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WO2025023139A1 - Stratifié et procédé de production de stratifié - Google Patents

Stratifié et procédé de production de stratifié Download PDF

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Publication number
WO2025023139A1
WO2025023139A1 PCT/JP2024/025772 JP2024025772W WO2025023139A1 WO 2025023139 A1 WO2025023139 A1 WO 2025023139A1 JP 2024025772 W JP2024025772 W JP 2024025772W WO 2025023139 A1 WO2025023139 A1 WO 2025023139A1
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WO
WIPO (PCT)
Prior art keywords
material layer
adhesive layer
adhesive
organic material
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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PCT/JP2024/025772
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English (en)
Japanese (ja)
Inventor
拓生 四釜
佳保里 田村
穣 久宗
航 岡太
靖剛 茅場
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Filing date
Publication date
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Publication of WO2025023139A1 publication Critical patent/WO2025023139A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds

Definitions

  • This disclosure relates to a laminate and a method for manufacturing the laminate.
  • Patent Document 1 describes an adhesive that does not exhibit adhesive properties during stacking operations for semiconductor chips and the like, but softens when heated to exhibit adhesive properties, and then hardens quickly.
  • Patent Document 1 a laminate is produced by bonding a glass plate and a silicon plate using an adhesive, but there is no description of an example in which an adhesive is used to bond an inorganic material and an organic material. Furthermore, in recent years, the integration of semiconductor chips has progressed, and measures against heat generation from semiconductor chips have become increasingly important. Therefore, studies have been conducted to improve the heat dissipation of semiconductor chips by reducing the thickness of the adhesive layer. However, there is a risk that reducing the thickness of the adhesive layer will reduce the bonding strength.
  • An embodiment of the present disclosure aims to provide a laminate including an adhesive layer that exhibits excellent bonding strength to both inorganic materials and organic materials even when the adhesive layer has a small thickness, and a method for manufacturing the laminate.
  • a substrate-forming material for a laminate including an inorganic material layer, an organic material layer, and an adhesive layer disposed between the inorganic material layer and the organic material layer to bond the inorganic material layer and the organic material layer, a ratio (X/Y) of a die shear strength X (MPa) between the inorganic material layer and the organic material layer to a thickness Y ( ⁇ m) of the adhesive layer is 1 or more.
  • X/Y a ratio (X/Y) of a die shear strength X (MPa) between the inorganic material layer and the organic material layer to a thickness Y ( ⁇ m) of the adhesive layer is 1 or more.
  • MPa die shear strength X
  • ⁇ m thickness Y
  • ⁇ 3> The laminate according to ⁇ 1> or ⁇ 2>, having a die shear strength of 3 MPa or more.
  • ⁇ 4> The laminate according to any one of ⁇ 1> to ⁇ 3>, wherein the adhesive layer has an elastic modulus of 5 GPa or more.
  • ⁇ 6> The method for producing a laminate according to ⁇ 5>, wherein an adhesive is applied to a surface of the organic material layer in the step of forming the adhesive layer.
  • ⁇ 7> The method for producing a laminate according to ⁇ 6>, further comprising the step of subjecting a surface of the organic material layer to a plasma treatment before the step of forming the adhesive layer.
  • ⁇ 8> The method for producing a laminate according to any one of ⁇ 5> to ⁇ 7>, wherein the step of forming the adhesive layer includes a step of curing the adhesive.
  • a laminate having an adhesive layer that exhibits excellent bonding strength to both inorganic and organic materials even when it is thin, and a method for manufacturing the laminate are provided.
  • a numerical range expressed using “to” means a range that includes the numerical values before and after "to” as the lower and upper limits.
  • the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages.
  • the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.
  • the term "laminate” refers to a structure in which an inorganic material layer, an adhesive layer, and an organic material layer are arranged in this order, and the inorganic material layer and the organic material layer are bonded via the adhesive layer.
  • the first embodiment of the present disclosure is an inorganic material layer, an organic material layer, and an adhesive layer disposed between the inorganic material layer and the organic material layer to bond the inorganic material layer and the organic material layer;
  • the laminate has a ratio (X/Y) of a die shear strength X (MPa) between the inorganic material layer and the organic material layer to a thickness Y ( ⁇ m) of the adhesive layer of 1 or more.
  • an inorganic material layer and an organic material layer are bonded to each other via an adhesive layer, that is, the adhesive layer included in the laminate of the present disclosure exhibits excellent adhesion to both the inorganic material layer and the organic material layer.
  • the ratio (X/Y) of the die shear strength X (MPa) between the inorganic material layer and the organic material layer to the thickness Y ( ⁇ m) of the adhesive layer is at least 1. That is, the adhesive layer included in the laminate of the present disclosure exhibits excellent bonding strength between the inorganic material layer and the organic material layer even when the thickness Y is small.
  • the ratio (X/Y) of the die shear strength X (MPa) between the inorganic material layer and the organic material layer to the thickness Y ( ⁇ m) of the adhesive layer is preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 2.0 or more.
  • the upper limit of the ratio (X/Y) of the die shear strength X (MPa) between the inorganic material layer and the organic material layer to the thickness Y ( ⁇ m) of the adhesive layer is not particularly limited, and may be, for example, 10 or less, 8 or less, or 6 or less.
  • the die shear strength between the inorganic material layer and the organic material layer is measured by fixing either the inorganic material layer or the organic material layer, which are joined via an adhesive layer, and applying force from the side of the other. More specifically, the die shear strength between the inorganic material layer and the organic material layer is measured by the method described in the Examples.
  • the thickness Y of the adhesive layer is preferably 0.2 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 0.75 ⁇ m or more, and even more preferably 1.0 ⁇ m or more. From the viewpoint of ensuring sufficient heat dissipation, the thickness Y of the adhesive layer is preferably 10 ⁇ m or less, more preferably 7.5 ⁇ m or less, further preferably 5.0 ⁇ m or less, and even more preferably 3.0 ⁇ m or less. The thickness Y of the adhesive layer may be 2.6 ⁇ m or more.
  • the thickness of the adhesive layer is measured by the method described in the Examples.
  • the die shear strength X between the inorganic material layer and the organic material layer is preferably 3 MPa or more, more preferably 4 MPa or more, and even more preferably 5 MPa or more.
  • the upper limit of the die shear strength X between the inorganic material layer and the organic material layer is not particularly limited, but may be, for example, 10 MPa or less, 8 MPa or less, or 6 MPa or less.
  • the adhesive layer preferably has a modulus of elasticity of 5 GPa or more.
  • the adhesive layer has an elastic modulus of 5 GPa or more, the adhesive layer is sufficiently hard, and it is possible to effectively suppress misalignment when bonding the inorganic material layer and the organic material layer.
  • the elastic modulus of the adhesive layer means the complex elastic modulus at 23° C., and is measured by the method described below.
  • a sample is prepared by forming an adhesive layer on a silicon substrate.
  • a nanoindenter product name TI-950 Tribo Indenter, manufactured by Hysitron, Berkovich type indenter
  • TI-950 Tribo Indenter manufactured by Hysitron, Berkovich type indenter
  • the composite elastic modulus (GPa) at 23°C is calculated from the maximum load and maximum displacement according to the calculation method in the reference literature (Handbook of Micro/nano Tribology (second Edition), edited by Bharat Bhushan, CRC Press).
  • the composite elastic modulus is defined by the following formula (1):
  • E r represents the composite elastic modulus
  • E i represents the Young's modulus of the indenter and is 1140 GPa
  • v i represents the Poisson's ratio of the indenter and is 0.07
  • E s and v s represent the Young's modulus and Poisson's ratio of the adhesive layer, respectively.
  • the adhesive layer preferably contains a cured adhesive.
  • the adhesive layer is sufficiently hard, and misalignment when bonding the inorganic material layer and the organic material layer can be effectively suppressed.
  • the adhesive layer may be in a completely cured state or in a not completely cured state.
  • the curing rate of the adhesive layer is more preferably 80% or more, even more preferably 85% or more, particularly preferably 90% or more, and even more preferably 93% or more.
  • the curing rate of the adhesive layer may be 100%, 99% or less, 95% or less, or 90% or less.
  • the curing rate of the adhesive layer may be confirmed, for example, by measuring the peak intensity of a specific bond and structure (the sum of the peak intensities when there are multiple peaks such as imide, amide, etc.) using FT-IR (Fourier transform infrared spectroscopy) in the adhesive layer to be measured and in the fully cured adhesive layer obtained by fully curing the adhesive layer, and determining the rate of increase or decrease in the peak intensity.
  • FT-IR Fastier transform infrared spectroscopy
  • the increase rate of the peak strength may be calculated by the following formula, and the calculated value may be regarded as the curing rate of the adhesive layer.
  • Peak strength increase rate (curing rate of adhesive layer) [(peak strength of specific bonds and structures of the adhesive layer to be measured) / (peak strength of specific bonds and structures of the completely cured adhesive layer obtained by heating the adhesive layer to be measured at 300 ° C. for 1 hour)] ⁇ 100
  • the background signal can be removed by a conventional method. If necessary, the FT-IR measurement can be performed by a transmission method or a reflection method.
  • the peak intensity may be interpreted as the total intensity of the multiple peak intensities.
  • the second embodiment of the present disclosure is A method for producing the laminate described above, A step of applying an adhesive to a surface of at least one of the organic material layer and the inorganic material layer to form an adhesive layer; and bonding the inorganic material layer and the organic material layer via the adhesive layer.
  • the method for applying the adhesive to the surface of at least one of the organic material layer and the inorganic material layer is not particularly limited, and can be carried out by a known method.
  • it may be performed by a spin coating method, an ink jet method, a screen printing method, or the like.
  • the surface of the organic material layer on which the adhesive layer is formed may be in a state where it has been subjected to plasma treatment.
  • plasma treatment for example, the wettability of the adhesive to the organic material layer is improved.
  • the method for bonding the inorganic material layer and the organic material layer via the adhesive layer is not particularly limited.
  • a method in which the adhesive layer disposed between the organic material layer and the inorganic material layer is pressurized while being heated can be mentioned.
  • the temperature at which the adhesive layer is heated is not particularly limited and can be selected depending on the type of adhesive.
  • the temperature at which the adhesive layer is heated may be, for example, 150° C. or higher, 200° C. or higher, or 400° C. or lower, or 300° C. or lower.
  • the pressure to be applied to the adhesive layer is not particularly limited and can be selected depending on the type of adhesive.
  • the step of forming the adhesive layer may include a step of curing the adhesive. That is, the adhesive layer may be in a state including a cured product of the adhesive when the inorganic material layer and the organic material layer are bonded together. In the step of curing the adhesive, the adhesive may or may not be completely cured. When the inorganic material layer and the organic material layer are bonded together, if the adhesive layer contains a cured product of the adhesive, it is possible to effectively prevent misalignment when bonding the inorganic material layer and the organic material layer. Furthermore, the adhesive layer has low adhesion when bonding the inorganic material layer and the organic material layer, and the bonding operation can be performed efficiently.
  • the method for curing the adhesive is not particularly limited and can be selected depending on the type of adhesive.
  • the adhesive when the adhesive is thermosetting, the adhesive is heated to a temperature at which a curing reaction of the adhesive occurs.
  • the temperature at which the adhesive is heated is not particularly limited, but may be, for example, 150° C. or higher and 350° C. or lower.
  • the details and preferred aspects of the inorganic material layer, organic material layer, and adhesive layer in the method of the present disclosure are the same as the details and preferred aspects of the inorganic material layer, organic material layer, and adhesive layer in the laminate of the present disclosure described above.
  • the type of inorganic material constituting the inorganic material layer is not particularly limited.
  • specific examples of inorganic materials include semiconductors such as Si, InP, GaN, GaAs, InGaAs, InGaAlAs, SiGe, and SiC; oxides, carbides, and nitrides such as boron silicate glass (Pyrex (registered trademark) ) , quartz glass ( SiO2 ), sapphire ( Al2O3 ) , ZrO2 , Si3N4 , SiCN, AlN, and MgAl2O4 ; piezoelectrics or dielectrics such as BaTiO3 , LiNbO3 , SrTiO3 , and LiTaO3 ; diamond ; metals such as Al, Ti, Fe, Cu, Ag, Au, Pt, Pd, Ta, and Nb;
  • organic material layer In the laminate of the present disclosure, the type of organic material constituting the organic material layer is not particularly limited. Specific examples of the organic material include epoxy resin, phenol resin, silicone resin, polyimide, benzocyclobutene resin, and polybenzoxazole.
  • the organic material layer may be a self-supporting object, or may be formed in a layer on the surface of another object.
  • the type of the other object is not particularly limited, and may be an inorganic material or an organic material.
  • the organic material layer may have an electrode on the surface facing the inorganic material layer.
  • the organic material layer may have hydrophilic groups such as hydroxyl groups on the surface facing the inorganic material layer. Hydrophilic groups such as hydroxyl groups can be formed by subjecting the surface of the organic material layer facing the inorganic material layer to a surface treatment such as plasma treatment.
  • the organic material layer may contain a filler.
  • the filler material include silica and alumina.
  • the filler content may be 30% to 90% by mass of the organic material layer.
  • a composition containing the following compound (A), a crosslinking agent (B), and a polar solvent (C) may be used as an adhesive.
  • Compound (A) A compound having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom and an Si-O bond.
  • the functional group represented by formula (a) may be a functional group constituting a part of a secondary amino group (-NHR a group; here, R a represents an alkyl group), or may be a divalent linking group contained in the skeleton of a polymer.
  • the weight average molecular weight of compound (A) is preferably 130 or more and 10,000 or less, more preferably 130 or more and 5,000 or less, and even more preferably 130 or more and 2,000 or less.
  • the weight average molecular weight of a compound refers to the weight average molecular weight calculated as polyethylene glycol, measured by GPC (Gel Permeation Chromatography). Specifically, the weight-average molecular weight of the compound is calculated by detecting the refractive index at a flow rate of 1.0 mL/min using an analytical device, Shodex DET RI-101, and two types of analytical columns (TSKgel G6000PWXL-CP and TSKgel G3000PWXL-CP, manufactured by Tosoh Corporation) in an aqueous solution of sodium nitrate having a concentration of 0.1 mol/L as a developing solvent, and using polyethylene glycol/polyethylene oxide as standards with analytical software (Empower3, manufactured by Waters Corporation).
  • GPC Gel Permeation Chromatography
  • the compound (A) may be a compound having a Si—O bond and an amino group.
  • Examples of compounds having an Si--O bond and an amino group include siloxane diamines, silane coupling agents having an amino group, and siloxane polymers.
  • An example of the silane coupling agent having an amino group is a compound represented by the following formula (A-3).
  • R 1 represents an alkyl group having 1 to 4 carbon atoms which may be substituted.
  • R 2 and R 3 each independently represent an alkylene group having 1 to 12 carbon atoms, an ether group, or a carbonyl group which may be substituted (the skeleton may contain a carbonyl group, an ether group, etc.).
  • R 4 and R 5 each independently represent an alkylene group having 1 to 4 carbon atoms which may be substituted or a single bond.
  • Ar represents a divalent or trivalent aromatic ring.
  • X 1 represents hydrogen or an alkyl group having 1 to 5 carbon atoms which may be substituted.
  • X 2 represents hydrogen, a cycloalkyl group, a heterocyclic group, an aryl group, or an alkyl group having 1 to 5 carbon atoms which may be substituted (the skeleton may contain a carbonyl group, an ether group, etc.).
  • a plurality of R 1 , R 2 , R 3 , R 4 , R 5 , and X 1 may be the same or different.
  • Substituents of the alkyl and alkylene groups in R1 , R2 , R3 , R4 , R5 , X1 and X2 each independently include an amino group, a hydroxy group, an alkoxy group, a cyano group, a carboxylic acid group, a sulfonic acid group and halogens.
  • Examples of the divalent or trivalent aromatic ring in Ar include a divalent or trivalent benzene ring.
  • Examples of the aryl group in X2 include a phenyl group, a methylbenzyl group, and a vinylbenzyl group.
  • silane coupling agents represented by formula (A-3) include, for example, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (aminoethylaminoethyl)phenyltriethoxysilane, methylbenzylaminoethyla
  • silane coupling agents having an amino group other than that of formula (A-3) include N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis[(3-triethoxysilyl)propyl]amine, piperazinylpropylmethyldimethoxysilane, bis[3-(triethoxysilyl)propyl]urea, bis(methyldiethoxysilylpropyl)amine, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, 3,5-diamino-N-(4-(methoxydimethylsilyl)phenyl)benzamide, 3,5-diamino-N-(4-(triethoxysilyl)phenyl)benzamide, 5-(ethoxydimethylsilyl)benzene-1,3-diamine, and
  • silane coupling agents having an amino group may be used alone or in combination of two or more.
  • a silane coupling agent having an amino group may also be used in combination with a silane coupling agent not having an amino group.
  • a silane coupling agent having a mercapto group may be used to improve adhesion to metals.
  • Compound (A) may be a polymer (siloxane polymer) formed from the above-mentioned silane coupling agent via a siloxane bond (Si-O-Si).
  • siloxane polymer formed from the above-mentioned silane coupling agent via a siloxane bond (Si-O-Si).
  • a polymer having a linear siloxane structure, a polymer having a branched siloxane structure, a polymer having a cyclic siloxane structure, a polymer having a cage siloxane structure, etc. can be obtained from the hydrolyzate of 3-aminopropyltrimethoxysilane.
  • the cage siloxane structure is represented, for example, by the following formula (A-1).
  • siloxane diamines examples include compounds represented by the following formula (A-2).
  • i is an integer from 0 to 4
  • j is an integer from 1 to 3
  • Me is a methyl group.
  • compound (A) has a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom, it can strongly adhere to the surface of the inorganic material layer and/or the organic material layer by electrostatic interaction with functional groups such as hydroxyl groups, epoxy groups, carboxy groups, amino groups, and mercapto groups that may be present on the surface of the inorganic material layer and/or the organic material layer, or by forming a covalent bond with the functional groups.
  • functional groups such as hydroxyl groups, epoxy groups, carboxy groups, amino groups, and mercapto groups that may be present on the surface of the inorganic material layer and/or the organic material layer, or by forming a covalent bond with the functional groups.
  • Compound (A) has a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom, and therefore is easily soluble in polar solvent (C).
  • polar solvent (C) By using compound (A) that is easily soluble in polar solvent (C), affinity with the surface of the inorganic material layer or organic material layer is increased when the surface of the layer is hydrophilic. This allows the formation of a smooth adhesive layer.
  • the molar ratio of the Si element in the molecule of compound (A) to the non-crosslinkable group such as a methyl group bonded to the Si element (non-crosslinkable group/Si element) is less than 2 (satisfying the relationship non-crosslinkable group/Si element ⁇ 2).
  • compound (A) contains a primary nitrogen atom
  • the proportion of primary nitrogen atoms in the total nitrogen atoms in compound (A) is preferably 20 mol% or more, more preferably 25 mol% or more, and even more preferably 30 mol% or more.
  • Compound (A) may also have a cationic functional group that contains a primary nitrogen atom and does not contain any nitrogen atoms other than the primary nitrogen atom (e.g., secondary nitrogen atom, tertiary nitrogen atom).
  • the ratio of secondary nitrogen atoms to the total nitrogen atoms in compound (A) is preferably 5 mol% or more and 50 mol% or less, and more preferably 10 mol% or more and 45 mol% or less.
  • Compound (A) may contain a tertiary nitrogen atom in addition to a primary nitrogen atom and a secondary nitrogen atom.
  • the ratio of tertiary nitrogen atoms to the total nitrogen atoms in compound (A) is preferably 20 mol % or more and 50 mol % or less, and more preferably 25 mol % or more and 45 mol % or less.
  • the content of compound (A) in the composition is not particularly limited, but can be, for example, 0.001% by mass or more and 20% by mass or less, preferably 0.01% by mass or more and 20% by mass or less, and more preferably 0.04% by mass or more and 20% by mass or less, relative to the entire composition.
  • the weight average molecular weight of the compound (B) is not particularly limited.
  • the weight average molecular weight of the compound (B) may be 200 or more and 600 or less, 200 or more and 500 or less, 200 or more and 450 or less, or 200 or more and 400 or less.
  • the weight average molecular weight of the compound (B) is within the above range, the solubility in the composition is improved.
  • the crosslinking agent (B) has a ring structure in the molecule.
  • the ring structure include an alicyclic structure and an aromatic ring structure.
  • the crosslinking agent (B) may have multiple ring structures in the molecule, and the multiple ring structures may be the same or different.
  • the heat resistance of the adhesive layer is improved.
  • Examples of the alicyclic structure include alicyclic structures having 3 to 8 carbon atoms, preferably alicyclic structures having 4 to 6 carbon atoms, and the ring structure may be saturated or unsaturated. More specifically, examples of the alicyclic structure include saturated alicyclic structures such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring; and unsaturated alicyclic structures such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring.
  • saturated alicyclic structures such as a cyclopropane ring, a cyclobutane ring
  • the aromatic ring structure is not particularly limited as long as it is a ring structure that exhibits aromaticity, and examples thereof include benzene-based aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a perylene ring, aromatic heterocycles such as a pyridine ring and a thiophene ring, and non-benzene-based aromatic rings such as an indene ring and an azulene ring.
  • benzene-based aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a perylene ring
  • aromatic heterocycles such as a pyridine ring and a thiophene ring
  • non-benzene-based aromatic rings such as an indene ring and an azulene ring.
  • the ring structure that the crosslinking agent (B) has in its molecule is preferably at least one selected from the group consisting of a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a benzene ring, and a naphthalene ring, and from the viewpoint of further increasing the heat resistance of the adhesive layer, at least one of a benzene ring and a naphthalene ring is more preferable.
  • crosslinking agent (B) examples include carboxylic acid compounds such as alicyclic carboxylic acids, benzene carboxylic acids, naphthalene carboxylic acids, diphthalic acids, and fluorinated aromatic carboxylic acids, and carboxylic acid ester compounds such as alicyclic carboxylic acid esters, benzene carboxylic acid esters, naphthalene carboxylic acid esters, diphthalic acid esters, and fluorinated aromatic carboxylic acid esters.
  • carboxylic acid compounds such as alicyclic carboxylic acids, benzene carboxylic acids, naphthalene carboxylic acids, diphthalic acids, and fluorinated aromatic carboxylic acid esters
  • carboxylic acid ester compounds such as alicyclic carboxylic acid esters, benzene carboxylic acid esters, naphthalene carboxylic acid esters, diphthalic acid esters, and fluorinated aromatic carboxylic acid esters.
  • the crosslinking agent (B) contained in the adhesive is a carboxylate compound, aggregation due to association between the compound (A) and the crosslinking agent (B) in the composition is suppressed, and aggregates and pits in the cured product are reduced, resulting in an adhesive layer with higher smoothness and making it easier to adjust the thickness of the adhesive layer.
  • X is preferably a methyl group, an ethyl group, a propyl group, or a butyl group
  • X is preferably an ethyl group or a propyl group.
  • carboxylic acid compound examples include, but are not limited to, alicyclic carboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; benzene carboxylic acids such as 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, benzenepentacarboxylic acid, and mellitic acid; naphthalene carboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and 2,3,6,7-naphthalenetetracarboxylic acid; 3,3'
  • carboxylate compound examples include compounds in which at least one carboxy group in the specific examples of the carboxylate compound described above is substituted with an ester group.
  • carboxylate compound examples include half-esterified compounds such as the compounds represented by the following general formulas (B-1) to (B-6).
  • the carboxylate compound is preferably a carboxylate compound having two aromatic rings in the molecule, and more preferably a carboxylate compound represented by the following formulae (B-2) to (B-5).
  • R is an alkyl group having 1 to 6 carbon atoms, and among them, a methyl group, an ethyl group, a propyl group, or a butyl group is preferable, and an ethyl group or a propyl group is more preferable.
  • a half-esterified compound can be produced, for example, by mixing a carboxylic acid anhydride, which is the anhydride of the aforementioned carboxylic acid compound, with an alcohol solvent and opening the ring of the carboxylic acid anhydride.
  • the content of the crosslinking agent (B) in the composition is, for example, preferably an amount such that the ratio (COOH/N) of the number of carboxy groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A) is 0.1 or more and 3.0 or less, more preferably an amount such that the ratio is 0.3 or more and 2.5 or less, and even more preferably an amount such that the ratio is 0.4 or more and 2.2 or less.
  • a crosslinked structure such as an amide bond or an imide bond is sufficiently formed between the compound (A) and the crosslinking agent (B) after heat treatment, and an adhesive layer with excellent heat resistance and insulating properties is formed.
  • the ratio (COOH/N) of the number of carboxy groups in crosslinking agent (B) to the total number of all nitrogen atoms contained therein and in compound (A) is preferably 0.1 or more and 3.0 or less.
  • the content ratio (feed ratio) of the compound (A) to the crosslinking agent (B) in the composition is preferably a molar ratio of compound (A):crosslinking agent (B) of 2:0.9 to 2:1.1, and more preferably a molar ratio of 2:1. It is believed that the compound (A) and the crosslinking agent (B) in the composition exist as a mixture in a state in which the amino group of the compound (A) and the carboxy group of the crosslinking agent (B) form a salt in the polar solvent (C).
  • a cured product obtained by heating a composition containing compound (A) and crosslinking agent (B) is considered to contain, as a structural unit, a reaction product between compound (A) and crosslinking agent (B) as exemplified below.
  • the composition includes a polar solvent (C).
  • a polar solvent refers to a solvent having a relative dielectric constant of 5 or greater at room temperature (25° C.).
  • the polar solvent (C) may be used alone or in combination of two or more kinds.
  • polar solvent (C) examples include protic solvents such as water and heavy water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, benzyl alcohol, diethylene glycol, triethylene glycol, and glycerin; ethers such as tetrahydrofuran and dimethoxyethane; aldehydes and ketones such as furfural, acetone, ethyl methyl ketone, and cyclohexanone; acid derivatives such as ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, formaldehyde, N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylace,
  • the content of the polar solvent (C) in the composition is not particularly limited, and may be, for example, 1.0% by mass or more and 99.99896% by mass or less, or 40% by mass or more and 99.99896% by mass or less, relative to the entire composition.
  • the boiling point of the polar solvent (C) is preferably 150°C or lower, and more preferably 120°C or lower.
  • the composition may contain known additives.
  • the additive include an acid having a carboxy group and a weight average molecular weight of 46 to 195, a base having a nitrogen atom and no ring structure and a weight average molecular weight of 17 to 120, and a solvent other than the polar solvent (C).
  • the composition may contain a solvent other than the polar solvent (C).
  • a solvent other than the polar solvent include normal hexane.
  • the composition may contain benzotriazole or a derivative thereof, for example to inhibit copper corrosion.
  • the pH of the composition is not particularly limited, but is preferably from 2.0 to 12.0. When the pH of the composition is 2.0 or more and 12.0 or less, damage to the substrate caused by the composition is suppressed.
  • the composition preferably contains 10 ppb by mass or less of sodium and potassium on an elemental basis, respectively. If the content of sodium or potassium is 10 ppb by mass or less on an elemental basis, the occurrence of problems in the electrical characteristics of the semiconductor device, such as malfunction of a transistor, can be suppressed.
  • the total content of the compound (A) and the crosslinking agent (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more of the total mass of the non-volatile components in the composition.
  • non-volatile components refers to components other than components (solvents, etc.) that are removed when the composition becomes a cured product.
  • the method for producing the composition is not particularly limited, and can be carried out by a known method.
  • the composition can be produced by a method including the following steps (a), (b) and (c).
  • the composition can be cured by heating.
  • the heating temperature for curing the composition is preferably 150° C. to 450° C., more preferably 150° C. to 400° C., and even more preferably 180° C. to 400° C.
  • the above temperature refers to the temperature of the surface of the composition.
  • the heating time of the composition is not particularly limited and may be, for example, 3 hours or less or 1 hour or less.
  • the lower limit of the heating time is not particularly limited and may be, for example, 5 minutes or more.
  • the composition may be irradiated with ultraviolet (UV) rays.
  • Whether the composition is cured after heating can be confirmed, for example, by measuring the peak intensity of specific bonds and structures by Fourier transform infrared spectroscopy (FT-IR).
  • specific bonds and structures include bonds and structures generated by a crosslinking reaction.
  • FT-IR Fourier transform infrared spectroscopy
  • the composition is cured.
  • the presence or absence of an amide bond can be confirmed by the presence or absence of vibration peaks at about 1650 cm -1 and about 1520 cm -1 .
  • the presence or absence of an imide bond can be confirmed by the presence or absence of vibration peaks at about 1770 cm -1 and about 1720 cm -1 .
  • Example 1 Preparation of Adhesive 50% by mass of 3-aminopropyldiethoxymethylsilane (3APDES: structure shown below) and 50% by mass of water were mixed to obtain a solution A containing a hydrolysate of 3APDES.
  • 3APDES 3-aminopropyldiethoxymethylsilane
  • eheODPA ethyl oxydiphthalate half ester
  • the adhesive prepared in (1) above was applied by spin coating onto a plasma-treated epoxy resin substrate and dried at 150°C for 1 minute. It was then heated at 200°C for 1 hour in a nitrogen atmosphere to form an adhesive layer containing imide-crosslinked siloxane (structure below). The adhesive layer had a tack-free surface. The concentration of the adhesive was adjusted so that the thickness of the adhesive layer formed would be the value shown in Table 1.
  • ⁇ Comparative Example 1> Preparation of adhesive 180 parts by mass of epoxy resin (DIC Corporation, EPICLON 840) as a thermosetting compound, 300 parts by mass of phenol novolac resin (Meiwa Kasei Co., Ltd., HF-4M) as a heat curing agent, 200 parts by mass of silica particles (Nippon Shokubai Co., Ltd., S-100) as an inorganic filler, 280 parts by mass of thermoplastic resin particles (Aica Kogyo Co., Ltd., fine particle polymer F351), 20 parts by mass of imidazole catalyst (Shikoku Kasei Co., Ltd., 2E4MZ) as a curing accelerator, and 20 parts by mass of silane coupling agent (Shin-Etsu Chemical Co., Ltd., KBM-403) were thoroughly mixed using a three-roll mill to form a uniform liquid, and an adhesive of Comparative Example 1 was obtained.
  • epoxy resin DIC Corporation, EPICLON 840
  • the laminate of Example 1 in which the ratio (X/Y) of the die shear strength X (MPa) between the inorganic material layer and the organic material layer to the thickness Y ( ⁇ m) of the adhesive layer is 1 or more, exhibits sufficient bonding strength even though the adhesive layer is thinner, compared to the laminate of Comparative Example 1, in which the ratio (X/Y) of the die shear strength X (MPa) between the inorganic material layer and the organic material layer to the thickness Y ( ⁇ m) of the adhesive layer is less than 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

Ce stratifié comprend : une couche de matériau inorganique ; une couche de matériau organique ; et une couche adhésive qui est disposée entre la couche de matériau inorganique et la couche de matériau organique, et lie la couche de matériau inorganique et la couche de matériau organique. Le rapport (X/Y) de la résistance au cisaillement de puces X (MPa) entre la couche de matériau inorganique et la couche de matériau organique à l'épaisseur Y (µm) de la couche adhésive est supérieur ou égal à 1.
PCT/JP2024/025772 2023-07-21 2024-07-18 Stratifié et procédé de production de stratifié Pending WO2025023139A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000277571A (ja) * 1999-03-25 2000-10-06 Sumitomo Bakelite Co Ltd 半導体素子搭載用基板
JP2005023301A (ja) * 2003-04-30 2005-01-27 Mec Kk 接着層形成液、その液を用いた銅と樹脂の接着層の製造方法及びその積層体
WO2018199117A1 (fr) * 2017-04-28 2018-11-01 三井化学株式会社 Stratifié de substrat et procédé de fabrication de stratifié de substrat
WO2023002919A1 (fr) * 2021-07-20 2023-01-26 東洋紡株式会社 Stratifié
WO2023032923A1 (fr) * 2021-09-06 2023-03-09 三井化学株式会社 Composition pour former un film pour semi-conducteur, stratifié et stratifié de substrat

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000277571A (ja) * 1999-03-25 2000-10-06 Sumitomo Bakelite Co Ltd 半導体素子搭載用基板
JP2005023301A (ja) * 2003-04-30 2005-01-27 Mec Kk 接着層形成液、その液を用いた銅と樹脂の接着層の製造方法及びその積層体
WO2018199117A1 (fr) * 2017-04-28 2018-11-01 三井化学株式会社 Stratifié de substrat et procédé de fabrication de stratifié de substrat
WO2023002919A1 (fr) * 2021-07-20 2023-01-26 東洋紡株式会社 Stratifié
WO2023032923A1 (fr) * 2021-09-06 2023-03-09 三井化学株式会社 Composition pour former un film pour semi-conducteur, stratifié et stratifié de substrat

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