WO2024071234A1 - Composition durcissable, produit durci, procédé de production de produit durci, boîtier de semi-conducteur, et procédé de production de boîtier de semi-conducteur - Google Patents

Composition durcissable, produit durci, procédé de production de produit durci, boîtier de semi-conducteur, et procédé de production de boîtier de semi-conducteur Download PDF

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Publication number
WO2024071234A1
WO2024071234A1 PCT/JP2023/035236 JP2023035236W WO2024071234A1 WO 2024071234 A1 WO2024071234 A1 WO 2024071234A1 JP 2023035236 W JP2023035236 W JP 2023035236W WO 2024071234 A1 WO2024071234 A1 WO 2024071234A1
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group
curable composition
compound
cured product
composition according
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PCT/JP2023/035236
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English (en)
Japanese (ja)
Inventor
俊栄 青島
和人 嶋田
啓介 野越
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富士フイルム株式会社
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Publication of WO2024071234A1 publication Critical patent/WO2024071234A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention relates to a curable composition, a cured product, a method for producing the cured product, a semiconductor package, and a method for producing a semiconductor package.
  • curable compositions are being used in various fields.
  • semiconductors are encapsulated with an encapsulant to protect them from the outside.
  • the sealant a cured product obtained by curing a curable composition may be used.
  • a curable composition containing a resin such as an epoxy resin, a curing agent, a filler, and the like is applied to at least a part of a semiconductor, and then cured to seal the semiconductor.
  • the curable composition can be applied to a target object by a known coating method or the like, it can be said to have excellent adaptability in manufacturing, for example, high degree of freedom in designing the shape, size, application position, etc., of the applied curable composition. From the viewpoint of such excellent adaptability in manufacturing, industrial application development of the above-mentioned curable composition is expected to become more and more.
  • Patent Document 1 describes a resin composition for encapsulating semiconductor elements, which comprises the following essential components (a), (b), (c), and (d), characterized in that the fluorine atom-containing radically polymerizable monomer of component (c) is uniformly dispersed in the system in the presence of a dispersion stabilizer.
  • an epoxy resin having two or more epoxy groups in the molecule (b) an epoxy resin curing agent; (c) a radically polymerizable monomer containing a fluorine atom; and (d) a radical polymerization initiator.
  • Patent Document 2 describes a method for producing a polymerizable composition comprising: (a) 100 parts by mass of a linear fluoropolyether compound having at least two ester groups in one molecule, a divalent perfluoroalkyl ether structure in the main chain, and a number average molecular weight of 3,000 to 100,000;
  • the document describes a fluoropolyether-based composition comprising: (b) 0.1 to 50 parts by mass of a compound which contains at least one carboxylate in one molecule, has a perfluoroalkyl or alkylene structure having 4 or more carbon atoms in its main chain, or a monovalent or divalent perfluoroalkyl ether structure, and has a number average molecular weight of 200 to 30,000; and (c) 0.5 to 300 parts by mass of an inorganic filler.
  • the resulting cured product is required to have low water absorption in order to improve reliability and simplify the manufacturing process.
  • the present invention aims to provide a curable composition that provides a cured product with low water absorption, a cured product obtained by curing the curable composition, a method for producing a cured product using the curable composition, a semiconductor package that includes the cured product, and a method for producing a semiconductor package that includes the method for producing the cured product.
  • a curable composition comprising: ⁇ 2> The curable composition according to ⁇ 1>, in which the compound A contains, as the group B, at least one group selected from the group consisting of a hydroxy group, a mercapto group, an amino group, a carboxy group, and groups obtained by protecting these groups.
  • ⁇ 5> The curable composition according to ⁇ 1>, in which the compound A contains, as the group B, a group represented by the following formula (2):
  • R4 and R5 each independently represent a hydrogen atom or a monovalent organic group, and * represents a bonding site to another structure.
  • R4 and R5 each independently represent a hydrogen atom or a monovalent organic group, and * represents a bonding site to another structure.
  • R4 and R5 each independently represent a hydrogen atom or a monovalent organic group, and * represents a bonding site to another structure.
  • R4 and R5 each independently represent a hydrogen atom or a monovalent organic group, and * represents a bonding site to another structure.
  • R4 and R5 each independently represent a hydrogen atom or a monovalent organic group, and * represents a bonding site to another structure.
  • R4 and R5 each independently represent a hydrogen atom or a monovalent organic group, and * represents a bonding site to another structure.
  • R4 and R5
  • ⁇ 8> The curable composition according to any one of ⁇ 1> to ⁇ 7>, further comprising at least one resin selected from the group consisting of an epoxy resin, a phenolic resin, and a maleimide resin.
  • ⁇ 9> The curable composition according to any one of ⁇ 1> to ⁇ 8>, wherein the compound A contains a group represented by the following formula (3): In formula (3), x represents an integer of 1 to 10.
  • x represents an integer of 1 to 10.
  • ⁇ 10> The curable composition according to any one of ⁇ 1> to ⁇ 9>, wherein the compound A has two or more of the groups B.
  • ⁇ 11> The curable composition according to any one of ⁇ 1> to ⁇ 10>, which is for forming a semiconductor encapsulant.
  • ⁇ 12> A cured product obtained by curing the curable composition according to any one of ⁇ 1> to ⁇ 10>.
  • ⁇ 13> A method for producing a cured product, comprising a step of heating the curable composition according to any one of ⁇ 1> to ⁇ 10>.
  • ⁇ 14> A semiconductor package comprising a semiconductor element and the cured product according to ⁇ 12>.
  • ⁇ 15> A step of applying the curable composition according to any one of ⁇ 1> to ⁇ 10> to the surface of a substrate having a semiconductor element; and A method for producing a semiconductor package, comprising the step of heating the curable composition.
  • the present invention provides a curable composition that provides a cured product with low water absorption, a cured product obtained by curing the curable composition, a method for producing a cured product using the curable composition, a semiconductor package that includes the cured product, and a method for producing a semiconductor package that includes the method for producing the cured product.
  • a numerical range expressed using the symbol "to” means a range that includes the numerical values before and after "to” as the lower limit and upper limit, respectively.
  • the term “step” includes not only an independent step, but also a step that cannot be clearly distinguished from another step, so long as the intended effect of the step can be achieved.
  • groups (atomic groups) when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups).
  • an "alkyl group” encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
  • exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
  • (meth)acrylate means both or either of “acrylate” and “methacrylate”
  • (meth)acrylic means both or either of “acrylic” and “methacrylic”
  • (meth)acryloyl means both or either of “acryloyl” and “methacryloyl”.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the total solid content refers to the total mass of all components of the composition excluding the solvent
  • the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) unless otherwise specified, and are defined as polystyrene equivalent values.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series as columns.
  • these molecular weights are measured using THF (tetrahydrofuran) as the eluent.
  • THF tetrahydrofuran
  • NMP N-methyl-2-pyrrolidone
  • detection in GPC measurement is performed using a UV (ultraviolet) ray (wavelength 254 nm detector).
  • a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer.
  • the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as “upper”, and the opposite direction is referred to as "lower”. Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper” direction in this specification may be different from the vertical upward direction.
  • the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component.
  • the content of each component in the composition means the total content of all compounds corresponding to that component.
  • the temperature is 23° C.
  • the pressure is 101,325 Pa (1 atm)
  • the relative humidity is 50% RH.
  • combinations of preferred aspects are more preferred aspects.
  • curable composition of the present invention contains compound A having group A which is a hydrocarbon group in which at least one hydrogen atom is substituted with a fluorine atom, and group B which is at least one group selected from the group consisting of optionally protected nucleophilic functional groups, electrophilic functional groups, alkoxysilyl groups, and groups having an ethylenically unsaturated bond, and a filler.
  • the curable composition of the present invention a cured product having low water absorbency can be obtained.
  • the mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.
  • the curable composition of the present invention contains a compound A having a specific structure of the group A and the group B. Therefore, the cured product obtained from the curable composition of the present invention also contains a structure having a fluorine atom. As a result, it is presumed that the obtained cured product is hydrophobized and has a reduced water absorption property.
  • the cured product obtained from the curable composition of the present invention is considered to have a high thermal decomposition temperature and excellent heat resistance due to the inclusion of a structure having fluorine atoms in the cured product as described above.
  • the curable composition of the present invention is also preferably used as an encapsulant for semiconductors that generate a large amount of heat, such as power semiconductors (semiconductors that can handle high voltages and large currents) in the fields of automotive and industrial use.
  • semiconductors that generate a large amount of heat
  • power semiconductors semiconductors that can handle high voltages and large currents
  • compound A has two or more groups B
  • a crosslinked structure is formed by compound A, which is believed to further reduce water absorption and provide excellent adhesion of the resulting cured product to a substrate.
  • the reactive group has a protected structure, such as a protected carboxy group, the composition is believed to have excellent storage stability.
  • Patent Documents 1 and 2 do not describe compositions containing compound A.
  • Compound A has group A which is a hydrocarbon group in which at least one hydrogen atom is substituted with a fluorine atom, and group B which is at least one type of group selected from the group consisting of optionally protected nucleophilic functional groups, electrophilic functional groups, alkoxysilyl groups, and groups having an ethylenically unsaturated bond.
  • the group A is a hydrocarbon group in which at least one hydrogen atom has been replaced by a fluorine atom.
  • Compound A may have only one group corresponding to group A, or may have two or more groups corresponding to group A.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but is preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group (preferably a saturated aliphatic hydrocarbon group) preferably has 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 4 to 10 carbon atoms.
  • the aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • the group A is preferably a monovalent to decavalent hydrocarbon group in which at least one hydrogen atom is replaced by a fluorine atom, more preferably a divalent to hexavalent hydrocarbon group in which at least one hydrogen atom is replaced by a fluorine atom, and even more preferably a divalent to tetravalent hydrocarbon group in which at least one hydrogen atom is replaced by a fluorine atom. It is also preferable that the group A is a divalent hydrocarbon group.
  • the group A may be such that at least one hydrogen atom in the hydrocarbon group is substituted with a fluorine atom, but it is preferable that 50% or more of the hydrogen atoms are substituted with fluorine atoms, more preferably 70% or more of the hydrogen atoms are substituted with fluorine atoms, and even more preferably 90% or more of the hydrogen atoms are substituted with fluorine atoms.
  • Another preferred embodiment of the present invention is one in which the group A is a hydrocarbon group in which all of the hydrogen atoms have been substituted with fluorine atoms.
  • the group A is a group represented by the following formula (A-1).
  • R A1 each independently represents a hydrogen atom, a fluorine atom, or a substituent which does not correspond to any of group B or a fluorine atom
  • R A2 each independently represents a hydrogen atom, a fluorine atom, or a substituent which does not correspond to any of group B or a fluorine atom
  • x is an integer from 1 to 10
  • at least one of the x R A1s and the x R A2s is a fluorine atom
  • * represents a bonding site to another structure.
  • R A1 is preferably a fluorine atom.
  • R A1 is a substituent which does not correspond to either Group B or a fluorine atom
  • examples of R A1 include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkyloxycarbonyl group, and an arylcarbonyloxy group.
  • R A2 are the same as the preferred embodiments of R A1 described above.
  • x is preferably an integer from 2 to 8, and more preferably an integer from 4 to 6.
  • x R A1s and the x R A2s preferably 50% or more are fluorine atoms, more preferably 70% or more are fluorine atoms, and even more preferably 90% or more are fluorine atoms.
  • An embodiment in which all of the x R A1s and x R A2s are fluorine atoms is also one of the preferred embodiments of the present invention.
  • * represents a bonding site with another structure, and is preferably a bonding site with group B.
  • the group A is a group represented by the following formula (A-2).
  • Ar represents a structure in which all hydrogen atoms have been removed from an aromatic hydrocarbon ring ;
  • R represents a hydrogen atom, a fluorine atom, or a substituent that does not correspond to either group B or a fluorine atom;
  • n1 represents an integer of 1 or more and not more than the number of hydrogen atoms removed from Ar , at least one of the n1 R is a fluorine atom;
  • * represents a bonding site with another structure;
  • n2 represents an integer of 1 or more and not more than the number of hydrogen atoms removed from Ar, and the sum of n1 and n2 is the same as the number of hydrogen atoms removed from Ar.
  • Ar preferably has a structure in which all hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 20 carbon atoms, more preferably has a structure in which all hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and even more preferably has a structure in which all hydrogen atoms have been removed from a benzene ring.
  • Formula (A-2) indicates that all hydrogen atoms in the aromatic hydrocarbon ring are either replaced by R , are hydrogen atoms which are R , or are bonding sites to another structure represented by *.
  • R A3 preferred embodiments of R A3 are the same as the preferred embodiments of R A1 in formula (A-1) described above.
  • n1 R A3 preferably 50% or more are fluorine atoms, more preferably 70% or more are fluorine atoms, and even more preferably 90% or more are fluorine atoms.
  • An embodiment in which all of the n1 R A3 are fluorine atoms is also one of the preferred embodiments of the present invention.
  • * represents a bonding site with another structure, and is preferably a bonding site with group B.
  • n2 is preferably 1 to 5, more preferably 2 to 4, and even more preferably 2.
  • the sum of n1 and n2 is the same as the number of hydrogen atoms removed from Ar.
  • the number of hydrogen atoms removed from Ar is 6, and when n1 is 4, n2 is 2.
  • n1 is preferably 1 to 5, more preferably 2 to 4, and even more preferably 4.
  • Group B is at least one group selected from the group consisting of optionally protected nucleophilic functional groups, electrophilic functional groups, alkoxysilyl groups, and groups having an ethylenically unsaturated bond.
  • compound A preferably has at least one group selected from the group consisting of a nucleophilic functional group and a group having an ethylenically unsaturated bond, and more preferably has a group having an ethylenically unsaturated bond.
  • the copolymer it is preferable for the copolymer to have at least one group selected from the group consisting of a nucleophilic functional group and an electrophilic functional group.
  • compound A has two or more groups B.
  • the number of groups B in compound A is preferably 2 to 10, more preferably 2 to 4, and even more preferably 2.
  • nucleophilic functional group refers to a group that reacts with an atom having low electron density to form a bond, and is preferably a group that undergoes a nucleophilic substitution reaction.
  • Compound A preferably contains, as a nucleophilic functional group, at least one group selected from the group consisting of a hydroxy group, a mercapto group, an amino group, a carboxy group, and groups obtained by protecting these groups, more preferably contains at least one group selected from the group consisting of a hydroxy group, a carboxy group, and groups obtained by protecting these groups, and even more preferably contains at least one group selected from the group consisting of groups obtained by protecting a carboxy group.
  • the protecting group in the above-mentioned protected group is not particularly limited, but is preferably a protecting group that does not leave at room temperature. From the viewpoint of storage stability, it is preferable that the protecting group is a group that is deprotected by heat of 120°C or higher, and more preferably a group that is deprotected by heat of 140°C or higher.
  • Compound A preferably contains a group represented by the following formula (1) as the group B.
  • the group represented by the following formula (1) is preferably a protected carboxy group.
  • the group represented by the following formula (1) is preferably a group that decomposes by heat to generate a carboxy group.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent organic group, and * represents a bonding site to other structures.
  • R 1 , R 2 and R 3 are each independently preferably a monovalent organic group, more preferably an alkyl group, even more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group.
  • * in formula (1) is the bonding site with the above-mentioned group A.
  • Compound A preferably contains a group represented by the following formula (2) as the group B.
  • the group represented by the following formula (2) is preferably a protected carboxy group.
  • the group represented by the following formula (2) is preferably a group that decomposes by heat to generate a carboxy group.
  • R4 and R5 each independently represent a hydrogen atom or a monovalent organic group, and * represents a bonding site to another structure.
  • R 4 is preferably a monovalent organic group, more preferably an alkyl group, even more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group.
  • R 5 is preferably a monovalent organic group, more preferably an alkyl group, and even more preferably an alkyl group having 1 to 4 carbon atoms.
  • R4 and R5 may be bonded to form a ring structure.
  • * in formula (2) is the bonding site with the above-mentioned group A.
  • the number of nucleophilic functional groups in compound A is not particularly limited, but is preferably 1 to 10, more preferably 2 to 6, and even more preferably 2 to 4. An embodiment in which the number of nucleophilic functional groups in compound A is 2 is also one of the preferred embodiments of the present invention.
  • the content of the nucleophilic functional group in compound A is not particularly limited, but is preferably 0.001 to 3000 mmol/g, more preferably 0.01 to 2000 mmol/g, and even more preferably 0.1 to 1000 mmol/g.
  • the electrophilic functional group refers to a group that reacts with an atom having high electron density to form a bond, and is preferably a group that undergoes an electrophilic substitution reaction.
  • Compound A preferably contains, as the electrophilic functional group, at least one type of group selected from the group consisting of an epoxy group, an oxetanyl group, a maleimide group, and an oxazoline group, and more preferably contains at least one type of group selected from the group consisting of an epoxy group and a maleimide group.
  • the maleimide group also corresponds to a group having an ethylenically unsaturated bond, which will be described later.
  • the maleimide group may act, for example, as an electrophilic functional group or may act, for example, as a radically polymerizable group, depending on other components contained in the composition, curing conditions of a film formed from the composition, and the like.
  • the number of electrophilic functional groups in compound A is not particularly limited, but is preferably 1 to 10, more preferably 2 to 6, and even more preferably 2 to 4. An embodiment in which the number of electrophilic functional groups in compound A is 2 is also one of the preferred embodiments of the present invention.
  • the content of the electrophilic functional group in compound A is not particularly limited, but is preferably 0.001 to 3000 mmol/g, more preferably 0.01 to 2000 mmol/g, and even more preferably 0.1 to 1000 mmol/g.
  • the alkoxysilyl group is preferably a trialkoxysilyl group or a dialkoxysilyl group, and more preferably a trialkoxysilyl group.
  • the alkoxysilyl group is preferably a group represented by the following formula (S). *-Si(R 1 ) 3-n (OR 2 ) n formula (S)
  • R 1 is a hydrocarbon group having 1 to 20 carbon atoms
  • R 2 is an alkyl group having 1 to 4 carbon atoms or a phenyl group
  • n is an integer of 1 to 3
  • * represents a bonding site to another structure.
  • R 1 is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group.
  • R2 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
  • n is preferably 2 or 3, and more preferably 3.
  • * is preferably a bonding site with group A.
  • the number of alkoxysilyl groups in compound A is not particularly limited, but is preferably 1 to 10, more preferably 2 to 6, and even more preferably 2 to 4. An embodiment in which the number of alkoxysilyl groups in compound A is 2 is also one of the preferred embodiments of the present invention.
  • the content of alkoxysilyl groups in compound A is not particularly limited, but is preferably 0.001 to 3000 mmol/g, more preferably 0.01 to 2000 mmol/g, and even more preferably 0.1 to 1000 mmol/g.
  • the group having an ethylenically unsaturated bond is preferably a radically polymerizable group, such as a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a maleimide group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, or a (meth)acryloyloxy group, of which a group having an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferred, and a (meth)acryloyloxy group is more preferred.
  • a radically polymerizable group such as a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a maleimide group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group
  • the number of groups having an ethylenically unsaturated bond in compound A is not particularly limited, but is preferably 1 to 10, more preferably 2 to 6, and even more preferably 2 to 4.
  • An embodiment in which the number of groups having an ethylenically unsaturated bond in compound A is 2 is also one of the preferred embodiments of the present invention.
  • the content of the group having an ethylenically unsaturated bond in compound A is not particularly limited, but is preferably 0.001 to 3000 mmol/g, more preferably 0.01 to 2000 mmol/g, and even more preferably 0.1 to 1000 mmol/g.
  • compound A contains a group represented by the following formula (3).
  • x represents an integer of 1 to 10.
  • the group represented by formula (3) is a group containing the group A described above.
  • x is preferably an integer of 2 to 10, more preferably an integer of 2 to 8, and even more preferably an integer of 4 to 8.
  • * is preferably a bonding site with an oxygen atom.
  • compound A is a compound represented by the following formula (4).
  • R 41 and R 42 each independently represent a hydrogen atom or a group represented by any one of the following formulae (R-1) to (R-3), and x represents an integer of 1 to 10.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent organic group, and * represents a bonding site with the oxygen atom in formula (4).
  • R 4 and R 5 each independently represent a hydrogen atom or a monovalent organic group, and * represents a bonding site with the oxygen atom in formula (4).
  • L R1 represents an (n+1)-valent linking group
  • R R1 represents a group corresponding to group B
  • n is an integer of 1 or more
  • * represents a bonding site with the oxygen atom in formula (4).
  • R 41 and R 42 are each preferably independently a hydrogen atom or a group represented by any one of formulas (R-1) and (R-2), and more preferably a group represented by formula (R-1) or (R-2).
  • the preferred embodiments of x are the same as those in the formula (3).
  • L R1 is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group.
  • the number of carbon atoms in L R1 is preferably 1 to 20, more preferably 2 to 10, and even more preferably 2 to 8.
  • R 1 is preferably an electrophilic functional group or a group having an ethylenically unsaturated bond, and more preferably an epoxy group or a (meth)acryloyloxy group.
  • n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and further preferably 1 or 2.
  • compound A is a compound consisting only of group A and group B.
  • the molecular weight of compound A is preferably 100 or more and less than 2000, more preferably 200 to 1000, and even more preferably 300 to 800.
  • the fluorine atom content in compound A is preferably 5 to 50 mmol/g, more preferably 10 to 40 mmol/g, and even more preferably 15 to 35 mmol/g.
  • the ClogP value of compound A is preferably 2 to 15.
  • the ClogP value of a compound is defined as follows.
  • the octanol-water partition coefficient (log P value) can generally be measured by the flask shaking method described in JIS Z7260-107 (2000).
  • the octanol-water partition coefficient (log P value) can also be estimated by a computational chemistry method or an empirical method instead of an actual measurement.
  • a calculation method it is known to use Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29, 163 (1989)), Broto's fragmentation method (Eur. J. Med. Chem.-Chim.
  • Crippen's fragmentation method J. Chem. Inf. Comput. Sci., 27, 21 (1987)
  • the ClogP value is a value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water.
  • Known methods and software can be used for calculating the ClogP value, but unless otherwise specified, the present invention uses the ClogP program incorporated in the PCModels system of Daylight Chemical Information Systems.
  • the compound A can be synthesized by the method described in the Examples below.
  • the compound may be synthesized by other methods, and the synthesis method is not particularly limited.
  • compound A examples include, but are not limited to, L-1 to L-10 used in the examples.
  • the content of compound A relative to the total solid content of the curable composition of the present invention is preferably 0.5 to 20 mass %.
  • the lower limit is more preferably 1.0 mass % or more, and even more preferably 2.0 mass % or more.
  • the upper limit is more preferably 15 mass % or less, and even more preferably 10 mass % or less.
  • Compound A may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.
  • the curable composition of the present invention includes a filler.
  • inorganic particles are preferred.
  • inorganic particles include silica, alumina, aluminum oxide, aluminum nitride, titania, zirconia, glass fiber, talc, asbestos, smectite, bentonite, calcium carbonate, magnesium carbonate, montmorillonite, diatomaceous earth, magnesium oxide, titanium oxide, titanium nitride, magnesium hydroxide, aluminum hydroxide, glass beads, barium sulfate, gypsum, calcium silicate, sericite activated clay, boron nitride, hollow silica, silicon carbide, diamond, and silicon carbide surface-modified by plasma spraying ( ZrO2 , Al2O3 , other oxides).
  • the curable composition of the present invention preferably contains at least one selected from the group consisting of silica, alumina, aluminum oxide, aluminum nitride, titania, zirconia, and glass fiber, and more preferably contains at least one selected from the group consisting of silica, alumina, and titania.
  • the volume average particle size of the filler is not particularly limited, but is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 50 ⁇ m or less, from the viewpoint of forming a fine pattern, etc.
  • the lower limit of the volume average particle size is not particularly limited, but is preferably 0.1 ⁇ m or more.
  • the volume average particle size is not particularly limited, but can be measured, for example, by dynamic light scattering using a known Nanotrack particle size analyzer or the like.
  • the shape of the filler is not particularly limited, but it is preferable that the filler be approximately spherical.
  • the filler may also be hollow or solid.
  • the content of the filler in the curable composition of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on the total solid content of the curable composition.
  • the upper limit of the content is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.
  • the curable composition of the present invention may contain only one type of filler, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably within the above-mentioned range.
  • the curable composition of the present invention preferably contains a resin.
  • the resin include epoxy resin and maleimide resin.
  • the resin contained in the curable composition of the present invention is preferably a thermosetting resin.
  • the epoxy resin is a compound having one or more, preferably two or more, epoxy groups in one molecule, and there are no limitations on its molecular weight and molecular structure.
  • the epoxy resin may be any one of a monomer, an oligomer, and a polymer.
  • the epoxy resin is preferably a naphthylene ether type epoxy resin.
  • Specific examples of epoxy resins include those represented by the following general formula (NE). As used herein, a bond that crosses an edge of a ring structure is meant to replace one of the hydrogen atoms in the ring structure.
  • R 1 each independently represents a hydrogen atom or a methyl group
  • Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon group
  • m and n each independently represent an integer of 0 to 4, provided that either m or n is 1 or greater
  • m+n R 2s each independently represent a hydrogen atom, an aralkyl group, or an epoxy group-containing aromatic hydrocarbon group.
  • R 1 is preferably a hydrogen atom.
  • the hydrogen atom in the naphthylene group described in formula (NE) may be substituted with an alkyl group or an aralkyl group having 1 to 4 carbon atoms.
  • Ar 1 and Ar 2 each independently represent a phenylene group or a naphthylene group.
  • the hydrocarbon groups in Ar 1 and Ar 2 may each have an alkyl group having 1 to 4 carbon atoms or a phenylene group as a substituent.
  • Each of m and n is preferably an integer of 1 to 4.
  • the aralkyl group when R 2 is an aralkyl group, can be an aralkyl group represented by the following general formula (A). In addition, in the above formula (NE), when R 2 is an aralkyl group, the aralkyl group can be an aralkyl group represented by the following formula (A).
  • R3 and R4 each independently represent a hydrogen atom or a methyl group
  • Ar3 represents a phenylene group or a naphthylene group
  • n is an average value of 0.1 to 4
  • * represents a bonding site with Ar1 or Ar2 .
  • the hydrogen atom of the phenylene group or naphthylene group in Ar3 may be substituted with a substituent, such as an alkyl group.
  • the epoxy group-containing aromatic hydrocarbon group can be an epoxy group-containing aromatic hydrocarbon group represented by the following general formula (E).
  • R 5 each independently represents a hydrogen atom or a methyl group
  • Ar 4 represents a naphthylene group
  • n is an integer of 1 or 2
  • * represents a bonding site with Ar 1 or Ar 2 .
  • the hydrogen atom of the naphthylene group in Ar4 may be substituted with a substituent such as an alkyl group having 1 to 4 carbon atoms, an aralkyl group, or a phenylene group.
  • the content of the naphthylene ether type epoxy resin in the curable composition is preferably 3 mass % or more, more preferably 5 mass % or more, and even more preferably 7 mass % or more, based on the entire curable composition.
  • the content of the naphthylene ether type epoxy resin in the curable composition is preferably 30 mass % or less, more preferably 25 mass % or less, even more preferably 20 mass % or less, and still more preferably 15 mass % or less, based on the entire curable composition.
  • the epoxy resin may be an epoxy resin that does not have a naphthylene ether skeleton.
  • Such epoxy resins may be one or more selected from the group consisting of bisphenol-type epoxy resins such as biphenyl-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and tetramethylbisphenol F-type epoxy resins; stilbene-type epoxy resins; novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins; multifunctional epoxy resins such as triphenol methane-type epoxy resins and alkyl-modified triphenol methane-type epoxy resins; phenol aralkyl-type epoxy resins such as phenol aralkyl-type epoxy resins having a phenylene skeleton and phenol aralkyl-type epoxy resins having a biphenylene skeleton; triazine nucleus-containing epoxy resins such as triglycidyl isocyan
  • the total content of the epoxy resins in the curable composition is preferably 3 mass % or more, more preferably 5 mass % or more, and even more preferably 7 mass % or more, based on the total solid content of the curable composition.
  • the total content of the epoxy resins in the curable composition is preferably 30 mass % or less, more preferably 25 mass % or less, even more preferably 20 mass % or less, and still more preferably 15 mass % or less, based on the total solid content of the curable composition.
  • the maleimide resin may be a compound having two or more maleimide groups.
  • the compound having two or more maleimide groups is preferably a compound represented by any one of the following formulas (M-1) to (M-3).
  • L M1 represents a divalent organic group having 30 or less carbon atoms.
  • R M1 each independently represents a monovalent organic group
  • L M2 each independently represents a single bond or a divalent organic group
  • n represents an integer of 1 to 10
  • the aromatic ring structure in the formula may have a substituent.
  • R 1 M2 each independently represents a monovalent organic group
  • n represents an integer of 1 to 10
  • the aromatic ring structure in the formula may have a substituent.
  • the above-mentioned hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms.
  • the above-mentioned hydrocarbon group includes a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
  • R N represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.
  • L M1 preferably contains an aromatic group.
  • L M1 is preferably a group represented by the following formula (LM-1).
  • L M3 represents a single bond or a divalent linking group, more preferably a single bond, a hydrocarbon group, or a group represented by a bond between a hydrocarbon group and at least one group selected from the group consisting of -O- and -NR N -, and more preferably a hydrocarbon group.
  • L M3 is a divalent linking group, it preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 8 carbon atoms.
  • R 1 M1 is preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • L M2 is more preferably a single bond, a hydrocarbon group, or a group represented by a bond between a hydrocarbon group and at least one group selected from the group consisting of -O- and -NR N -, and more preferably a single bond.
  • the hydrogen atom in the benzene ring shown in formula (M-2) may be substituted with an alkyl group having 1 to 5 carbon atoms or a phenyl group.
  • R 1 M2 is preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the total content of the maleimide resins in the curable composition is preferably 3 mass % or more, more preferably 5 mass % or more, and even more preferably 7 mass % or more, relative to the total solid content of the curable composition.
  • the total content of the maleimide resins in the curable composition is preferably 30 mass % or less, more preferably 25 mass % or less, even more preferably 20 mass % or less, and still more preferably 15 mass % or less, based on the total solid content of the curable composition.
  • the curable composition of the present invention preferably contains a curing agent.
  • the curing agent include a phenol resin curing agent, an amine-based curing agent, an acid anhydride-based curing agent, a mercaptan-based curing agent, etc.
  • the curing agent preferably includes a phenol resin curing agent in terms of a balance of flame resistance, moisture resistance, electrical properties, curability, storage stability, etc. Also, a combination of multiple types of curing agents may be used.
  • phenolic resin curing agent examples include one or more selected from the group consisting of novolak resins obtained by condensing or co-condensing phenols such as phenol novolak resins and cresol novolak resins with formaldehyde or ketones under an acidic catalyst; phenol aralkyl resins having a phenylene skeleton synthesized from the above-mentioned phenols and dimethoxy-para-xylene or bis(methoxymethyl)biphenyl; phenol aralkyl resins such as phenol aralkyl resins having a biphenylene skeleton; phenol resins having a trisphenylmethane skeleton; and phenol-p-xylene glycol dimethyl ether polycondensates.
  • novolak resins obtained by condensing or co-condensing phenols such as phenol novolak resins and cresol novolak resins with formaldehyde or ketones under an acidic
  • the curing agent contains one or more phenol resins selected from the group consisting of phenol novolac type phenol curing agents, phenol aralkyl type curing agents, trisphenylmethane type curing agents, and Zylok type phenol aralkyl type curing agents, and more preferably contains a phenol novolac resin. It is also preferable that the curing agent contains one or more phenol resins selected from the group consisting of phenol aralkyl type curing agents, trisphenylmethane type curing agents, and Zylok type phenol aralkyl type curing agents.
  • Amine-based curing agents include, for example, one or more selected from the group consisting of aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA); aromatic polyamines such as diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diaminodiphenylsulfone (DDS); and polyamine compounds such as dicyandiamide (DICY) and organic acid dihydrazides.
  • aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA)
  • aromatic polyamines such as diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diaminodiphenylsulfone (DDS)
  • DDM diaminodiphenylmethane
  • MPDA
  • acid anhydride curing agents include one or more selected from the group consisting of alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), and maleic anhydride; and aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenonetetracarboxylic acid (BTDA), and phthalic anhydride.
  • alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), and maleic anhydride
  • aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenonetetracarboxylic acid (BTDA), and phthalic anhydride.
  • Examples of mercaptan-based hardeners include one or more compounds selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate) and trimethylolethane tris(3-mercaptobutyrate).
  • curing agents include isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; and organic acids such as carboxylic acid-containing polyester resins.
  • the content of the curing agent in the curable composition is preferably 1 mass % or more, more preferably 2 mass % or more, even more preferably 3 mass % or more, and still more preferably 5 mass % or more, based on the total solid content of the curable composition.
  • the content of the curing agent in the curable composition is preferably 20 mass % or less, and more preferably 10 mass % or less, based on the total solid content of the curable composition.
  • the curable composition of the present invention further contains at least one resin selected from the group consisting of epoxy resins, phenolic resins (phenolic resin-based curing agents), and maleimide resins.
  • the cured product of the present invention contains an epoxy resin and at least one resin selected from the group consisting of phenolic resins and maleimide resins.
  • the curable composition of the present invention preferably contains a curing accelerator.
  • a curing accelerator for example, one that accelerates the crosslinking reaction between the epoxy resin and the curing agent can be used.
  • the curing accelerator include phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds, and nitrogen atom-containing compounds such as amidines and tertiary amines, exemplified by 1,8-diazabicyclo[5.4.0]undecene-7, benzyldimethylamine, and 2-methylimidazole, and quaternary salts of the above amidines and amines.
  • a phosphorus atom-containing compound from the viewpoint of improving curability.
  • compounds having latency such as tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. These compounds may be used alone or in combination of two or more.
  • organic phosphines examples include primary phosphines such as ethylphosphine and phenylphosphine, secondary phosphines such as dimethylphosphine and diphenylphosphine, and tertiary phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine and triphenylphosphine.
  • the curing accelerator may contain an adduct of a phosphonium compound and a silane compound from the viewpoint of improving the strength and toughness of the cured product in a well-balanced manner.
  • the content of the curing accelerator in the curable composition is preferably 0.1 mass % or more, and more preferably 0.2 mass % or more, based on the total solid content of the curable composition.
  • the content of the curing accelerator in the curable composition is preferably 2 mass % or less, more preferably 1.5 mass % or less, even more preferably 1 mass % or less, and still more preferably 0.4 mass % or less, based on the total solid content of the curable composition.
  • the curable composition of the present invention preferably contains a coupling agent.
  • the coupling agent can include one or more types selected from known coupling agents such as aminosilanes such as epoxysilane, mercaptosilane, phenylaminosilane, etc., various silane-based compounds such as alkylsilane, ureidosilane, vinylsilane, and methacrylsilane, titanium-based compounds, aluminum chelates, and aluminum/zirconium-based compounds.
  • the coupling agent is preferably a silane coupling agent, and more preferably a silane coupling agent having an alkylene group bonded to a Si atom.
  • the alkylene group preferably has 4 or more carbon atoms, more preferably 6 or more carbon atoms, and preferably 15 or less, more preferably 10 or less carbon atoms.
  • the silane coupling agent having an alkylene group bonded to a Si atom preferably has an epoxy group, a (meth)acrylic group or an amine group.
  • the coupling agent is N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 7-octenyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane or N-2-(aminoethyl)-8-aminooctyltrimethoxysilane.
  • the content of the coupling agent in the curable composition is preferably 0.05 mass % or more, more preferably 0.1 mass % or more, and even more preferably 0.15 mass % or more, based on the total solid content of the curable composition.
  • the content of the curing accelerator in the curable composition is preferably 2 mass % or less, more preferably 1 mass % or less, and even more preferably 0.5 mass % or less, based on the total solid content of the curable composition.
  • the coupling agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.
  • the curable composition of the present invention may contain a solvent.
  • an embodiment in which the content of the solvent relative to the total mass of the curable composition is 1 mass % or less is also one of the preferred embodiments of the present invention.
  • the content of the solvent is preferably 0.5% by mass or less, and more preferably 0.1% by mass or less.
  • the solvent is not particularly limited, but examples thereof include ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl methoxybutanol, and ⁇ -terpineol.
  • ⁇ -terpineol hexylene glycol, benzyl alcohol, 2-phenylethyl alcohol, isopalmityl alcohol, isostearyl alcohol, lauryl alcohol, ethylene glycol, propylene glycol, butylpropylene triglyceride, or glycerin; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3,5,5-trimethyl-2-cyclohexen-1-one), or diisobutyl ketone (2,6-dimethyl-4-heptanone); acetic acid Esters such as ethyl, butyl acetate, diethyl phthalate, dibutyl phthalate, acetoxyethane, methyl butyrate, methyl hexanoate, methyl
  • the curable composition contains a solvent
  • one or more of these may be used in combination.
  • the content of the solvent is preferably from 10 to 90 mass %, and more preferably from 20 to 80 mass %, based on the total mass of the curable composition.
  • the curable composition may further include components other than the above-mentioned components.
  • the curable composition may further include one or more selected from the group consisting of a flame retardant, a release agent, an ion scavenger, a colorant, a stress reducing agent, and an antioxidant.
  • the amount of each of these components in the curable composition can be about 0.01 to 7 mass % based on the total solid content of the curable composition.
  • those used as components of semiconductor encapsulation materials can be included without any particular limitation.
  • Examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene, etc. These may be used alone or in combination of two or more kinds.
  • Examples of the release agent include natural waxes such as carnauba wax, oxidized polyethylene wax, montanic acid ester wax, synthetic waxes such as a reaction product of a polycondensate of 1-alkene-1-maleic anhydride having 10 or more carbon atoms with stearyl alcohol, higher fatty acids such as zinc stearate and metal salts thereof, paraffins, etc. These may be used alone or in combination of two or more kinds.
  • An example of the ion scavenger is hydrotalcite.
  • Examples of the colorant include carbon black, red iron oxide, etc. These may be used alone or in combination of two or more kinds.
  • Examples of the low stress agent include silicone oil, silicone rubber, and carboxy-terminated butadiene acrylonitrile rubber. These may be used alone or in combination of two or more.
  • Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, and thioether compounds. These may be used alone or in combination of two or more.
  • the curable composition is, for example, in the form of particles or sheets.
  • Specific examples of particulate curable compositions include those in the form of tablets or powders.
  • the curable composition can be molded, for example, by transfer molding.
  • the curable composition is in the form of powder or granules
  • the curable composition can be molded, for example, by compression molding or transfer molding.
  • the term "the curable composition is in the form of powder or granules" refers to the case where the curable composition is in the form of powder or granules.
  • the curable composition of the present invention is preferably used for forming a semiconductor encapsulant.
  • the method for producing the semiconductor encapsulant will be described later as a method for producing a semiconductor package.
  • the curable composition can be obtained, for example, by mixing the above-mentioned components by known means, melt-kneading them with a kneader such as a roll, a kneader or an extruder, cooling, and then pulverizing them. If necessary, the pulverization in the above method may be tableted to obtain a particulate curable composition. After the pulverization in the above method, a sheet-shaped curable composition may be obtained by, for example, vacuum lamination molding or compression molding. The obtained curable composition may also have an appropriate degree of dispersion, flowability, etc.
  • the viscosity ⁇ 1 of the curable composition measured at 110° C. and 0.2 rad/s is preferably 1 ⁇ 10 5 Pa ⁇ s to 1 ⁇ 10 8 Pa ⁇ s, more preferably 1 ⁇ 10 5 Pa ⁇ s to 1 ⁇ 10 7 Pa ⁇ s, and even more preferably 1 ⁇ 10 5 Pa ⁇ s to 1 ⁇ 10 6 Pa ⁇ s.
  • the viscosity ⁇ 1 can be measured, for example, by an Ares rheometer (ARES-2KSTD-FCO-STD, manufactured by Rheometric Scientific).
  • a rotational frequency of 500 rad/s is preferably 1 ⁇ 10 1 Pa ⁇ s to 1 ⁇ 10 7 Pa ⁇ s, more preferably 1 ⁇ 10 1 Pa ⁇ s to 1 ⁇ 10 6 Pa ⁇ s, and even more preferably 1 ⁇ 10 2 Pa ⁇ s to 1 ⁇ 10 6 Pa ⁇ s.
  • the viscosity ⁇ 2 can be measured, for example, with an Ares rheometer (for example, ARES-2KSTD-FCO-STD, manufactured by Rheometric Scientific).
  • a cured product of the curable composition By curing the curable composition of the present invention, a cured product of the curable composition can be obtained.
  • the cured product of the present invention is a cured product obtained by curing the curable composition of the present invention.
  • the curable composition is preferably cured by heating.
  • the heating temperature is preferably from 130 to 220°C, more preferably from 150 to 200°C, and even more preferably from 160 to 190°C.
  • the water absorption rate of the cured product of the present invention is preferably 0.5% or less, more preferably less than 0.4% by mass, and even more preferably less than 0.3% by mass.
  • the water absorption rate is calculated by the method described in the examples below.
  • the volume resistivity of the cured product of the present invention is preferably 1.0 ⁇ 10 11 ⁇ cm or more, more preferably 3.0 ⁇ 10 11 ⁇ cm or more, and even more preferably 5.0 ⁇ 10 11 ⁇ cm or more.
  • the upper limit of the volume resistivity is not particularly limited, but is preferably, for example, 1.0 ⁇ 10 18 ⁇ cm or less.
  • the coefficient of thermal expansion (CTE) of the cured product of the present invention at 25°C to 100°C is preferably 100 ppm/°C or less, more preferably 80 ppm/°C or less, and even more preferably 50 ppm/°C or less.
  • the lower limit of the thermal expansion coefficient is not particularly limited, and may be 0 ppm/° C. or more.
  • the thermal expansion coefficient can be measured using a known thermomechanical analyzer, thermal expansion measuring instrument, or similar instrument, such as a TMA450 (TA Instruments).
  • the glass transition temperature of the cured product of the present invention is preferably 180° C. or higher, more preferably 190° C. or higher, and even more preferably 200° C. or higher.
  • the upper limit of the thermal expansion coefficient is not particularly limited, and may be, for example, 300° C. or less.
  • the glass transition temperature can be measured using a known thermomechanical analyzer, a thermal expansion coefficient measuring device, or a similar device, such as DMA850 (TA Instruments).
  • the relative dielectric constant of the cured product of the present invention is preferably 3.0 or less, more preferably 2.9 or less, and even more preferably 2.8 or less.
  • the lower limit of the relative dielectric constant is not particularly limited, and may be, for example, 1.0 or more.
  • the dielectric constant can be measured using a known thermomechanical analyzer, a thermal expansion coefficient measuring device, or a similar device, such as DMA850 (TA Instruments).
  • the dielectric loss tangent of the cured product of the present invention is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably 0.001 or less.
  • the lower limit of the relative dielectric constant is not particularly limited, and may be, for example, 0 or more.
  • the dielectric constant and dielectric tangent can be measured in accordance with JIS (Japanese Industrial Standards) R 1641:2007 "Method of measurement of micro dielectric properties of fine ceramic substrates.”
  • the cured product of the present invention is preferably used as an encapsulant in a semiconductor package, the details of which will be described later.
  • the method for producing a cured product of the present invention includes a step of heating the curable composition (heating step).
  • the curable composition is cured by the heating step to form a cured product.
  • the method for producing the cured product is not particularly limited, and can be performed using a known method or a method prepared by using a known method while taking into consideration the physical properties, etc. of the curable composition of the present invention.
  • the heating temperature (maximum heating temperature) in the heating step is preferably from 130 to 220°C, more preferably from 150 to 200°C, and even more preferably from 160 to 190°C.
  • the heating temperature can be appropriately set so as to cure the curable composition, taking into consideration the composition of the curable composition and the like.
  • the heating time (heating time at the maximum heating temperature) is preferably from 1 to 20 hours, more preferably from 2 to 10 hours, and even more preferably from 3 to 8 hours. However, the heating time can be appropriately set in consideration of the composition of the curable composition, so that the time is sufficient for the curable composition to harden.
  • the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C./min.
  • the heating means used in the heating step is not particularly limited, and means conventionally used in the transfer molding method, compression molding method, potting method, etc. described below (for example, heating means attached to the sealing device used in these methods) can be used.
  • the transfer molding method is a method in which, for example, a liquid curable composition stored inside a plunger or the like is poured into a cavity in which a substrate having a semiconductor element to be sealed is placed, and then heated to thermally cure the curable composition.
  • the compression molding method is a method in which, for example, a liquid curable composition is prepared in a mold, a substrate having a semiconductor element to be encapsulated is immersed in the curable composition, and the curable composition is then thermally cured.
  • the potting method is a method in which, for example, a liquid curable composition is applied by dripping or the like onto a substrate having a semiconductor element, and then the substrate is heated to thermally cure the curable composition. Heating may also be performed by referring to other methods known in the field of semiconductor encapsulation methods.
  • the method for producing a cured product of the present invention may further include a step of preparing a liquid curable composition.
  • the step of preparing the liquid curable composition preferably includes a step of preheating the curable composition (preheating step).
  • the curable composition melted and liquid by preheating can be used as the liquid curable composition in the above-mentioned transfer molding method, compression molding method, potting method, etc.
  • the heating temperature (maximum heating temperature) in the pre-heating step is preferably lower than the heating temperature in the above-mentioned heating step, and is preferably 100 to 150°C, more preferably 110 to 140°C, and even more preferably 120 to 130°C. However, this temperature may be determined in a range in which the curable composition does not harden, taking into consideration the physical properties of the molten curable composition, such as the viscosity.
  • the semiconductor package of the present invention includes a semiconductor element and the cured product of the present invention.
  • the semiconductor package of the present invention it is preferable that at least a portion of the semiconductor element is covered with the cured product of the present invention, and it is more preferable that the semiconductor element is encapsulated with the cured product of the present invention.
  • the semiconductor element is preferably disposed on a substrate.
  • a die attach material, an adhesive layer, a heat sink, etc. may be disposed between the substrate and the semiconductor package.
  • the types of semiconductor element and substrate are not particularly limited, and any known semiconductor element and substrate in the field of semiconductor packaging can be used without particular limitation.
  • the form of the semiconductor package is not particularly limited as long as it contains a semiconductor element and the cured product of the present invention.
  • semiconductor packages include QFP (Quad Flat Package), CSP (Chip Size Package), FC-CSP (Flip Chip-Chip Size Package), QFN (Quad Flat Non-leaded Package), BGA (Ball Grid Array), FC-BGA (Flip Chip BGA), eWLB (Embedded Wafer-Level BGA), FI-WLP (Fan-In wafer level package), and FO-WLP (Fan-Out wafer level package).
  • the method for producing a semiconductor package of the present invention includes a step of applying the curable composition of the present invention to a surface of a substrate having a semiconductor element (application step), and a step of heating the curable composition (heating step).
  • the application method in the application step is not particularly limited and may be selected depending on the form of the curable composition.
  • a sheet-like curable composition may be placed on a semiconductor element, a liquid curable composition may be poured as described in the transfer molding method above, a substrate having a semiconductor element may be immersed in a liquid curable composition as described in the compression molding method above, or a liquid curable composition may be dripped onto a substrate as described in the potting method above.
  • a method known in the art for producing a semiconductor encapsulation material may be used.
  • the types of semiconductor element and substrate are not particularly limited, and any known semiconductor element and substrate in the field of semiconductor packaging can be used without particular limitation.
  • the method for producing a semiconductor package of the present invention may further include the above-mentioned preparation steps, particularly the pre-curing step. Preferred aspects of these steps are as described above.
  • the uncured curable composition is disposed on the semiconductor element, and more preferably, the semiconductor element is covered with the uncured curable composition, by the unnecessary step.
  • a preferred embodiment of the heating step in the method for producing a semiconductor package of the present invention is the same as the preferred embodiment of the heating step in the method for producing a cured product of the present invention described above.
  • the cured product of the present invention is preferably placed on a semiconductor element, more preferably the semiconductor element is covered with the cured product of the present invention, and even more preferably the semiconductor element is encapsulated with the cured product of the present invention.
  • the method for producing a semiconductor package of the present invention may include the cured product of the present invention after the heating step and a semiconductor.
  • the method may include a step of using a substrate having a plurality of semiconductor elements as the substrate in the application step, and dicing the wafer-level semiconductor package obtained after the application step and the heating step into individual pieces.
  • the individualization step a known method can be used.
  • the method for manufacturing a semiconductor package of the present invention may further include steps known in the field of semiconductor package manufacturing. For example, these include a process for bonding a semiconductor element and a wiring element to a substrate, a process for forming an external terminal, a process for forming a rewiring layer that electrically connects the external terminal and the semiconductor element, and a screening process for detecting defects in the semiconductor element.
  • Examples and Comparative Examples> In each of the examples, the components shown in the following table were mixed to obtain a curable composition. In each of the comparative examples, the components shown in the following table were mixed to obtain a comparative composition.
  • a mixer was used as a mixing means for mixing each of the curable compositions and the comparative composition. Specifically, the filler and the silane compound were first mixed. Then, the components other than the filler and the silane compound were mixed in the mixer, and the mixture was roll-kneaded at 70 to 100°C to obtain each of the curable compositions.
  • the content (blended amount) of each component shown in the table is the amount (parts by mass) shown in the "parts by mass" column of each column in the table. In the table, "-" indicates that the composition does not contain the corresponding component.
  • A-1 75 ⁇ m cut silica (Micron Corporation)
  • A-2 ML-902SK: synthetic fused silica, median diameter 24 ⁇ m, (manufactured by Tokuyama Corporation)
  • A-3 Titanium oxide (TM-HPD, manufactured by Ako Kasei Co., Ltd.)
  • A-4 Titanium oxide/titanium nitride (Mitsubishi Materials Corporation, 13M-C)
  • A-5 Alumina particles (DAB-30FC, manufactured by Denka)
  • ⁇ Silane coupling agent ⁇ C-1 N-phenyl-3-aminopropyltrimethoxysilane, CF-4083 (manufactured by Dow Corning Toray Co., Ltd.)
  • C-2 3-glycidoxypropyltrimethoxysilane, manufactured by Chisso Corporation, organosilane (Sila Ace)
  • E-1 Phenol novolac (PN) type phenolic hardener, PR-HF-3 (manufactured by Sumitomo Bakelite Co., Ltd.)
  • E-2 Phenol aralkyl type curing agent, NC-3000 (manufactured by Nippon Kayaku Co., Ltd.)
  • E-3 Phenolic resin having a trisphenylmethane skeleton (MEH-7500, manufactured by Meiwa Kasei Co., Ltd.)
  • E-4 Zylok type phenol aralkyl type phenol resin (Meiwa Chemical Industry Co., Ltd., MEH-7800-4S)
  • E-5 Phenol resin (manufactured by Nippon Kayaku Co., Ltd., KAYAHARD GPH-65)
  • E-6 Maleimide resin (manufactured by Nippon Kayaku Co., Ltd., MIR-3000-70MT)
  • H-1 Montan acid ester wax, WE-4, manufactured by Clariant Japan
  • H-2 Carnauba wax
  • TOWAX-132 manufactured by Toa Kasei H-3: Oxidized polyethylene wax, PED191m100, manufactured by Clariant Japan
  • K-1 Silicone oil (Dow Corning Toray Co., Ltd., FZ-3730)
  • L-1 to L-10 Compounds having the following structure, L-1 to L-10 are compounds corresponding to the above-mentioned compound A.
  • CL-1 A compound having the following structure. CL-1 is a compound that does not fall under the above-mentioned compound A.
  • THB temperature humidity bias
  • An IGBT (insulated gate bipolar transistor) element with a rated voltage of 1200V was die-bonded to a TO-247 frame using solder, and then wire-bonded with an Al wire. This was sealed with the prepared curable composition or comparative composition in each of the Examples and Comparative Examples to produce a package for THB evaluation.
  • the molding conditions for the composition were 175°C for 2 minutes, and the after-cure conditions were 175°C for 4 hours.
  • the evaluation samples of each example obtained by the above-mentioned method were treated in a THB tester at 85°C, 85%, and a voltage of 960V for 1500 hours.
  • the leakage current was measured before and after the treatment and evaluated according to the following criteria.
  • the evaluation results are shown in the "THB resistance" column in the table. It can be said that the smaller the leakage current failure rate after treatment, the better the THB resistance.
  • B The leakage current defect rate after treatment was more than 0% and 50% or less.
  • C The leakage current defect rate after treatment was more than 50% and not more than 100%.
  • Boiling water absorption rate (%) (mass after boiling treatment ⁇ mass before boiling treatment)/mass before boiling treatment ⁇ 100 -Evaluation criteria- A: The boiled water absorption rate was less than 0.3%. B: The boiled water absorption was 0.3% or more and 0.5% or less. C: The boiled water absorption rate was more than 0.5%.
  • the cured product formed from the curable composition of the present invention has low water absorbency.
  • the comparative composition according to Comparative Example 1 does not contain compound A. It is clear that such a comparative composition has high water absorption.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne : une composition durcissable qui contient une charge et un composé A ayant un groupe A qui est un groupe hydrocarboné dans lequel au moins un atome d'hydrogène est substitué par un atome de fluor et un groupe B qui est au moins un groupe qui est choisi dans le groupe constitué par un groupe fonctionnel nucléophile, un groupe fonctionnel électrophile, un groupe alcoxysilyle et un groupe ayant une liaison éthyléniquement insaturée et peut être protégé ; un produit durci obtenu par durcissement de ladite composition durcissable ; un procédé de production d'un produit durci ; un boîtier de semi-conducteur comprenant ledit produit durci ; et un procédé de production d'un boîtier de semi-conducteur, comprenant ledit procédé de production d'un produit durci.
PCT/JP2023/035236 2022-09-29 2023-09-27 Composition durcissable, produit durci, procédé de production de produit durci, boîtier de semi-conducteur, et procédé de production de boîtier de semi-conducteur WO2024071234A1 (fr)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62187752A (ja) * 1986-02-14 1987-08-17 Hitachi Ltd 耐熱性樹脂組成物及び樹脂封止型半導体装置
JPH01108221A (ja) * 1987-10-21 1989-04-25 Hitachi Ltd エポキシ樹脂組成物
JPH01249827A (ja) * 1988-03-31 1989-10-05 Toshiba Corp 半導体封止用エポキシ樹脂成形材料
JPH04206759A (ja) * 1990-11-30 1992-07-28 Mitsui Petrochem Ind Ltd 半導体装置およびそのパッケージ材料
JPH0570562A (ja) * 1991-09-10 1993-03-23 Toshiba Chem Corp 封止用樹脂組成物および半導体封止装置
JPH05331355A (ja) * 1992-06-02 1993-12-14 Toshiba Chem Corp 導電性ペースト
JPH0797563A (ja) * 1993-09-28 1995-04-11 Sumitomo Chem Co Ltd 半導体素子の封止用樹脂組成物および樹脂封止型半導体装置
JP2002060464A (ja) * 2000-06-08 2002-02-26 Nec Corp 電子部品装置
JP2015044903A (ja) * 2013-08-27 2015-03-12 日立化成株式会社 光反射用熱硬化性樹脂組成物、光半導体素子搭載用基板及びその製造方法、並びに光半導体装置
JP2017115006A (ja) * 2015-12-24 2017-06-29 株式会社ダイセル 硬化性エポキシ樹脂組成物
JP2018111750A (ja) * 2017-01-10 2018-07-19 信越化学工業株式会社 光半導体素子封止用熱硬化性エポキシ樹脂組成物及びそれを用いた光半導体装置

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62187752A (ja) * 1986-02-14 1987-08-17 Hitachi Ltd 耐熱性樹脂組成物及び樹脂封止型半導体装置
JPH01108221A (ja) * 1987-10-21 1989-04-25 Hitachi Ltd エポキシ樹脂組成物
JPH01249827A (ja) * 1988-03-31 1989-10-05 Toshiba Corp 半導体封止用エポキシ樹脂成形材料
JPH04206759A (ja) * 1990-11-30 1992-07-28 Mitsui Petrochem Ind Ltd 半導体装置およびそのパッケージ材料
JPH0570562A (ja) * 1991-09-10 1993-03-23 Toshiba Chem Corp 封止用樹脂組成物および半導体封止装置
JPH05331355A (ja) * 1992-06-02 1993-12-14 Toshiba Chem Corp 導電性ペースト
JPH0797563A (ja) * 1993-09-28 1995-04-11 Sumitomo Chem Co Ltd 半導体素子の封止用樹脂組成物および樹脂封止型半導体装置
JP2002060464A (ja) * 2000-06-08 2002-02-26 Nec Corp 電子部品装置
JP2015044903A (ja) * 2013-08-27 2015-03-12 日立化成株式会社 光反射用熱硬化性樹脂組成物、光半導体素子搭載用基板及びその製造方法、並びに光半導体装置
JP2017115006A (ja) * 2015-12-24 2017-06-29 株式会社ダイセル 硬化性エポキシ樹脂組成物
JP2018111750A (ja) * 2017-01-10 2018-07-19 信越化学工業株式会社 光半導体素子封止用熱硬化性エポキシ樹脂組成物及びそれを用いた光半導体装置

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