Method for manufacturing semiconductor device and sealing material

Abstract

The present disclosure relates to a method for manufacturing a semiconductor device having a semiconductor element and a sealing material, the method including heating at a heating temperature of 175 DEG C for a heating time of 2 hours to obtain a cured product, the sealing material is formed using a sealing material that satisfies the glass transition temperature of the cured product of 200 DEG C or more.

Description

Technical Field

[0001] This disclosure relates to a method for manufacturing a semiconductor device and a sealing material. Background Technology

[0002] Semiconductor devices are used in a wide variety of electronic machines. With advancements in miniaturization, weight reduction, and increased functionality of electronic machines, the applications of semiconductor devices are expanding. Furthermore, in recent years, semiconductor devices have been used more and more frequently in high-current or high-voltage environments such as automobiles, trams, wind power generation, and solar power generation.

[0003] In semiconductor devices, as packaging materials for semiconductor elements, cured products containing thermosetting resin composition, curing agent and inorganic filler are widely used (see Patent Document 1) from the perspectives of productivity and cost.

[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 manufacturing method capable of efficiently manufacturing semiconductor devices. Furthermore, this disclosure provides packaging materials for use in the manufacturing method of said semiconductor devices.

[0009] [Technical means to solve the problem]

[0010] This invention includes the following embodiments. However, this invention is not limited to these embodiments. One embodiment relates to a method for manufacturing a semiconductor device, specifically a method for manufacturing a semiconductor device having semiconductor elements and a packaging material. The method includes, when a cured product is obtained by heating at a temperature of 175°C for 2 hours, forming the packaging material using a packaging material having a glass transition temperature of 200°C or higher. Another embodiment relates to a packaging material used in the method for manufacturing the semiconductor device, wherein the packaging material satisfies the following condition: when a cured product is obtained by heating at a temperature of 175°C for 2 hours, the glass transition temperature of the cured product is 200°C or higher.

[0011] [The effects of the invention]

[0012] According to this disclosure, a method for manufacturing semiconductor devices that can be efficiently manufactured is provided. Furthermore, according to this disclosure, a packaging material for use in the method for manufacturing said semiconductor devices is also provided. Attached Figure Description

[0013] none Detailed Implementation

[0014] 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.

[0015] In this disclosure, the numerical range represented by “~” means the range containing the values ​​before and after “~” as the minimum and maximum values, respectively.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, as long as the initial function of the process is achieved.

[0022] <Methods for Manufacturing Semiconductor Devices>

[0023] In some embodiments, the method for manufacturing a semiconductor device is a method for manufacturing a semiconductor device having semiconductor elements and a packaging material. The method includes, when a cured product is obtained by heating at a temperature of 175°C for 2 hours, forming the packaging material using a packaging material that satisfies the condition that the cured product has a glass transition temperature of 200°C or higher. The method for manufacturing a semiconductor device may include any step. The packaging material may include at least one selected from the group consisting of vinylphenyl compounds and vinyl compounds described later.

[0024] In some embodiments, the method for manufacturing a semiconductor device is a method for manufacturing a semiconductor device having semiconductor elements and a packaging material, including: forming the packaging material using a packaging material, the packaging material containing a compound having a vinyl phenyl group. The method for manufacturing a semiconductor device may include any steps. The packaging material may further include the vinyl compound described later. The packaging material may be a packaging material that satisfies the following condition: when a cured product is obtained by heating at a heating temperature of 175°C for 2 hours, the glass transition temperature of the cured product is 200°C or higher.

[0025] In semiconductor device manufacturing methods, the process of forming a package material using packaging materials is sometimes called a "forming process." Depending on the type, package shape, and application of the target semiconductor device, the manufacturing method may further include arbitrary processes. Examples of arbitrary processes include: grinding the back side of a semiconductor wafer (backside grinding process); dicing the semiconductor wafer to obtain individualized semiconductor elements (dicing process); attaching semiconductor elements to support members such as lead frames and wiring boards (die bonding process); electrically connecting semiconductor elements to support members using wires such as gold, silver, copper, and aluminum (wire bonding process); cutting the dam bars and / or die bars of the lead frame (dam bar / die bar cutting process); electroplating tin, tin / bismuth, tin / silver, iron / nickel, copper, etc., on the lead frame (electroplating process); forming bumps such as solder balls on the support members (bump forming process); cutting the support members after the forming process to obtain individualized semiconductor devices (dicing process); printing product numbers and other information on the semiconductor device (marking process), etc. Arbitrary processes can be implemented according to the processes used in known semiconductor device manufacturing methods.

[0026] A method for manufacturing a semiconductor device having a leadframe as a support member includes, for example, a back-grinding process, a dicing process, a die bonding process, a wire bonding process, a forming process, a barrier / connector strip cutting process, an electroplating process, a marking process, and a dicing process. A method for manufacturing a semiconductor device having a wiring board as a support member includes, for example, a back-grinding process, a dicing process, a die bonding process, a wire bonding process, a forming process, a marking process, a bump forming process, and a dicing process.

[0027] In this disclosure, a method for manufacturing a semiconductor device includes at least a forming step, in which an encapsulation material is formed using an encapsulation material. The method for manufacturing a semiconductor device may, for example, include: preparing a support member to which a semiconductor element is adhered; and forming an encapsulation material to encapsulate at least a portion of the semiconductor element using an encapsulation material. More specifically, the method for manufacturing a semiconductor device may include: preparing a support member to which a semiconductor element is adhered; forming a molded article that contacts at least a portion of the semiconductor element using an encapsulation material; and heating the molded article to form an encapsulation material to encapsulate at least a portion of the semiconductor element.

[0028] The packaging material can be formed using mold-based forming methods such as transfer molding, compression molding, and injection molding, with transfer molding or compression molding being preferred. In some embodiments, the semiconductor device manufacturing method includes forming the packaging material by transfer molding or compression molding. For example, when the support member is a lead frame, the packaging material is preferably formed by transfer molding. For example, when the support member is a wiring board, the packaging material is preferably formed by compression molding or transfer molding.

[0029] The molding temperature is, for example, below 180°C, below 170°C, below 160°C, below 150°C, or below 140°C. By using the specific encapsulation material described later, sufficient curing can be achieved even at lower molding temperatures, thus enabling efficient manufacturing of semiconductor devices. The molding temperature is, for example, above 120°C, above 130°C, above 140°C, above 150°C, above 160°C, or above 170°C. In this disclosure, the molding temperature can be the mold temperature. These molding temperature ranges are particularly suitable for transfer molding methods. The molding temperature can be, for example, 120°C to 180°C, 120°C to 140°C, or 140°C to 180°C.

[0030] The forming pressure is, for example, 5.0 MPa to 10 MPa, 6.0 MPa to 8.0 MPa, or 6.5 MPa to 7.5 MPa. The forming time is, for example, 60 seconds to 120 seconds, 60 seconds to 100 seconds, 60 seconds to 90 seconds, 90 seconds to 120 seconds, or 100 seconds to 120 seconds.

[0031] The heating temperature of the molded article is, for example, below 180°C, below 170°C, below 160°C, below 150°C, or below 140°C. By using the specific encapsulation material described later, sufficient curing can be achieved even at lower heating temperatures, thus enabling efficient manufacturing of semiconductor devices. The heating temperature is, for example, above 120°C, above 130°C, above 140°C, above 150°C, above 160°C, or above 170°C. The heating temperature can be, for example, 120°C to 180°C, 140°C to 180°C, or 160°C to 175°C. The heating time of the molded article is, for example, below 16 hours, below 10 hours, below 6 hours, below 4 hours, or below 2 hours. By using the specific encapsulation material described later, sufficient curing can be achieved even at shorter heating times, thus enabling efficient manufacturing of semiconductor devices. The heating time is, for example, above 1 hour, above 3 hours, above 5 hours, or above 7 hours. The heating time can be, for example, 1 hour to 10 hours, 1 hour to 6 hours, or 1 hour to 3 hours. A method for manufacturing a semiconductor device includes, for example, heating a shaped article obtained after forming at a heating temperature of 175°C or below and a heating time of 3 hours or below.

[0032] <Materials for Packaging>

[0033] In some embodiments, the encapsulation material satisfies the following condition: when heated to a temperature of 175°C for 2 hours to obtain a cured product, the glass transition temperature of the cured product is 200°C or higher. In some embodiments, the encapsulation material comprises at least one selected from the group consisting of compounds having a vinyl phenyl group and compounds having a vinyl group. In this disclosure, a compound having a vinyl group is a compound different from a compound having a vinyl phenyl group, and is a compound that does not belong to the category of compounds having a vinyl phenyl group. Compounds having a vinyl bond do not have a vinyl phenyl group. In this disclosure, compounds having a vinyl phenyl group are sometimes referred to as "vinyl phenyl compounds." In this disclosure, compounds having a vinyl bond are sometimes referred to as "vinyl compounds." By using these specific encapsulation materials, production efficiency can be improved in semiconductor device manufacturing methods.

[0034] The cured product obtained using the encapsulation material can be used as an encapsulation material for encapsulating 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. The encapsulation material can be a free-radical polymerizable composition containing various compounds.

[0035] [Glass transition temperature of cured product]

[0036] In some embodiments, the encapsulation material satisfies the following condition: when heated to a temperature of 175°C for 2 hours to obtain a cured product, the glass transition temperature of the cured product is 200°C or higher. The cured product can be prepared by: using the encapsulation material, using a transfer molding machine, obtaining a 4 mm × 4 mm × 20 mm molded product under conditions of a mold temperature of 175°C, a molding time of 90 seconds, and a molding pressure of 6.9 MPa. The obtained molded product is then cured at 175°C for 2 hours to obtain the cured product. The glass transition temperature (Tg) of the cured product can be measured by: performing thermomechanical analysis (TMA) on the cured product using a thermomechanical analysis apparatus and generating a TMA curve. The measurement temperature range is 30°C to 260°C, and the heating rate is 10°C / min. In the TMA curve, the temperature corresponding to the intersection of the extended linear portion of the low-temperature region and the extended linear portion of the high-temperature region is defined as the glass transition temperature Tg (°C).

[0037] The Tg of the cured product can be, for example, above 210°C, above 220°C, or above 230°C. The higher the Tg of the cured product obtained after heating for 2 hours, the easier it is to achieve a significant improvement in production efficiency. There is no particular upper limit to the Tg of the cured product, but the Tg can be, for example, below 350°C. The Tg can be, for example, between 210°C and 350°C.

[0038] Vinylphenyl compounds and vinyl compounds have good curability; therefore, when the encapsulation material contains vinylphenyl compounds, vinyl compounds, or both, a cured product with a high crosslinking density can be obtained, resulting in an increase in Tg. Furthermore, the Tg of the cured product tends to increase when the backbone of the resin component (vinylphenyl compound, vinyl compound, etc.) forming the cured product contains aromatic rings; the content of aromatic rings in the resin component backbone is high; the crosslinking density of the resin component is high; or the volume fraction of the filler material is large.

[0039] [Compounds containing vinylphenyl groups]

[0040] In some embodiments, the encapsulation material may contain a vinylphenyl compound. A vinylphenyl compound is a compound having at least one vinylphenyl group. The vinylphenyl compound may have, for example, 1 to 20, 1 to 15, or 1 to 10 vinylphenyl groups. The 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 glass transition temperature of the cured product tends to be higher. One reason for this is the high reactivity of the vinylphenyl compound. When the vinylphenyl compound is highly reactive, the curing reaction of the encapsulation material is more likely to proceed sufficiently. As a result, the crosslinking density of the obtained cured product is higher, and therefore the glass transition temperature tends to be higher. Furthermore, when the crosslinking density is higher, the molding shrinkage rate of the cured product tends to be lower.

[0041] Vinylphenyl can be represented by any of the following formulas. From the viewpoint of obtaining cured products with low dielectric constant and low dielectric tangent, vinylphenyl compounds may contain compounds having a group represented by formula (p). * indicates the bonding position with other atoms.

[0042] [Chemistry 1]

[0043]

[0044] 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 of the cured product.

[0045] 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.

[0046] 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, monomers can be compounds that do not contain repeating structural units. Polymers can be compounds that contain repeating structural units. Polymers can be low-degree polymers (i.e., oligomers) or high-degree polymers.

[0047] 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.

[0048] Vinylphenyl compounds, for example, include compounds having structural units represented by the following formula (Bb).

[0049] [Chemistry 2]

[0050]

[0051] (In the formula, X represents an organic group, B represents an individual group containing vinylphenyl, R represents an individual 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.)

[0052] The term "independent" regarding B means, for example, that when l is 2 or more and the structural unit represented by formula (Bb) has multiple Bs, the multiple Bs can be the same "containing a vinylphenyl group," or, partially or entirely, can be different "containing a vinylphenyl group." In this case, "independent" does not preclude l from being 1, and the structural unit represented by formula (Bb) can also be a structural unit having one "containing a vinylphenyl group." Regarding terms similar to "(B)" in this disclosure... l The record is the same as that.

[0053] As an example of X, the following X can be listed. b1 and X B1 Examples of compounds having the structural unit represented by formula (Bb) include compounds represented by formula (b1) and polymers represented by formula (B1) described later.

[0054] (Contains vinylphenyl monomer)

[0055] In some embodiments, the vinylphenyl compound comprises a vinylphenyl-containing monomer. 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; alternatively, 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.

[0056] The vinylphenyl monomer may further possess 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, for example, benzene, naphthalene, anthracene, tetracene, 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 the vinylphenyl monomer contains indene, it tends to produce cured products that exhibit lower dielectric constants and dielectric tangents.

[0057] 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.

[0058] 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".

[0059] Monomers containing vinylphenyl groups can replace aromatic rings, or together with aromatic rings, have saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, heteroatom-containing groups, etc.

[0060] 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.

[0061] In some embodiments, the vinylphenyl compound comprises a compound represented by the following formula (b1).

[0062] [Chemistry 3]

[0063]

[0064] (where X) b1 The symbols represent organic groups, where B independently represents a group containing a vinylphenyl group, l represents an integer from 1 to 5, R independently represents a substituent, and m represents an integer from 0 to 5.

[0065] The organic group may be a group containing at least one carbon atom, for example, it may be a group comprising at least one group selected from the group consisting of saturated aliphatic hydrocarbon group, unsaturated aliphatic hydrocarbon group, saturated alicyclic hydrocarbon group, unsaturated alicyclic hydrocarbon group, aromatic hydrocarbon ring group, and aromatic heterocyclic group. The organic group may further comprise or not comprise heteroatoms. The organic group may, for example, be an aromatic hydrocarbon ring group or an aromatic heterocyclic group; or it may be an aromatic hydrocarbon ring group. Examples of aromatic hydrocarbon rings and aromatic heterocycles are as described above.

[0066] l can be 1 to 3. A vinylphenyl-containing monomer may, for example, include compounds in formula (b1) where l is 2, and may further include at least one selected from the group consisting of compounds with l of 1 and l of 3; or, it may include compounds with l of 2, compounds with l of 1, and compounds with l of 3. When a vinylphenyl-containing monomer includes multiple compounds represented by formula (b1), the average value of l in the compounds represented by formula (b1) is, for example, 1.2 to 2.8, 1.4 to 2.7, or 1.6 to 2.6.

[0067] 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 exceed 0.0, 0.1 or more, 0.5 or more, or 1.0 or more.

[0068] 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, the glass transition temperature tends to be higher.

[0069] [Chemistry 4]

[0070]

[0071] (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.

[0072] [Chemistry 5]

[0073]

[0074] (In the formula, * indicates the location of the bond.)

[0075] Examples of aromatic hydrocarbon rings in aromatic hydrocarbon cyclic groups are as described above. X b2For example, it could be a fused polycyclic aromatic hydrocarbon ring group.

[0076] 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, L signifies "direct bonding," meaning X... b2 With B p Direct bonding. This is also the case in descriptions such as "L is a direct bonding" in this disclosure.

[0077] The vinylphenyl monomer may, for example, include compounds 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 compounds where l is 3; or, it may include compounds where l is 2, compounds where l is 1, and compounds where l is 3. When the vinylphenyl 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.

[0078] Examples of substituents represented by R are listed in formula (b1). m can be 0 to 2, or 0 or 1. When the vinylphenyl monomer contains multiple compounds represented by formula (b1), the average value of m in the compound represented by formula (b2) is, for example, 0.0 to 1.8, 0.0 to 1.6, or 0.0 to 1.4. In some embodiments, the average value of m can exceed 0.0, 0.1 or more, 0.5 or more, or 1.0 or more.

[0079] From the viewpoint of obtaining a cured product with low dielectric constant and low dielectric tangent, the base represented by formula (Ph) may include the base represented by formula (p).

[0080] 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, the glass transition temperature tends to be higher, and a lower dielectric constant and dielectric tangent can also be obtained.

[0081] [Chemistry 6]

[0082]

[0083] (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).

[0084] [Chemistry 7]

[0085]

[0086] (In the formula, A represents an alkyl group, and * represents the bond position.)

[0087] [Chemistry 8]

[0088]

[0089] (In the formula, * indicates the location of the bond.)

[0090] The number of carbon atoms in the alkyl group represented by A is, for example, 1 to 6.

[0091] 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. The average number of groups represented by formula (Ba) in the compounds represented by formula (b3) 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) may exceed 0.0, 0.1 or more, 0.5 or more, or 1.0 or more.

[0092] 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 para position relative to the position of the methylene group bonded to the benzene ring.

[0093] 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.

[0094] 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.

[0095] (Contains vinylphenyl polymer)

[0096] In some embodiments, the vinylphenyl compound comprises a vinylphenyl-containing polymer. 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 hydrocarbon chain backbone and containing vinylphenyl groups; polymers having a phenolic resin-type backbone and containing vinylphenyl groups. Examples of polymers having a hydrocarbon chain backbone include polyolefins, vinyl polymers, acrylic polymers, and polydicyclopentadiene. Examples of phenolic resins include novolac phenolic resins, aralkyl phenolic resins, dicyclopentadiene phenolic resins, and triphenylmethane phenolic resins, among which resins may substitute for the phenol structure or contain a naphthol structure based on the phenol structure.

[0097] 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.

[0098] In some embodiments, the vinylphenyl compound comprises a polymer having the structure represented by the following formula (B1).

[0099] [Chemistry 9]

[0100]

[0101] (where X) B1 The symbol represents an organic group, B represents a group containing a vinylphenyl group, R represents a substituent independently, and m represents an integer from 0 to 10. * indicates the bond position with other atoms.

[0102] The organic group may be a group containing at least one carbon atom, for example, it may be a group comprising at least one group 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 include or exclude a group containing a heteroatom.

[0103] Examples of substituents represented by R include alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl. When the number of carbon atoms is 3 or more, the alkyl group can be a straight-chain alkyl group. m represents, for example, an integer from 0 to 5, an integer from 0 to 2, or 0.

[0104] In some embodiments, the vinylphenyl compound comprises a polymer represented by formula (B2) below. When the vinylphenyl compound comprises a polymer represented by formula (B2) below, the glass transition temperature tends to be higher.

[0105] [Chemistry 10]

[0106]

[0107] (where X) B2 Each of the following independently represents a benzene ring or a naphthalene ring, and each of the following independently represents an organogroup: B p Each of the following groups independently represents the base represented by the following formula (Ph), each of the groups L independently represents the direct bond or linking base, each of the groups R independently represents the substituent, each of the groups m independently represents an integer from 0 to 5, and each of the groups n represents a number from 2 to 10.

[0108] [Chemistry 11]

[0109]

[0110] (In the formula, * indicates the location of the bond.)

[0111] The organic group can be a group containing at least one carbon atom, such as alkylene groups like methylene and ethylene group; cycloalkylene groups like tetrahydrodicyclopentadiene; arylalkylene groups like phenylmethylene group; and divalent organic groups containing alkylene and arylene groups.

[0112] From the viewpoint of obtaining a cured product with low dielectric constant and low dielectric tangent, the base represented by formula (Ph) may include the base represented by formula (p).

[0113] 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.

[0114] Examples of substituents represented by R are listed in formula (B1). Substituents may be alkyl groups having 1 to 5 carbon atoms, or they may be methyl groups. When there are 3 or more carbon atoms, the alkyl group may be a straight-chain alkyl group. Each m independently represents, for example, an integer from 0 to 4, an integer from 0 to 2, or 0.

[0115] n is the average value of the polymer represented by formula (B2). n can be a number from 2 to 8, or from 3 to 5.

[0116] In some embodiments, the vinylphenyl compound may comprise at least one polymer selected from the group consisting of polymers represented by the following formula.

[0117] [Chemistry 12-1]

[0118]

[0119] [Chemistry 12-2]

[0120]

[0121] (In each formula, B) p Each group independently represents a group represented by the formula (Ph), each L independently represents a directly bonded or linked group, and n represents a value from 2 to 10. The benzene ring and naphthalene ring can each independently have substituents at substituted positions.

[0122] From the viewpoint of obtaining a cured product with low dielectric constant and low dielectric tangent, the base represented by formula (Ph) may include the base represented by formula (p).

[0123] Examples of linking groups are listed in formula (B2). 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-*.

[0124] When the benzene ring and naphthalene ring in various formulas have substituents, examples of substituents are listed as R in formula (B1). 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 each formula can be unsubstituted, or except for B. p It may not have any other substituents other than -L-*.

[0125] n is the average value of the polymer represented by the formula. For example, n can represent a value from 2 to 8, or a value from 3 to 5.

[0126] 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 (B2-11), a high glass transition temperature is readily obtained. 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), a low dielectric constant and a low dielectric tangent are readily obtained. In particular, when a vinylphenyl compound contains a polymer represented by formula (B2-3), an even lower dielectric constant and dielectric tangent are readily obtained.

[0127] In some embodiments, the vinylphenyl compound comprises a polymer represented by formula (B3-3), a polymer represented by formula (B3-7), or both.

[0128] [Chemistry 13]

[0129]

[0130] (In the formula, B) b Each of these can independently represent a base as indicated by the following formula (Bz), where n represents a number from 3 to 5.

[0131] [Chemistry 14]

[0132]

[0133] (In the formula, B) b Each of these can independently represent a base as indicated by the following formula (Bz), where n represents a number from 3 to 5.

[0134] [Chemistry 15]

[0135]

[0136] (In the formula, * indicates the location of the bond.)

[0137] From the viewpoint of obtaining cured products with low dielectric constant and low dielectric tangent, the group represented by formula (Bz) may include groups represented by formula (Bz) in which the vinyl group is bonded to the benzene ring in the para position relative to the methylene group bonded to the benzene ring.

[0138] 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 (B2), 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 (B2) has a methylene oxy group as a linking group.

[0139] 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.

[0140] Examples of phenolic resins include novolac-type phenolic resins, aralkyl-type phenolic resins, dicyclopentadiene-type phenolic resins, biphenyl-type phenolic resins, triphenylmethane-type phenolic resins, and resins in which the phenol structure is replaced or where a naphthol structure is contained in addition to the phenol structure. Commercially available phenolic resins can be used.

[0141] The weight-average molecular weight (Mw) of phenolic resin, from the viewpoint of formability 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 resin, from the viewpoint of formability and handling, is, for example, 200–10,000, 300–5,000, or 400–1,500. The hydroxyl equivalent of phenolic resin, from the viewpoint of the glass transition temperature 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.

[0142] (content)

[0143] When the encapsulation material contains a vinylphenyl compound, it may contain only one type of vinylphenyl compound, or it may contain two or more types of vinylphenyl compounds. Based on the mass of the encapsulation material (however, excluding the mass of the 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 a high glass transition temperature. Specifically, from the viewpoint of obtaining a high glass transition temperature, the content of the vinylphenyl compound is 80% by mass or less, 60% by mass or less, or 50% by mass or less. If the addition of any component such as a polymerization initiator or colorant is considered, the content of the vinylphenyl compound may be less than 100% by mass.

[0144] 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.

[0145] When a vinylphenyl compound contains 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% to 95% by mass, 50% to 90% by mass, or 70% to 88% by mass. The content of the vinylphenyl-containing polymer, based on the mass of the vinylphenyl compound, is, for example, 5% to 95% by mass, 10% to 50% by mass, or 12% to 30% by mass.

[0146] 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 a high glass transition temperature. Taking into account the addition of any components such as polymerization initiators and colorants, the total content may be less than 100% by mass.

[0147] 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 a high glass transition temperature. From the viewpoint of obtaining sufficient effect from 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.

[0148] [Compounds containing vinyl bonds]

[0149] In some embodiments, the encapsulation material may contain a vinyl compound. A vinyl compound is a compound having at least one vinyl bond. The vinyl bond may be a carbon-carbon unsaturated bond capable of free radical polymerization. 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 type of vinyl compound or may contain two or more types of vinyl compounds. The vinyl compound does not have a vinylphenyl group. When the encapsulation material contains a vinyl compound, the cured product tends to have a high glass transition temperature. One reason for this is the high reactivity of the vinyl compound. When the vinyl compound is highly reactive, 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 high, and therefore it tends to have a high glass transition temperature. Furthermore, as the crosslinking density increases, the molding shrinkage of the cured product tends to decrease. When the encapsulation material contains vinyl phenyl compounds and vinyl compounds, the curing properties are particularly good, and cured products with high glass transition temperatures and low molding shrinkage can be obtained.

[0150] 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."

[0151] 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.

[0152] 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; (meth)acrylic acid, itaconic acid, maleic acid, and fumaric acid, etc., containing carboxyl group-containing vinyl compounds; vinyl acetate, vinyl propionate, etc., containing ester group-containing vinyl compounds; vinyl chloride, vinylidene chloride, etc., containing halogen group-containing vinyl compounds; acrylonitrile, methacrylonitrile, etc., containing nitrile group-containing vinyl compounds.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.

[0153] Examples of vinyl-bonded polymers 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 polymers with a hydrocarbon backbone and phenolic resins are the same as those listed for vinyl-phenyl-containing polymers.

[0154] (maleimide compound)

[0155] 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 a higher glass transition temperature can be obtained.

[0156] The maleimide group can be represented by the following formula. * indicates the bonding position with other atoms.

[0157] [Chemistry 16]

[0158]

[0159] 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".

[0160] In some embodiments, the vinyl compound comprises a compound represented by the following formula (m1).

[0161] [Chemistry 17]

[0162]

[0163] (where X) m (This indicates an organic group; M represents maleimide.)

[0164] 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 a heteroatom. From the viewpoint of increasing the glass transition temperature 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.

[0165] In some embodiments, the vinyl compound may comprise at least one of the groups selected from compounds represented by the following formulas.

[0166] [Chemistry 18]

[0167]

[0168] (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.

[0169] 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.

[0170] [Chemistry 19]

[0171]

[0172] (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.

[0173] 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 include L... 2 listed in.

[0174] In formulas (m-1), (m-2), and (m-2L), each benzene ring is independently unsubstituted, or may have a substituent at a substituted position. 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. The substituent may be an alkyl group having 1 to 3 carbon atoms, or it may be methyl.

[0175] 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.

[0176] 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 achieve a high glass transition temperature. The vinyl compound may contain compounds represented by formula (m-2) and L 2 It is a compound represented by the group of formula (m-2L). Vinyl compounds may include compounds represented by formula (m-3) where n is 4 to 8.

[0177] 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 vinylphenyl-containing polymers.

[0178] In some embodiments, the maleimide compound comprises a polymer represented by the following formula (M1).

[0179] [Chemistry 20]

[0180]

[0181] (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.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] n is the average value of the polymer represented by formula (M). n can represent a number from 2 to 8, or a number from 3 to 5.

[0186] 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 maleimide compound comprises at least one polymer selected from the group consisting of polymers represented by the following formulas, a higher glass transition temperature is tended to be obtained.

[0187] [Chemistry 21]

[0188]

[0189] (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.)

[0190] When the benzene ring and naphthalene ring in each formula have substituents, the examples of substituents are the same as those listed under R in formula (M1). The substituents can be alkyl groups having 1 to 3 carbon atoms, or they can be methyl groups. Alternatively, the benzene ring and naphthalene ring in each formula can be unsubstituted, or they can be without any substituents other than ML-*.

[0191] 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.

[0192] 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.

[0193] 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.

[0194] (content)

[0195] When the encapsulation material contains a vinyl compound, it may contain only one vinyl compound or two or more 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.

[0196] When the encapsulation material contains vinyl phenyl compounds and vinyl compounds, the content of the vinyl compounds is based on the total mass of the vinyl phenyl compounds and vinyl compounds, 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 more, it tends to be easier to obtain the full effect brought by the vinyl compounds. The content of vinyl compounds 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 vinyl compounds is 90% by mass or less, it tends to be easier to obtain the improved heat resistance effect brought by the vinyl phenyl compounds.

[0197] When a 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.

[0198] When the encapsulation material contains a maleimide compound, it 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 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 of the maleimide compound is 10% by mass or more, the cured product tends to exhibit a higher glass transition temperature. Specifically, from the viewpoint of increasing the glass transition temperature, 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.

[0199] When the encapsulation material contains vinylphenyl compounds and maleimide compounds, the content of the maleimide compound is based on the total mass of the vinylphenyl compounds and maleimide compounds, 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 a higher glass transition temperature. In particular, from the viewpoint of improving the glass transition temperature, 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 improvement in heat resistance brought about by the vinylphenyl compounds tends to be more easily obtained.

[0200] When the encapsulation material contains vinylphenyl compounds and maleimide compounds, from the viewpoint of dielectric properties, curability, formability and conductor adhesion, the ratio of the vinylphenyl content to the maleimide content in the encapsulation material (vinylphenyl (mol) / maleimide (mol)) can be, for example, 0.05 to 5.0, 0.20 to 3.0 or 0.30 to 1.0.

[0201] [Any ingredients]

[0202] The encapsulation material may contain any components. In addition to the aforementioned vinylphenyl compounds and vinyl compounds, examples of such components include free radical polymerization initiators, fillers, coupling agents, release agents, colorants, polymerization inhibitors, ion exchangers, flame retardants, stress relief agents, and various other additives. Besides the examples listed below, the encapsulation material may also contain various additives as needed.

[0203] (Free radical polymerization initiator)

[0204] 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.

[0205] 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.

[0206] 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).

[0207] 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 the vinyl compound (or the mass of said one when the encapsulation material contains only one; 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.

[0208] (Filling material)

[0209] 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.

[0210] 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.

[0211] 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.

[0212] 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.

[0213] Inorganic filler materials may contain silicon dioxide from the perspective of reducing the coefficient of linear expansion. Inorganic filler materials may 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.

[0214] 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 (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 more, 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 less, 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 (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.

[0215] (Coupling agent)

[0216] 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 (and, if necessary, vinyl phenyl compounds, vinyl compounds, etc.) 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. Silane coupling agents may include, for example, 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 vinyl phenyl groups are removed from the scope of vinyl phenyl compounds, and coupling agents having vinyl groups are removed from the scope of vinyl compounds. That is, vinyl phenyl 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.

[0217] 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-aminopropyltrimethoxysilane. 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,N-diethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)aminopropyltrimethoxysilane, γ-(N-ethyl)aminopropyltrimethoxysilane, γ-(N-ethyl)aminopropyltrimethoxysilane, γ-(N-ethyl)aminopropyltrimethoxysilane, γ-(N,N-di ... 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.

[0218] 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.

[0219] (Mold release agent)

[0220] 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.

[0221] 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, based on the total mass of the vinyl phenyl compound and the vinyl compound, is, for example, 0.01% to 10% by mass, 0.05% to 5% by mass, or 0.1% to 2% by mass. 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.

[0222] (Coloring agent)

[0223] 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 filler materials.

[0224] 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 the vinyl compound.

[0225] (Polymerization inhibitor)

[0226] 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.

[0227] (Ion exchanger)

[0228] 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 semiconductor devices. 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.

[0229] (Flame retardant)

[0230] 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.

[0231] (Stress reliever)

[0232] Encapsulation materials may contain stress-relieving agents. When encapsulation materials contain stress-relieving agents, they tend to reduce warpage and cracking of semiconductor device packages. 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 core-shell structures such as methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-silicone resin copolymer, and methyl methacrylate-butyl acrylate copolymer (excluding compounds belonging to vinylphenyl compounds or vinyl compounds). 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.

[0233] [Curved shrinkage rate]

[0234] In some embodiments, the molding shrinkage rate of the cured encapsulation material is, for example, 0.25% or less, 0.20% or less, 0.18% or less, or 0.15% or less. The smaller the shrinkage rate, the more likely it is to suppress the warpage of the semiconductor device.

[0235] 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.

[0236] Molding shrinkage rate (%) = (Rd - Rm) / Rd × 100

[0237] When the resin component (vinylphenyl compound, vinyl compound, etc.) that forms the cured product has a high content of aromatic rings in its skeleton and the resin component is relatively rigid, the molding shrinkage rate tends to be smaller.

[0238] [Water absorption rate of the solidified material]

[0239] In some embodiments, the water absorption rate of the cured encapsulation material is, for example, less than 0.4%, less than 0.3%, less than 0.2%, or less than 0.1%. The lower the water absorption rate, the more likely it is to improve the reliability of the semiconductor device.

[0240] 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.

[0241] Water absorption rate (mass%) = ((mass after treatment - mass before treatment) / mass before treatment) × 100

[0242] Unlike epoxy and phenolic resins, vinyl phenyl compounds do not produce hydroxyl groups during polymerization. Therefore, the water absorption of the cured product can be kept low.

[0243] [Manufacturing Method of Packaging Materials]

[0244] 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.

[0245] <Encapsulation Materials>

[0246] 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 semiconductor elements, semiconductor devices, etc. The cured product can be manufactured, for example, by shaping the encapsulation material and heating the resulting molded product. Heating conditions are, for example, at 150°C to 180°C for 2 to 16 hours.

[0247] Semiconductor Devices

[0248] In some embodiments, the semiconductor device includes, for example, a semiconductor element and a package material of the embodiment that encapsulates at least a portion of the semiconductor element. The 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.

[0249] 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 solder ball packages. Specific examples include common resin-packaged integrated circuits (ICs) 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.

[0250] 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 attached to the surface of a support member on the back side where terminals for connecting to a wiring board are formed; 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.

[0251] <Examples of Implementation Modes>

[0252] Examples of embodiments are listed below. This invention is not limited to these embodiments.

[0253] (1) A method for manufacturing a semiconductor device, comprising a method for manufacturing a semiconductor device having semiconductor elements and a packaging material, the method comprising: when obtaining a cured material by heating at a heating temperature of 175°C and a heating time of 2 hours, using a packaging material having a glass transition temperature of 200°C or higher for the cured material to form the packaging material.

[0254] (2) A method for manufacturing a semiconductor device, comprising a method for manufacturing a semiconductor device having semiconductor elements and a packaging material, the method comprising: forming the packaging material using a packaging material, the packaging material containing a compound having a vinylphenyl group.

[0255] (3) The method of manufacturing a semiconductor device according to (1) or (2) includes forming the packaging material by transfer forming or compression forming.

[0256] (4) The method for manufacturing a semiconductor device according to (3), wherein the forming temperature is 140°C or below.

[0257] (5) The semiconductor device manufacturing method described in (3) or (4) includes a molded article obtained by heating and forming under conditions of heating temperature below 175°C and heating time below 3 hours.

[0258] (6) A method for manufacturing a semiconductor device according to any one of (1) to (5), wherein the packaging material contains a compound having a vinylphenyl group.

[0259] (7) A method for manufacturing a semiconductor device according to any one of (1) to (6), wherein the packaging material contains a compound having vinyl bonds.

[0260] (8) A packaging material for use in a method of manufacturing a semiconductor device according to any one of (1) to (7), wherein the packaging material satisfies the following conditions:

[0261] When a cured material is obtained by heating at a temperature of 175°C for 2 hours, the glass transition temperature of the cured material is above 200°C.

[0262] The disclosure of this application relates to the subject matter described in Japanese Patent Application No. 2023-128619, filed on August 7, 2023, the entire disclosure of which is incorporated herein by reference.

[0263] [Example]

[0264] 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.

[0265] <Synthesis of Vinylphenyl Compounds>

[0266] (Synthetic Example 1: Synthesis of Vinylphenyl Compound 1)

[0267] 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.

[0268] (Synthetic Example 2: Synthesis of Vinylphenyl Compound 2)

[0269] 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.

[0270] (Synthetic Example 3: Synthesis of Vinylphenyl Compound 3)

[0271] 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.

[0272] In the embodiments, the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured under the following conditions.

[0273] 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).

[0274] Equipment: High-speed GPC device HLC-8320GPC (Tosoh Corporation)

[0275] Detector: UV-8320 ultraviolet absorbance detector (Tosoh Corporation)

[0276] 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)

[0277] Tubing string dimensions: 4.6×20 mm (protective tubing string), 4.6×150 mm (tubing string), 6.0×150 mm (reference tubing string)

[0278] Eluent: Tetrahydrofuran

[0279] Sample concentration: 10 mg / 1 mL

[0280] Injection volume: 20 μL or 2 μL

[0281] Flow rate: 0.35 mL / min

[0282] Temperature measured: 40℃

[0283] 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.

[0284] (Phenolic resin)

[0285] 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

[0286] 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.

[0287] (Aromatic hydrocarbons)

[0288] Indene: Molecular weight 116.2

[0289] [Chemistry 22]

[0290]

[0291] (chloromethylstyrene)

[0292] • 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.

[0293] • 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.

[0294] (Phase transfer catalyst)

[0295] Tetrabutylphosphonium bromide: Kanto Chemical Co., Inc.

[0296] Tetra-n-butylammonium bromide: Kanto Chemical Co., Ltd.

[0297] (Polymerization inhibitor)

[0298] ·Phenothiazine

[0299] (Organic solvent)

[0300] Toluene

[0301] 2-Propanol

[0302] (Alkaline compounds)

[0303] • Sodium hydroxide aqueous solution: Kanto Chemical Co., Ltd., concentration 48% by mass

[0304] [Table 1]

[0305]

[0306] <Preparation of Encapsulation Materials (Encapsulation Material Compositions)>

[0307] 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.

[0308] [Examples 1 to 9 and Comparative Example 1]

[0309] 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), and the mixture was cooled and pulverized to produce a powdered composition for packaging materials.

[0310] (Tg measurement of the solidified material)

[0311] Using an encapsulation material composition, a 4 mm × 4 mm × 20 mm molded article was obtained using a transfer molding machine (manufactured by Techno Marushichi Co., Ltd.) at a mold temperature of 175 °C, a molding time of 90 seconds, and a molding pressure of 6.9 MPa. The resulting molded article was cured at 175 °C for 2 hours to obtain a cured article. Thermomechanical analysis (TMA) was performed on the cured article using a thermomechanical analysis apparatus (TA Instruments' TMA450), and a TMA curve was generated. The measurement temperature range was 30 °C to 260 °C, with a heating rate of 10 °C / min. In the TMA curve, the temperature corresponding to the intersection of the extended linear portion of the low-temperature region and the extended linear portion of the high-temperature region was defined as the glass transition temperature (Tg) (°C). Table 2 shows the Tg (°C) of the cured article.

[0312] 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.

[0313] <Vinylphenyl Compounds>

[0314] • Vinylphenyl compound 1: The vinylphenyl compound (vinyl benzyl ether compound) obtained in Synthesis Example 1

[0315] • Vinylphenyl compound 2: The vinylphenyl compound (vinyl benzyl ether compound) obtained in Synthesis Example 2

[0316] • Vinylphenyl compound 3: The vinylphenyl compound (vinylbenzyl compound) obtained in Synthesis Example 3

[0317] (Vinyl compounds)

[0318] Maleimide compound 1: 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, KI Chemical Co., Ltd. "BMI-80"

[0319] • Maleimide compound 2: Polyphenylmethane maleimide, Daiwa Chemical Industries, Ltd. "BMI-2300"

[0320] Maleimide compound 3: 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, produced by Daiwa Chemical Industries, Ltd. under the brand name "BMI-TMH".

[0321] (epoxy compound)

[0322] • Epoxy Resin 1: Triphenylmethane type epoxy resin, Nippon Kayaku Co., Ltd.'s "EPPN-501HY"

[0323] • Epoxy Resin 2: Biphenyl type epoxy resin, Mitsubishi Chemical Corporation "YX4000H"

[0324] (Phenolic resin)

[0325] • Phenolic resin: Biphenyl aralkyl resin, UBE Corporation "MEHC7851-SS"

[0326] (Other raw materials)

[0327] • Free radical polymerization initiator: α,α'-Di(t-butylperoxy)diisopropylbenzene, Nippon Oil Co., Ltd.'s "Perbutyl P"

[0328] • Curing accelerator: phosphorus-based accelerator

[0329] • Coupling agent: 3-mercaptopropyltrimethoxysilane, Shin-Etsu Chemical Industry Co., Ltd. "KBM-803"

[0330] Coupling agent 2: N-phenyl-3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Industry Co., Ltd. "KBM-573"

[0331] • Release agent: Montan wax, Clariant Ltd. (Japan) "HW-E"

[0332] • Colorant: Carbon black, Mitsubishi Chemical Corporation "MA600"

[0333] • Inorganic filler material: Silica (average particle size 26.9 μm), Zhejiang Huafeng Electronic Substrate Co., Ltd. "SS-205"

[0334] <Preparation of cured products>

[0335] Cured products were prepared using encapsulation material compositions, and their formability, curing properties, molding shrinkage, and water absorption were evaluated. The results are shown in Table 2.

[0336] (Formability)

[0337] For the encapsulation material composition, using a transfer molding machine (manufactured by Techno Marushichi Co., Ltd.), under conditions of mold temperature of 175°C or 135°C, molding time of 120 seconds, and molding pressure of 6.9 MPa, it was confirmed whether a molded part with a shape of 127 mm × 12.7 mm × 4 mm could be produced. The evaluation criteria are as follows. The evaluation results are shown in Table 2.

[0338] A: The resin has cured and detached from the mold.

[0339] B: The resin was not fully cured and adhered to the mold.

[0340] (Curing properties)

[0341] For the encapsulation material composition, a 127mm × 12.7mm × 4mm shaped part was produced by a transfer molding machine (manufactured by Techno Marushichi Co., Ltd.) under the conditions of mold temperature 175°C, molding pressure 6.9 MPa, and molding time 90 seconds. The shaped part was cured at a temperature of 175°C for a heating time of 2 to 6 hours to obtain a cured part. The heating time varied from 2 hours to 6 hours in 1-hour intervals. For each obtained cured part, a bending test was performed using a Tensilon universal testing machine (Instron 5948, INSTRON Corporation) under the conditions of fulcrum spacing 32 mm and crosshead speed 1 mm / min. Using the measured results, a bending stress (σ)-displacement curve was plotted according to Equation (1), and the maximum bending stress was taken as the bending strength.

[0342] σ (MPa) = (3PL / 2bh2) / 9.8···Equation (1)

[0343] P: Bending load (kgf)

[0344] L: Distance between pivots (mm)

[0345] b: Width of cured material (mm)

[0346] h: Thickness of cured material (mm)

[0347] The minimum value of n(h) that satisfies (flexural strength (MPa) of cured material with heating time n (h)) / (flexural strength (MPa) of cured material with heating time 6 (h)) ≥ 0.95 is shown in Table 2. A small minimum value of n(h) indicates that the encapsulant composition can cure in a short time and has excellent curability.

[0348] (Measurement of molding shrinkage)

[0349] Using a mold and a transfer molding machine (manufactured by Techno Marushichi Co., Ltd.), a disc-shaped object (approximately 80 mm in diameter × approximately 4 mm in thickness) was formed under the conditions of mold temperature 175°C, molding time 120 seconds, and molding pressure 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 the diameter of its back side were measured, and the average of the two measurements was taken as Rm (mm). The inner diameter of the mold corresponding to the surface of the cured object and the inner diameter of the mold 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.

[0350] Molding shrinkage rate (%) = (Rd - Rm) / Rd × 100

[0351] (Measurement of water absorption rate)

[0352] A disc-shaped molded object (50 mm in diameter × 3 mm in thickness) was obtained using a transfer molding machine (Techno Marushichi Co., Ltd.) under conditions of mold temperature 175°C, molding time 120 seconds, and molding pressure 6.9 MPa. The resulting molded object was then cured by heating at 175°C for 6 hours to obtain a cured product. Using a pressure cooker testing apparatus (Hirayama Manufacturing Co., Ltd.), the cured product was pressure-cooked for 20 hours under conditions of pressure 2 atm (0.2 MPa), temperature 121°C, and relative humidity 100%RH. The mass of the cured product before and after pressure cooker treatment was measured, and the water absorption rate (mass%) was calculated using the following formula.

[0353] Water absorption rate (mass%) = ((mass after treatment - mass before treatment) / mass before treatment) × 100

[0354] [Table 2]

[0355]

Claims

1. A method for manufacturing a semiconductor device, comprising: When a cured product is obtained by heating at a temperature of 175°C for 2 hours, the encapsulation material is formed using an encapsulation material having a glass transition temperature of 200°C or higher.

2. A method for manufacturing a semiconductor device, comprising: The encapsulation material is formed using an encapsulation material containing a compound having a vinylphenyl group.

3. The method of manufacturing a semiconductor device according to claim 1 or 2, comprising forming the packaging material by transfer forming or compression forming.

4. The method for manufacturing a semiconductor device according to claim 3, wherein, The molding temperature is below 140℃.

5. The method for manufacturing a semiconductor device according to claim 3 or 4, comprising heating and forming a molded article obtained under conditions of heating temperature below 175°C and heating time below 3 hours.

6. The method for manufacturing a semiconductor device according to claim 1, wherein, The encapsulation material contains a compound having a vinylphenyl group.

7. A method for manufacturing a semiconductor device according to any one of claims 1 to 6, wherein, The encapsulation material contains compounds with vinyl bonds.

8. A packaging material for use in a method of manufacturing a semiconductor device according to any one of claims 1 to 7, wherein the packaging material satisfies the following conditions: When a cured product is obtained by heating at a temperature of 175°C for 2 hours, the glass transition temperature of the cured product is above 200°C.

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