at 80° C. for 3 hours to synthesize maleamic acid. The mixture was then heated to 150° C. and stirred for 2 hours while distilling off the by-product water, to obtain 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 was 12,000. Anisole was added so that the non-volatile content of the varnish was 17% by mass. [ka] (In formula (A-1), P and Q are independently a divalent group represented by the following formula.) [ka]

[0047] [Synthesis Example 2] 65.06g (0.125 mol) of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride, 35.26g (0.115 mol) of 4,4-methylenebis(2,6-diethylaniline), and 250g of anisole were added to a 1L glass four-neck flask equipped with a stirrer, a Dean-Stark tube, a cooling condenser, and a thermometer, and the mixture was stirred at 80°C for 3 hours to synthesize an amic acid. The mixture was then heated to 150°C and stirred for 2 hours while distilling off the by-product water to synthesize a copolymer. After that, 7.05 g (0.015 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane was added to the flask containing the copolymer solution that had been cooled to room temperature, and the mixture was stirred at 80°C for 3 hours to synthesize an amic acid. The mixture was then heated to 150°C and stirred for 2 hours while distilling off the by-product water, synthesizing a diamine at both ends. The flask containing the obtained solution of diamines at both ends was cooled to room temperature, and then 1.45 g (0.015 mol) of maleic anhydride was added and stirred at 80° C. for 3 hours to synthesize maleamic acid. The mixture was then heated to 150° C. and stirred for 2 hours while distilling off the by-product water, to obtain a varnish of an aromatic bismaleimide compound represented by the following formula (A-2). The number average molecular weight (Mn) of the aromatic bismaleimide compound was 15,500. Anisole was added so that the non-volatile components of the varnish became 17% by mass. [ka]

[0048] Other maleimide compounds (for comparison) (A-3): A bismaleimide compound represented by the following formula (product name: BMI-5000, Mn: 8000, manufactured by Designer Molecules Inc.) [ka] -C 36 H 70 - represents a hydrocarbon group derived from a dimer acid skeleton. n≒8 (average value) (A-4): 4,4'-diphenylmethane bismaleimide (BMI-1000, Mn: 410, manufactured by Daiwa Chemical Industry Co., Ltd.)

[0049] (B) Reaction initiator (B-1): Dicumyl peroxide (trade name: Perkadox BC-FF, manufactured by Kayaku Nouryon Co., Ltd., 1-hour half-life temperature 132°C) (B-2): 1,6-bis(t-butylperoxycarbonyloxy)hexane (trade name: Kayalene 6-70, manufactured by Kayaku Nouryon Co., Ltd., 1-hour half-life temperature 117° C.)

[0050] (C) Silane coupling agent (C-1): 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (product name: KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.) (C-2): 3-glycidoxypropyltriethoxysilane (product name: KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.) (C-3): 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (C-1) component hydrolyzate ((C-1) component:water = 4:1 (mass ratio) mixed at 25°C for 12 hours) (C-4): N-phenyl-3-aminopropyltrimethoxysilane (product name: KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) (for comparison) (C-5): 3-methacryloxypropyltrimethoxysilane (product name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) (for comparison)

[0051] (D) Imidazole having a diaminotriazine ring (D-1): 2,4-diamino-6-[2-(4-methyl-1-imidazolyl)ethyl]-1,3,5-triazine (trade name: 2E4MZ-A, manufactured by Shikoku Kasei Holdings Co., Ltd.)

[0052] Comparative Example Polyimide Polyamic acid varnish (KJR-655, manufactured by Shin-Etsu Chemical Co., Ltd., NMP-based varnish, non-volatile content 15% by mass) was used as is.

[0053] (Composition Examples 1 to 16, Examples 1 to 8, Comparative Examples 1 to 13) A varnish of a curable maleimide resin composition was prepared by mixing the components according to the formulation shown in Table 1. In all formulations, anisole was added so that component (A) was 16.7 mass % and all of the component (A) was dissolved.

[0054] <Adhesive strength and failure mode> The varnishes of the compositions obtained in Formulation Examples 1 to 16 were spray-coated onto 20 mm x 20 mm cut pieces of Si, SiN or SiC, and cured under the curing conditions shown in Tables 2 or 3 to form cured films (primers). On the cured film, a semiconductor encapsulation epoxy resin molding material KMC-2284 (Shin-Etsu Chemical Co., Ltd.) was applied to a substrate with a base area of ​​10 mm 2 The test pieces were then post-cured at 180°C for 4 hours, and the adhesive strength was measured at 25°C at a speed of 0.2 mm / sec using a universal bond tester (DAGE SERIES 4000: manufactured by Nordson DAGE). The fracture modes after the adhesive strength measurement were classified as ◯, △, or × as shown below, with the order of favorability of the fracture mode being ◯>△>×. ○: Semiconductor element destruction △: Cohesive failure of the encapsulant on the semiconductor element ×: Interfacial peeling of the encapsulant from the semiconductor element

[0055] The results of these measurements are shown in Tables 2 and 3. The detailed conditions of the curing conditions A to C are as follows. Curing condition A: 110℃ 30 minutes + 180℃ 2 hours Curing condition B: 110℃ 30 minutes + 220℃ 2 hours Curing condition C: 150℃ 1 hour + 200℃ 1 hour + 250℃ 4 hours In addition, Comparative Example 1 is a result of measuring adhesive strength without using a primer (varnish of composition), and therefore, no information is provided in the column for curing conditions. [Table 1] [Table 2] [Table 3]

Claims

1. (A) a maleimide compound represented by the following formula (1) and having a number average molecular weight of 5,000 to 50,000: (B) a reaction initiator, and (C) Silane coupling agent wherein the silane coupling agent of component (C) has one or more epoxy groups in one molecule. 【Chemistry 1】 (In formula (2), Q 1 are independently expressed by the following formula: 【Chemistry 2】 In the above formula, X 1 are independently expressed by the following formula: 【Chemistry 3】 In addition, a is a number from 0 to 50, b is a number from 1 to 50, and A 1 and A 2 are each independently represented by the following formula (2) or the following formula (3): 【Chemistry 4】 (In formula (3) and formula (4), X 2 is expressed as follows: 【Chemistry 5】 In the 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.

2. The curable maleimide resin composition according to claim 1 , further comprising (D) an imidazole having a diaminotriazine ring.

3. 2. The curable maleimide resin composition according to claim 1, further comprising (E) an organic solvent (excluding N-methylpyrrolidone (NMP)).

4. 2. The curable maleimide resin composition according to claim 1, wherein the reaction initiator (B) is an organic peroxide having a one-hour half-life temperature of 150° C. or lower.

5. An adhesive comprising the curable maleimide resin composition according to any one of claims 1 to 4.

6. A primer comprising the curable maleimide resin composition according to any one of claims 1 to 4.

7. A chip coating agent comprising the curable maleimide resin composition according to any one of claims 1 to 4.

8. A semiconductor device comprising a cured product of the curable maleimide resin composition according to any one of claims 1 to 4.

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