A composition for curing resins, a cured product of the composition, a method for manufacturing the composition and the cured product, and a semiconductor device.

Abstract

To provide a composition for a cured resin with a low weight reduction rate in heat curing for obtaining a cured product with a reduced mold shrinkage factor and a linear expansion coefficient while having high heat resistance, the cured product, and a production method of the composition for the cured resin and the cured product, and to provide a semiconductor device using the cured product as a sealing material.SOLUTION: A composition for a cured resin of the invention contains a benzoxazine compound (A), an epoxy compound (B), and a phenolic curing agent (C), in which the number of epoxy groups in the epoxy compound (B), the number of benzoxazine rings in the benzoxazine compound (A), and the number of hydroxy groups in the phenolic curing agent (C) satisfy a mathematical equation (1), and a content of the alicyclic epoxy compound (B) based on a sum total of (A), (B), and (C) is 3-12 mass%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a composition for a curable resin for obtaining a highly heat-resistant cured product, the cured product, and a method for producing the curable resin composition and the cured product. Further, the present invention relates to a semiconductor device using the cured product as a sealing material.

Background Art

[0002] Curable resins are used in various applications such as semiconductor sealing materials and fiber reinforced plastics, and a benzoxazine compound is used as one of the raw materials. The benzoxazine compound refers to a compound containing a benzoxazine ring having a benzene skeleton and an oxazine skeleton, and the cured product (polymer), benzoxazine resin, is excellent in physical properties such as heat resistance and mechanical strength, and is used as a high-performance material in various applications.

[0003] Furthermore, when using a curable resin for a semiconductor sealing material or the like, improvement of molding defects such as reduction of the molding shrinkage rate is also required. Here, as factors affecting the molding shrinkage rate, the weight loss rate and the linear expansion rate during heat curing are known. The weight loss rate during heat curing is considered to reflect the volatilization of low molecular weight components, and by suppressing the weight loss rate, it is possible to improve the working environment and stabilize the composition of the resin composition.

[0004] 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 parts characterized by containing an aliphatic epoxy compound and a benzoxazine compound as curing agents and containing a phenolic curing agent.

[0005] Patent Document 2 describes an epoxy resin composition that does not use a benzoxazine compound, but contains an epoxy resin selected from trifunctional epoxy resins and tetrafunctional epoxy resins, 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 can provide a semiconductor device that is excellent in flame retardancy, solder crack resistance, and fluidity, and further exhibits minimal warping even at low temperatures such as after molding, during soldering, and in temperature cycle tests. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2013-008800 [Patent Document 2] International Publication No. 2007 / 037500 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, the present inventors have found that the following technical problems exist in Patent Documents 1 and 2. The adhesive for electronic components described in Patent Document 1 has the problem that a cured product with a high glass transition temperature cannot be obtained. The epoxy resin composition described in Patent Document 2 has the problem that there is a limit to the reduction of the coefficient of linear expansion.

[0008] The inventors of the present invention conducted diligent research to solve the above problems and developed a curing resin composition containing a benzoxazine compound, an epoxy compound, and a phenolic curing agent in specific proportions. They found that this curing resin composition exhibits a low weight loss rate during heat curing, the cured product has excellent heat resistance, and the molding shrinkage rate and linear expansion rate of the cured product are reduced.

[0009] Therefore, the object of the present invention is to provide a curing resin composition that has a low weight loss rate during heat curing, which is required to obtain a cured product that has high heat resistance, low molding shrinkage rate and low coefficient of linear expansion. Another object of the present invention is to provide a cured product obtained by curing the above curing resin composition, as well as the above curing resin composition and a method for producing the cured product. Another object of the present invention is to provide a semiconductor device that uses the cured product as a encapsulant. [Means for solving the problem]

[0010] In other words, the present invention provides the following invention. [1] (A) Benzooxazine compound, (B) Epoxy compound and (C) Phenolic curing agent and It contains, The number of benzoxazine rings in the (A) benzoxazine compound, the number of epoxy groups in the (B) epoxy compound, and the number of hydroxyl groups in the (C) phenolic curing agent satisfy the following formula (1): (B) The epoxy compound comprises an alicyclic epoxy compound, A composition for curing resins in which the content of the alicyclic epoxy compound (B) is 3 to 12% by mass relative to the total of the benzoxazine compound (A), the epoxy compound (B), and the phenolic curing agent (C).

number

[10] The content rate of the said (F) inorganic filler is 80 to 95 mass% with respect to the whole composition for a cured resin, The composition for a cured resin according to [9].

[11] A cured object obtained by curing the composition for a cured resin according to any one of [1] to

[10] .

[12] A semiconductor device in which a semiconductor element is installed in a cured object obtained by curing the composition for a cured resin according to any one of [1] to

[10] .

[13] A method for producing a composition for a cured resin according to any one of [1] to

[10] , (A) A benzoxazine compound, (B) An epoxy compound, (C) A phenolic curing agent And a step of mixing to obtain a mixture, A step of processing the mixture into a powdery, pellet状, or granular composition for a cured resin A method for producing a composition for a cured resin having.

[14] In the step of obtaining the said 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 a mixture, The production method according to

[13] .

[15]

[13] Or a step of heating and curing the composition for a cured resin produced by the method according to

[14] at 150 to 300 ° C for 20 seconds to 6 hours A method for producing a cured object having. [Advantages of the Invention]

[0011] The curing resin composition of the present invention is a novel curing resin composition containing components (A) to (C) in specific proportions, and optionally containing components (D), (E), and (F). This composition has the characteristics of a low weight loss rate during heat curing, high heat resistance in its cured product, and excellent molding shrinkage rate and linear expansion coefficient. Furthermore, the curing resin composition also has the characteristic of having low melt viscosity. Therefore, the curing resin composition of the present invention can be used in applications that require heat resistance while also requiring improvement of molding defects and optionally low melt viscosity, such as adhesives, sealants, paints, and matrix resins for composite materials. In particular, it can be suitably used as a WLP sealant or PLP sealant. [Modes for carrying out the invention]

[0012] [Composition for cured resin] The present invention will be described in detail below. Note that the terms "compound," "curing agent," and "silane coupling agent" in components (A) to (D) of the present invention include not only monomers but also oligomers formed by polymerization of the monomers, for example, oligomers polymerized in small quantities, i.e., prepolymers before the formation of a cured resin. Therefore, the cured resin composition of the present invention may also be a curable resin composition.

[0013] (Component (A)) Component (A) of the curing resin composition is a benzoxazine compound, preferably at least one polyfunctional benzoxazine compound having at least two benzoxazine rings, selected from polyfunctional benzoxazine compounds having the structural unit of formula (1) and polyfunctional benzoxazine compounds represented by the structure of formula (2). In formula (1), Z represents hydrogen, a substituent, and / or a linking group (spacer), which may be the same or different, and at least one is a linking group, which links the benzoxazine rings together. Here, a linking group includes a group in which two benzoxazine rings are directly bonded without other groups in between. The substituent is, for example, a hydrocarbon group having 1 to 8 carbon atoms. Therefore, formula (1) above represents the structural unit of a compound among the options for component (A) in which two or more benzoxazine rings are linked at the benzene ring portion.

[0014] More specifically, the polyfunctional benzoxazine compound of formula (1) can be represented by the structure shown in formula (1a). [ka] [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. Each of the R groups may be the same or different. X is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and each of the X groups 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.]

[0015] The following are examples of specific R values ​​in equations (1) and (1a). Examples of chain alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. Examples of cyclic alkyl groups having 3 to 8 carbon atoms include the cyclopentyl group and the cyclohexyl group. Examples of aryl groups having 6 to 14 carbon atoms include the phenyl group, 1-naphthyl group, 2-naphthyl group, phenanthryl group, and biphenyl group. The aryl group having 6 to 14 carbon atoms may be substituted, and examples of substituents include a linear alkyl group having 1 to 12 carbon atoms or a halogen. Examples of aryl groups having 6 to 14 carbon atoms substituted with a linear alkyl group having 1 to 12 carbon atoms or a halogen include o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, ot-butylphenyl group, mt-butylphenyl group, pt-butylphenyl group, o-chlorophenyl group, and o-bromophenyl group. In terms of ease of handling, R is a methyl group, ethyl group, propyl group, phenyl group, Preferably, the group is selected from the p-tolyl group. Furthermore, component (A) may be a mixture of multiple compounds shown in formula (1) or (1a), each with a different R.

[0016] Examples of C1-C8 hydrocarbon groups in X of formulas (1) and (1a) include alkyl groups, aryl groups, and aralkyl groups, with aryl groups being preferred.

[0017] Examples of polyfunctional benzoxazine compounds represented by formula (1) or (1a) include compounds represented by the following formula (1X), and oligomers obtained by polymerizing a small amount of said compound. [ka] JPEG0007862142000007.jpg116153

[0018] Another option for component (A), the polyfunctional benzoxazine compound of formula (2), is a compound in which the nitrogen atoms (N atoms) of two benzoxazine rings are linked together via a linking group L. [ka] [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 the organic group and alkylene group may contain oxygen and / or sulfur.] The composition of the present invention may contain as component (A) multiple types of polyfunctional benzoxazine compounds represented by formula (2) with different L values.

[0019] When L in formula (2) is a group having an aromatic ring, the number of aromatic rings can be 1 to 5, and examples include monocyclic compounds, polycyclic compounds, and fused ring compounds. L may also contain at least one selected from the group consisting of oxygen and sulfur. As a specific example, the group shown in formula (2a) below can be cited. [ka]

[0020] When L in formula (2) is an alkylene group, its carbon number can be 1 to 10, preferably 1 to 6. Specific examples of the alkylene group include a methylene group, an ethylene group, an isopropylidene group, and the like, with a methylene group being preferred.

[0021] Examples of the polyfunctional benzoxazine compound of formula (2) include the compound represented by the following formula (2X), and oligomers obtained by polymerization of said compound, for example, oligomers obtained by polymerization in small amounts. [ka]

[0022] The polyfunctional benzoxazine compound of component (A) is preferably bisphenol F-aniline (Fa) type benzoxazine, phenol-diaminodiphenylmethane (Pd) type benzoxazine, or 3-[4-[4-(2,4-dihydro-1,3-benzoxazin-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-benzoxa The compound is 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 produced based on the description in Synthesis Example 1 of Japanese Patent Application Publication No. 2018-184533.

[0023] Commercially available polyfunctional benzoxazine compounds can also be used for component (A). Examples of commercially available products include bisphenol F-aniline (Fa) type benzoxazine and phenol-diaminodiphenylmethane (Pd) type benzoxazine (both manufactured by Shikoku Chemicals Co., Ltd.).

[0024] The benzoxazine equivalent of component (A) benzoxazine compound is preferably 135 g / eq to 600 g / eq, and more preferably 140 g / eq to 400 g / eq, from the viewpoint of improving reactivity. Here, the benzoxazine equivalent of component (A) benzoxazine compound refers to the equivalent when the benzoxazine ring in component (A) benzoxazine compound is treated as a single functional compound.

[0025] The number of benzoxazine rings (mol) in component (A) benzoxazine compound is calculated from the benzoxazine equivalent of component (A) benzoxazine compound. If the composition of the present invention contains multiple types of benzoxazine compounds as component (A), the above number of benzoxazine rings shall be the sum of the number of rings calculated from the benzoxazine equivalents of these compounds.

[0026] (Component (B)) Component (B) of the curing resin composition is an epoxy compound. Such epoxy compounds are not particularly limited as long as they do not depart from the spirit of the present invention, and include alicyclic epoxy compounds, biphenyl-type epoxy compounds, trisphenolmethane-type epoxy compounds, naphthalene-type epoxy compounds, novolac-type epoxy compounds, phenolaralkyl-type epoxy compounds, and epoxy compounds having a cyclohexene oxide group, but are preferred to be alicyclic epoxy compounds, trisphenolmethane-type epoxy compounds, and naphthalene-type epoxy compounds.

[0027] According to a preferred embodiment of the present invention, the curing resin composition contains a mixture of several epoxy compounds as component (B). The mixture of epoxy compounds preferably includes an alicyclic epoxy compound. Examples of the mixture of epoxy compounds include a combination of an alicyclic epoxy compound and an epoxy compound other than an alicyclic epoxy compound. The epoxy compound other than the alicyclic epoxy compound is preferably at least one epoxy compound selected from biphenyl-type epoxy compounds, trisphenolmethane-type epoxy compounds, naphthalene-type epoxy compounds, novolac-type epoxy compounds, phenolaralkyl-type epoxy compounds, and epoxy compounds having a cyclohexene oxide group, and more preferably a trisphenolmethane-type epoxy compound, a naphthalene-type epoxy compound, or a combination thereof.

[0028] The epoxy equivalent of component (B) epoxy compound is preferably 50 g / eq to 400 g / eq, and more preferably 80 g / eq to 300 g / eq, from the viewpoint of improving reactivity.

[0029] The number of epoxy groups (mol) in the epoxy compound of component (B) is calculated from the epoxy equivalent. If the composition of the present invention contains multiple types of epoxy compounds as component (B), the number of epoxy groups shall be the sum of the number of epoxy groups in these compounds.

[0030] (Alicyclic epoxy compound) The alicyclic epoxy compound is not particularly limited as long as it does not depart from the spirit of the present invention, but examples include epoxy compounds having one or more alicyclic hydrocarbon structures and epoxy groups in the molecule, preferably epoxy compounds having at least one alicyclic hydrocarbon structure and at least two epoxy groups, and more preferably epoxy compounds having at least one norbornane structure and at least two epoxy groups. Furthermore, it is preferable that the above alicyclic epoxy compound does not have a glycidyl group.

[0031] (An epoxy compound having at least one norbornane structure and at least two epoxy groups) The epoxy compound having at least one norbornane structure and at least two epoxy groups is preferably one that has an epoxy structure bonded to a five-membered ring, a six-membered ring, or a norbornane ring, as shown in formula (4) below. One or more of these may be used in combination. [ka]

[0032] According to a preferred embodiment of the present invention, an epoxy compound having at least one norbornane structure and at least two epoxy groups does not have a glycidyl group.

[0033] Examples of specific alicyclic epoxy compounds include the compound represented by the following formula (5). [ka]

[0034] An example of the preparation of the alicyclic epoxy compound of component (B) will be described. The compound of formula (5-1) below (epoxy equivalent: 109 g / eq) can be produced, for example, by synthesizing compound (a) having the norbornane structure shown below by a Diels-Alder reaction between butadiene and dicyclopentadiene, and then reacting compound (a) with metachloroperbenzoic acid as shown in formula (6) below. [ka]

[0035] The compound of formula (5-2) below (epoxy equivalent: 115 g / eq) can be produced, for example, by synthesizing compound (b) (tricyclopentadiene) having the norbornane structure shown below by a Diels-Alder reaction between cyclopentadiene and dicyclopentadiene, and then reacting compound (b) with metachloroperbenzoic acid as shown in formula (7) below. [ka]

[0036] The compound of formula (5-3) below (epoxy equivalent: 109 g / eq) can be produced, for example, by synthesizing compound (c) having the norbornane structure shown below by a Diels-Alder reaction between butadiene and cyclopentadiene, and then reacting compound (c) with metachloroperbenzoic acid as shown in formula (8) below. [ka]

[0037] The compound of formula (5-4) below (epoxy equivalent: 82.1 g / eq) can be produced, for example, by reacting dicyclopentadiene with potassium peroxymonosulfate (Oxone). The dicyclopentadiene diepoxide, which is the compound of formula (5-4), may be a commercially available product, and an example of a commercially available product is the dicyclopentadiene diepoxide manufactured by SHANDONG QIHUAN BIOCHEMICAL CO., LTD. [ka]

[0038] (Trisphenolmethane-type epoxy compound) The trisphenolmethane-type epoxy compound is not particularly limited as long as it does not depart from the spirit of the present invention, but it is preferably an epoxy compound represented by the structure of formula (9) below. [ka] [In formula (9), R is a substituent, each independently representing an alkyl group, allyl group, or phenyl group having 1 to 6 carbon atoms. m is the number of substituents R, each representing an integer from 0 to 3. n is the average value, 0 ≤ n ≤ 10.]

[0039] In formula (9), m is preferably 0 to 2, and more preferably 0. In formula (9), n is preferably 0 or more and 5 or less. Examples of C1 to C6 alkyl groups in substituent R of formula (9) include methyl, ethyl, propyl, butyl, and cyclohexyl groups. A methyl group is preferred as substituent R. Furthermore, the trisphenolmethane-type epoxy compound may be a mixture of the compounds shown in formula (9) in which R, m, and n are different.

[0040] Commercially available trisphenolmethane-type epoxy compounds can also be used. Examples of commercially available products include EPPN-501H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 162-172 g / eq, softening point 51-57°C), EPPN-501HY (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 163-175 g / eq, softening point 57-63°C), EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 158-178 g / eq, softening point 60-72°C), and EPPN-503 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 170-190 g / eq, softening point 80-100°C). These may be used individually or in combination of two or more.

[0041] (Naphthalene-type epoxy compound) The naphthalene-type epoxy compound is not particularly limited as long as it does not depart from the spirit of the present invention, but examples include naphthol-type epoxy compounds, naphthylene ether-type epoxy compounds, binaphthalene-type epoxy compounds, etc., and is preferably a naphthol-type epoxy compound.

[0042] (Naphthol-type epoxy compound) The naphthol-type epoxy compound is not particularly limited as long as it does not depart from the spirit of the present invention, but it is preferably an epoxy compound represented by the structure of the following formula (10).

[0043] [ka] (In formula (10) above, A and B independently represent substituted or unsubstituted benzene, or substituted or unsubstituted naphthalene. n represents the repeating unit and is an integer between 1 and 10.)

[0044] Unsubstituted benzene or naphthalene consists solely of benzene or naphthalene, while substituted benzene or naphthalene has substituents on the aromatic hydrocarbon group of the benzene or naphthalene ring. A substituent on an aromatic hydrocarbon group means that some or all of the hydrogen atoms constituting the aromatic hydrocarbon group are substituted by substituents. Examples of substituents include organic groups containing glycidyl ether groups and alkyl groups.

[0045] The alkyl group used as a substituent is preferably a chain-like alkyl group. Furthermore, its carbon number is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, and sec-butyl groups.

[0046] Preferred specific examples of the naphthol-type epoxy compound represented by formula (10) above include, for example, the naphthol-type epoxy compounds represented by the following formulas (10-1) to (10-4). These may be used individually or in combination of two or more.

[0047] [ka] [ka] [ka] [ka] In the above formulas (10-1) to (10-4), n is, for example, an integer between 0 and 10, preferably an integer between 0 and 6, more preferably an integer between 0 and 4, and even more preferably an integer between 0 and 3.

[0048] Commercial naphthol-type epoxy compounds can also be used. Examples of commercially available naphthol-type epoxy compounds include 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 Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent 332 g / eq), and ESN-375 (trade name, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent 170 g / eq). These may be used individually or in combination of two or more.

[0049] The mixing ratio of component (A) benzoxazine compound and component (B) epoxy compound is preferably 10 to 300 parts by mass of component (B) per 100 parts by mass of component (A), and more preferably 30 to 200 parts by mass of component (B). When the mixing ratio of components (A) and (B) is within the above range, better heat resistance can be obtained. Here, if the composition of the present invention contains multiple types of benzoxazine compounds as component (A), the total amount of these compounds is considered to be 100 parts by mass. If the composition of the present invention contains multiple types of epoxy compounds as component (B), the amount of component (B) refers to the total amount of the multiple compounds.

[0050] The content of component (B) the alicyclic epoxy compound is preferably 3 to 12 parts by mass (i.e., 3 to 12% by mass), more preferably 3 to 10 parts by mass (i.e., 3 to 10% by mass), and even more preferably 4 to 10 parts by mass (i.e., 4 to 10% by mass), based on 100 parts by mass of the total of component (A) the benzoxazine compound, component (B) the epoxy compound, and component (C) the phenolic curing agent. When the blending ratio of component (B) the alicyclic epoxy compound is within the above range, better heat resistance and a better weight loss rate can be observed. Here, if the composition of the present invention contains multiple types of benzoxazine compounds as component (A), the amount of component (A) refers to the total amount of the multiple compounds. The same applies if the composition of the present invention contains multiple types of epoxy compounds as component (B). If the composition of the present invention contains multiple types of alicyclic epoxy compounds as component (B), the content of the alicyclic epoxy compounds in component (B) refers to the total content of the multiple alicyclic epoxy compounds.

[0051] The content of the alicyclic epoxy compound in component (B) epoxy compound 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, per 100 parts by mass of component (B) epoxy compound. When the blending ratio of component (B) is within the above range, better low melt viscosity and better weight loss rate can be obtained. Here, if the composition of the present invention contains multiple types of benzoxazine compounds as component (A) and / or multiple types of alicyclic epoxy compounds or epoxy compounds as component (B), the amounts of these compounds are the same as described above.

[0052] (Component C) Component (C) of the curing resin composition is a phenolic curing agent. Component (C) is not particularly limited as long as it does not depart from the spirit of the present invention, but examples include monofunctional phenols, polyfunctional phenol compounds (e.g., bisphenol A, bisphenol F, dihydroxynaphthalene, bisphenol sulfide (e.g., bis(4-hydroxyphenyl) sulfide, etc.), polyphenol compounds (e.g., pyrogallol, etc.), etc.), phenol novolac resins, phenol aralkyl resins (e.g., phenol aralkyl resins having a biphenylene skeleton, phenol aralkyl resins having a phenylene skeleton), etc., and preferably bisphenol F and phenol novolac resins. These may be used individually or as a mixture of two or more.

[0053] Commercially available phenolic curing agents can be used for component (C). For example, bisphenol F (manufactured by Honshu Chemical Industry Co., Ltd., hydroxyl equivalent 100 g / eq), bis(4-hydroxyphenyl) sulfide (TDP, manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl equivalent 109 g / eq), 2,7-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl equivalent 80 g / eq), pyrogallol (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl equivalent 42 g / eq), and phenol novolac resin (e.g., Phenolite TD-2). Examples include 131, DIC Corporation, hydroxyl equivalent 104 g / eq; Phenolite TD-2106, DIC Corporation, hydroxyl equivalent 104 g / eq; Phenolite TD-2090, DIC Corporation, hydroxyl equivalent 105 g / eq), and phenol aralkyl resins (e.g., MEHC-7851SS, 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.). These may be used individually or in combination of two or more.

[0054] The mixing ratio of component (C) is preferably in the range of 5 to 30 parts by mass, and more preferably 10 to 20 parts by mass, per 100 parts by mass of the total of components (A) and (B). By including component (C) within this range, a cured product with superior heat resistance can be obtained. Furthermore, if 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 the same as described above.

[0055] The hydroxyl group equivalent of component (C), the phenolic curing agent, is preferably 80 g / eq to 400 g / eq, and more preferably 90 g / eq to 250 g / eq, from the viewpoint of improving reactivity.

[0056] The number of hydroxyl groups (mol) of the phenolic curing agent in component (C) is calculated from the hydroxyl group equivalent. If the composition of the present invention contains multiple types of phenolic curing agents as component (C), the above number of hydroxyl groups shall be the sum of the hydroxyl groups of these curing agents.

[0057] In the present invention, it is preferable that the ratio of the number of functional groups in the curing resin composition, specifically the number of epoxy groups in component (B) epoxy compound, the number of benzoxazine rings in component (A) benzoxazine compound, and the number of hydroxyl groups in component (C) phenolic curing agent, satisfies the following formula (2).

number

[0058] (Component D) The curing resin composition of the present invention may further contain (D) a silane coupling agent if desired. The component (D) silane coupling agent is not particularly limited as long as it does not depart from the spirit of the present invention, but examples include silane coupling agents having reactive functional groups or combinations thereof as reactive groups such as vinyl groups, epoxy groups, styryl groups, methacrylic groups, acrylic groups, amino groups, ureido groups, mercapto groups, sulfide groups, isocyanate groups, thiocarbonyl groups, halogen groups, triazinethiol groups, etc. 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 at least one secondary amino group in one molecule. (D) Examples of silane coupling agents include vinyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatetopropyltriethoxysilane, and others, with N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and 3-aminopropyltrimethoxysilane being preferred. These silane coupling agents may be used individually or in combination of two or more types.

[0059] The blending ratio of component (D) is preferably in the range of 0.01 parts by mass to 10 parts by mass, and more preferably in the range of 0.1 parts by mass to 5 parts by mass, per 100 parts by mass of the total of components (A), (B), and (C). By including component (D) within this range, a curing resin composition with superior mechanical strength can be obtained.

[0060] (Component E) The curing resin composition of the present invention may optionally further contain (E) a curing accelerator. As component (E) the curing accelerator, known curing accelerators can be used, but are not limited to these. Examples include, but are not limited to, amine compounds such as tributylamine and 1,8-diazabicyclo(5,4,0)undecene-7; imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, and 1,2-dimethylimidazole; organophosphorus compounds in which phosphorus is bonded only by covalent bonds, such as triphenylphosphine; and salt-type organophosphorus 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). Furthermore, the above-mentioned curing accelerators may be used alone or in combination of two or more. Among these, organophosphorus compounds such as triphenylphosphine, tetraphenylphosphonium tetraphenylborate, and tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate are preferred because they have a significant effect in improving the curing speed. The above organophosphorus compound is preferably one that exhibits the function of promoting the crosslinking reaction between the epoxy group and the phenolic hydroxyl group, as described in Japanese Patent Publication No. 55-157594. Furthermore, it is preferable that the above organophosphorus compound also exhibits the function of promoting the reaction between the hydroxyl group and the epoxy group generated when the (A) benzoxazine compound undergoes a cleavage reaction at high temperature.

[0061] The blending ratio of component (E) is preferably in the range of 0.01 parts by mass to 10 parts by mass, and more preferably in the range of 0.1 parts by mass to 5 parts by mass, per 100 parts by mass of the total of components (A), (B), and (C). By including component (E) within this range, a curing resin composition with superior rapid curing properties can be obtained.

[0062] (Component F) The curing resin composition of the present invention may further contain an inorganic filler (F) if desired. For example, when the curing resin composition of the present invention is used as a encapsulant for semiconductor devices and the like, it is preferable to include component (F). The inorganic filler used in the present invention is not particularly limited and can be selected considering the application of the curing resin composition or its cured product or the properties to be imparted. Hereinafter, this inorganic filler will be referred to as component (F). 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, and iron oxide; carbonates such as calcium carbonate, magnesium carbonate, barium carbonate, and strontium carbonate; sulfates such as barium sulfate, aluminum sulfate, and calcium sulfate; nitrides such as aluminum nitride, silicon nitride, titanium nitride, boron nitride, and manganese nitride; silicon compounds such as calcium silicate, magnesium silicate, and aluminum silicate; boron compounds such as aluminum borate; zirconium compounds such as barium zirconate and calcium zirconate; phosphorus compounds such as zirconium phosphate and magnesium phosphate; strontium titanate, calcium titanate, and titanium dioxide. Examples include titanium compounds such as magnesium nitrate, bismuth titanate, barium titanate, and potassium titanate; minerals such as mica, talc, kaolin, kaolin clay, kaolinite, halloysite, cordierite, pyrophyllite, montmorillonite, sericite, amethyst, bentonite, asbestos, wollastonite, sepiolite, xonotlite, zeolite, hydrotalcite, hydrated gypsum, alum, diatomaceous earth, and boehmite; fly ash, dewatered sludge, glass beads, glass fibers, silica sand, magnesium oxysulfate, silicon oxide, silicon carbide, etc.; metals such as copper, iron, cobalt, and nickel, or alloys containing any of them; magnetic materials such as Sendust, Alnico magnets, and ferrite; graphite, coke, etc. Component (F) is preferably silica or alumina. Examples of silica include fused silica, spherical silica, crystalline silica, amorphous silica, synthetic silica, and hollow silica, with spherical silica such as fused spherical silica and crystalline silica being preferred. Component (F) may be used alone or in combination of two or more types.

[0063] Component (F) may be granular, and in that case, the average particle size is not particularly limited, but for example, it is 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 a encapsulant for semiconductor devices, the filling properties into the mold cavity will be better. The average particle size of component (F) can be measured by laser diffraction and scattering. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis using a laser diffraction particle size distribution analyzer, and the average particle size can be measured by taking the median diameter as the average particle size. Preferably, the measurement sample is an inorganic filler dispersed in water by ultrasound. As a laser diffraction particle size distribution analyzer, models such as "LA-500", "LA-750", "LA-950", and "LA-960" manufactured by Horiba, Ltd. can be used.

[0064] The blending ratio of component (F) is not particularly limited as long as a highly heat-resistant cured product of the curing resin composition can be obtained, and can be set appropriately according to the application. For example, when the composition is used for semiconductor encapsulation applications, the following blending ratio is preferred. The lower limit of the blending ratio of component (F) is, for example, 80 parts by mass or more (i.e., 80% by mass or more) per 100 parts by mass of the curing resin composition, preferably 81 parts by mass or more, and more preferably 85 parts by mass or more. The upper limit of the blending ratio of component (F) is, for example, 99 parts by mass or less per 100 parts by mass of the curing resin composition, preferably 95 parts by mass or less, and more preferably 90 parts by mass or less. If the lower limit of the blending ratio of component (F) is 80 parts by mass or more, the increase in moisture absorption and decrease in strength associated with the curing of the curing resin composition can be further suppressed, and therefore a cured product with better solder crack resistance can be obtained. Furthermore, if the upper limit of the blending ratio of component (F) is 95 parts by mass or less, the fluidity of the curing resin composition will be improved, making it easier to fill into molds, and the cured product will exhibit better sealing performance.

[0065] (Other ingredients) The compositions of the present invention may contain benzoxazine compounds other than component (A) without departing from the spirit of the invention. For example, if it is desired to reduce the viscosity of the composition, a monofunctional benzoxazine compound having one benzoxazine ring may be added to the composition.

[0066] Furthermore, the curing resin composition of the present invention may contain, to the extent that it does not impair its performance, for example, nanocarbon, flame retardants, mold release agents, colorants, low-stress additives, metal hydroxides, and the like. Examples of nanocarbons include carbon nanotubes, fullerenes, or their derivatives. Examples of flame retardants include phosphate esters such as red phosphorus, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol bisphenyl phosphate, and bisphenol A bisdiphenyl phosphate, as well as borate esters and phosphazenes. Examples of release agents include natural waxes such as stearic acid esters and carnauba wax, synthetic waxes such as polyethylene oxide wax, higher fatty acids such as stearic acid or their esters, metal salts such as zinc stearate, paraffin, and silicone oil. Examples of colorants include carbon black, red iron oxide, and titanium dioxide. Examples of low-stress additives include silicone oil and silicone rubber. Examples of metal hydroxides include calcium hydroxide, aluminum hydroxide, and magnesium hydroxide.

[0067] Regarding the proportion of other components, it is preferable that the other components be in the range of 0.01 parts by mass or more and 10 parts by mass or less, and more preferably in the range of 0.1 parts by mass or more and 7 parts by mass or less, relative to 100 parts by mass of the total of components (A), (B), and (C).

[0068] (Properties of compositions for curing resins) The weight loss rate of the curing resin composition of the present invention during heat curing is, for example, 1.5% by mass or less, preferably 1.3% by mass or less, more preferably 1.2% by mass or less, and even more preferably 1.0% by mass or less. The lower limit is not particularly limited, but 0.05% by mass or more is preferred. The above weight loss rate can be measured by a thermogravimetric differential thermal analyzer. Such measurement can be easily performed using a commercially available thermogravimetric differential thermal analyzer (for example, one manufactured by Hitachi High-Tech Science Corporation).

[0069] The viscosity of the curing resin composition of the present invention at 100°C is, from the viewpoint of the fluidity and handling of the curing resin composition, for example, 2.0 Pa·s or less, 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 called low melt viscosity). The lower limit is not particularly limited, but 0.1 Pa·s or more is preferred. Furthermore, by measuring the viscosity of the curing resin composition that does not contain inorganic fillers and / or curing accelerators, it is possible to predict the amount of inorganic filler that does not worsen the fluidity in a curing resin composition containing inorganic fillers. The above viscosity can be measured using a cone plate viscometer. Such measurements can be easily performed using commercially available cone plate viscometers (e.g., Brookfield Corporation).

[0070] [Method for manufacturing compositions for curing resins] Next, a method for producing the curing resin composition of the present invention will be described. The curing resin composition of the present invention can be produced by kneading or mixing components (A) to (C), and optionally components (D), (E), (F), other components, and solvents in appropriate amounts. The kneading or mixing method is not particularly limited, and can be mixed using, for example, a planetary mixer, a twin-screw extruder, a hot roll or kneader, or other mixing device or kneader. Furthermore, if components (A), (B), and (C) are in a highly viscous liquid or solid state at room temperature, or if component (F) is included, the mixture may be heated and kneaded as necessary, or kneaded under pressurized or reduced pressure. A heating temperature of 80 to 120°C is preferred. Since the curing resin composition containing component (F) is solid at room temperature, after heating and kneading, it may be cooled and pulverized to become a powder, and the powder may be compressed into tablets to form pellets. Alternatively, the powder may be granulated to become granules.

[0071] When the curing resin composition of the present invention does not contain component (F) and is used for FRP prepreg applications, 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 even more preferably, 100 to 2000 Pa·s. When used as a sealing material or coating application, the viscosity is not particularly limited as long as it does not interfere with sealing, coating, or other operations.

[0072] [Cured product] The cured product of the curing resin composition of the present invention has the characteristics of 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 are thought to be as follows. First, in the homopolymerization of benzoxazine, phenolic hydroxyl groups are generated during polymerization. These phenolic hydroxyl groups are thought to have low heat resistance and a low glass transition temperature because, at high temperatures, such as above 200°C, they undergo ketoenol tautomerization, which cleaves the polymer chain. In contrast, the curing resin composition of the present invention satisfies the above formula (1) in which (A) the number of benzoxazine rings of the benzoxazine compound, (B) the number of epoxy groups of the epoxy compound, and (C) the number of hydroxyl groups of the phenolic curing agent. As a result, the phenolic hydroxyl groups generated by the homopolymerization of benzoxazine react rapidly with the epoxy compound, forming a dense crosslinked structure, which is thought to result in excellent heat resistance.

[0073] (Properties of the hardened material) 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. There is no particular upper limit, but 400°C or lower is preferred. The glass transition temperature can be measured by differential scanning calorimetry (DSC). Such measurements can be easily performed using commercially available differential scanning calorimetry analyzers (for example, those manufactured by Hitachi High-Tech Science Corporation).

[0074] The linear expansion coefficient of the cured product of the present invention is, 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 / K or higher is preferred. The linear expansion coefficient can be measured in accordance with JIS K7197, the test method for linear expansion coefficient of plastics by thermomechanical analysis. Such measurements can be easily performed in accordance with JIS K7197, the test method for linear expansion coefficient of plastics by thermomechanical analysis, by using a commercially available thermomechanical analyzer (for example, Hitachi High-Tech Science Co., Ltd., product name: TMA7100).

[0075] The molding shrinkage rate of the cured product of the present invention is, 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 cured product is left to stand overnight in a constant temperature chamber (temperature 23°C, humidity 50%) after molding, and the length dimension is measured with a caliper, and the molding shrinkage rate can be calculated from the following formula. Molding shrinkage rate [%] = (Mold dimensions - Test piece dimensions) / Mold dimensions × 100

[0076] [Method for manufacturing hardened products] The cured product of the present invention can be produced by ring-opening polymerization and curing under curing conditions similar to those for known benzoxazine compounds and / or epoxy compounds. For example, the following methods can be used. First, the curing resin composition of the present invention is manufactured by the method described above. Subsequently, the obtained curing resin composition is 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 continuously producing cured products, a curing time of 1 to 3 minutes is sufficient, but to obtain higher strength, it is preferable to heat for a further 5 minutes to 6 hours as a post-curing step. Furthermore, without departing from the spirit of the present invention, a cured product can also be obtained by incorporating a benzoxazine compound other than component (A) and / or an epoxy compound other than component (B).

[0077] When obtaining a film-like molded product as a cured product, a solvent can be further added to create a composition with a solution viscosity suitable for thin film formation. The solvent is not particularly limited as long as it can dissolve components (A) to (E), and examples include hydrocarbons, ethers, esters, halogen-containing compounds, etc. Thus, in the case of a solution-type curing resin composition dissolved in a solvent, a cured product can be obtained by applying the solution-type curing resin composition to a substrate or the like, allowing the solvent to evaporate, and then performing thermal curing.

[0078] [Semiconductor device] The semiconductor device of the present invention is a semiconductor device in which a semiconductor element is installed in a cured product obtained by curing a curable resin composition of the present invention containing components (A) to (C), optionally (D), (E), (F), and other components. Here, the semiconductor element is usually supported and fixed by a lead frame, which is a thin plate of metal material. "A semiconductor element is installed in a cured product" means that the semiconductor element is sealed in the cured product of the curable resin composition, and represents a state in which the semiconductor element is covered with the cured product. In this case, the entire semiconductor element may be covered, or only the surface of the semiconductor element installed on the substrate may be covered.

[0079] When using the cured product of the present invention to encapsulate various electronic components such as semiconductor elements and manufacture a semiconductor device, the semiconductor device can be manufactured by carrying out the encapsulation process using conventional molding methods such as transfer molding, compression molding, or injection molding. [Examples]

[0080] 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.

[0081] <Component (A): Polyfunctional benzoxazine compound> The following (A1) and (A2) were used as component (A). (A1): Phenol-diaminodiphenylmethane (Pd) type benzoxazine shown in the formula below (manufactured by Shikoku Chemicals Co., Ltd.) (benzoxazine equivalent (g / eq): 217) [ka]

[0082] (A2): Benzoxazine shown in the following formula (1-1-1) (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 Chemical Industry Co., Ltd., product under development) [ka]

[0083] <Component (B): Epoxy compound> The following (B1) to (B5) were used as component (B).

[0084] (B1) Epoxy compound 1: Compound of formula (5-1) Compound (a) shown in formula (6) above 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 Japan Petroleum Society, 1972, Vol. 15, No. 3, pp. 189-192". Next, the reaction of formula (6) above was carried out as follows: 23.5 kg of chloroform and 1.6 kg of compound (a) were placed in a reaction vessel, and 4.5 kg of metachloroperbenzoic 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. Next, after removing the by-product metachlorobenzoic acid by filtration, the filtrate was washed three times with 1N sodium hydroxide aqueous solution, and then washed with saturated saline solution. The organic layer was dried over magnesium sulfate, and the magnesium sulfate was removed by filtration. The filtrate was concentrated to obtain the crude product. Two kilograms of toluene were added to the crude material and dissolved at room temperature. Six kilograms of heptane were added dropwise to crystallize, and the mixture was aged at 5°C for one hour. The crystallized material was filtered and washed with hexane. By drying under reduced pressure at 35°C for 24 hours, 1.4 kg of the compound shown in formula (5-1) below was obtained as a white solid. [ka]

[0085] (B2) Epoxy compound 2: Compound of formula (5-2) (tricyclopentadiene diepoxide) Compound (b) shown in formula (7) above 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 Japan Petroleum Society, 1972, Vol. 15, No. 3, pp. 189-192". Next, the reaction of formula (7) above was carried out as follows: 59.2 kg of chloroform and 4.0 kg of compound (b) were placed in a reaction vessel, and 10.6 kg of metachloroperbenzoic 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. Next, after removing the by-product metachlorobenzoic acid by filtration, the filtrate was washed with 42.0 kg of 5% sodium sulfite aqueous solution. The organic layer was further washed four times with 41.6 kg of 1N sodium hydroxide aqueous solution, and then washed with 48.0 kg of saturated brine. After drying the organic layer over magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated to obtain 5.1 kg of crude material. 3.5 kg of toluene was added to the crude material and dissolved at room temperature. 13.7 kg of heptane was added dropwise to crystallize, and the mixture was aged at 5°C for 1 hour. The crystallized material was filtered and washed with heptane. By drying under reduced pressure at 35°C for 12 hours, 2.8 kg of the compound shown in formula (5-2) below was obtained as a white solid. [ka]

[0086] (B3) Epoxy compound 3: The epoxy compound shown in formula (9-1) below (EPPN-501H, epoxy equivalent (g / eq): 162-172, manufactured by Nippon Kayaku Co., Ltd.) [ka] (In equation (9-1), n ​​is the mean value, which is 1.3.)

[0087] (B4) Epoxy compound 4: The epoxy compound shown in formula (9-2) below (EPPN-502H, epoxy equivalent (g / eq): 158-178, manufactured by Nippon Kayaku Co., Ltd.) [ka] (In equation (9-2), n is the mean value, which is 1.8.)

[0088] (B5) Epoxy compound 5: Naphthol-type epoxy compound (NC-7300L, epoxy equivalent (g / eq): 207-221, manufactured by Nippon Kayaku Co., Ltd.)

[0089] <Component (C): Phenolic hardener> The following (C1) and (C2) were used as component (C). (C1) Phenolic curing agent 1: Bisphenol F (Bisphenol F, hydroxyl group equivalent 100.115, manufactured by Honshu Chemical Industry Co., Ltd.)

[0090] (C2) Phenolic curing agent 2: Phenolic novolac resin (TD-2131, hydroxyl group equivalent 104, manufactured by DIC Corporation)

[0091] <Component (D): Silane coupling agent> The following (D1) and (D2) were used as components (D). (D1) Silane coupling agent 1: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (KBM-603, manufactured by Shin-Etsu Silicone Co., Ltd.)

[0092] (D2) Silane coupling agent 2: 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Silicone Co., Ltd.)

[0093] <Ingredient (E): Curing accelerator> As component (E), tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate (TBP-3PC, manufactured by Hokko Chemical Industry Co., Ltd.) was used.

[0094] <Component (F): Inorganic filler> As component (F), molten spherical silica (FB-820, manufactured by Denka Co., Ltd.) with an average particle size D50 of 22 μm was used.

[0095] <Other ingredients> Carnauba wax (WE-4, manufactured by Clariant Chemicals Co., Ltd.) was used as a release agent, and carbon black (MA600, manufactured by Mitsubishi Chemical Corporation) was used as a coloring agent.

[0096] (Example 1) A composition for curing resin (hereinafter simply referred to as "the composition") and a cured product were prepared as follows, and the weight loss rate, molding shrinkage rate, glass transition temperature, linear expansion coefficient, and viscosity were measured.

[0097] Components (A) benzoxazine compound, (B) epoxy compound, (C) phenolic curing agent, (D) silane coupling agent, (E) curing accelerator, (F) inorganic filler, mold release agent (carnauba wax), and carbon black were mixed in the proportions shown in Table 1 using a hot roll kneader (model "BR-150HCV", manufactured by AIMEX Co., Ltd.) with two rolls having surface temperatures of 90°C and 100°C, under atmospheric pressure for 10 minutes, and then cooled to room temperature to obtain a mixture. The obtained mixture was then pulverized into a powder using a mini speed mill (model "MS-09", manufactured by Labonect Co., Ltd.) to obtain a composition that could be easily filled into a mold.

[0098] <Weight reduction rate> Approximately 10 mg of the obtained composition powder was weighed into an aluminum sample pan and heated 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 Corporation). After reaching 175°C, the temperature was held for 1 hour, and the weight loss rate was measured. The results are shown in Table 1.

[0099] <Molding shrinkage rate> Using a transfer molding machine (model "ADM-5", manufactured by Meiho Co., Ltd.), the composition prepared above was cured under the conditions of a mold temperature of 175°C, injection pressure of 4 MPa, and curing time of 3 minutes to create a test specimen measuring 3 mm in length, 10 mm in width, and 70 mm in length. After molding, the test specimen was left to stand overnight in a constant temperature chamber (temperature 23°C, humidity 50%), and its length was measured with calipers. The molding shrinkage rate was then calculated using the following formula. Molding shrinkage rate [%] = (Mold dimensions - Test piece dimensions) / Mold dimensions × 100

[0100] <Glass transition temperature (Tg)> The test specimens obtained by the above transfer molding process were further heated in an oven at 175°C for 5 hours as a post-treatment to obtain cured material. The obtained cured material was cut into specimens measuring 3 mm in length, 2 mm in width, and 2 mm in length, and the glass transition temperature of the resulting specimens was measured using a differential scanning calorimetry analyzer (model "X-DSC-7000", heating rate 20°C per minute, manufactured by Hitachi High-Tech Science Corporation). The results are shown in Table 1.

[0101] <Coefficient of thermal expansion (CTE)> The test specimens obtained by the above transfer molding were further heated in an oven at 175°C for 5 hours as a post-treatment to obtain cured material. The obtained cured material was cut into pieces measuring 3 mm in length, 5 mm in width, and 10 mm in length to obtain test specimens. The obtained test specimens were examined using a thermomechanical analyzer (model "TMA7100", manufactured by Hitachi High-Tech Science Corporation) in accordance with JIS K7197, a test method for linear expansion coefficient of plastics by thermomechanical analysis. The temperature was raised from 25 to 150°C with a compressive load of 20 mN and a heating rate of 5°C per minute, and the linear expansion coefficient was determined from the slope of the SS curve at that time. The results are shown in Table 1.

[0102] <Viscosity> Components (A) benzoxazine compound, (B) epoxy compound, and (C) phenolic curing agent were measured in the proportions shown in Table 1 into a φ50 mm aluminum pan and melted and mixed on a hot plate heated to 110°C for 5 minutes to obtain the formulation. The viscosity of the formulation at 100°C was measured using a cone plate viscometer (model "CAP2000+H", cone angle 3°, rotation speed 100 rpm, Brookfield Corporation). The results are shown in Table 1.

[0103] (Examples 2-9) The compositions for each example were prepared in the same manner as in Example 1, except that the mixing ratios of each component were as shown in Table 1. For each composition and their cured products, the weight loss rate, molding shrinkage rate, glass transition temperature, linear expansion coefficient, and viscosity were measured in the same manner as in Example 1. The results are shown in Table 1.

[0104] (Comparative Examples 1-5) The compositions for each comparative example were prepared in the same manner as in Example 1, except that the mixing ratios of each component were as shown in Table 1. For each composition and their cured products, the weight loss rate, molding shrinkage rate, glass transition temperature, coefficient of linear expansion, and viscosity were measured in the same manner as in Example 1. The results are shown in Table 1. [Table 1]

[0105] The weight loss rate of the curable resin compositions in each example during heat curing is 1.0% by mass or less, indicating a low weight loss rate. The viscosity of the curable resin compositions in each example is 2.0 Pa·s or less, indicating a low viscosity. Furthermore, the Tg of the cured product is 185°C or higher, indicating high heat resistance. In addition, the linear expansion coefficient of the cured product is 13.5 ppm / °C or less, indicating a low linear expansion coefficient. The molding shrinkage rate of the cured product is 0.45% or less, indicating a low molding shrinkage rate. On the other hand, the weight loss rate of the curable resin composition in Comparative Example 1 during heat curing is high. Also, the weight loss rate of the curable resin composition in Comparative Example 2 during heat curing is high, and the cured product has poor heat resistance due to its low Tg, and its linear expansion coefficient and molding shrinkage rate are high. The cured product obtained by curing the curable resin composition in Comparative Example 3 also has poor heat resistance due to its low Tg, and the viscosity of the curable resin composition is high. Comparative Example 4's curing resin composition exhibits a high weight loss rate during heat curing, a high coefficient of linear expansion and molding shrinkage of its cured product, a low Tg of its cured product, and a high viscosity of the curing resin composition. Comparative Example 5's curing resin composition exhibits a high weight loss rate during heat curing, a high molding shrinkage of its cured product, and a low Tg of its cured product. From the above results, it can be seen that the curing resin composition according to the embodiment of the present invention has a low weight loss rate during heat curing, low melt viscosity, and the cured product has high heat resistance, low molding shrinkage rate and low linear expansion rate.

Claims

1. (A) Benzooxazine compounds, (B) Epoxy compounds and (C) Phenolic curing agent, (F) Inorganic fillers and It contains, The number of benzoxazine rings in (A) the benzoxazine compound, the number of epoxy groups in (B) the epoxy compound, and the number of hydroxyl groups in (C) the phenolic curing agent satisfy the following formula (1): (B) The epoxy compound comprises a combination of an alicyclic epoxy compound and at least one epoxy compound selected from trisphenolmethane-type epoxy compounds and naphthalene-type epoxy compounds. The content of the alicyclic epoxy compound (B) relative to the total of the benzoxazine compound (A), the epoxy compound (B), and the phenolic curing agent (C) is 3 to 12% by mass. The content of the alicyclic epoxy compound in the epoxy compound (B) is 5 to 45 parts by mass per 100 parts by mass of the epoxy compound (B), and A curing resin composition in which the content of the inorganic filler (F) is 80 to 95% by mass of the entire curing resin composition. [Math 1]

2. The curing resin composition 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 polyfunctional benzoxazine compounds having the structural unit of formula (1) and polyfunctional benzoxazine compounds represented by the structure of formula (2). 【Chemistry 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, or a linking group, and these may be the same or different, and at least one is a linking group, which links the benzoxazine rings together.] 【Chemistry 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 the organic group and alkylene group may contain oxygen and / or sulfur.]

3. The curing resin composition according to claim 1 or 2, wherein the alicyclic epoxy compound is an epoxy compound having at least one norbornane structure and at least two epoxy groups.

4. The curing resin composition according to any one of claims 1 to 3, 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 norbornane ring structure represented by formula (3). 【Transformation 3】

5. The curing resin composition according to any one of claims 1 to 4, wherein the alicyclic epoxy compound does not have a glycidyl group.

6. (D) The curing resin composition according to any one of claims 1 to 5, further comprising a silane coupling agent.

7. The curing resin composition according to claim 6, wherein the (D) silane coupling agent contains at least one primary amino group and at least one secondary amino group in one molecule.

8. (E) A composition for curing resin according to any one of claims 1 to 7, further comprising a curing accelerator.

9. A cured product obtained by curing the curing resin composition according to any one of claims 1 to 8.

10. A semiconductor device in which a semiconductor element is installed in a cured product obtained by curing a curing resin composition according to any one of claims 1 to 8.

11. A method for producing a curing resin composition according to any one of claims 1 to 8, (A) Benzooxazine compounds, (B) Epoxy compounds and (C) Phenolic curing agent, (F) Inorganic fillers and A process of mixing to obtain a mixture, A process of processing the mixture into a powder, pellet, or granular composition for curing resins. A method for producing a composition for curing resins having the following characteristics.

12. The manufacturing method according to claim 11, wherein in the step of obtaining the mixture, at least one component selected from (D) a silane coupling agent and (E) a curing accelerator is further mixed to obtain the mixture.

13. A step of curing the curing resin composition produced by the method of claim 11 or 12 by heating it at 150 to 300°C for 20 seconds to 6 hours. A method for producing a cured product having the following characteristics.

Images