Composition for curing resin, cured product of said composition, method for manufacturing said composition and said cured product, and semiconductor device

Abstract

[Problem] To obtain a cured product having high heat resistance and reduced molding shrinkage or linear expansion coefficient, the present invention provides a composition for a cured resin having a low weight loss rate during heat curing, the cured product thereof, and a method for manufacturing the composition for a cured resin and the cured product. Furthermore, the present invention provides a semiconductor device utilizing the cured product as an encapsulant. [Solution] The composition for curing resin of the present invention contains (A) a benzoxazine compound, (B) an epoxy compound, and (C) a phenolic curing agent, wherein the number of epoxy groups of (B) the epoxy compound, the number of benzoxazine rings of (A) the benzoxazine compound, and the number of hydroxyl groups of (C) the phenolic curing agent satisfy Formula (1), and furthermore, the content of the alicyclic epoxy compound (B) relative to the sum of (A), (B), and (C) is 3 to 12 mass%.

Description

Technology Field

[0001] [Reference to related applications]

[0002] This patent application carries a claim of priority based on Japanese patent application No. 2021-15288 filed on February 2, 2021, and the entire disclosure of this prior patent application is considered by reference to be part of this specification.

[0003] The present invention relates to a composition for a curing resin for obtaining a high-heat-resistant cured product, the cured product, and a method for manufacturing said composition for the curing resin and said cured product. Additionally, the invention relates to a semiconductor device utilizing said cured product as an encapsulant. Background Technology

[0004] Cured resins are used in various applications, such as semiconductor encapsulating materials and fiber-reinforced plastics, and benzoxazine compounds are used as raw materials for them. Benzooxazine compounds refer to compounds containing benzoxazine rings having benzene and oxazine backbones. Benzooxazine resins, which are their cured products (polymers), possess excellent physical properties such as heat resistance and mechanical strength, and are used as high-performance materials for a wide range of applications.

[0005] Additionally, when using cured resins for semiconductor encapsulation materials, there is a demand for improvements in molding defects, such as the reduction of molding shrinkage. Here, the weight loss rate during heat curing and the linear expansion rate are known to influence the molding shrinkage rate. The weight loss rate during heat curing is thought to reflect the volatilization of low-molecular-weight components, and suppressing this weight loss rate makes it possible to improve the working environment and stabilize the composition of the resin.

[0006] Patent Document 1 describes that a highly reliable cured product having a low linear expansion rate after curing can be obtained from an adhesive for electronic components characterized by containing an aliphatic epoxy compound and a benzoxazine compound as a curing agent and also containing a phenolic curing agent.

[0007] Patent Document 2 describes that an epoxy resin composition containing an epoxy resin selected from trifunctional epoxy resin and tetrafunctional epoxy resin, a curing agent having at least two hydroxyl groups in one molecule, a compound having at least two cyanate groups in one molecule, and an inorganic filler, which does not use a benzoxazine compound, can provide a semiconductor device having excellent resistance to heat, resistance to solder cracking, and fluidity, and additionally, a semiconductor device having minimal warping even at low temperatures such as during temperature cycle testing after molding or soldering treatment. Prior art literature

[0008] Patent Document 1: Japanese Patent Publication No. 2013-008800 Patent Document 2: International Publication No. 2007 / 037500 The problem to be solved

[0009] However, the inventors have discovered that the following technical problems exist in Patent Documents 1 and 2. The adhesive for electronic components described in Patent Document 1 had the problem that it is not possible to obtain a cured product having a high glass transition point. The epoxy resin composition described in Patent Document 2 had the problem that there is a limit to the reduction of the coefficient of linear expansion.

[0010] As a result of diligently conducting research to solve the above problem, the inventors developed a composition for curing resin containing a benzoxazine compound, an epoxy compound, and a phenolic curing agent in specific proportions, and found that the weight loss rate during heat curing of the composition for curing resin is low, the cured product has excellent heat resistance, and the molding shrinkage rate or linear expansion rate of the cured product is reduced.

[0011] Accordingly, the present invention aims to provide a composition for a curing resin having a low weight loss rate during heat curing, for obtaining a cured product having high heat resistance and low molding shrinkage or linear expansion coefficients. Furthermore, another objective of the present invention is to provide a cured product formed by curing the above-mentioned composition for a curing resin, and a method for manufacturing the above-mentioned composition for a curing resin and the above-mentioned cured product. Furthermore, another objective of the present invention is to provide a semiconductor device utilizing the above-mentioned cured product as an encapsulant. means of solving the problem

[0012] That is, according to the present invention, the following invention is provided.

[0013] [1] (A) Benzooxazine compound and,

[0014] (B) Epoxy compound and,

[0015] (C) Contains a phenolic curing agent, and

[0016] The number of benzoxazine rings of the above (A) benzoxazine compound, the number of epoxy groups of the above (B) epoxy compound, and the number of hydroxyl groups of the above (C) phenolic curing agent satisfy the following formula (1), and

[0017] (B) The epoxy compound comprises a cycloaliphatic epoxy compound, and also,

[0018] A composition for a curing resin, wherein the content of the alicyclic epoxy compound (B) is 3 to 12 mass% relative to the total of the benzoxazine compound (A), the epoxy compound (B), and the phenolic curing agent (C).

[0019] [Mathematical Formula 1]

[0020] (Number of benzoxane rings + Number of hydroxyl groups) / Number of epoxy groups = 0.8~5 (1)

[0021] [2] A composition for a cured resin described in [1], wherein the above (A) benzoxazine compound is a polyfunctional benzoxazine compound having at least two benzoxazine rings, and is selected from at least one polyfunctional benzoxazine compound having a structural unit of formula (1) and a polyfunctional benzoxazine compound represented by the structure of formula (2).

[0022]

[0023] [In Formula (1), R represents a chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and the aryl group may have a halogen or a chain alkyl group having 1 to 12 carbon atoms as a substituent. Z represents hydrogen, a hydrocarbon group having 1 to 8 carbon atoms, and / or a linker, each of which may be the same or different, and at least one is a linker, and the benzoxazine rings are connected to each other by the linker.]

[0024]

[0025] [In formula (2), L is a divalent organic group having 1 to 5 aromatic rings or an alkylene group having 2 to 10 carbon atoms, and said organic group and alkylene group may include oxygen and / or sulfur.]

[0026] [3] A composition for a curing resin described in [1] or [2], wherein the above-mentioned cycloaliphatic epoxy compound is an epoxy compound having at least one norbornan structure and at least two epoxy groups.

[0027] [4] A curing resin composition described in any one of [1] to [3], wherein the above-mentioned cycloaliphatic epoxy compound has at least one structure selected from the group consisting of a 5-membered ring structure, a 6-membered ring structure and a norbornan ring structure represented by formula (3).

[0028]

[0029] [5] A curing resin composition described in any one of [1] to [4], wherein the above-mentioned cycloaliphatic epoxy compound does not have a glycidyl group.

[0030] [6] (D) A composition for a cured resin described in any one of [1] to [5], further containing a silane coupling agent.

[0031] [7] A composition for a cured resin described in [6], wherein the above (D) silane coupling agent contains at least one primary amino group and one secondary amino group in one molecule.

[0032] [8] (E) A composition for a curing resin described in any one of [1] to [7], further containing a curing accelerator.

[0033] [9] (F) A composition for curing resins described in any one of [1] to [8], additionally containing an inorganic filler.

[0034]

[10] A curing resin composition described in [9], wherein the content of the above (F) inorganic filler is 80 to 95 mass% of the total curing resin composition.

[0035]

[11] A cured product formed by curing a cured resin composition described in any one of [1] to

[10] .

[0036]

[12] A semiconductor device having a semiconductor element installed in a cured product formed by curing a cured resin composition described in any one of [1]~

[10] .

[0037]

[13] A method for manufacturing a curing resin composition as described in any one of [1] to

[10] ,

[0038] (A) Benzooxazine compound and,

[0039] (B) Epoxy compound and,

[0040] (C) A process of obtaining a mixture by mixing a phenolic curing agent,

[0041] A method for manufacturing a composition for curing a resin, comprising a process of processing the above mixture into a powder, pellet, or granular composition for curing a resin.

[0042]

[14] A method of manufacturing as described in

[13] , wherein in the process of obtaining the above mixture, at least one component selected from the group consisting of (D) a silane coupling agent, (E) a curing accelerator, and (F) an inorganic filler is additionally mixed to obtain the mixture.

[0043]

[15] A method for manufacturing a cured product having a process of curing the above cured resin composition prepared by the method described in

[13] or

[14] by heating it at 150 to 300°C for 20 seconds to 6 hours. Effects of the invention

[0044] The curing resin composition of the present invention is a novel curing resin composition containing components (A) to (C) in specific proportions and additionally containing components (D), (E), and (F) as desired. The composition has the characteristics of having a low weight loss rate upon heat curing, high heat resistance, and excellent molding shrinkage and linear expansion rates. Additionally, the curing resin composition has the characteristic of having low melt viscosity. Accordingly, the curing resin composition of the present invention can be used in applications requiring heat resistance while low melt viscosity is desired and molding defects are improved, such as adhesives, encapsulants, paints, and matrix resins for composites. In particular, as an encapsulant, it can be suitably used as a WLP encapsulant or a PLP encapsulant. Specific details for implementing the invention

[0045] [Composition for Cured Resin]

[0046] The present invention will be described in detail below. Additionally, the "compound," "curing agent," and "silane coupling agent" in components (A) to (D) of the present invention include not only monomers but also oligomers polymerized from the monomers, for example, oligomers polymerized in small quantities, i.e., prepolymers before forming a cured resin. Accordingly, the cured resin composition of the present invention may be a curable resin composition.

[0047] (Ingredient(A))

[0048] The component (A) constituting the composition for the curing resin is a benzoxazine compound, preferably a polyfunctional benzoxazine compound having at least two benzoxazine rings selected from at least one polyfunctional benzoxazine compound having a structural unit of Formula (1) and a polyfunctional benzoxazine compound represented by the structure of Formula (2). Additionally, Z in Formula (1) represents hydrogen, a substituent, and / or a linker (spacer), and each may be the same or different, and at least one is a linker, and the benzoxazine rings are connected to each other by said linker. Additionally, the term "linker" here includes cases where two benzoxazine rings are directly bonded without interposing other groups. Furthermore, the term "substituent" may include, for example, a hydrocarbon group having 1 to 8 carbon atoms.

[0049] Accordingly, the above formula (1) represents the structural unit for a compound in which two or more benzoxazine rings are connected in the benzene ring portion within the choice of component (A).

[0050] The polyfunctional benzoxazine compound of formula (1) can be represented more specifically as the structure shown in formula (1a).

[0051]

[0052] [In Formula (1a), R represents a chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and the aryl group may have a halogen or a chain alkyl group having 1 to 12 carbon atoms as a substituent. R may be the same or different. X is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different. Y is an alkylene group having 1 to 6 carbon atoms, oxygen, sulfur, an SO2 group, or a carbonyl group. m is 0 or 1. n is an integer from 1 to 10.]

[0053] As specific examples of R in formulas (1) and (1a), the following can be exemplified.

[0054] Examples of chain alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups.

[0055] Examples of cyclic alkyl groups having 3 to 8 carbon atoms include cyclopentyl groups and cyclohexyl groups.

[0056] Examples of aryl groups having 6 to 14 carbon atoms include phenyl groups, 1-naphthyl groups, 2-naphthyl groups, phenanthyl groups, and biphenyl groups.

[0057] The aryl group having 6 to 14 carbon atoms may be substituted, and the substituent may be a chain alkyl group having 1 to 12 carbon atoms or a halogen. Examples of aryl groups having 6 to 14 carbon atoms substituted with a chain alkyl group having 1 to 12 carbon atoms or a halogen include an o-tolyl group, a m-tolyl group, a p-tolyl group, a xylyl group, an o-ethylphenyl group, a m-ethylphenyl group, a p-ethylphenyl group, an ot-butylphenyl group, an mt-butylphenyl group, a pt-butylphenyl group, an o-chlorophenyl group, and an o-bromophenyl group.

[0058] For good handling properties, it is preferable that R be selected from methyl, ethyl, propyl, phenyl, and p-tolyl groups.

[0059] Additionally, component (A) may be a mixture of compounds represented by formula (1) or (1a), each having a different R.

[0060] As for the hydrocarbon group having 1 to 8 carbon atoms in X of formulas (1) and (1a), examples include alkyl groups, aryl groups, aralkyl groups, etc., and preferably, aryl groups.

[0061] Examples of polyfunctional benzoxazine compounds represented by formula (1) or (1a) include a compound represented by the following formula (1X) and an oligomer formed by the small amount polymerization of said compound.

[0062]

[0063]

[0064] The polyfunctional benzoxazine compound of formula (2), which is an alternative to component (A), is a compound in which the nitrogen atoms (N atoms) of two benzoxazine rings are bonded together via a linker L.

[0065]

[0066] [In Formula (2), L is a divalent organic group having 1 to 5 aromatic rings or an alkylene group having 2 to 10 carbon atoms, and said organic group and alkylene group may include oxygen and / or sulfur.]

[0067] The composition of the present invention may contain a plurality of polyfunctional benzoxazine compounds with different L represented by formula (2) as component (A).

[0068] In the case where L in Equation (2) is a group having an aromatic ring, the number of aromatic rings is 1 to 5, and examples include monocyclic compounds, polycyclic compounds, and condensed ring compounds. In addition, L may contain at least one selected from the group consisting of oxygen and sulfur.

[0069] As a specific example, the following formula (2a) can be used.

[0070]

[0071] When L in formula (2) is an alkylene group, the number of carbon atoms can be 1 to 10, and preferably 1 to 6. Specific examples of the alkylene group include a methylene group, an ethylene group, an isopropylidene group, etc., and preferably a methylene group.

[0072] Examples of polyfunctional benzoxazine compounds of formula (2) include compounds represented by the following formula (2X) and oligomers polymerized from said compounds, for example, oligomers polymerized in small amounts.

[0073]

[0074] As the polyfunctional benzoxazine compound of component (A), preferably, bisphenol F-aniline (Fa) type benzoxazine, phenol-diaminodiphenylmethane (Pd) type benzoxazine, 3-[4-[4-(2,4-dihydro-1,3-benzoxazine-3-yl)phenoxy]phenyl]-2,4-dihydro-1,3-benzoxazine(3-[4-[4-(2,4-dihydro-1,3-benzoxazin-3-yl)phenoxy]phenyl]-2,4-dihydro-1,3-benzoxazine), 3-[3-[4-(2H-1,3-benzoxazine-3(4H)-yl) It is phenoxy]phenyl]-3,4-dihydro-2H-1,3-benzoxazine (3-[3-[4-(2H-1,3-benzoxazin-3(4H)-yl)phenoxy]phenyl]-3,4-dihydro-2H-1,3-Benzoxazine) (hereinafter also referred to as 3,4'-APE-BOZ), and more preferably, phenol-diaminodiphenylmethane (Pd) type benzoxazine, 3,4'-APE-BOZ. Here, 3,4'-APE-BOZ can be prepared based on the description of Synthesis Example 1 of Japanese Patent Publication No. 2018-184533.

[0075] As the polyfunctional benzoxazine compound of component (A), commercially available products may be used. Examples of commercially available products include bisphenol F-aniline (Fa) type benzoxazine and phenol-diaminodiphenylmethane (Pd) type benzoxazine (both manufactured by Shikoku Kasei Co., Ltd.).

[0076] The benzoxazine equivalent of component (A) benzoxazine compound is preferably 135 g / eq or more and 600 g / eq or less from the perspective of quantifying reactivity, and more preferably 140 g / eq or more and 400 g / eq or less. Here, the benzoxazine equivalent of component (A) benzoxazine compound refers to the equivalent when the benzoxazine ring in component (A) benzoxazine compound is monofunctional.

[0077] The number of benzoxazine rings (mol) of the benzoxazine compound of component (A) is calculated from the benzoxazine equivalent of the benzoxazine compound of component (A). Additionally, if the composition of the present invention contains multiple types of benzoxazine compounds as component (A), the number of benzoxazine rings is the sum of the number of rings calculated from the benzoxazine equivalents of these compounds.

[0078] ( Component(B) )

[0079] The component (B) constituting the composition for curing resin is an epoxy compound. Such epoxy compounds are not particularly limited as long as they do not deviate from the spirit of the present invention, and may include alicyclic epoxy compounds, biphenyl-type epoxy compounds, trisphenolmethane-type epoxy compounds, naphthalene-type epoxy compounds, novolak-type epoxy compounds, phenolaryl-type epoxy compounds, and epoxy compounds having a cyclohexene oxide group, but preferably, they are alicyclic epoxy compounds, trisphenolmethane-type epoxy compounds, and naphthalene-type epoxy compounds.

[0080] According to a preferred embodiment of the present invention, a composition for curing resin contains a mixture of multiple types of epoxy compounds as component (B). The mixture of epoxy compounds preferably comprises alicyclic epoxy compounds. Examples of the mixture of epoxy compounds include a combination of alicyclic epoxy compounds and epoxy compounds other than alicyclic epoxy compounds. The epoxy compounds other than alicyclic epoxy compounds are preferably at least one epoxy compound selected from biphenyl-type epoxy compounds, trisphenolmethane-type epoxy compounds, naphthalene-type epoxy compounds, novolak-type epoxy compounds, phenol-aralkyl-type epoxy compounds, and epoxy compounds having cyclohexene oxide groups, and more preferably, trisphenolmethane-type epoxy compounds, naphthalene-type epoxy compounds, or a combination thereof.

[0081] The epoxy equivalent of the epoxy compound of component (B) is preferably 50 g / eq or more and 400 g / eq or less from the perspective of quantifying reactivity, and more preferably 80 g / eq or more and 300 g / eq or less.

[0082] The number of epoxy groups (mol) of the epoxy compound of component (B) is calculated from the epoxy equivalent. Additionally, if the composition of the present invention contains multiple types of epoxy compounds as component (B), the number of epoxy groups is the sum of the number of epoxy groups of these compounds.

[0083] (Alicyclic epoxy compounds)

[0084] As for the alicyclic epoxy compound, it is not particularly limited as long as it does not deviate from the spirit of the present invention, but may be an epoxy compound having at least one alicyclic hydrocarbon structure and at least one epoxy group in the molecule, preferably an epoxy compound having at least one alicyclic hydrocarbon structure and at least two epoxy groups, and more preferably an epoxy compound having at least one norbornane structure and at least two epoxy groups. In addition, it is preferable that the alicyclic epoxy compound does not have a glycidyl group.

[0085] (An epoxy compound having at least one norbornane structure and at least two epoxy groups)

[0086] As an epoxy compound having at least one norbornan structure and at least two epoxy groups, it is preferable to have an epoxy structure bonded to a five-membered ring, a six-membered ring, or a norbornan ring as represented by the following formula (4). One or more of these may be used in combination.

[0087]

[0088] According to a preferred embodiment of the present invention, an epoxy compound having at least one norbornan structure and at least two epoxy groups does not have a glycidyl group.

[0089] As a specific cycloaliphatic epoxy compound, a compound represented by the following formula (5) can be exemplified.

[0090]

[0091] An example of the preparation of a cycloaliphatic epoxy compound of component (B) is described.

[0092] The compound of formula (5-1) below (epoxy equivalent: 109 g / eq) can be prepared by, for example, by synthesizing compound (a) having the following norbornan structure by the Diels-Alder reaction of butadiene and dicyclopentadiene, and then reacting compound (a) with metachloroperbenzoic acid as shown in formula (6) below.

[0093]

[0094] The compound of formula (5-2) below (epoxy equivalent: 115 g / eq) can be prepared, for example, by synthesizing compound (b) (tricyclopentadiene) having the following norbornane structure by the Diels-Alder reaction of cyclopentadiene and dicyclopentadiene, and then reacting compound (b) with metachloroperbenzoic acid as shown in formula (7) below.

[0095]

[0096] The compound of formula (5-3) below (epoxy equivalent: 109 g / eq) can be prepared by, for example, by synthesizing a compound (c) having the following norbornan structure by the Diels-Alder reaction of butadiene and cyclopentadiene, and then reacting the compound (c) with metachloroperbenzoic acid as shown in formula (8) below.

[0097]

[0098] The compound of Formula (5-4) below (epoxy equivalent: 82.1 g / eq) can be prepared, for example, by reacting dicyclopentadiene with potassium peroxymonosulfate (Oxone). The dicyclopentadiene diepoxide, which is the compound of Formula (5-4), may be a commercial product, and an example of a commercial product is the dicyclopentadiene diepoxide manufactured by SHANDONG QIHUAN BIOCHEMICAL CO., LTD.

[0099]

[0100] (Trisphenolmethane-type epoxy compound)

[0101] As for the trisphenolmethane-type epoxy compound, it is not particularly limited as long as it does not deviate from the spirit of the present invention, but it is preferable to have an epoxy compound represented by the structure of the following formula (9).

[0102]

[0103] [In formula (9), R is a substituent and each independently represents an alkyl group, an allyl group, or a phenyl group having 1 to 6 carbon atoms. m is the number of substituents R and represents an integer from 0 to 3. n is the average value, and 0 ≤ n ≤ 10.]

[0104] m in Formula (9) is preferably 0 to 2, and more preferably 0. n in Formula (9) is preferably 0 or more and 5 or less. Examples of alkyl groups having 1 to 6 carbon atoms in substituent R of Formula (9) include methyl groups, ethyl groups, propyl groups, butyl groups, and cyclohexyl groups. A methyl group is preferred as the substituent R. Additionally, the trisphenolmethane-type epoxy compound may be a mixture of compounds represented by Formula (9), each having different R, m, and n.

[0105] Commercially available products may be used as trisphenolmethane-type epoxy compounds. Examples of commercially available products include EPPN-501H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight 162–172 g / eq, softening point 51–57°C), EPPN-501HY (trade name, manufactured by Nippon Kayaku Co., Ltd.), EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight 158–178 g / eq, softening point 60–72°C), EPPN-503 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight 170–190 g / eq, softening point 80–100°C), etc. One of these or a combination of two or more may be used.

[0106] (Naphthalene-type epoxy compound)

[0107] Naphthalene-type epoxy compounds are not particularly limited as long as they do not deviate from the spirit of the present invention, but examples include naphthol-type epoxy compounds, naphthol ether-type epoxy compounds, non-naphthalene-type epoxy compounds, etc., and preferably, naphthol-type epoxy compounds, etc.

[0108] (Naphthol-type epoxy compound)

[0109] As for the naphthol-type epoxy compound, it is not particularly limited as long as it does not deviate from the spirit of the present invention, but it is preferable to have an epoxy compound represented by the structure of the following formula (10).

[0110]

[0111] (In the above formula (10), A and B each independently represent substituted or unsubstituted benzene or substituted or unsubstituted naphthalene. n represents a repeating unit and is an integer between 1 and 10.)

[0112] Unsubstituted benzene or naphthalene refers to a substance composed solely of benzene or naphthalene, while substituted benzene or naphthalene refers to a substance in which the aromatic hydrocarbon group of the benzene or naphthalene ring has a substituent. An aromatic hydrocarbon group having a substituent means that some or all of the hydrogen atoms constituting the aromatic hydrocarbon group are substituted by a substituent. Examples of substituents include organic groups containing glycidyl ether groups or alkyl groups.

[0113] As for the alkyl group as a substituent, it is preferable that it be a chain-type alkyl group. In addition, it is preferable that the number of carbon atoms is 1 or more and 10 or less, more preferable that it is 1 or more and 6 or less, and particularly preferable that it is 1 or more and 4 or less. Specifically, examples include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, tert-butyl groups, sec-butyl groups, etc.

[0114] Preferred specific examples of the naphthol-type epoxy compound represented by the above formula (10) include, for example, naphthol-type epoxy compounds represented by the following formulas (10-1) to (10-4). One or more of these may be used in combination.

[0115]

[0116]

[0117]

[0118]

[0119] In the above formulas (10-1) to (10-4), n is, for example, an integer greater than or equal to 0 and less than or equal to 10, preferably an integer greater than or equal to 0 and less than or equal to 6, more preferably an integer greater than or equal to 0 and less than or equal to 4, and even more preferably an integer greater than or equal to 0 and less than or equal to 3.

[0120] Commercially available naphthol-type epoxy compounds may be used. As commercially available naphthol-type epoxy compounds, NC-7000L (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 223-238 g / eq), NC-7300L (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 207-221 g / eq), ESN-475V (trade name, manufactured by Shin-Nitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent 332 g / eq), ESN-375 (trade name, manufactured by Shin-Nitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent 170 g / eq), etc., may be used. One of these or a combination of two or more may be used.

[0121] The mixing ratio of component (A) benzoxazine compound and component (B) epoxy compound is preferably 10 to 300 parts by mass of component (B) and more preferably 30 to 200 parts by mass, with respect to 100 parts by mass of component (A). If the mixing ratio of components (A) and (B) is within the above range, superior heat resistance can be obtained.

[0122] Here, when the composition of the present invention contains multiple types of benzoxazine compounds as component (A), the sum of the blended amounts of these compounds is considered to be 100 parts by mass. When the composition of the present invention contains multiple types of epoxy compounds as component (B), the blended amount of component (B) refers to the sum of the blended amounts of the multiple types of compounds.

[0123] The content of component (B), a cycloaliphatic epoxy compound, is preferably 3 to 12 parts by mass (i.e., 3 to 12 mass%) with respect to 100 parts by mass of the total of component (A), benzoxazine compound, component (B), epoxy compound, and component (C), phenolic curing agent, more preferably 3 to 10 parts by mass (i.e., 3 to 10 mass%), and even more preferably 4 to 10 parts by mass (i.e., 4 to 10 mass%). If the mixing ratio of component (B), a cycloaliphatic epoxy compound, is within the above range, superior heat resistance or a superior weight loss rate can be exhibited.

[0124] Here, when the composition of the present invention contains multiple types of benzoxazine compounds as component (A), the amount of said component (A) refers to the sum of the amounts of said compounds. In addition, when the composition of the present invention contains multiple types of epoxy compounds as component (B), the same applies as above. When the composition of the present invention contains multiple types of alicyclic epoxy compounds as component (B), the content of said alicyclic epoxy compounds refers to the sum of the content of said alicyclic epoxy compounds.

[0125] The content of the alicyclic epoxy compound in the epoxy compound of component (B) is preferably 5 to 45 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 15 to 35 parts by mass, with respect to 100 parts by mass of the epoxy compound of component (B). If the mixing ratio of component (B) is within the above range, it can exhibit superior low-melt viscosity and superior weight loss rate.

[0126] Here, when the composition of the present invention contains a plurality of benzoxazine compounds as component (A) and / or contains a plurality of alicyclic epoxy compounds or epoxy compounds as component (B), the amounts of these are as described above.

[0127] (Ingredient C)

[0128] The component (C) constituting the composition for the cured resin is a phenolic curing agent. The component (C) is not particularly limited as long as it does not deviate from the spirit of the present invention, but examples include monofunctional phenol, polyfunctional phenolic compounds (e.g., bisphenol A, bisphenol F, dihydroxynaphthalene, bisphenol sulfide (e.g., bis(4-hydroxyphenyl) sulfide, etc.), polyphenol compounds (e.g., pyrogallol, etc.), phenol novolak resin, phenol aralyl resin (e.g., phenol aralyl resin having a biphenylene backbone, phenol aralyl resin having a phenylene backbone), etc., and preferably, bisphenol F and phenol novolak resin. These may be used alone or as a mixture of two or more types.

[0129] Commercially available products may be used as the phenolic curing agent of component (C). For example, bisphenol F (manufactured by Honshu Kagaku High School Co., Ltd., hydroxyl equivalent 100 g / eq), bis(4-hydroxyphenyl)sulfide (TDP, manufactured by Tokyo Kasei High School Co., Ltd., hydroxyl equivalent 109 g / eq), 2,7-dihydroxynaphthalene (manufactured by Tokyo Kasei High School Co., Ltd., hydroxyl equivalent 80 g / eq), pyrogallol (manufactured by Tokyo Kasei High School Co., Ltd., hydroxyl equivalent 42 g / eq), phenolnovolak resin (for example, phenolite TD-2131, DIC Co., Ltd., hydroxyl equivalent 104 g / eq; phenolite TD-2106, DIC Co., Ltd., hydroxyl equivalent 104 g / eq; phenolite TD-2090, DIC Examples include phenol-aralkyl resins (e.g., MEHC-7851 SS, hydroxyl equivalent 203 g / eq, manufactured by Meiwa Kasei Co., Ltd.; MEH-7800-4S, hydroxyl equivalent 169 g / eq, manufactured by Meiwa Kasei Co., Ltd.). One or more of these may be used in combination.

[0130] As for the mixing ratio of component (C), it is preferable to have component (C) in the range of 5 to 30 parts by mass with respect to 100 parts by mass of the total of components (A) and (B), and more preferable to have 10 to 20 parts by mass. By including component (C) in this range, a cured product with superior high heat resistance can be obtained.

[0131] In addition, when the composition of the present invention contains multiple types of benzoxazine compounds as component (A) and / or multiple types of epoxy compounds as component (B), the amounts of these compounds are as described above.

[0132] The hydroxyl group equivalent of component (C), a phenolic curing agent, is preferably 80 g / eq or more and 400 g / eq or less from the perspective of quantifying reactivity, and more preferably 90 g / eq or more and 250 g / eq or less.

[0133] The number of hydroxyl groups (mol) of the phenolic curing agent of component (C) is calculated from the hydroxyl equivalent. Additionally, if the composition of the present invention contains multiple types of phenolic curing agents as component (C), the number of hydroxyl groups is the sum of the number of hydroxyl groups of these curing agents.

[0134] In the present invention, it is preferable that the ratio of the number of functional groups of the number of epoxy groups of the component (B) epoxy compound, the number of benzoxazine rings of the component (A) benzoxazine compound, and the number of hydroxyl groups of the component (C) phenolic curing agent in the composition for curing resin satisfies the following formula (2).

[0135] [Mathematical Formula 2]

[0136] (Number of benzoxane rings + Number of hydroxyl groups) / Number of epoxy groups = 0.8~5 (2)

[0137] The ratio of the number of functional groups in the above formula (2) is more preferably 0.9 to 4, even more preferably 1 to 3.5, and even more preferably 2.5 to 3. If the ratio of the number of functional groups of each component of the formula (2) is within the corresponding range, a composition for a cured resin having superior low-melt viscosity, and a cured product having a lower molding shrinkage rate and a lower linear expansion rate, and superior heat resistance can be obtained.

[0138] (Ingredient D)

[0139] The composition for curing resin of the present invention may additionally contain (D) a silane coupling agent as desired. As for the component (D) silane coupling agent, it is not particularly limited as long as it does not deviate from the spirit of the present invention, but for example, as a reactive group, a silane coupling agent having a reactive functional group such as a vinyl group, an epoxy group, a styryl group, a methacrylic group, an acrylic group, an amino group, a ureido group, a mercapto group, a sulfide group, an isocyanate group, a thiocarbonyl group, a halogen group, a triazine thiol group, or a combination thereof may be cited, and preferably, a silane coupling agent having an amino group, more preferably a silane coupling agent having a primary amino group, a secondary amino group, or a combination thereof, and even more preferably, a silane coupling agent having at least one primary amino group and a secondary amino group each in one molecule. (D) As a silane coupling agent, specifically, examples include vinyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacrylooxypropyltrimethoxysilane, 3-acrylooxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc., and preferably, These are N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and 3-aminopropyltrimethoxysilane. These silane coupling agents may be used individually, or two or more may be used in combination.

[0140] As for the mixing ratio of component (D), it is preferable to have component (D) in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total of components (A), (B), and (C), and it is more preferable to have it in the range of 0.1 to 5 parts by mass. By containing component (D) in this range, a cured resin composition having superior mechanical strength can be produced.

[0141] (Ingredient E)

[0142] The composition for the curing resin of the present invention may additionally contain (E) a curing accelerator if desired. As for the component (E) curing accelerator, known curing accelerators may be used, and examples include amine-based compounds such as tributylamine and 1,8-diazabicyclo(5,4,0)undecen-7, imidazole-based compounds such as 2-methylimidazole, 2-ethylimidazole, and 1,2-dimethylimidazole, organic phosphorus compounds in which phosphorus is bonded only by covalent bonds such as triphenylphosphine, salt-type organic phosphorus compounds in which phosphorus is bonded by covalent and ionic bonds such as tetraphenylphosphonium tetraphenylborate, bis(tetrabutylphosphonium)(BTBP)-pyromellitic acid, and tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate (TBP-3PC), but are not limited to these. In addition, the above-mentioned curing accelerator may be used alone or in combination of two or more types. Among these, organic phosphorus compounds such as triphenylphosphine, tetraphenylphosphonium tetraphenylborate, and tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate are preferred because they have a greater effect in improving the curing speed.

[0143] It is preferable that the above-mentioned organic phosphorus compound exhibits a function of promoting a cross-linking reaction between an epoxy group and a phenolic hydroxyl group, as described in Japanese Patent Publication No. 55-157594. Additionally, it is preferable that the above-mentioned organic phosphorus compound also exhibits a function of promoting a reaction between a hydroxyl group and an epoxy group that occurs when (A) a benzoxazine compound undergoes a cleavage reaction at high temperature.

[0144] As for the mixing ratio of component (E), it is preferable to have component (E) in a range of 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total of components (A), (B), and (C), and it is more preferable to have it in a range of 0.1 parts by mass or more and 5 parts by mass or less. By including component (E) in this range, a curing resin composition having superior rapid curing properties can be produced.

[0145] (Ingredient F)

[0146] The curing resin composition of the present invention may additionally contain an inorganic filler (F) if desired. For example, when the curing resin composition of the present invention is used as an encapsulant for semiconductor devices, it is preferable to contain component (F). The inorganic filler used in the present invention is not particularly limited and can be selected considering the use of the curing resin composition or the cured product, or the properties to be imparted. Hereinafter, this inorganic filler is referred to as component (F).

[0147] Examples of component (F) include oxides such as silica, alumina, titanium oxide, zirconium oxide, magnesium oxide, cerium oxide, yttrium oxide, calcium oxide, antimony trioxide, zinc oxide, iron oxide, etc.; carbonates such as calcium carbonate, magnesium carbonate, barium carbonate, strontium carbonate, etc.; sulfates such as barium sulfate, aluminum sulfate, calcium sulfate, etc.; nitrides such as aluminum nitride, silicon nitride, titanium nitride, boron nitride, manganese nitride, etc.; silicon compounds such as calcium silicate, magnesium silicate, aluminum silicate, etc.; boron compounds such as aluminum borate, etc.; zirconium compounds such as barium zirconate, calcium zirconate, etc.; phosphorus compounds such as zirconium phosphate, magnesium phosphate, etc.; titanium compounds such as strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, barium titanate, potassium titanate, etc.; Examples include minerals such as mica, talc, kaolin, kaolin clay, kaolinite, halloysite, cordierite, pyrophyllite, montmorillonite, sericite, aimite, bentonite, asbestos, wollastonite, sepiolite, zonotrite, zeolite, hydrotalsite, hydrated gypsum, alum, diatomite, and boehmite; fly ash, dehydrated sludge, glass beads, glass fiber, silica sand, magnesium oxysulfate, silicon oxide, silicon carbide, etc.; metals such as copper, iron, cobalt, and nickel, or alloys containing any one of them; magnetic materials such as sentust, Alnico magnets, and ferrite; graphite, coke, etc. The component (F) is preferably silica or alumina. Examples of silica include fused silica, spherical silica, crystalline silica, amorphous silica, synthetic silica, hollow silica, etc., and preferably spherical silica such as fused spherical silica, crystalline silica. The component (F) may be used as a single type or as a combination of two or more types.

[0148] The component (F) may be in granular form, and in that case, the average particle size is not particularly limited, but for example, it may be 0.01 μm or more and 150 μm or less, preferably 0.1 μm or more and 120 μm or less, and more preferably 0.5 μm or more and 75 μm or less. Within this range, for example, when the composition of the present invention is used as an encapsulant for a semiconductor device, the filling performance into the mold cavity becomes better. The average particle size of the component (F) can be measured by the laser diffraction and scattering method. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis using a laser diffraction particle size distribution measuring device and taking its median diameter as the average particle size. Preferably, the measurement sample can be one in which the inorganic filler is dispersed in water by ultrasound. As a laser diffraction type particle size distribution measuring device, the “LA-500,” “LA-750,” “LA-950,” “LA-960” manufactured by Horiba Inc. can be used.

[0149] The mixing ratio of component (F) is not particularly limited as long as a high-heat-resistant cured product of the curing resin composition can be obtained, and can be appropriately set according to the application. For example, when the composition is used for semiconductor encapsulation, the mixing ratio shown below is preferred.

[0150] The lower limit of the mixing ratio of component (F) can be, for example, 80 parts by mass or more (i.e., 80 mass% or more) per 100 parts by mass of the composition for curing resin, preferably 81 parts by mass or more, and more preferably 85 parts by mass or more. In addition, the upper limit of the mixing ratio of component (F) can be, for example, 99 parts by mass or less per 100 parts by mass of the composition for curing resin, preferably 95 parts by mass or less, and more preferably 90 parts by mass or less. If the lower limit of the mixing ratio of component (F) is 80 parts by mass or more, the increase in moisture absorption or decrease in strength accompanying the curing of the composition for curing resin can be further suppressed, and thus a cured product having better solder crack resistance can be obtained. In addition, if the upper limit of the mixing ratio of component (F) is 95 parts by mass or less, the fluidity of the composition for curing resin is improved, making it easier to fill into the mold, and the cured product exhibits better encapsulation performance.

[0151] (Other ingredients)

[0152] The composition of the present invention may contain a benzoxazine compound other than component (A) to the extent that it does not deviate from the spirit of the present invention. For example, if one wishes to reduce the viscosity of the composition, a monofunctional benzoxazine compound having one benzoxazine ring may be added to the composition.

[0153] In addition, the composition for the curing resin of the present invention may incorporate, for example, nano carbon, flame retardants, release agents, colorants, low-stress additives, metal hydroxides, etc., within a range that does not impair the performance.

[0154] Examples of nanocarbons include carbon nanotubes, fullerenes, or their respective derivatives.

[0155] Examples of flame retardants include phosphate esters such as red phosphorus, triphenyl phosphate, tricresyl phosphate, tricyllenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol bisphenyl phosphate, and bisphenol A bisdiphenyl phosphate, as well as boric acid esters and phosphazene.

[0156] Examples of release agents include natural waxes such as stearic acid esters and carnauba wax, synthetic waxes such as polyethylene oxidized wax, higher fatty acids such as stearic acid or their esters, metal salts such as zinc stearate, paraffin, and silicone oil.

[0157] Examples of coloring agents include carbon black, Bengala, and titanium oxide.

[0158] Examples of low-stress additives include silicone oil and silicone rubber.

[0159] Examples of metal hydroxides include calcium hydroxide, aluminum hydroxide, and magnesium hydroxide.

[0160] As for the mixing ratio of the other components, with respect to 100 parts by mass of the total of components (A), (B) and (C), it is preferable to have the other components in a range of 0.01 parts by mass or more and 10 parts by mass or less, and more preferable to have them in a range of 0.1 parts by mass or more and 7 parts by mass or less.

[0161] (Characteristics of compositions for curing resins)

[0162] The weight loss rate of the curing resin composition of the present invention upon heat curing can be, for example, 1.5 mass% or less, preferably 1.3 mass% or less, more preferably 1.2 mass% or less, and even more preferably 1.0 mass% or less. The lower limit is not particularly limited, but 0.05 mass% or more is preferred. The weight loss rate can be measured by a thermogravimetric differential thermal analysis device. Such measurement can be easily performed by using a commercially available thermogravimetric differential thermal analysis device (e.g., manufactured by Hitachi High-Tech Science Co., Ltd.).

[0163] The viscosity of the curing resin composition of the present invention at 100°C is, for example, 2.0 Pa·s or less, from the perspective of fluidity or handling of the curing resin composition, preferably 1.9 Pa·s or less, more preferably 1.8 Pa·s or less, and even more preferably 1.4 Pa·s or less (also referred to as low-melt viscosity). The lower limit is not particularly limited, but 0.1 Pa·s or more is preferred. In addition, by measuring the viscosity of a curing resin composition that does not contain inorganic fillers and / or curing accelerators, the amount of inorganic filler in a curing resin composition containing inorganic fillers can be estimated within a range that does not impair fluidity. The above viscosity can be measured by a cone plate viscometer. Such measurement can be easily performed by using a commercially available cone plate viscometer (e.g., manufactured by Brookfield).

[0164] [Method for preparing a composition for curing resin]

[0165] Next, a method for manufacturing a composition for a cured resin according to the present invention will be described.

[0166] A composition for a cured resin according to the present invention can be prepared by adding and mixing components (A) to (C), additionally, components (D), (E), (F), other components, and a solvent as desired.

[0167] The kneading or mixing method is not particularly limited, and mixing can be performed using, for example, a mixing device such as a planetary mixer, a twin-screw extruder, a hot roller, or a kneader, or a kneader. In addition, if components (A), (B), and (C) are in a high-viscosity liquid or solid state at room temperature, or if component (F) is included, the composition may be kneaded by heating as necessary, or additionally kneaded under pressurized or reduced pressure conditions. The heating temperature is preferably 80 to 120°C. Since the curing resin composition containing component (F) is in a solid state at room temperature, it may be cooled and ground into a powder after heating and kneading, or the powder may be compressed into pellets. In addition, the powder may be granulated into granules.

[0168] When the curing resin composition of the present invention does not contain component (F) and is used for purposes such as prepreg for FRP, it is preferable that the curing resin composition has a viscosity of 10 to 3000 Pa·s at 50°C. More preferably, it is 10 to 2500 Pa·s, and additionally preferably 100 to 2000 Pa·s. When used for encapsulating materials or coating purposes, the viscosity is not particularly limited as long as there is no hindrance to operations such as encapsulating or coating.

[0169] When the curing resin composition of the present invention does not contain component (F) and is used for purposes such as prepreg for FRP, it is preferable that the curing resin composition has a viscosity of 10 to 3000 Pa·s at 50°C. More preferably, it is 10 to 2500 Pa·s, and additionally preferably 100 to 2000 Pa·s. When used for encapsulating materials or coating purposes, the viscosity is not particularly limited as long as there is no hindrance to operations such as encapsulating or coating.

[0170] [Hardened material]

[0171] The cured product of the curing resin composition of the present invention has the characteristics of having a high glass transition temperature and excellent heat resistance. The reasons why the curing resin composition of the present invention forms such an excellent cured product can be considered as follows.

[0172] First, in the homopolymerization of benzoxazine, phenolic hydroxyl groups are generated by the polymerization. It is believed that these phenolic hydroxyl groups pass through keto-enol tautomers at high temperatures, for example, above 200°C, and as a result, the polymer chain is cleaved, which is why the heat resistance is low and the glass transition temperature is also low.

[0173] In this regard, the composition for curing resin of the present invention is thought to have excellent heat resistance because the number of benzoxazine rings of (A) the benzoxazine compound, the number of epoxy groups of (B) the epoxy compound, and the number of hydroxyl groups of (C) the phenolic curing agent satisfy the formula (1), thereby causing the phenolic hydroxyl groups generated by the homopolymerization of benzoxazine to react rapidly with the epoxy compound to form a dense cross-linked structure.

[0174] (Properties of hardened materials)

[0175] The heat resistance of the cured product of the present invention can be evaluated by measuring the glass transition temperature. The glass transition temperature is, for example, 185°C or higher, preferably 190°C or higher, and more preferably 200°C or higher. The upper limit is not particularly limited, but 400°C or lower is preferred. The glass transition temperature can be measured by differential scanning calorimetry (DSC). Such measurement can be easily performed by using a commercially available differential scanning calorimeter (e.g., manufactured by Hitachi High-Tech Science Co., Ltd.).

[0176] The linear expansion coefficient of the cured product of the present invention may be, for example, 13.5 ppm / °C or less, preferably 13.0 ppm / °C or less, and more preferably 12.5 ppm / °C or less. The lower limit is not particularly limited, but 0.1 ppm / °C or more is preferred. The linear expansion coefficient can be measured in accordance with the JIS K7197 linear expansion coefficient test method by thermomechanical analysis of plastics. Such measurement can be easily performed in accordance with the JIS K7197 linear expansion coefficient test method by thermomechanical analysis of plastics by using a commercially available thermomechanical analysis device (for example, manufactured by Hitachi High-Tech Science Co., Ltd., product name: TMA7100).

[0177] The molding shrinkage rate of the cured product of the present invention may be, for example, 0.50% or less, and preferably 0.45% or less. The lower limit is not particularly limited, but 0.01% or more is preferred. Here, the lengthwise dimension of the cured product is measured with a vernier caliper after it has been set in a constant temperature room (temperature 23℃, humidity 50%) overnight after molding, and the molding shrinkage rate can be calculated from the following formula.

[0178] Molding Shrinkage Rate [%] = (Mold Dimensions - Specimen Dimensions) / Mold Dimensions × 100

[0179] [Method for manufacturing hardened material]

[0180] The cured product of the present invention can be prepared by curing by performing ring-opening polymerization under curing conditions similar to those of known benzoxazine compounds and / or epoxy compounds. For example, the following methods may be used.

[0181] First, the composition for curing resin of the present invention is prepared according to the above method. Subsequently, the obtained composition for curing resin can be heated at, for example, 150 to 300°C for a curing time of, for example, 20 seconds to 5 hours, preferably 20 seconds to 1 hour, to obtain a cured product. When producing the cured product continuously, a curing time of 1 to 3 minutes is sufficient, but to obtain higher strength, it is preferable to heat for an additional 5 minutes to 6 hours as post-curing.

[0182] In addition, within the scope of not departing from the spirit of the present invention, a cured product may be obtained by combining a benzoxazine compound other than component (A) and / or an epoxy compound other than component (B).

[0183] When obtaining a film-like molded article as a cured product, a solvent may be additionally added to form a composition having a solution viscosity suitable for thin film formation. As long as the solvent is capable of dissolving components (A) to (E), it is not particularly limited, and examples include hydrocarbons, ethers, esters, halogens, etc.

[0184] In this way, in the case of a solution-phase curing resin composition dissolved in a solvent, a cured product can be obtained by applying the solution-phase curing resin composition to a substrate, etc., volatilizing the solvent, and then performing heat curing.

[0185] [Semiconductor device]

[0186] The semiconductor device of the present invention is a semiconductor device in which a semiconductor element is installed in a cured product formed by curing a composition for curing resin of the present invention containing components (A) to (C), optionally (D), (E), (F), and other components. Here, typically, the semiconductor element is supported and fixed by a lead frame which is a thin sheet of metal material. "In which a semiconductor element is installed in a cured product" means that the semiconductor element is encapsulated in the cured product of the composition for curing resin, and indicates a state in which the semiconductor element is coated with the cured product. In this case, the entire semiconductor element may be coated, or the surface of the semiconductor element installed on the substrate may be coated.

[0187] When various electronic components, such as semiconductor devices, are encapsulated using the cured product of the present invention and a semiconductor device is manufactured, the semiconductor device can be manufactured by performing the encapsulation process using conventional molding methods such as a transfer mold, a compression mold, or an injection mold.

[0188] Examples

[0189] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0190] <Component (A): Polyfunctional Benzoxazine Compound>

[0191] The following (A1) and (A2) were used as component (A).

[0192] (A1): Phenol-diaminodiphenylmethane (Pd) type benzoxazine represented by the following formula (Shikoku Kasei Co., Ltd.) (Benzoxazine equivalent (g / eq): 217)

[0193]

[0194] (A2): Benzoxazine (3-[3-[4-(2H-1,3-benzoxazine-3(4H)-yl)phenoxy]phenyl]-3,4-dihydro-2H-1,3-benzoxazine)(3,4'-APE-BOZ)(benzoxazine equivalent (g / eq): 218, Honshu Kagaku Kogyo Co., Ltd., developed product) represented by the following formula (1-1-1)

[0195]

[0196] <Component (B): Epoxy Compound>

[0197] The following (B1) to (B5) were used as ingredient (B).

[0198] (B1) Epoxy compound 1: Compound of formula (5-1)

[0199] The compound (a) shown in the above formula (6) was synthesized according to the method described in “Shoichi Tsuchida et al., ‘Diels-Alder reaction of butadiene and cyclopentadiene - determination of trimer -, Journal of the Petroleum Society, 1972, Vol. 15, No. 3, pp. 189-192”.

[0200] Next, the reaction of the above formula (6) was carried out as follows. 23.5 kg of chloroform and 1.6 kg of compound (a) were added to a reaction vessel, and 4.5 kg of metachloroperoxybenzoic acid was added dropwise while stirring at 0°C. The temperature was raised to room temperature, and the reaction was carried out for 12 hours.

[0201] Next, after removing the byproduct metachlorobenzoic acid by filtration, the filtrate was washed three times with a 1N sodium hydroxide aqueous solution and then washed with saturated saline solution. After drying the organic layer with magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated to obtain a crude body.

[0202] 2 kg of toluene was added to the mixture and dissolved at room temperature. 6 kg of heptane was added dropwise to this, crystallized, and aged at 5°C for 1 hour. The crystallized product was filtered and washed with hexane. By drying under reduced pressure at 35°C for 24 hours, 1.4 kg of the compound represented by the following formula (5-1) was obtained as a white solid.

[0203]

[0204] (B2) Epoxy compound 2: Compound of formula (5-2) (tricyclopentadiene diepoxide)

[0205] The compound (b) represented by the above formula (7) was synthesized in accordance with the method described in Shoichi Tsuchida et al., “Diels-Alder reaction of butadiene and cyclopentadiene - determination of trimer -,” Journal of the Petrochemical Society, 1972, Vol. 15, No. 3, pp. 189-192.

[0206] Next, the reaction of the above formula (7) was carried out as follows. 59.2 kg of chloroform and 4.0 kg of compound (b) were added to a reaction vessel, and 10.6 kg of metachloroperoxybenzoic acid was added dropwise while stirring at -10°C. The temperature was raised to room temperature, and the reaction was carried out for 12 hours.

[0207] Next, after removing the byproduct metachlorobenzoic acid by filtration, the filtrate was washed with 42.0 kg of a 5% aqueous sodium sulfite solution. The organic layer was further washed four times with 41.6 kg of a 1N aqueous sodium hydroxide solution, followed by washing with 48.0 kg of saturated saline solution. After drying the organic layer with magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated to obtain 5.1 kg of a crude body.

[0208] 3.5 kg of toluene was added to the mixture and dissolved at room temperature. 13.7 kg of heptane was added dropwise to this, crystallized, and aged at 5°C for 1 hour. The crystallized product was filtered and washed with heptane. By drying under reduced pressure at 35°C for 12 hours, 2.8 kg of the compound represented by the following formula (5-2) was obtained as a white solid.

[0209]

[0210] (B3) Epoxy compound 3: Epoxy compound represented by the following formula (9-1) (EPPN-501H, epoxy equivalent (g / eq): 162~172, manufactured by Nippon Kayaku Co., Ltd.)

[0211]

[0212] (In Equation (9-1), n ​​is the mean value and is 1.3.)

[0213] (B4) Epoxy compound 4: Epoxy compound represented by the following formula (9-2) (EPPN-502H, epoxy equivalent (g / eq): 158~178, manufactured by Nippon Kayaku Co., Ltd.)

[0214]

[0215] (In Equation (9-2), n is the mean value and is 1.8.)

[0216] (B5) Epoxy Compound 5: Naphthol-type epoxy compound (NC-7300L, epoxy equivalent (g / eq): 207~221, manufactured by Nippon Kayaku Co., Ltd.)

[0217] <Component (C): Phenolic Curing Agent>

[0218] The following (C1) and (C2) were used as components (C).

[0219] (C1) Phenolic curing agent 1: Bisphenol F (Bisphenol F, hydroxyl equivalent 100.115, manufactured by Honshu Kagaku Kogyo Co., Ltd.)

[0220] (C2) Phenolic curing agent 2: Phenol novolak resin (TD-2131, hydroxyl equivalent 104, manufactured by DIC Co., Ltd.)

[0221] <Ingredient (D): Silane Coupling Agent>

[0222] The following (D1) and (D2) were used as components (D).

[0223] (D1) Silane coupling agent 1: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (KBM-603, manufactured by Shin-Etsu Silicon Co., Ltd.)

[0224] (D2) Silane coupling agent 2: 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Silicon Co., Ltd.)

[0225] <Ingredient (E): Curing Accelerator>

[0226] As component (E), tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate (TBP-3PC, manufactured by Hokkoku Kogaku Kogyo Co., Ltd.) was used.

[0227] <Ingredient (F): Inorganic Filler>

[0228] As a component (F), fused spherical silica (FB-820, manufactured by Denka Co., Ltd.) with an average particle size D50 of 22 μm was used.

[0229] Other ingredients

[0230] Carnauba wax (WE-4, manufactured by Clariant Chemicals Co., Ltd.) was used as a mold release agent, and carbon black (MA600, manufactured by Mitsubishi Chemical Co., Ltd.) was used as a coloring agent.

[0231] (Example 1)

[0232] A composition for curing resin (hereinafter simply referred to as "composition") and a cured product were prepared as follows, and the weight loss rate, molding shrinkage rate, glass transition temperature, linear expansion rate, and viscosity were measured.

[0233] Components (A) benzoxazine compound, (B) epoxy compound, (C) phenolic curing agent, (D) silane coupling agent, (E) curing accelerator, (F) inorganic filler, release agent (carnauba wax), and carbon black were mixed for 10 minutes under atmospheric pressure using a hot roll mixer (model “BR-150HCV”, manufactured by Imex Co.) having two rolls with surface temperatures of 90°C and 100°C, in the mixing ratios shown in Table 1, and then cooled to room temperature to obtain a mixture. The obtained mixture was ground into a powder using a mini speed mill (model “MS-09”, manufactured by Labonecto Co.) so that filling into a mold could be performed well, thereby obtaining a composition.

[0234] <Weight Reduction Rate>

[0235] Approximately 10 mg of the obtained composition powder was cut onto an aluminum sample plate, and the temperature was raised from 40°C to 175°C at a heating rate of 10°C / min using a thermogravimetric differential thermal analyzer (model “STA7200RV”, manufactured by Hitachi High-Tech Science Co., Ltd.), maintained at 175°C for 1 hour after reaching the temperature, and the weight loss rate was measured. The results are shown in Table 1.

[0236] <Molding Shrinkage Rate>

[0237] A transfer molding machine (model “ADM-5”, manufactured by Meiho Co., Ltd.) was used, and the composition prepared above was cured under conditions of a mold temperature of 175°C, an injection pressure of 4 MPa, and a curing time of 3 minutes to produce a test specimen with dimensions of 3 mm in length x 10 mm in width x 70 mm in length. After molding, the test specimen was left to stand overnight in a constant temperature room (temperature 23°C, humidity 50%), and its lengthwise dimensions were measured using a vernier caliper. The molding shrinkage rate was then calculated using the following formula.

[0238] Molding Shrinkage Rate [%] = (Mold Dimensions - Specimen Dimensions) / Mold Dimensions × 100

[0239] Glass Transition Temperature (Tg)

[0240] As a post-treatment, the test specimen obtained by the above transfer molding was further heated in an oven at 175°C for 5 hours to obtain a cured product. The glass transition temperature of the test specimen obtained by cutting the cured product into pieces measuring 3 mm x 2 mm x 2 mm was measured using a differential scanning calorimeter (model "X-DSC-7000", heating rate 20°C / min, manufactured by Hitachi High-Tech Science Co., Ltd.). The results are shown in Table 1.

[0241] Coefficient of Linear Expansion (CTE)

[0242] As a post-treatment, the test specimen obtained by the above transfer molding was further heated in an oven at 175°C for 5 hours to obtain a cured product. The obtained cured product was cut into pieces measuring 3 mm in length x 5 mm in width x 10 mm in length to obtain test specimens. For the obtained test specimens, a thermomechanical analyzer (model "TMA7100", manufactured by Hitachi High-Tech Science Co., Ltd.) was used, and in accordance with the JIS K7197 method for testing the coefficient of linear expansion of plastics by thermomechanical analysis, the temperature was raised from 25°C to 150°C at a compressive load of 20 mN and a heating rate of 5°C / min, and the coefficient of linear expansion was calculated from the slope of the SS curve at that time. The results are shown in Table 1.

[0243] Viscosity

[0244] Components (A) a benzoxazine compound, (B) an epoxy compound, and (C) a phenolic curing agent were weighed onto a φ50 mm aluminum plate in the proportions shown in Table 1 and melt-mixed for 5 minutes on a hot plate heated to 110°C to obtain a mixture. The viscosity of the mixture at 100°C was measured using a cone plate viscometer (model “CAP2000+H”, cone angle 3°, rotation speed 100 rpm, manufactured by Brookfield). The results are shown in Table 1.

[0245] (Examples 2-9)

[0246] The compositions of each example were prepared in the same manner as in Example 1, except that the mixing ratio of each component was as shown in Table 1. For each composition and its cured product, the weight loss rate, molding shrinkage rate, glass transition temperature, linear expansion rate, and viscosity were measured in the same manner as in Example 1. The results are shown in Table 1.

[0247] (Comparative Examples 1~5)

[0248] The compositions of each comparative example were prepared in the same manner as in Example 1, except that the mixing ratio of each component was as shown in Table 1. For each composition and its cured product, the weight loss rate, molding shrinkage rate, glass transition temperature, linear expansion rate, and viscosity were measured in the same manner as in Example 1. The results are shown in Table 1.

[0249]

[0250] Since the weight loss rate upon heat curing of the curing resin composition of each example is 1.0 mass% or less, the weight loss rate of the composition is low. Since the viscosity of the curing resin composition of each example is 2.0 Pa·s or less, the viscosity of the composition is low. In addition, the Tg of the cured product is 185°C or higher, indicating high heat resistance. Furthermore, since the linear expansion rate of the cured product is 13.5 ppm / °C or lower, the linear expansion rate of the composition is low. Since the molding shrinkage rate of the cured product is 0.45% or lower, the molding shrinkage rate of the composition is low. On the other hand, the weight loss rate upon heat curing of the curing resin composition of Comparative Example 1 is increasing. In addition, the weight loss rate upon heat curing of the curing resin composition of Comparative Example 2 is increasing, and furthermore, since its cured product has a low Tg, its heat resistance is inferior, and its linear expansion rate and molding shrinkage rate are increasing. The cured product obtained by curing the curing resin composition of Comparative Example 3 also has poor heat resistance because its Tg is low, and the viscosity of the curing resin composition is high. The weight loss rate during heat curing of the curing resin composition of Comparative Example 4 is high, and furthermore, the linear expansion rate and molding shrinkage rate of its cured product are high, the Tg of its cured product is low, and the viscosity of the curing resin composition is high. The weight loss rate during heat curing of the curing resin composition of Comparative Example 5 is high, and furthermore, the molding shrinkage rate of its cured product is high, and the Tg of its cured product is low.

[0251] From the above results, it can be seen that the composition for curing resin, which is an embodiment of the present invention, has a low weight loss rate upon heat curing and low melt viscosity, and furthermore, the cured product has high heat resistance and low molding shrinkage rate and linear expansion rate.

Claims

Claim 1 A composition for a curing resin comprising (A) a benzoxazine compound, (B) an epoxy compound, and (C) a phenolic curing agent, wherein the number of benzoxazine rings of the (A) benzoxazine compound, the number of epoxy groups of the (B) epoxy compound, and the number of hydroxyl groups of the (C) phenolic curing agent satisfy the following formula (1), wherein (B) the epoxy compound comprises an alicyclic epoxy compound, and furthermore, the content of the (B) alicyclic epoxy compound relative to the total of the (A) benzoxazine compound, the (B) epoxy compound, and the (C) phenolic curing agent is 3 to 10 mass%. [Formula 1] (Number of benzoxazine rings + Number of hydroxyl groups) / Number of epoxy groups = 0.8 to 5 (1) Claim 2 A composition for a curing resin according to claim 1, wherein the number of benzoxazine rings of the (A) benzoxazine compound, the number of epoxy groups of the (B) epoxy compound, and the number of hydroxyl groups of the (C) phenolic curing agent satisfy the following formula (2). [Formula 2] (Number of benzoxazine rings + Number of hydroxyl groups) / Number of epoxy groups = 2~5 (2) Claim 3 A composition for a cured resin according to claim 1, wherein the (A) benzoxazine compound is a polyfunctional benzoxazine compound having at least two benzoxazine rings, and is at least one polyfunctional benzoxazine compound selected from a polyfunctional benzoxazine compound having a structural unit of formula (1) and a polyfunctional benzoxazine compound represented by the structure of formula (2). [Formula 1] [In Formula (1), R represents a chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and the aryl group may have a halogen or a chain alkyl group having 1 to 12 carbon atoms as a substituent. Z represents hydrogen, a hydrocarbon group having 1 to 8 carbon atoms, and / or a linker, each of which may be the same or different, and at least one is a linker, and the benzoxazine rings are connected to each other by the linker.][Phenomenon 2] [In formula (2), L is a divalent organic group having 1 to 5 aromatic rings or an alkylene group having 2 to 10 carbon atoms, and said organic group and alkylene group may include oxygen and / or sulfur.] Claim 4 A composition for a curing resin according to claim 1, wherein the alicyclic epoxy compound is an epoxy compound having at least one norbornan structure and at least two epoxy groups. Claim 5 A composition for a curing resin according to claim 1, wherein the alicyclic epoxy compound has at least one structure selected from the group consisting of a five-membered ring structure, a six-membered ring structure, and a norbornan ring structure represented by formula (3). [Form 3] Claim 6 A composition for a curing resin according to claim 1, wherein the alicyclic epoxy compound does not have a glycidyl group. Claim 7 A composition for a cured resin according to claim 1, further comprising (D) a silane coupling agent. Claim 8 A composition for a cured resin according to claim 7, wherein the (D) silane coupling agent contains at least one primary amino group and at least one secondary amino group in one molecule. Claim 9 A composition for a cured resin according to claim 1, further comprising (E) a curing accelerator. Claim 10 A composition for a cured resin according to claim 1, further comprising (F) an inorganic filler. Claim 11 A composition for a cured resin according to claim 10, wherein the content of the (F) inorganic filler is 80 to 95 mass% with respect to the entire composition for the cured resin. Claim 12 A cured product formed by curing a curing resin composition of any one of claims 1 to 11. Claim 13 A semiconductor device having a semiconductor element installed in a cured product formed by curing a curing resin composition of any one of claims 1 to 11. Claim 14 A method for manufacturing a curing resin composition according to any one of claims 1 to 11, comprising: (A) a benzoxazine compound, (B) an epoxy compound, and (C) a phenolic curing agent to obtain a mixture, and a process of processing the mixture into a powder, pellet, or granular curing resin composition. Claim 15 A method of manufacturing according to claim 14, wherein in the process of obtaining the mixture, at least one component selected from the group consisting of (D) a silane coupling agent, (E) a curing accelerator, and (F) an inorganic filler is further mixed to obtain the mixture. Claim 16 A method for manufacturing a cured product having a process of curing the cured resin composition prepared by the method of claim 14 by heating it at 150 to 300°C for 20 seconds to 6 hours.

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