Sealing material, sealing material, and semiconductor device

Abstract

The present disclosure relates to an encapsulating material including a compound having a structural unit represented by formula (Bb1) (in formula (Bb1), XE represents an organic group including an aromatic ring (wherein the organic group does not include a structure represented by formula (X1) or formula (X2)), each B independently represents a group including a vinyl phenyl group, each R independently represents a substituent, and each R independently represents a substituent. L represents an integer of 1-5, and m represents an integer of 0-10).

Description

Technical Field

[0001] This disclosure relates to sealing materials, sealing agents, electronic component devices, semiconductor devices, and semiconductor modules. Background Technology

[0002] Semiconductor devices are used in a wide variety of electronic devices. With advancements in miniaturization, weight reduction, and increased functionality of electronic devices, the heat generated by semiconductor devices processing high-speed, high-capacity information is increasing. Furthermore, in recent years, semiconductor devices have been used more frequently in high-current or high-voltage environments such as automobiles, trams, wind power generation, and solar power generation. The higher the current or voltage, the greater the heat released by the semiconductor device. Consequently, the heat resistance of semiconductor devices is receiving increasing attention.

[0003] In semiconductor devices, as packaging materials for semiconductor elements, cured products containing thermosetting resin compositions (refer to Patent Document 1) are widely used, considering factors such as productivity and cost. To improve the heat resistance of semiconductor devices, even better heat resistance requirements are being placed on packaging materials.

[0004] [Existing Technical Documents]

[0005] [Patent Literature]

[0006] Patent Document 1: Japanese Patent Application Publication No. 2021-130743 Summary of the Invention

[0007] [The problem the invention aims to solve]

[0008] This disclosure provides a packaging material that provides packaging materials with excellent heat resistance. Furthermore, this disclosure provides a packaging material with excellent heat resistance. Additionally, this disclosure provides electronic component devices, semiconductor devices, and semiconductor modules with excellent heat resistance.

[0009] [Technical means to solve the problem]

[0010] The present invention includes the following embodiments. The present invention is not limited to the following embodiments. One embodiment relates to a packaging material comprising a compound having structural units represented by the following formula (Bb1).

[0011] [Chemistry 1]

[0012]

[0013] (where X) E The symbol represents an organic group containing an aromatic ring (wherein the organic group does not contain the structure represented by formula (X1) or formula (X2) below). Each B independently represents a group containing a vinylphenyl group, each R independently represents a substituent, l represents an integer from 1 to 5, and m represents an integer from 0 to 10. * indicates the bond position with other atoms.

[0014] [Chemistry 2]

[0015]

[0016] (In the formula, * indicates the bond position with atoms other than hydrogen atoms.)

[0017] Another embodiment relates to a packaging material comprising a cured product obtained using the packaging material. Another embodiment relates to an electronic component device having the packaging material. Another embodiment relates to a semiconductor device having a semiconductor element and the packaging material encapsulating at least a portion of the semiconductor element. Another embodiment relates to a semiconductor module having a plurality of semiconductor elements and semiconductor devices selected from the group consisting of semiconductor elements and semiconductor devices, and the packaging material encapsulating at least a portion of the plurality of semiconductor elements.

[0018] [The effects of the invention]

[0019] According to this disclosure, a packaging material with excellent heat resistance is provided. Furthermore, according to this disclosure, a packaging material with excellent heat resistance is provided. Additionally, according to this disclosure, electronic component devices, semiconductor devices, and semiconductor modules with excellent heat resistance are provided. Attached Figure Description

[0020] none Detailed Implementation

[0021] The present invention is described in the following embodiments. The present invention is not limited to the following embodiments. The following embodiments can be implemented individually or in combination. Combinations of multiple embodiments are also included in the present invention.

[0022] In this disclosure, the numerical range represented by “~” means the range containing the values ​​before and after “~” as the minimum and maximum values, respectively.

[0023] In the numerical ranges described progressively in this disclosure, the upper or lower limit of a certain numerical range can be replaced with the upper or lower limit of another numerical range. The upper or lower limit of the numerical ranges described in this disclosure can be replaced with the values ​​shown in the embodiments.

[0024] In this disclosure, a value can be selected from the upper and lower limits of the segmented values ​​to represent the segmented numerical range. The upper and lower limits of the values ​​recorded in this disclosure can be replaced with the values ​​shown in the embodiments.

[0025] In this disclosure, each component may comprise multiple corresponding substances. When multiple substances corresponding to each component are present in the composition, the content or percentage of each component, unless otherwise specified, refers to the total content or percentage of the multiple substances present in the composition.

[0026] In this disclosure, each structure in the polymer may include multiple corresponding structures. When multiple structures corresponding to each structure are present in the polymer, the content or percentage of each structure, unless otherwise specified, refers to the total content or percentage of the multiple structures present in the polymer.

[0027] In this disclosure, the particles corresponding to each component may comprise a variety of particles. When a variety of particles corresponding to each component are present in the composition, the particle size of each component, unless otherwise specified, refers to the value of the mixture of the various particles present in the composition.

[0028] <Materials for Packaging>

[0029] The encapsulation material contains at least a compound having a structural unit represented by formula (Bb1). In this disclosure, a compound having a structural unit represented by formula (Bb1) is sometimes referred to as a "compound having a vinylphenyl group" or a "vinylphenyl compound." The encapsulation material may also contain a vinyl compound. In this disclosure, a vinyl compound is a compound different from a vinylphenyl compound, and is a compound that does not belong to the category of vinylphenyl compounds. A vinyl compound may be a compound that does not have a vinylphenyl group. In this disclosure, a vinyl compound is sometimes referred to as a "vinyl compound."

[0030] The cured product obtained using the encapsulation material can be used as an encapsulation material for encapsulating electronic components such as semiconductor devices. The encapsulation material can be an encapsulation material composition containing various compounds. In some embodiments, the encapsulation material is a free-radical polymerizable encapsulation material that can be polymerized to form a cured product through free-radical polymerization. The encapsulation material can be a free-radical polymerizable composition containing various compounds.

[0031] [Compounds containing vinylphenyl groups]

[0032] Vinylphenyl compounds are compounds having structural units represented by formula (Bb1), and having at least one vinylphenyl group. Vinylphenyl compounds have, for example, 1 to 20, 1 to 15, or 1 to 10 vinylphenyl groups. A vinylphenyl compound may consist of one type of vinylphenyl compound or may contain two or more types. When the encapsulation material contains a vinylphenyl compound, the heat resistance of the cured product is improved. One reason for this is the high reactivity of vinylphenyl compounds. When the reactivity of vinylphenyl compounds is high, the curing reaction of the encapsulation material is easily and fully carried out. As a result, the crosslinking density of the obtained cured product is higher, thereby increasing the thermal decomposition temperature and improving heat resistance. Furthermore, when the crosslinking density is higher, the expansion of the cured product with increasing temperature is also reduced. A smaller expansion amount can suppress the warping of electronic components. However, these are merely speculations, and the present invention is not limited to these speculations.

[0033] Vinylphenyl can be represented by any of the following formulas. From the viewpoint of obtaining cured products with low dielectric constants and low dielectric tangents, vinylphenyl compounds may contain compounds having a group represented by formula (p). * indicates the bonding position with other atoms.

[0034] [Chemistry 3]

[0035]

[0036] The ratio of groups represented by formula (p), groups represented by formula (m), and groups represented by formula (o) in the total amount of vinylphenyl compounds contained in the encapsulation material (molar ratio of groups represented by formula (p): groups represented by formula (m): groups represented by formula (o)) is, for example, 40–100:0–60:0–60, 70–90:0:10–30, or 40–60:40–60:0. The higher the ratio of groups represented by formula (p), the lower the dielectric constant and dielectric tangent tendency of the cured product.

[0037] Vinylphenyl compounds can be compounds having a vinylphenyl methyl group (also called "vinylbenzyl"). In this disclosure, compounds having a vinylbenzyl group are sometimes referred to as "vinylbenzyl compounds." Examples of vinylbenzyl compounds correspond to vinylphenyl compounds. Vinylphenyl compounds can also be compounds having a vinylphenyl methyloxy group (also called "vinylbenzyl ether group"). In this disclosure, compounds having a vinylbenzyl ether group are sometimes referred to as "vinyl benzyl ether compounds." Examples of vinylbenzyl ether compounds correspond to both vinylbenzyl compounds and vinylphenyl compounds.

[0038] Vinylphenyl compounds can be monomers or polymers capable of free radical polymerization. Vinylphenyl compounds, for example, comprise monomers having a vinylphenyl group. In this disclosure, monomers having a vinylphenyl group are sometimes referred to as "vinylphenyl-containing monomers." Vinylphenyl compounds, for example, comprise polymers having a vinylphenyl group. In this disclosure, polymers having a vinylphenyl group are sometimes referred to as "vinylphenyl-containing polymers." In this disclosure, a monomer can be a compound having one structural unit represented by formula (Bb1) and not containing repeating units of the structural unit represented by formula (Bb1). A polymer can be a compound having two or more structural units represented by formula (Bb1) and containing repeating units of the structural unit represented by formula (Bb1). The polymer can be a low-degree polymer (i.e., an oligomer) or a high-degree polymer.

[0039] In some embodiments, the vinylphenyl compound comprises a compound having two vinylphenyl groups. The compound having two vinylphenyl groups can be a monomer or a polymer. In some embodiments, the vinylphenyl compound comprises a compound having three or more vinylphenyl groups. The compound having three or more vinylphenyl groups can be a monomer or a polymer.

[0040] The encapsulation material comprises a compound having a structural unit represented by the following formula (Bb1).

[0041] [Chemistry 4]

[0042]

[0043] (where X) E The symbol represents an organic group containing an aromatic ring (wherein the organic group does not contain the structure represented by the following formula (X1) or formula (X2)). l represents an integer from 1 to 5, B each independently represents a group containing a vinylphenyl group, R each independently represents a substituent, and m represents an integer from 0 to 10. * indicates the bond position with other atoms.

[0044] [Chemistry 5]

[0045]

[0046] (In the formula, * indicates the bond position with atoms other than hydrogen atoms.)

[0047] The term "independent" regarding B means, for example, that when l is 2 or more and the structural unit represented by formula (Bb1) has multiple Bs, the multiple Bs can be the same "containing vinylphenyl group," or can be partially or entirely different "containing vinylphenyl groups." In this case, "independent" does not prevent l from being 1, and the structural unit represented by formula (Bb1) can also be a structural unit having one "containing vinylphenyl group." Similar to "(B)" in this disclosure... l The way “” is expressed is also the same.

[0048] As X E Examples can be listed later, such as "X". b2 "and "Y E -X B4 (where X) E It does not contain structures represented by formula (X1) or formula (X2). Examples of compounds having structural units represented by formula (Bb1) include compounds represented by formula (b2) described later and polymers represented by formula (B4) described later. Furthermore, in the compounds represented by formula (b2) described later and the polymers represented by formula (B4) described later, the structure represented by formula (X1) or formula (X2) may be included as a ring-forming part of a fused polycyclic aromatic ring. That is, in X... E In an organogroup containing an aromatic ring (wherein the organogroup does not contain a structure represented by formula (X1) or formula (X2)), when X E When a fused polycyclic aromatic ring is included, the fused polycyclic aromatic ring may include a structure represented by formula (X1) or formula (X2) as a ring component.

[0049] (Contains vinylphenyl monomer)

[0050] In some embodiments, the vinylphenyl compound comprises a vinylphenyl-containing monomer having a structural unit represented by formula (Bb1). The vinylphenyl-containing monomer comprises a monomer having two vinylphenyl groups, and may further comprise at least one selected from the group consisting of monomers having one vinylphenyl group and monomers having three vinylphenyl groups; or, it may comprise a monomer having two vinylphenyl groups, a monomer having one vinylphenyl group, and a monomer having three vinylphenyl groups. When the vinylphenyl-containing monomer comprises two or more vinylphenyl-containing monomers, the average number of vinylphenyl groups in the vinylphenyl-containing monomer is, for example, 1.2 to 2.8, 1.4 to 2.7, or 1.6 to 2.6.

[0051] The vinylphenyl monomer may further have an aromatic ring. The vinylphenyl monomer may have only one aromatic ring, or it may have two or more aromatic rings. The number of carbon atoms in the aromatic ring may be, for example, 2–30, 6–20, or 9–15. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle. The aromatic ring may be a monocyclic or fused polycyclic ring. Examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, tetraphenylene, fluorene, phenanthrene, indene, indane, and biphenylene. Examples of aromatic heterocyclic compounds include pyridine, pyrazine, quinoline, isoquinoline, acridine, phenanthroline, furan, pyrrole, thiophene, carbazole, oxazole, oxadiazole, thiadiazole, triazole, benzoxazole, benzoxadiazole, benzothiadiazole, benzotriazole, and benzothiophene. From the viewpoint of the dielectric properties of the cured product, the aromatic ring can be an aromatic hydrocarbon ring or a fused polycyclic aromatic hydrocarbon ring. From the viewpoint of dielectric constant and dielectric tangent, the aromatic ring can be, for example, fluorene or indene; or it can be indene. When vinylphenyl monomers contain indene, cured products tend to exhibit lower dielectric constants and dielectric tangents.

[0052] The aromatic ring, aromatic hydrocarbon rings, aromatic heterocycles, and fused polycyclic aromatic hydrocarbon rings, as well as the specifically listed rings, can all be substituted or unsubstituted. Substituents used in substitution include, for example, alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, and monovalent groups formed by two or more bonds of these selections. The number of carbon atoms in alkyl and alkenyl groups can be 1–18, 2–12, or 3–6. The number of carbon atoms in aryl and heteroaryl groups can be 2–30, 6–20, or 9–15. Monovalent groups include, for example, alkylaryl groups, arylalkyl groups, and alkylarylalkyl groups.

[0053] Monomers containing vinylphenyl groups may include, for example, monomers having one to three vinylphenyl groups having an aromatic ring and being directly or via a linker group bonded to the aromatic ring; monomers having one to three vinylphenyl groups having an aromatic hydrocarbon ring and being directly or via a linker group bonded to the aromatic hydrocarbon ring; or monomers having one to three vinylphenyl groups having an inden ring and being directly or via a linker group bonded to the inden ring. In these forms, the aromatic ring, aromatic hydrocarbon ring, and inden ring may be substituted or unsubstituted, respectively. Examples of substituents are as described above. Linker groups may be, for example, groups selected from the group consisting of alkylene (e.g., having 1 to 5 carbon atoms), oxy group, thio group, sulfonyl group, sulfinyl group, carbonyl group, carbonyloxy group, imino group, and divalent groups formed by two or more of these selected groups. Furthermore, "having an aromatic ring and one to three vinylphenyl groups bonded to the aromatic ring via a linker" means "having an aromatic ring and one to three vinylphenyl groups bonded to the aromatic ring and bonded to the linker".

[0054] Monomers containing vinylphenyl groups may have organic groups that, together with aromatic rings, include saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, heteroatom-containing groups, etc.

[0055] The weight-average molecular weight (Mw) of the vinylphenyl-containing monomer, from a formability and operability point of view, is, for example, 200–2,000, 200–1,000, 200–800, 250–750, or 300–700. In this disclosure, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) refer to values ​​measured using gel permeation chromatography (GPC) with polystyrene as a standard. Specifically, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this disclosure can be measured according to the methods described in the examples.

[0056] In some embodiments, the vinylphenyl compound comprises a compound represented by formula (b2) below. When the vinylphenyl compound comprises a compound represented by formula (b2) below, it tends to have better heat resistance and a smaller expansion.

[0057] [Chemistry 6]

[0058]

[0059] (where X) b2 B represents an aromatic hydrocarbon cyclic group. p Each of the following bases is represented independently by the following formula (Ph), where L represents a direct bond or linking base, l represents an integer from 1 to 3, R represents a substituent, and m represents an integer from 0 to 3.

[0060] [Chemistry 7]

[0061]

[0062] (In the formula, * indicates the location of the bond.)

[0063] Examples of aromatic hydrocarbon rings in aromatic hydrocarbon cyclic groups are as described above. X b2 For example, it could be a fused polycyclic aromatic hydrocarbon ring group.

[0064] Examples of linking groups are as described above. Linking groups can be, for example, alkylene groups (with, for example, 1 to 5 carbon atoms) or methylene groups. Furthermore, when L represents "direct bond," it refers to X. b2 With B p Directly connected. The same applies to descriptions in this disclosure such as "L is a direct bond".

[0065] A vinylphenyl-containing monomer may, for example, include a compound in formula (b2) where l is 2, and may further include at least one selected from the group consisting of compounds where l is 1 and l is 3; or, it may include a compound where l is 2, a compound where l is 1, and a compound where l is 3. When the vinylphenyl-containing monomer includes multiple compounds represented by formula (b2), the average value of l in the compounds represented by formula (b2) is, for example, 1.2–2.8, 1.4–2.7, or 1.6–2.6.

[0066] Examples of substituents represented by R include alkyl, alkenyl, aryl, heteroaryl, and monovalent groups formed by two or more bonds of these selections. The number of carbon atoms in alkyl and alkenyl groups can be 1–18, 2–12, or 3–6. The number of carbon atoms in aryl and heteroaryl groups can be 2–30, 6–20, or 9–15. Examples of monovalent groups include alkylaryl, arylalkyl, and alkylarylalkyl. m can be 0–2, or 0 or 1. When the vinylphenyl monomer contains multiple compounds represented by formula (b1), the average value of m in the compounds represented by formula (b2) is, for example, 0.0–1.8, 0.0–1.6, or 0.0–1.4. In some embodiments, the average value of m can be greater than 0.0, greater than 0.1, greater than 0.5, or greater than 1.0.

[0067] From the viewpoint of obtaining a cured material with low dielectric constant and low dielectric tangent, the base represented by formula (Ph) may include the base represented by formula (p).

[0068] In some embodiments, the vinylphenyl compound comprises a compound represented by formula (b3) below. When the vinylphenyl compound comprises a compound represented by formula (b3) below, it tends to obtain superior heat resistance, less expansion, and also lower dielectric constant and dielectric tangent.

[0069] [Chemistry 8]

[0070]

[0071] (In the formula, B) hb Each of the following independently represents a hydrogen atom, a group represented by the following formula (Ba), or a group represented by the following formula (Bz), and at least one B hb It is a basis represented by the following formula (Bz).

[0072] [Chemistry 9]

[0073]

[0074] (In the formula, A represents an alkyl group, and * represents the bond position.)

[0075] [Chemistry 10]

[0076]

[0077] (In the formula, * indicates the location of the bond.)

[0078] The number of carbon atoms in the alkyl group represented by A is, for example, 1 to 6.

[0079] The vinylphenyl-containing monomer comprises compounds having two groups represented by formula (Bz) in formula (b3), and may further comprise at least one selected from the group consisting of compounds having one or three groups; or, may comprise compounds having two, one, or three groups represented by formula (Bz). When the vinylphenyl-containing monomer comprises multiple compounds represented by formula (b3), the average number of groups represented by formula (Bz) in the compounds represented by formula (b3) is, for example, 1.2 to 2.8, 1.4 to 2.7, or 1.6 to 2.6. In the compounds represented by formula (b3), the average number of groups represented by formula (Ba) is, for example, 0.0 to 1.8, 0.0 to 1.6, or 0.0 to 1.4. In some implementations, the average number of bases represented by formula (Ba) can be greater than 0.0, greater than 0.1, greater than 0.5, or greater than 1.0.

[0080] From the viewpoint of obtaining cured products with low dielectric constant and low dielectric tangent, the group represented by formula (Bz) may include a group represented by formula (Bz) in which the position of the vinyl group bonded to the benzene ring is paraposition relative to the position of the methylene group bonded to the benzene ring.

[0081] There are no particular limitations on the method for synthesizing vinylphenyl monomers. For example, when the vinylphenyl monomer is a compound represented by formula (b2), a method can be listed that involves reacting an aromatic hydrocarbon ring with styrene having a halogenated methyl group in the presence of a basic compound. When synthesized by such a method, the compound represented by formula (b2) has a methylene group as a linking group.

[0082] Examples of styrene containing halogenated methyl groups include o-chloromethylstyrene, m-chloromethylstyrene, and p-chloromethylstyrene; these can be used alone or in combination of two or more. Examples of basic compounds include alkali metal hydroxides and alkali metal alkoxides. A phase transfer catalyst can be used in this reaction. Examples of phase transfer catalysts include tetrabutylphosphonium bromide and tetra-n-butylammonium bromide. The reaction can be carried out in a solvent. The reaction can be carried out under heating and stirring conditions. Polymerization inhibitors can be added to the reaction system. The obtained product can be purified as needed by known methods such as concentration, reprecipitation, and washing.

[0083] (Contains vinylphenyl polymer)

[0084] In some embodiments, the vinylphenyl compound comprises a vinylphenyl-containing polymer having two or more structural units represented by formula (BX). The vinylphenyl compound may comprise a polymer having two vinylphenyl groups; or it may comprise a polymer having three or more vinylphenyl groups. Examples of vinylphenyl-containing polymers include polymers having a phenolic resin-type backbone and containing vinylphenyl groups. Examples of phenolic resins include novolacic phenolic resins, aralkyl phenolic resins, dicyclopentadiene phenolic resins, and triphenylmethane phenolic resins, among which resins may substitute the phenolic structure or contain a naphthol structure based on the phenolic structure.

[0085] From the viewpoint of formability and handling, the weight average molecular weight (Mw) of the vinylphenyl-containing polymer is, for example, 300–50,000, 500–30,000, or 1,000–10,000. From the viewpoint of improving the flowability of the encapsulation material and obtaining good formability, the weight average molecular weight (Mw) can be 5,000 or less, or 2,500 or less.

[0086] In some embodiments, the vinylphenyl compound comprises a polymer having the structure represented by formula (B4) below. When the vinylphenyl compound comprises a polymer represented by formula (B4) below, it tends to obtain better heat resistance and the amount of expansion also tends to be smaller.

[0087] [Chemistry 11]

[0088]

[0089] (where X) B4 Each can independently represent a benzene ring or a naphthalene ring, Y E Each of the following equations (Y1) to (Y4) independently represents a basis, B p Each of the following groups independently represents the base represented by the following formula (Ph), where L independently represents a directly bonded or linked group, and R independently represents a substituent. E Each substituent independently represents a group bonded to a benzene or naphthalene ring, where m independently represents an integer from 0 to 5, and n represents a number from 2 to 10.

[0090] [Chemistry 12]

[0091]

[0092] (In each formula, * indicates the bonding position; the benzene ring and naphthalene ring can each independently have substituents at substituted positions.)

[0093] [Chemistry 13]

[0094]

[0095] (In the formula, * indicates the location of the bond.)

[0096] From the viewpoint of obtaining a cured material with low dielectric constant and low dielectric tangent, the base represented by formula (Ph) may include the base represented by formula (p).

[0097] Examples of linking groups include alkylene groups (with, for example, 1 to 5 carbon atoms), oxy groups, thio groups, sulfonyl groups, sulfinyl groups, carbonyl groups, carbonyloxy groups, imino groups, and divalent groups formed by two or more of these selections.

[0098] Examples of substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl. When the number of carbon atoms is 3 or more, the alkyl group can be a straight-chain alkyl group. Substituents can be alkyl groups having 1 to 5 carbon atoms, and can be methyl. Each 'm' independently represents, for example, an integer from 0 to 4, an integer from 0 to 2, or 0.

[0099] n is the average value of the polymer represented by formula (B4). n can be a number from 2 to 8, or from 3 to 5.

[0100] In some embodiments, the vinylphenyl compound may comprise at least one polymer selected from the group consisting of polymers represented by the following formula.

[0101] [Chemistry 14-1]

[0102]

[0103] [Chemistry 14-2]

[0104]

[0105] (In each formula, B) p Each group independently represents the group represented by the formula (Ph), each L independently represents a directly bonded or linking group, and n represents a number from 2 to 10. The benzene ring and naphthalene ring can each independently have substituents at substituted positions.

[0106] From the viewpoint of obtaining a cured material with low dielectric constant and low dielectric tangent, the base represented by formula (Ph) may include the base represented by formula (p).

[0107] Examples of linking groups are listed in formula (B4). From the viewpoint of obtaining good tracking resistance, the linking group may contain an oxygen group. For example, the linking group may contain a methyleneoxy group; in this case, the polymer represented by the formula comprises a group consisting of B... p The structure represented by -CH2-O-*.

[0108] When the benzene ring and naphthalene ring in the various formulas have substituents, examples of substituents are listed as R in formula (B4). The substituents can be alkyl groups having 1 to 5 carbon atoms, and can be methyl groups. When there are 3 or more carbon atoms, the alkyl group can be a straight-chain alkyl group. Alternatively, the benzene ring and naphthalene ring in the various formulas can be unsubstituted, or except for B. p It may not have any other substituents other than -L-*.

[0109] n is the average value of the polymer represented by the formula. n can represent, for example, a number from 2 to 8, or a number from 3 to 5.

[0110] When a vinylphenyl compound contains at least one polymer selected from the group consisting of polymers represented by formula (B2-1) to polymers represented by formula (B2-8), it tends to readily obtain excellent heat resistance and a small amount of expansion. When a vinylphenyl compound contains at least one polymer selected from the group consisting of polymers represented by formula (B2-3) and polymers represented by formula (B2-7), it tends to readily obtain a low dielectric constant and a low dielectric tangent. In particular, when a vinylphenyl compound contains a polymer represented by formula (B2-3), it tends to obtain an even lower dielectric constant and dielectric tangent.

[0111] In some embodiments, the vinylphenyl compound comprises a polymer represented by formula (B3-3), a polymer represented by formula (B3-7), or both.

[0112] [Chemistry 15]

[0113]

[0114] (In the formula, B) b Each of these can be independently represented by a base as shown in the following formula (Bz), where n represents a number from 3 to 5.

[0115] [Chemistry 16]

[0116]

[0117] (In the formula, B) b Each of these can be independently represented by a base as shown in the following formula (Bz), where n represents a number from 3 to 5.

[0118] [Chemistry 17]

[0119]

[0120] (In the formula, * indicates the location of the bond.)

[0121] From the viewpoint of obtaining cured products with low dielectric constant and low dielectric tangent, the group represented by formula (Bz) may include the group represented by formula (Bz) and the position of the vinyl group bonded to the benzene ring is para relative to the position of the methylene group bonded to the benzene ring.

[0122] There are no particular limitations on the method for synthesizing polymers containing vinylphenyl groups. For example, when the polymer containing vinylphenyl groups is a compound represented by formula (B4), a method can be listed that involves reacting a phenolic resin with styrene having a halogenated methyl group in the presence of a basic compound. When synthesized by this method, the compound represented by formula (B4) has a methylene oxy group as a linking group.

[0123] Examples of styrene with halogenated methyl groups, basic compounds, and phase transfer catalysts are described above. The reaction can be carried out in a solvent. The reaction can be carried out under heating and stirring. A polymerization inhibitor may be added to the reaction system. The obtained product can be purified as needed by known methods such as concentration, reprecipitation, and washing.

[0124] Examples of phenolic resins include novolac-type phenolic resin, aralkyl-type phenolic resin, dicyclopentadiene-type phenolic resin, biphenyl-type phenolic resin, and triphenylmethane-type phenolic resin. Among these phenolic resins, resins that substitute for the phenol structure or contain a naphthol structure based on the phenol structure are also examples. Commercially available phenolic resins can be used.

[0125] The weight-average molecular weight (Mw) of phenolic resins, from the viewpoint of moldability and handling of encapsulation materials, is, for example, 300–30,000, 500–10,000, or 1,000–5,000. The number-average molecular weight (Mn) of phenolic resins, from the viewpoint of moldability and handling, is, for example, 200–10,000, 300–5,000, or 400–1,500. The hydroxyl equivalent of phenolic resins, from the viewpoint of heat resistance and expansion of the cured product, is, for example, 50 g / eq–500 g / eq, 100 g / eq–400 g / eq, or 150 g / eq–300 g / eq. The hydroxyl equivalent can be measured according to the method of Japanese Industrial Standards (JIS) K 0070:1992.

[0126] (content)

[0127] The encapsulation material may contain only one vinylphenyl compound, or it may contain two or more vinylphenyl compounds. Based on the mass of the encapsulation material (however, excluding the mass of filler material if the encapsulation material contains filler material), the content of the vinylphenyl compound is, for example, 10% to 100% by mass, 15% to 98% by mass, or 20% to 95% by mass. When the content of the vinylphenyl compound is 10% by mass or more, the cured product tends to exhibit better heat resistance and less expansion. From the viewpoint of obtaining particularly excellent heat resistance, the content of the vinylphenyl compound may be, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more. If the addition of any components such as polymerization initiators and colorants is taken into account, the content of the vinylphenyl compound may be less than 100% by mass.

[0128] When the vinylphenyl compound contains a vinylbenzyl compound, the content of the vinylbenzyl compound, based on the mass of the vinylphenyl compound, is, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more. The upper limit for the content of the vinylbenzyl compound can be 100% by mass. When the vinylphenyl compound contains a vinylbenzyl ether compound, the content of the vinylbenzyl ether compound, based on the mass of the vinylphenyl compound, is, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more. The upper limit for the content of the vinylbenzyl ether compound can be 100% by mass. When the encapsulation material contains a vinylbenzyl ether compound, the resistance to tracking tends to improve.

[0129] When a vinylphenyl compound contains both a vinylphenyl-containing monomer and a vinylphenyl-containing polymer, the content of the vinylphenyl-containing monomer, based on the mass of the vinylphenyl compound, is, for example, 5%–95% by mass, 50%–90% by mass, or 70%–88% by mass. The content of the vinylphenyl-containing polymer, based on the mass of the vinylphenyl compound, is, for example, 5%–95% by mass, 10%–50% by mass, or 12%–30% by mass.

[0130] When the encapsulation material contains vinyl compounds, the content of vinylphenyl compounds and vinyl compounds is, for example, 70%–100% by mass, 80%–99% by mass, or 90%–98% by mass, based on the mass of the encapsulation material (however, excluding the mass of the filler material when the encapsulation material contains filler material). When the total content is 70% by mass or more, the cured product tends to exhibit better heat resistance. Taking into account the addition of polymerization initiators, colorants, and other arbitrary components, the total content may be less than 100% by mass.

[0131] When the encapsulation material contains vinyl compounds, the content of vinyl phenyl compounds is, for example, 10% to 90% by mass, 15% to 80% by mass, or 20% to 70% by mass, based on the total mass of vinyl phenyl compounds and vinyl compounds. When the content of vinyl phenyl compounds is 10% by mass or more, the cured product tends to exhibit better heat resistance and less expansion. From the viewpoint of obtaining the full effect of vinyl compounds, the content of vinyl phenyl compounds can be 90% by mass or less, or 60% by mass or less, 50% by mass or less, or 45% by mass or less.

[0132] [Compounds containing vinyl groups]

[0133] The encapsulation material may further contain a vinyl compound. A vinyl compound is a compound having at least one vinyl bond. The vinyl bond may be a free-radical polymerizable carbon-carbon unsaturated bond. Examples of vinyl compounds include compounds having a vinyl bond as a monovalent group represented by CH2=CH-*, compounds having a vinyl bond as a divalent group represented by *-CH=CH-*, or compounds having both the monovalent and divalent groups. For example, a vinyl compound may have 1 to 20, 1 to 15, or 1 to 10 vinyl bonds. The vinyl compound may consist of one vinyl compound or may contain two or more vinyl compounds. The vinyl compound may be a compound without a vinyl phenyl group. When the encapsulation material contains a vinyl compound, a cured product with good curability, glass transition temperature, and excellent heat resistance can be obtained.

[0134] Vinyl compounds can be monomers or polymers capable of free radical polymerization. Vinyl compounds, for example, comprise monomers having vinyl bonds. In this disclosure, monomers having vinyl bonds are sometimes referred to as "vinyl-bonded monomers." Vinyl compounds, for example, comprise polymers having vinyl bonds. In this disclosure, polymers having vinyl bonds are sometimes referred to as "vinyl-bonded polymers."

[0135] In some embodiments, the vinyl compound comprises a compound having two vinyl bonds. The compound having two vinyl bonds may be a monomer or a polymer. In some embodiments, the vinyl compound comprises a compound having three or more vinyl bonds. The compound having three or more vinyl bonds may be a monomer or a polymer.

[0136] Examples of monomers containing vinyl bonds include: olefin compounds such as ethylene, propylene, butadiene, isoprene, dimethylbutadiene, chloroprene, and 1,3-pentadiene; methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tetra(meth)acrylate, and bisphenol A diglycidyl ether. (meth)acrylate compounds such as di(meth)acrylate; (meth)acrylic acid ester compounds such as (meth)acrylic acid, itaconic acid, maleic acid, and fumaric acid; carboxyl group-containing vinyl compounds such as (meth)acrylic acid, itaconic acid, maleic acid, and fumaric acid; ester group-containing vinyl compounds such as vinyl acetate and vinylpropionate; halogen-containing vinyl compounds such as vinyl chloride and vinylidene chloride; and nitrile group-containing vinyl compounds such as acrylonitrile and methacrylonitrile.Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and other amide group-containing vinyl compounds; maleimide compounds such as maleimide, N-phenylmaleimide, and 4,4'-diphenylmethane bismaleimide; and nitrogen-containing vinyl compounds other than those mentioned above, such as N-vinylpyrrolidone, 1-vinylimidazole, and vinylcarbazole.

[0137] Examples of polymers containing vinyl bonds include: polymers with a hydrocarbon backbone containing vinyl bonds; polymers with a phenolic resin-type backbone containing vinyl bonds; and polyamides, polyamide imides, or polyimides containing vinyl bonds. Examples of phenolic resins are the same as those listed for polymers containing vinyl phenyl groups. Examples of polymers with a hydrocarbon backbone include polyolefins, vinyl polymers, acrylic polymers, and polydicyclopentadiene.

[0138] (maleimide compound)

[0139] In some embodiments, the vinyl compound comprises a compound having a maleimide group. In this disclosure, a compound having a maleimide group is sometimes referred to as a "maleimide compound." A maleimide compound is a compound having at least one maleimide group. A maleimide compound has, for example, 1 to 20, 1 to 15, or 1 to 10 maleimide groups. A maleimide compound may consist of one maleimide compound or may contain two or more maleimide compounds. When the encapsulation material contains a maleimide compound, better curability and a cured product with less expansion are obtained.

[0140] The maleimide group can be represented by the following formula. * indicates the bonding position with other atoms.

[0141] [Chemistry 18]

[0142]

[0143] In some embodiments, the maleimide compound comprises a compound having two maleimide groups. In this disclosure, a compound having two maleimide groups is sometimes referred to as a "bismaleimide".

[0144] In some embodiments, the vinyl compound comprises a compound represented by the following formula (m1).

[0145] [Chemistry 19]

[0146]

[0147] (where X) m (This indicates an organic group; M represents maleimide.)

[0148] The organic group may be a group containing at least one carbon atom, for example, it may be a group containing at least one selected from the group consisting of saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon cyclic groups, and aromatic heterocyclic groups. The organic group may further contain or not contain a group containing heteroatoms. From the viewpoint of improving the heat resistance of the cured product, the organic group is preferably a group containing at least one selected from the group consisting of aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups.

[0149] In some embodiments, the vinyl compound may comprise at least one of the groups selected from compounds represented by the following formulas.

[0150] [Chemistry 20]

[0151]

[0152] (In each formula, M represents maleimide group, L...) 2 R represents a direct bond or linker base. ha Each group independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n represents an integer from 1 to 8. Each benzene ring may independently have substituents at substituted positions.

[0153] As L 2 Examples of the linking groups may include alkylene groups (with 1 to 5 carbon atoms, for example), oxy groups, thio groups, sulfonyl groups, sulfinyl groups, carbonyl groups, carbonyloxy groups, imino groups, and groups represented by the following formula (m-2L). Examples of alkylene groups with 1 to 5 carbon atoms include straight-chain alkylene groups such as methylene, 1,2-dimethylene, 1,3-trimethylene, 1,4-tetramethylene, and 1,5-pentamethylene, as well as branched alkylene groups such as isopropylene, isobutylene, and tert-butylene.

[0154] [Chemistry 21]

[0155]

[0156] (where L) 2L Indicates a direct bond or a linking group. Each benzene ring can independently have substituents at substituted positions. * indicates a bond position.

[0157] As L 2L The linking group can be, for example, alkylene (with 1 to 5 carbon atoms), oxygen, thio, sulfonyl, sulfinyl, carbonyl, carbonyloxy, imino, etc. Examples of alkylene groups with 1 to 5 carbon atoms are similar to L... 2 The same as those listed in the document.

[0158] In formulas (m-1), (m-2), and (m-2L), each benzene ring may be independently unsubstituted or have a substituent at a substituted position. Examples of substituents include alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl. The substituent may be an alkyl group with 1 to 3 carbon atoms, or it may be methyl.

[0159] In the formula (m-3), R ha Examples of alkyl groups having 1 to 5 carbon atoms are as described above. n represents, for example, an integer from 1 to 6, an integer from 1 to 3, or an integer from 4 to 6.

[0160] When a vinyl compound contains at least one compound selected from the group consisting of compounds represented by formula (m-1) and compounds represented by formula (m-2), it tends to readily acquire excellent heat resistance. The vinyl compound may contain compounds represented by formula (m-2) and L 2 It is a compound with a group represented by formula (m-2L). Vinyl compounds may include compounds represented by formula (m-3) where n is 4 to 8.

[0161] In some embodiments, the vinyl compound comprises a polymer having maleimide groups. In this disclosure, polymers having maleimide groups are sometimes referred to as "maleimide-containing polymers." The vinyl compound may comprise a polymer having two maleimide groups; or, it may comprise a polymer having three or more maleimide groups. Examples of maleimide compounds include: polymers having a hydrocarbon backbone and maleimide groups; polymers having a phenolic resin-type backbone and maleimide groups; polyamides, polyamide-imides, or polyimides having maleimide groups, etc. Examples of polymers with hydrocarbon backbones and phenolic resins are the same as those listed in the vinyl-phenyl-containing polymers and vinyl-bonded polymers.

[0162] In some embodiments, the maleimide compound comprises a polymer represented by the following formula (M1).

[0163] [Chemistry 22]

[0164]

[0165] (where X) M Each group independently represents a benzene ring or a naphthalene ring; each Y group independently represents an organic group; each M group represents a maleimide group; each L group independently represents a direct bond or a linking group; each R group independently represents a substituent; each m group independently represents an integer from 0 to 5; and each n group represents a number from 2 to 10.

[0166] The organic group can be a group containing at least one carbon atom, such as alkylene groups like methylene and ethylene; cycloalkylene groups like tetrahydrodicyclopentadiene; arylalkylene groups like phenylmethylene; and divalent organic groups containing alkylene and arylene groups.

[0167] Examples of linking groups include alkylene groups (with, for example, 1 to 5 carbon atoms), oxy groups, thio groups, sulfonyl groups, sulfinyl groups, carbonyl groups, carbonyloxy groups, imino groups, and divalent groups formed by two or more of these selections.

[0168] Examples of substituents represented by R include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl. Substituents can be alkyl groups having 1 to 3 carbon atoms or methyl groups. m can independently represent, for example, an integer from 0 to 4, an integer from 0 to 2, or 0.

[0169] n is the average value of the polymer represented by formula (M). n can represent, for example, a number from 2 to 8, or a number from 3 to 5.

[0170] In some embodiments, the maleimide compound may comprise at least one polymer selected from the group consisting of polymers represented by the following formulas. When the vinyl compound comprises at least one polymer selected from the group consisting of polymers represented by the following formulas, there is a tendency to obtain excellent heat resistance.

[0171] [Chemistry 23]

[0172]

[0173] (In each formula, M represents a maleimide group, L independently represents a direct bonding or linking group, and n represents a number from 2 to 10. The benzene ring and naphthalene ring can each independently have substituents at substituted positions.)

[0174] When the benzene ring and naphthalene ring in each formula have substituents, the examples of substituents are the same as those listed in formula (M1). The substituents may be alkyl groups having 1 to 3 carbon atoms, or they may be methyl groups. Alternatively, the benzene ring and naphthalene ring in each formula may be unsubstituted, or they may not have any other substituents except for ML-*.

[0175] n is the average value of the polymer represented by each formula. For example, n can represent a number from 2 to 8, or a number from 3 to 5.

[0176] Specific examples of maleimide compounds include bis(4-maleimidephenyl)methane, polyphenylmethane maleimide, bis(4-maleimidephenyl) ether, bis(4-maleimidephenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis(4-(4-maleimidephenoxy)phenyl)propane, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, polyphenylmethane maleimide, and other phenolic varnish-type maleimide compounds and aralkyl-type maleimide compounds. Maleimide compounds include, for example, at least one selected from the group consisting of 2,2-bis(4-(4-maleimidephenoxy)phenyl)propane, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane and polyphenylmethane maleimide.

[0177] Commercially available products can be used as maleimide compounds. Examples of commercially available products include "BMI-80" (2,2-bis[4-(4-maleimidephenoxy)phenyl]propane), "BMI-1000, BMI-1000H, BMI-1100, BMI-1100H" (all 4,4'-diphenylmethane bismaleimide), and "BMI-2000, BMI-2300" (both phenylmethane maleimide) manufactured by Daiwa Chemical Industries, Ltd. maleimide), "BMI-3000, BMI-3000H" (both m-phenylene bismaleimide), "BMI-4000" (bisphenol A diphenyl ether bismaleimide), "BMI-5100" (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide), "BMI-7000, BMI-7000H" (both 4-methyl-1,3-phenylene bismaleimide), "BMI-TMH" (1,6'-bismaleimide-(2,2,4-trimethyl)hexane); Designer Molecules Products manufactured by Inc. include “BMI-2500, BMI-2560, BMI-3000, BMI-5000, BMI-6100”; “NE-X470S” by DIC Corporation; and “MIR-3000-70MT” by Nippon Kayaku Co., Ltd.

[0178] (content)

[0179] When the encapsulation material contains a vinyl compound, it may contain only one type of vinyl compound, or it may contain two or more types of vinyl compounds. The content of the vinyl compound is based on the mass of the encapsulation material (however, excluding the mass of the filler material if the encapsulation material contains filler material), for example, 10% to 90% by mass, 20% to 80% by mass, or 30% to 75% by mass. When the content is 10% by mass or more, it tends to be easier to obtain the full effect of the vinyl compound. The content of the vinyl compound may be 40% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more. When the content of the vinyl compound is 90% by mass or less, it tends to be easier to obtain the improved heat resistance effect of the vinylphenyl compound.

[0180] When the encapsulation material contains vinyl compounds, the content of the vinyl compounds is based on the total mass of the vinyl phenyl compound and the vinyl compound, for example, 10% to 90% by mass, 20% to 85% by mass, or 30% to 80% by mass. When the content is 10% by mass or higher, it tends to be easier to obtain the full effect of the vinyl compounds. The content of the vinyl compounds can be 40% by mass or higher, 50% by mass or higher, 60% by mass or higher, or 70% by mass or higher. When the content of the vinyl compounds is 90% by mass or lower, it tends to be easier to obtain the improved heat resistance effect of the vinyl phenyl compound.

[0181] If the vinyl compound contains a maleimide compound, the content of the maleimide compound is based on the mass of the vinyl compound, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more. The upper limit for the content of the maleimide compound can be 100% by mass.

[0182] When the encapsulation material contains a maleimide compound, the encapsulation material may contain only one maleimide compound, or it may contain two or more maleimide compounds. The content of the maleimide compound is based on the mass of the encapsulation material (however, excluding the mass of the filler material when the encapsulation material contains filler material), for example, 10% to 90% by mass, 20% to 80% by mass, or 30% to 75% by mass. When the content of the maleimide compound is 10% by mass or more, the cured product tends to exhibit less expansion. In particular, from the viewpoint of reducing expansion, the content of the maleimide compound can be 40% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more. When the content of the maleimide compound is 90% by mass or less, the improved heat resistance effect of the vinylphenyl compound tends to be more easily obtained.

[0183] When the encapsulation material contains maleimide compounds, the content of the maleimide compounds is based on the total mass of the vinylphenyl compound and the maleimide compound, for example, 10% to 90% by mass, 20% to 85% by mass, or 30% to 80% by mass. When the content of the maleimide compound is 10% by mass or more, the cured product tends to exhibit less expansion. In particular, from the viewpoint of reducing expansion, the content of the maleimide compound can be 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more. When the content of the maleimide compound is 90% by mass or less, the improved heat resistance effect brought about by the vinylphenyl compound tends to be more easily obtained.

[0184] When the encapsulation material contains a maleimide compound, from the viewpoint of dielectric properties, curability, formability and conductor adhesion, the ratio of the content of vinyl phenyl to the content of maleimide groups in the encapsulation material (vinyl phenyl (mol) / maleimide (mol)) can be, for example, 0.05 to 5.0, 0.20 to 3.0 or 0.30 to 1.0.

[0185] [Any ingredients]

[0186] The encapsulation material may contain any components. Examples of such components include vinyl compounds, free radical polymerization initiators, fillers, coupling agents, release agents, colorants, polymerization inhibitors, ion exchangers, flame retardants, stress relief agents, and various additives. In addition to the examples listed below, the encapsulation material may also contain various additives as needed.

[0187] (Free radical polymerization initiator)

[0188] The encapsulation material may contain a free radical polymerization initiator. When the encapsulation material is used for heat-based molding, the free radical polymerization initiator may be a thermal radical polymerization initiator that generates free radicals through heating. Examples of thermal radical polymerization initiators include organic peroxides such as peroxyketals and dialkyl peroxides, or azo compounds such as azobisbutyronitrile and azobispropionitrile.

[0189] Examples of organic peroxides include 1,1,3,3-tetramethylbutyl peroxyneodecanoate, di(4-t-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, cumyl peroxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butylperoxyneodecanoate, and t-butylperoxyneodecanoate. peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate peroxyneoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-amyl peroxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanate1-Dimethylbutyl peroxyneodecanoate, t-amylperoxyneodecanoate, di(3-methylbenzoyl) peroxide, dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, t-hexyl peroxyisopropylmonocarbonate, t-butyl peroxymalate, t-butyl peroxy-3,5,5-trimethylhexanoate peroxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(3-methylbenzoylperoxy)hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxybenzoate, dibutylperoxytrimethyl adipate, t-amyl peroxyoctanoate Peroxyoctanoate, t-amyl peroxyisononanoate, t-amyl peroxybenzoate, etc.

[0190] Examples of azo compounds include 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyanovalericacid), and 1,1'-azobis(1-cyclohexanecarbonitrile).

[0191] When the encapsulation material contains a free radical polymerization initiator, the encapsulation material may contain only one free radical polymerization initiator, or it may contain two or more free radical polymerization initiators. When the encapsulation material contains a free radical polymerization initiator, the content of the free radical polymerization initiator, based on the total mass of the vinyl phenyl compound and, if necessary, the vinyl compound (or, if the encapsulation material does not contain a vinyl compound, the mass of the vinyl phenyl compound; the same applies hereinafter), may be 0.1% to 5% by mass, or 0.2% to 3% by mass. For example, when the encapsulation material does not contain a vinyl compound, the encapsulation material may contain a free radical polymerization initiator.

[0192] (Filling material)

[0193] Encapsulation materials may contain fillers. When encapsulation materials contain fillers, the properties of the cured product, such as the coefficient of thermal expansion, thermal conductivity, and elastic modulus, tend to improve. Examples of fillers include inorganic and organic fillers. In some embodiments, the encapsulation material contains inorganic fillers.

[0194] The average particle size of inorganic filler material can be 5 μm or larger. From the viewpoint of improving the filling performance of encapsulation materials, the average particle size of inorganic filler material can be 100 μm or smaller. For example, the average particle size of inorganic filler material can be 5 μm to 100 μm, 8 μm to 50 μm, or 10 μm to 30 μm.

[0195] The average particle size of inorganic filler materials can be determined by the following method: Prepare a thin-film sample from the encapsulation material or a cured product of the encapsulation material. Randomly select 100 inorganic filler material particles from an image obtained using a scanning electron microscope (SEM). Measure the major diameter of each particle and calculate their arithmetic mean. Use this value as the average particle size of the inorganic filler material.

[0196] There are no particular limitations on the types of inorganic fillers. Examples include fused silica, crystalline silica, and other forms of silica; alumina, zirconia, titanium dioxide, glass, talc, clay, and mica. Inorganic fillers can also be flame-retardant. Examples of flame-retardant inorganic fillers include aluminum hydroxide; magnesium hydroxide; composite metal hydroxides such as magnesium and zinc hydroxides; and zinc borate.

[0197] Inorganic filler materials can contain silicon dioxide from the perspective of reducing the coefficient of linear expansion. Inorganic filler materials can contain alumina from the perspective of high thermal conductivity. Examples of the forms of inorganic filler materials include powders, powder shaped into spherical beads, and fibers.

[0198] When the encapsulation material contains filler, it may contain only one type of filler or two or more fillers. Based on the mass of the encapsulation material (however, excluding the mass of the filler), the filler content is, for example, 100% to 2,000% by mass, 250% to 1,500% by mass, or 350% to 700% by mass. When the filler content is 100% by mass or higher, the properties of the cured product, such as the coefficient of thermal expansion, thermal conductivity, and modulus of elasticity, tend to be further improved. When the filler content is 2,000% by mass or lower, the viscosity increase of the encapsulation material is suppressed, the flowability tends to be further improved, and the formability tends to be better. Based on the volume of the encapsulation material, the filler content (however, excluding carbon black) is, for example, 50% to 90% by volume, 55% to 85% by volume, or 60% to 80% by volume. When the filler content is above 50% by volume, the properties of the cured material, such as the coefficient of thermal expansion, thermal conductivity, and elastic modulus, tend to improve further. When the filler content is below 90% by volume, the viscosity increase of the encapsulation material is suppressed, the flowability tends to be more improved, and the formability tends to be better.

[0199] (Coupling agent)

[0200] The encapsulation material may contain a coupling agent. When the encapsulation material contains a coupling agent, the adhesion of the cured product, or the adhesion between the resin component (vinylphenyl compound, vinyl compound, etc., if necessary) and the inorganic filler material, tends to be improved. Examples of coupling agents include silane coupling agents, titanate coupling agents, aluminum chelate coupling agents, aluminum / zirconium coupling agents, etc. Examples of silane coupling agents include epoxy silane coupling agents, mercapto silane coupling agents, amino silane coupling agents, alkyl silane coupling agents, ureoyl silane coupling agents, vinyl silane coupling agents, (meth)acrylic acid silane coupling agents, disilazane coupling agents, etc. In this disclosure, when the encapsulation material contains a coupling agent, coupling agents having vinylphenyl groups are removed from the scope of said vinylphenyl compounds, and coupling agents having vinyl groups are removed from the scope of said vinyl compounds. That is, vinylphenyl compounds and vinyl compounds refer to compounds other than those corresponding to the coupling agent. When the encapsulation material contains mercapto-based or amino-based silane coupling agents, the adhesion of the cured product tends to be improved. When the encapsulation material contains vinyl-based or (meth)acrylate-based silane coupling agents, the formability and strength of the cured product tend to be improved.

[0201] Examples of silane coupling agents include vinyltrichlorosilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, γ-methacrylateoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and N-phenyl-3-amino γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinepropyltrimethoxysilane, γ-anilinepropyltriethoxysilane, γ-(N,N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)aminopropyltrimethoxysilane, γ-(N-methyl)anilinepropyltrimethoxysilane, γ-(N-ethyl)aminopropyltrimethoxysilane, γ-(N-ethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)aminopropyltrimethoxysilane, γ-(N-ethyl ... γ-(N,N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltriethoxysilane, γ-(N,N-dibutyl)aminopropyltriethoxysilane, γ-(N-methyl)anilinepropyltriethoxysilane, γ-(N-ethyl)anilinepropyltriethoxysilane, γ-(N,N-dimethyl)aminopropylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxysilane, γ-(N-ethyl)anilinepropyltriethoxysilane, γ-(N-dimethyl)aminopropylmethyldimethoxysilane, γ-(N-ethyl)anilinepropyltrieth ... N-Dibutylaminopropylmethyldimethoxysilane, γ-(N-methyl)anilinepropylmethyldimethoxysilane, γ-(N-ethyl)anilinepropylmethyldimethoxysilane, N-(trimethoxysilanepropyl)ethylenediamine, N-(dimethoxymethylsilaneisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.

[0202] When the encapsulation material contains a coupling agent, it may contain only one type of coupling agent or two or more coupling agents. When the encapsulation material contains inorganic filler and coupling agent, the coupling agent content, based on the mass of the inorganic filler, is, for example, 0.01% to 10% by mass, 0.05% to 5% by mass, or 0.1% to 2% by mass. When the coupling agent content is 0.1% by mass or more, the adhesion of the cured product tends to improve. When the coupling agent content is 2% by mass or less, the formability of the cured product tends to improve.

[0203] (Mold release agent)

[0204] The encapsulation material may contain a mold release agent. When the encapsulation material contains a mold release agent, it is easier to obtain good release properties from the mold (die) during molding. Examples of mold release agents include carnauba wax; higher fatty acids such as montanic acid and stearic acid, and metal salts of higher fatty acids; ester waxes such as montanate; and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene.

[0205] When the encapsulation material contains a release agent, it may contain only one type of release agent, or it may contain two or more types. When the encapsulation material contains a release agent, the release agent content is, for example, 0.01% to 10% by mass, 0.05% to 5% by mass, or 0.1% to 2% by mass, based on the total mass of the vinyl phenyl compound and, if necessary, the contained vinyl compound. When the release agent content is 0.01% by mass or more, sufficient release properties are tended to be obtained. When the release agent content is 10% by mass or less, better adhesion is tended to be obtained.

[0206] (Coloring agent)

[0207] Encapsulation materials may contain colorants. Examples of known colorants include carbon black, organic dyes, organic pigments, titanium dioxide, red lead, and red iron oxide. The content of the colorant can be appropriately selected based on the intended purpose. Colorants may also function as fillers.

[0208] When the encapsulation material contains a colorant, the encapsulation material may contain only one colorant, or it may contain two or more colorants. When the encapsulation material contains a colorant, the content of the colorant is, for example, 0.01% to 10% by mass, or 0.1% to 5% by mass, based on the total mass of the vinyl phenyl compound and, if necessary, the vinyl compound contained therein.

[0209] (Polymerization inhibitor)

[0210] The encapsulation material may contain polymerization inhibitors. Examples of polymerization inhibitors include: phenolic compounds such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; and hindered amine compounds.

[0211] (Ion exchanger)

[0212] Encapsulation materials may contain ion exchangers. When encapsulation materials contain ion exchangers, they tend to improve the moisture resistance and high-temperature storage characteristics of electronic components. Examples of ion exchangers include: hydrotalcite compounds; hydrated hydroxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. Ion exchangers may also function as filler materials. Encapsulation materials may contain only one type of ion exchanger, or they may contain two or more types of ion exchangers.

[0213] (Flame retardant)

[0214] Encapsulation materials may contain flame retardants. Examples of flame retardants include organic or inorganic compounds containing halogen, antimony, nitrogen, or phosphorus atoms, and metal hydroxides. Encapsulation materials may contain only one flame retardant or may contain two or more flame retardants.

[0215] (Stress reliever)

[0216] Encapsulation materials may contain stress-relieving agents. When encapsulation materials contain stress-relieving agents, they tend to reduce warpage and cracking of electronic components. Examples of stress-relieving agents include: silicone oil; thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, polyurethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based elastomers; rubber particles such as natural rubber (NR), acrylonitrile-butadiene rubber (NBR), acrylic rubber, polyurethane rubber, and silicone powder; and rubber particles with a core-shell structure such as methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-silicone resin copolymer, and methyl methacrylate-butyl acrylate copolymer (however, compounds belonging to vinylphenyl compounds or vinyl compounds are excluded). When encapsulation materials contain stress-relieving agents, they may contain only one type of stress-relieving agent or two or more types. Commercially available flexibility enhancers can be used as stress relievers.

[0217] [5% weight reduction temperature (Td5) of cured product]

[0218] In some embodiments, the 5% weight reduction temperature (Td5) of the cured material, as measured by thermogravimetric differential thermal analysis (TG-DTA), is, for example, above 400°C, 420°C, 430°C, or 450°C. The higher the Td5, the more likely the electronic component device tends to exhibit better heat resistance.

[0219] In this disclosure, Td5 (°C) is measured by heating the cured material at a temperature range of 40°C to 600°C and a heating rate of 10°C / min. The cured material used for measurement can be a cured material produced by transfer molding using an encapsulation material. The molding conditions are a mold temperature of 175°C, a molding time of 120 seconds, and a molding pressure of 6.9 MPa, while the curing conditions are a heating temperature of 175°C, a heating time of 6 hours, and a cured material size of 4 mm × 4 mm × 20 mm. The measurement can be performed using a thermogravimetric differential thermal analysis device (e.g., the "TG-DTASTA-7200" manufactured by Hitachi High-Tech Co., Ltd.).

[0220] Because vinylphenyl compounds have good curability, when encapsulation materials contain vinylphenyl compounds, cured products with high crosslinking density can be obtained. Since the backbone of vinylphenyl compounds contains aromatic rings, rigid cured products can be obtained. Furthermore, the backbone of vinylphenyl compounds does not contain structures represented by (X1) or (X2). Therefore, Td5 can be increased. In addition, when the aromatic ring content in the backbone of the resin component (vinylphenyl compound, vinyl compound, etc.) is high, or the crosslinking density of the cured product is high, the Td5 of the cured product tends to increase.

[0221] [Expansion of the cured product]

[0222] In some embodiments, the expansion of the cured material, measured by thermomechanical analysis (TMA), is, for example, less than 120 μm, less than 110 μm, less than 100 μm, or less than 90 μm. The smaller the expansion, the better it suppresses the warping tendency of electronic components. There is no particular limitation on the lower limit of the expansion, but the expansion is, for example, greater than 30 μm.

[0223] In this disclosure, the expansion amount (μm) can be obtained by measuring the displacement amount (μm) of the cured material under a compressive load of 0.1 N, a measurement temperature range of 30°C to 260°C, and a heating rate of 10°C / min. The cured material used for measurement can be a cured material produced by transfer molding using an encapsulation material. The molding conditions are a mold temperature of 175°C, a molding time of 120 seconds, and a molding pressure of 6.9 MPa, while the curing conditions are a heating temperature of 175°C, a heating time of 6 hours, and the dimensions of the cured material are 4 mm × 4 mm × 20 mm. The measurement can be performed using a thermomechanical analysis apparatus (e.g., the "TMA450" manufactured by TA Instruments). The expansion amount (μm) can be obtained from the displacement amount (μm) at 30°C and the displacement amount (μm) at 260°C using the following formula.

[0224] Expansion (μm) = Displacement at 260℃ (μm) - Displacement at 30℃ (μm)

[0225] Because vinylphenyl compounds have good curability, when encapsulation materials contain vinylphenyl compounds, cured products with high crosslinking density can be obtained. Since the backbone of vinylphenyl compounds contains aromatic rings, rigid cured products can be obtained. Furthermore, the backbone of vinylphenyl compounds does not contain structures represented by (X1) or (X2). Therefore, the amount of expansion can be minimized. In addition, the amount of expansion of the cured product tends to be smaller when the aromatic ring content in the backbone of the resin component (vinylphenyl compound, vinyl compound, etc.) is high; the crosslinking density of the resin component is high; silica, which has a low coefficient of linear expansion, is included as a filler material; or the volume fraction of the filler material is large.

[0226] [Curved shrinkage rate]

[0227] In some embodiments, the molding shrinkage rate of the cured encapsulation material is, for example, 0.30% or less, 0.28% or less, 0.26% or less, or 0.24% or less. The smaller the shrinkage rate, the more likely it is to suppress the warping of electronic components.

[0228] In this disclosure, the molding shrinkage rate (%) is measured by producing a disc-shaped cured material through transfer molding, using the dimensions of the cured material and the dimensions of the mold used for transfer molding. The molding conditions are: mold temperature 175°C, molding time 120 seconds, molding pressure 6.9 MPa, and the curing conditions are: heating temperature 175°C, heating time 6 hours. The dimensions of the disc-shaped cured material used for measurement are, for example, approximately 80 mm in diameter × approximately 4 mm in thickness. The molding shrinkage rate (%) can be obtained from the average of the surface diameter and back diameter of the cured material, Rm (mm), and the average of the mold inner diameter corresponding to the surface of the cured material and the mold inner diameter corresponding to the back of the cured material, Rd (mm), by the following formula.

[0229] Molding shrinkage rate (%) = (Rd - Rm) / Rd × 100

[0230] When the skeleton of the resin component (vinylphenyl compound, vinyl compound, etc.) that forms the cured product contains a high proportion of aromatic rings and the resin component is relatively rigid, the molding shrinkage rate tends to be smaller.

[0231] [Water absorption rate of the solidified material]

[0232] In some embodiments, the water absorption rate of the cured encapsulation material is, for example, less than 0.60%, less than 0.50%, less than 0.40%, or less than 0.30%. The lower the water absorption rate, the more likely it is to improve the reliability of electronic components.

[0233] In this disclosure, the water absorption rate (%) is measured by forming a disc-shaped cured material through transfer molding, subjecting the cured material to pressure cooking, and using the mass of the cured material before and after treatment. The molding conditions are a mold temperature of 175°C, a molding time of 120 seconds, and a molding pressure of 6.9 MPa, while the curing conditions are a heating temperature of 175°C and a heating time of 6 hours. The dimensions of the disc-shaped cured material used for measurement are, for example, a diameter of 50 mm × a thickness of 3 mm. The pressure cooking conditions are: pressure 2 atm (0.2 MPa), temperature 121°C, relative humidity 100%RH, and time 20 hours. The water absorption rate (mass %) is calculated by measuring the mass of the cured material before and after pressure cooking using the following formula.

[0234] Water absorption rate (mass%) = ((mass after treatment - mass before treatment) / mass before treatment) × 100

[0235] Unlike epoxy and phenolic resins, the polymerization of vinylphenyl compounds, and if necessary, vinyl compounds, does not produce hydroxyl groups. Therefore, the water absorption of the cured product can be kept low.

[0236] [Manufacturing Method of Packaging Materials]

[0237] There are no particular limitations on the manufacturing method of the encapsulation material. For example, methods include thoroughly mixing specific proportions of components using a mixer, followed by melt mixing, cooling, and pulverizing. Melt mixing can be performed using a kneader (e.g., a biaxial kneader), a roller (e.g., a mixing roller), or an extruder (e.g., an extruder). The melt mixing temperature is, for example, 70°C to 140°C, or 80°C to 130°C. The encapsulation material can be solid at room temperature and pressure (e.g., 25°C, atmospheric pressure). The shape of the solid encapsulation material is not particularly limited; examples include powder, granules, and tablets.

[0238] <Encapsulation Materials>

[0239] In some embodiments, the encapsulation material comprises a cured product obtained using the encapsulation material of the embodiment. The encapsulation material can be used to encapsulate electronic components, electronic component devices, semiconductor elements, semiconductor devices, etc. The cured product can be manufactured, for example, by molding the encapsulation material and heating the resulting molded article. Heating conditions, for example, are at 150°C to 180°C for 2 to 16 hours.

[0240] <Electronic Components and Devices>

[0241] In some embodiments, the electronic component device has a packaging material of the embodiment described above. The electronic component device, for example, has electronic components and a packaging material of the embodiment describing the embodiment that encapsulates at least a portion of the electronic components. The electronic component device may, for example, be an electronic component module having a plurality of components selected from the group consisting of electronic components and electronic component devices, and a packaging material of the embodiment describing the embodiment that encapsulates at least a portion of the plurality of components.

[0242] Examples of electronic components include active components or parts such as diodes, transistors, integrated circuits, and relays; passive components or parts such as resistors, capacitors, and coils; connectors, support members, terminals, and switches. Examples of electronic component devices include electronic component devices incorporating the aforementioned electronic components; and modules incorporating one or both of the aforementioned electronic components and electronic component devices. Electronic component devices may have support members. Examples of support members include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, and organic substrates.

[0243] A semiconductor device may include, for example, a semiconductor element and a package material of the embodiment that encapsulates at least a portion of the semiconductor element. A semiconductor device may be, for example, a semiconductor module having a plurality of semiconductor elements selected from the group consisting of semiconductor elements and semiconductor devices, and a package material of the embodiment that encapsulates at least a portion of the plurality of semiconductor elements.

[0244] Examples of semiconductor components include diodes, transistors, thyristors, power semiconductor devices, photoelectric conversion devices, sensors, integrated circuits (ICs), and memories. Semiconductor devices can be in known package forms, such as through-hole packages and surface-mount packages. Surface-mount packages include leadframe packages and bump packages. Specific examples include resin-packaged integrated circuits such as Single Inline Package (SIP), Dual Inline Package (DIP), Pin Grid Array (PGA), Plastic Leaded Chip Carrier (PLCC), Quad Flat Package (QFP), Small Outline Package (SOP), Small Outline J-lead Package (SOJ), Thin Small Outline Package (TSOP), and Thin Quad Flat Package (TQFP); Tape Carrier Package (TCP); Chip On Board (COB); Ball Grid Array (BGA); and Chip Size Package (CSP). In addition, specific examples include multi-chip modules (MCMs) and other multi-chip packages (MCPs); hybrid ICs, etc.

[0245] Resin-encapsulated ICs, for example, have the following structure: a semiconductor element is fixed on a lead frame, and the terminal portion of the semiconductor element is connected to the lead portion by wire bonding, bumping, etc., and then encapsulated using a packaging material through transfer molding or other methods. TCP, for example, has the following structure: a semiconductor element connected to a tape carrier by bumps is encapsulated using a packaging material. COB, for example, has the following structure: a semiconductor element with wiring formed on a support member by wire bonding, flip-chip bonding, soldering, etc., is encapsulated using a packaging material. BGA, CSP, and MCP, for example, have the following structure: a semiconductor element is mounted on the surface of a support member with terminals formed on the back side for connecting to a wiring board; the semiconductor element is connected to wiring formed on the support member by bumping or wire bonding, and then the semiconductor element is encapsulated using a packaging material. MCM, for example, has the following structure: multiple semiconductor elements with wiring formed on a support member by wire bonding, flip-chip bonding, soldering, etc., are encapsulated using a packaging material.

[0246] For example, a method for manufacturing an electronic component device includes placing an electronic component on a support member and encapsulating at least a portion of the electronic component using an encapsulation material of the embodiment described above. Examples of methods for encapsulating electronic components or electronic component devices include transfer molding, compression molding, and injection molding. Transfer molding can be performed, for example, under the following conditions: mold temperature 130°C to 180°C, molding pressure 6 MPa to 10 MPa, and molding time 60 to 120 seconds. Post-curing heating conditions are, for example, 150°C to 180°C for 2 to 16 hours.

[0247] Examples of embodiments are listed below. This invention is not limited to these embodiments.

[0248] (1) An encapsulation material comprising a compound having a structural unit represented by the following formula (Bb1).

[0249] (2) In the encapsulation material described in (1), the compound having a structural unit represented by formula (Bb1) includes a compound represented by formula (b2).

[0250] (3) In the encapsulation material described in (1) or (2), the compound having a structural unit represented by formula (Bb1) comprises a polymer represented by formula (B4).

[0251] (4) The encapsulation material described in any one of (1) to (3) contains a compound having a vinyl group.

[0252] (5) In the encapsulation material of claim 4, the vinyl compound comprises a compound having a maleimide group.

[0253] (6) The encapsulation material described in any one of (1) to (5) is a free radical polymerizable encapsulation material.

[0254] (7) An encapsulation material comprising a cured product obtained using any one of the encapsulation materials described in (1) to (6).

[0255] (8) An electronic component device having the encapsulation material described in (7).

[0256] (9) A semiconductor device having a semiconductor element and a package material described in (7) that encapsulates at least a portion of the semiconductor element.

[0257] (10) A semiconductor module having a plurality of semiconductor elements and semiconductor devices selected from the group consisting of semiconductor elements and semiconductor devices, and a package material described in (7), the package material encapsulating at least a portion of the plurality of semiconductor elements and devices.

[0258] The disclosure of this application relates to the subject matter described in Japanese Patent Application No. 2023-128624, filed on August 7, 2023, the entire disclosure of which is incorporated herein by reference.

[0259] [Example]

[0260] The embodiments of the present invention will be specifically described through examples. The embodiments of the present invention are not limited to the following examples.

[0261] <Synthesis of Vinylphenyl Compounds>

[0262] (Synthetic Example 1: Synthesis of Vinylphenyl Compound 1)

[0263] In a 500 mL reaction vessel equipped with a stirrer, thermometer, reflux pipe, and air pump, the phenolic resin, chloromethylstyrene, phase transfer catalyst, pure water, polymerization inhibitor, and solvent listed in Table 1 were added. The obtained composition was stirred at 40°C while air was blown in at a flow rate of 50 mL / min. Then, while maintaining the temperature at 70°C, the basic compound listed in Table 1 was added dropwise over 20 minutes, and the mixture was further stirred at 70°C for 4 hours. Air was continuously blown in during the reaction. The composition was cooled to room temperature (25°C), neutralized with 10% hydrochloric acid aqueous solution, and the organic phase was washed three times with pure water. Subsequently, the organic phase was precipitated in methanol to obtain the target vinylphenyl compound 1. Infrared absorption (IR) spectroscopy analysis confirmed that the structure of vinylphenyl compound 1 was such that the phenolic hydroxyl group contained in the phenolic resin was substantially entirely replaced by vinylbenzyl ether groups (vinylphenylmethyloxy groups). The weight-average molecular weight of vinylphenyl compound 1 is shown in Table 1.

[0264] (Synthetic Example 2: Synthesis of Vinylphenyl Compound 2)

[0265] Except for changing the raw materials to those listed in Table 1, vinylphenyl compound 2 was obtained using the same method as in Synthesis Example 1. Infrared absorption (IR) spectroscopy analysis confirmed that vinylphenyl compound 2 has a structure in which the phenolic hydroxyl groups in the phenolic resin are substantially entirely replaced by vinyl benzyl ether groups. The weight-average molecular weight of vinylphenyl compound 2 is shown in Table 1.

[0266] (Synthetic Example 3: Synthesis of Vinylphenyl Compound 3)

[0267] In a 500 mL reaction vessel equipped with a stirrer, thermometer, reflux tube, and nitrogen inlet, the aromatic hydrocarbons, chloromethylstyrene, phase transfer catalyst, polymerization inhibitor, and solvent listed in Table 1 were added. The resulting composition was stirred at 40°C while nitrogen was purged at a flow rate of 50 mL / min. Then, the basic compound listed in Table 1 was added dropwise over 20 minutes, and the mixture was further stirred at 60°C for 9 hours. Nitrogen was continuously purged during the reaction. The composition was cooled to room temperature (25°C), neutralized with 10% hydrochloric acid aqueous solution, and washed twice with pure water. Toluene was then removed by distillation under reduced pressure, and the resulting viscous liquid was washed with methanol and dried under vacuum to obtain vinylphenyl compound 3. 1 H-NMR ( 1 H-Nuclear Magnetic Resonance,1 ¹H-NMR analysis confirmed that vinylphenyl compound 3 has a structure in which the two hydrogen atoms directly bonded to the carbon atom at position 1 of indene are substantially entirely replaced by vinylbenzyl groups (vinylphenylmethyl). Furthermore, gel permeation chromatography (GPC) analysis confirmed that vinylphenyl compound 3 is a mixture of compounds with two and three vinylbenzyl groups, with an average number of vinylbenzyl groups ranging from 1.6 to 2.6. The weight-average molecular weight of vinylphenyl compound 3 is shown in Table 1.

[0268] In the embodiments, the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured under the following conditions.

[0269] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were calculated using gel permeation chromatography with a calibration curve for standard polystyrene. The calibration curve was approximated using a cubic equation with standard polystyrene: TSK standard POLYSTYRENE (models: A-2500, A-5000, F-20, F-80) (Tosoh Corporation).

[0270] Equipment: High-speed GPC device HLC-8320GPC (Tosoh Corporation)

[0271] Detector: UV-8320 ultraviolet absorbance detector (Tosoh Corporation)

[0272] Tubing: Protective tubing; TSKgel guardcolumn Super (HZ)-M+ tubing; TSKgel SuperMultipore HZ-M (2 pieces); Reference tubing; TSKgel SuperH-RC (2 pieces) (all from Tosoh Corporation)

[0273] Tubing string dimensions: 4.6×20 mm (protective tubing string), 4.6×150 mm (tubing string), 6.0×150 mm (reference tubing string)

[0274] Eluent: Tetrahydrofuran

[0275] Sample concentration: 10 mg / 1 mL

[0276] Injection volume: 20 μL or 2 μL

[0277] Flow rate: 0.35 mL / min

[0278] Temperature measured: 40℃

[0279] The compounds listed in Table 1 are described below. In Table 1, the unit for each compound is "parts of mass". "-" indicates that the corresponding compound was not used. The hydroxyl equivalent of the phenolic resin was measured using the method described above.

[0280] (Phenolic resin)

[0281] HE100C-30: Aralkyl type phenolic resin, AirWater Corporation, weight average molecular weight (Mw) 2,350, number average molecular weight (Mn) 450, hydroxyl equivalent 170 g / eq~175 g / eq

[0282] MEHC-7851M: Biphenyl aralkyl type phenolic resin, manufactured by Meiwa Chemical Co., Ltd., with a weight average molecular weight (Mw) of 1,500, a number average molecular weight (Mn) of 900, and a hydroxyl equivalent of 201 g / eq to 220 g / eq.

[0283] (Aromatic hydrocarbons)

[0284] Indene: Molecular weight 116.2

[0285] [Chemistry 24]

[0286]

[0287] (chloromethylstyrene)

[0288] • CMS: A mixture of o-chloromethylstyrene and p-chloromethylstyrene, manufactured by Wujin Linchuan Chemical Company. The o-chloromethylstyrene content is 17% by mass, and the p-chloromethylstyrene content is 83% by mass.

[0289] • CMS-P: A mixture of m-chloromethylstyrene and p-chloromethylstyrene, manufactured by AGC Seimi Chemical Co., Ltd., containing 50% m-chloromethylstyrene by mass and 50% p-chloromethylstyrene by mass.

[0290] (Phase transfer catalyst)

[0291] Tetrabutylphosphonium bromide: Kanto Chemical Co., Inc.

[0292] Tetra-n-butylammonium bromide: Kanto Chemical Co., Ltd.

[0293] (Polymerization inhibitor)

[0294] ·Phenothiazine

[0295] (Organic solvent)

[0296] Toluene

[0297] 2-Propanol

[0298] (Alkaline compounds)

[0299] • Sodium hydroxide aqueous solution: Kanto Chemical Co., Ltd., concentration 48% by mass

[0300] [Table 1]

[0301]

[0302] <Preparation of Encapsulation Materials (Encapsulation Material Compositions)>

[0303] The vinylphenyl compounds obtained from Synthesis Examples 1 to 3 were placed in shallow metal pans and allowed to stand in a vacuum dryer for 5 hours at a pressure below 0.1 MPa and a temperature of 70°C to remove the solvent.

[0304] [Examples 1 to 9 and Comparative Example 1]

[0305] The solvent-removed vinylphenyl compound was premixed with the compounds listed in Table 2 (dry mixing), then kneaded using a biaxial kneader (kneading temperature 120°C), the kneaded mixture was cooled and pulverized to produce a powdered composition for packaging materials.

[0306] The compounds listed in Table 2 are shown below. In Table 2, the unit for each compound is "mass fraction". "-" indicates that the corresponding compound is not present. The average particle size of the inorganic filler was measured according to the method described. The content (volume %) of the inorganic filler is the volume ratio of silica based on the volume of the encapsulation composition. "Vinylphenyl equivalent / maleimide equivalent" is the ratio of the vinylphenyl equivalent (weight average molecular weight / functionality) of the vinylphenyl compound to the maleimide equivalent (molecular weight / functionality calculated from the chemical formula) of the maleimide compound.

[0307] <Vinylphenyl Compounds>

[0308] • Vinylphenyl compound 1: The vinylphenyl compound (vinyl benzyl ether compound) obtained in Synthesis Example 1

[0309] • Vinylphenyl compound 2: The vinylphenyl compound (vinyl benzyl ether compound) obtained in Synthesis Example 2

[0310] • Vinylphenyl compound 3: The vinylphenyl compound (vinylbenzyl compound) obtained in Synthesis Example 3

[0311] (Vinyl compounds)

[0312] Maleimide compound 1: 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, KI Chemical Co., Ltd. "BMI-80"

[0313] • Maleimide compound 2: Polyphenylmethane maleimide, Daiwa Chemical Industries, Ltd. "BMI-2300"

[0314] • Maleimide compound 3: 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, Daiwa Chemical Industries, Ltd. "BMI-TMH"

[0315] (epoxy compound)

[0316] • Epoxy Resin 1: Triphenylmethane type epoxy resin, Nippon Kayaku Co., Ltd.'s "EPPN-501HY"

[0317] • Epoxy Resin 2: Biphenyl type epoxy resin, Mitsubishi Chemical Corporation "YX4000H"

[0318] (Phenolic resin)

[0319] • Phenolic resin: Biphenyl aralkyl resin, UBE Corporation "MEHC7851-SS"

[0320] (Other raw materials)

[0321] • Free radical polymerization initiator: α,α'-Di(t-butylperoxy)diisopropylbenzene, Nippon Oil Co., Ltd.'s "Perbutyl P"

[0322] • Curing accelerator: phosphorus-based accelerator

[0323] Coupling agent 1: 3-mercaptopropyltrimethoxysilane, Shin-Etsu Chemical Industry Co., Ltd. "KBM-803"

[0324] Coupling agent 2: N-phenyl-3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Industry Co., Ltd. "KBM-573"

[0325] • Release agent: Montan wax, Clariant Ltd. (Japan) "HW-E"

[0326] • Colorant: Carbon black, Mitsubishi Chemical Corporation "MA100RMJ"

[0327] • Inorganic filler: Silica (average particle size 26.9 μm), Zhejiang Huafeng Electronic Substrate Co., Ltd. "SS-205"

[0328] <Preparation of cured products>

[0329] Cured products were prepared using an encapsulation material composition, and the temperature reduction by 5% weight, expansion, molding shrinkage, and water absorption were measured. The measurement results are shown in Table 2.

[0330] (Measurement of temperature (Td5) at 5% weight reduction)

[0331] Using a transfer molding machine (Techno Marushichi, Inc.), a 4 mm × 4 mm × 20 mm molded part was obtained under the conditions of mold temperature 175 °C, molding time 120 seconds, and molding pressure 6.9 MPa. The resulting molded part was then cured at 175 °C for 6 hours to obtain a cured product. The 5% weight loss temperature (°C) of the cured product in atmosphere was measured using a thermogravimetric differential thermal analysis (TG-DTA STA-7200, Hitachi Advanced Technology Co., Ltd.). The measurement temperature range was 40 °C to 600 °C, and the heating rate was 10 °C / min.

[0332] (Measurement of expansion)

[0333] Using a transfer molding machine (Techno Marushichi, Inc.), a 4 mm × 4 mm × 20 mm molded part was obtained under the conditions of mold temperature 175 °C, molding time 120 seconds, and molding pressure 6.9 MPa. The obtained molded part was then heated at 175 °C for 6 hours to cure, resulting in a cured product. Using a thermomechanical analysis apparatus (TA Instruments "TMA450"), a compressive load was applied, and the displacement of the cured product was measured. The load was 0.1 N, the measurement temperature range was 30 °C to 260 °C, and the heating rate was 10 °C / min. The expansion (μm) was calculated from the displacement (μm) at 30 °C and the displacement (μm) at 260 °C using the following formula.

[0334] Expansion (μm) = Displacement at 260℃ (μm) - Displacement at 30℃ (μm)

[0335] (Measurement of molding shrinkage)

[0336] Using a mold and a transfer molding machine (Techno Marushichi, Inc.), a disc-shaped object (approximately 80 mm in diameter × approximately 4 mm in thickness) was formed at a mold temperature of 175°C, a molding time of 120 seconds, and a molding pressure of 6.9 MPa. The object was then cooled to 25°C. After cooling to 25°C, the object was placed in an oven at 175°C for 6 hours to cure it, and then the cured object was cooled to 25°C. After cooling, the diameter of the cured object's surface and back sides were measured, and the average of the two measurements was taken as Rm (mm). The mold inner diameter corresponding to the surface of the cured object and the mold inner diameter corresponding to the back side of the cured object were measured, and the average of the two measurements was taken as Rd (mm). The molding shrinkage rate (%) was calculated from Rm (mm) and Rd (mm) using the following formula.

[0337] Molding shrinkage rate (%) = (Rd - Rm) / Rd × 100

[0338] (Measurement of water absorption rate)

[0339] Using a transfer molding machine (Techno Marushichi Co., Ltd.), a disc-shaped molded object (50 mm in diameter × 3 mm in thickness) was obtained under the conditions of mold temperature 175°C, molding time 120 seconds, and molding pressure 6.9 MPa. The obtained molded object was heated at 175°C for 6 hours to cure, obtaining a cured object. Using a pressure cooker test apparatus (Hirayama Manufacturing Co., Ltd.), the cured object was pressure-cooked for 20 hours under the conditions of pressure 2 atm (0.2 MPa), temperature 121°C, and relative humidity 100%RH. The water absorption rate (mass%) was calculated by measuring the mass of the cured object before and after pressure cooker treatment using the following formula.

[0340] Water absorption rate (mass%) = ((mass after treatment - mass before treatment) / mass before treatment) × 100

[0341] [Table 2]

[0342]

Claims

1. An encapsulation material comprising a compound having a structural unit represented by the following formula (Bb1); [Chemistry 1] (where X) E This indicates an organic group containing an aromatic ring (wherein, The organic group does not contain the structure represented by the following formula (X1) or formula (X2), where B independently represents a group containing vinylphenyl, l represents an integer from 1 to 5, R independently represents a substituent, m represents an integer from 0 to 10, and * represents the bonding position with other atoms; [Chemistry 2] (In the formula, * indicates the bond position with atoms other than hydrogen atoms)).

2. The packaging material according to claim 1, wherein, The compound having the structural unit represented by formula (Bb1) includes the compound represented by formula (b2) below; [Chemistry 3] (where X) b2 B represents an aromatic hydrocarbon cyclic group. p Each of the following formulas (Ph) represents a base independently, L represents a direct bond or linking base independently, l represents an integer from 1 to 3, R represents a substituent independently, and m represents an integer from 0 to 3. [Chemistry 4] (In the formula, * indicates the location of the bond).

3. The packaging material according to claim 1 or 2, wherein, The compound having a structural unit represented by formula (Bb1) comprises a polymer represented by formula (B4); [Chemistry 5] (where X) B4 Each can independently represent a benzene ring or a naphthalene ring, Y E Each of the following equations (Y1) to (Y4) independently represents a basis, B p Each of the following groups independently represents the base represented by the following formula (Ph), where L independently represents a directly bonded or linked group, and R independently represents a substituent. E Each of them independently represents a substituent bonded to a benzene ring or a naphthalene ring, m independently represents an integer from 0 to 5, and n represents a number from 2 to 10; [Chemistry 6] (In each formula, * indicates the bonding position, and the benzene ring and naphthalene ring can each independently have substituents at the substituted positions.) [Chemistry 7] (In the formula, * indicates the location of the bond).

4. The encapsulation material according to any one of claims 1 to 3, wherein it contains a compound having a vinyl group.

5. The packaging material according to claim 4, wherein, The vinyl compounds include compounds having maleimide groups.

6. The encapsulation material according to any one of claims 1 to 5, wherein it is a free radical polymerizable encapsulation material.

7. An encapsulation material comprising a cured product obtained using an encapsulation material according to any one of claims 1 to 6.

8. An electronic component device having the encapsulation material according to claim 7.

9. A semiconductor device having a semiconductor element and a packaging material according to claim 7, the packaging material encapsulating at least a portion of the semiconductor element.

10. A semiconductor module having a plurality selected from the group consisting of semiconductor elements and semiconductor devices, and a package material according to claim 7, the package material encapsulating at least a portion of the plurality.

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