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WO2025205910A1 - Composition polymérisable, adhésif, matériau d'étanchéité, produit durci, dispositif à semi-conducteur, et composant électronique - Google Patents

Composition polymérisable, adhésif, matériau d'étanchéité, produit durci, dispositif à semi-conducteur, et composant électronique

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Publication number
WO2025205910A1
WO2025205910A1 PCT/JP2025/011969 JP2025011969W WO2025205910A1 WO 2025205910 A1 WO2025205910 A1 WO 2025205910A1 JP 2025011969 W JP2025011969 W JP 2025011969W WO 2025205910 A1 WO2025205910 A1 WO 2025205910A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymerizable composition
ppm
group
component
polydimethylsiloxane
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.)
Pending
Application number
PCT/JP2025/011969
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English (en)
Japanese (ja)
Inventor
幸紀 光主
文子 佐藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Namics Corp
Original Assignee
Namics Corp
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Filing date
Publication date
Application filed by Namics Corp filed Critical Namics Corp
Publication of WO2025205910A1 publication Critical patent/WO2025205910A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • 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 polymerizable composition, an adhesive or sealant containing the same, a cured product thereof, and a semiconductor device and electronic component containing the cured product.
  • curable resin compositions are often used to assemble and mount components used in semiconductor devices, such as semiconductor chips, in order to maintain reliability.
  • Patent Documents 1 and 2 disclose photocurable and low-temperature curable cationically curable resin compositions.
  • Bleeding is an issue in the assembly process of semiconductor modules. Bleeding is a phenomenon in which unreacted components seep out from the adhesive coating or cured product over time when an adhesive containing a curable resin composition is used to fix or bond components; the exuded components themselves are sometimes called "bleed.” If the bleed comes into contact with the metal wiring on the board, it can cause electrical defects, reducing the reliability of the semiconductor module. In particular, inner bleed, which occurs from uncured parts of the adhesive, tends to progress when the adhesive coating is left at room temperature and/or when it is thermally cured, and the bleed length tends to increase.
  • the present invention therefore aims to provide at least a photocurable or thermosetting polymerizable composition and adhesive that can suppress the bleeding phenomenon.
  • aspects of the present invention include the following polymerizable compositions, adhesives or sealants, cured products, and semiconductor devices or electronic components.
  • A a cationically polymerizable compound, (B) an acid generator, and (C) a modified polydimethylsiloxane that satisfies at least one of the following characteristics (a), (b), and (c): (a) an organic substituent containing a COOH group is bonded to polydimethylsiloxane directly or via a linker; (b) an organic substituent containing an OH group and optionally an ether group is bonded to the polydimethylsiloxane directly or via a linker, and when the organic substituent contains an ether group, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the organic substituent is less than 0.3; (c) In a 1 H NMR spectrum measured in deuterated chloroform
  • a polymerizable composition comprising: [2] The polymerizable composition according to the above [1], wherein the (A) cationically polymerizable compound includes a compound having an epoxy group and a compound having an oxetanyl group.
  • At least a photocurable or thermosetting polymerizable composition capable of suppressing bleeding, an adhesive or sealant containing the same, a cured product obtained by curing the composition or the like, and a semiconductor device or electronic component containing the cured product.
  • the polymerizable composition comprises: (A) a cationically polymerizable compound, (B) an acid generator, and (C) a modified polydimethylsiloxane that satisfies at least one of the following characteristics (a), (b), and (c): (a) an organic substituent containing a COOH group is bonded to polydimethylsiloxane directly or via a linker; (b) an organic substituent containing an OH group and optionally an ether group is bonded to the polydimethylsiloxane directly or via a linker, and when the organic substituent contains an ether group, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the organic substituent is less than 0.3; (c) In 1 H NMR measured in deuterated chloroform, it has signals in the ranges of 0.3 to ⁇ 0.3 ppm and 4.4 to 3.2 ppm
  • the polymerizable composition of this embodiment contains (A) a cationic polymerizable compound (hereinafter also referred to as "component (A)").
  • component (A) a cationic polymerizable compound
  • examples of the (A) cationic polymerizable compound include, but are not limited to, compounds having an epoxy group, compounds having an oxetanyl group, compounds having a vinyl ether group, compounds having other cationic polymerizable groups, and compounds having any combination of these cationic polymerizable groups.
  • the cationic polymerizable compound preferably contains a compound having an epoxy group and a compound having an oxetanyl group.
  • a compound having an epoxy group refers to a compound having at least one epoxy group in its molecule, and is also referred to as an epoxy compound.
  • examples include monofunctional epoxy compounds having one epoxy group and polyfunctional epoxy compounds having two or more epoxy groups.
  • the epoxy compound preferably contains at least a polyfunctional epoxy compound, and may contain a combination of a polyfunctional epoxy compound and a monofunctional epoxy compound.
  • Epoxy compounds can be broadly classified according to the type of skeleton into epoxy compounds having an aromatic ring skeleton, aliphatic epoxy compounds, and alicyclic epoxy compounds.
  • a compound having an oxetanyl group is a compound having at least one oxetane ring (e.g., a 3-oxetanyl group) in the molecule, and is also referred to as an oxetane compound.
  • the oxetane compound preferably has 1 to 6 oxetanyl groups in the molecule, and more preferably has 1 to 2 oxetanyl groups in the molecule.
  • a compound having a vinyl ether group is a compound having at least one vinyl ether group in the molecule.
  • cationic polymerizable compounds include glycidyl ethers of tetra(hydrophenyl)alkanes, glycidyl ethers of tetrahydroxybenzophenone, epoxidized polyvinylphenol, p-tert-butylphenyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, n-butyl glycidyl ether, 2-ethyl
  • EPICLON registered trademark
  • EXA-850CRP EXA-8067 manufactured by DIC Corporation
  • AER9000 manufactured by Asahi Kasei Corporation
  • EP-4000S, EP-4003S, and EP-4010S manufactured by ADEKA Corporation
  • EPICLON registered trademark 830-S and EXA-830 manufactured by DIC Corporation.
  • EXA-835LV LVP, EXA-835LV; EPICLON (registered trademark) HP-4032D, HP-720H manufactured by DIC Corporation; EPICLON (registered trademark) N-740, N-770 manufactured by DIC Corporation; EPICLON (registered trademark) N-660, N-670, N-655-EXP-S manufactured by DIC Corporation; ADEKA GLYCILOR (registered trademark) ED-5 manufactured by ADEKA Corporation 09E, ED-509S; OPP-G manufactured by Sanko Co., Ltd.; Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.; AER-9000 manufactured by Asahi Kasei Corporation; jER YX7400N manufactured by Mitsubishi Chemical Corporation; jER YX8000 manufactured by Mitsubishi Chemical Corporation; CELLOXIDE (registered trademark) 2021P manufactured by Daicel Corporation; CELLOXIDE (registered trademark) 8010 manufactured by Daicel Corporation; EHPE3150 manufactured
  • Examples of phosphonium cations include tetraarylphosphoniums such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, and tetrakis(4-methoxyphenyl)phosphonium; triarylphosphoniums such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium; and tetraalkylphosphoniums such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, and tributylphenacylphospho
  • modified polydimethylsiloxanes in which the organic substituents contain OH groups but not ether groups include those commercially available under the names carbinol-modified polydimethylsiloxanes or carbinol-modified silicones.
  • examples of commercially available products of this type include, but are not limited to, products sold by Shin-Etsu Chemical Co., Ltd. under the names: X-22-4039, X-22-4015, KF-6000, KF-6001, KF-6002, KF-6003, X-22-170BX, and X-22-170DX.
  • Reactive silicones whose hydroxyl values are disclosed in catalogs or the like can also be assumed to be modified polydimethylsiloxanes in which the organic substituents contain OH groups and, optionally, ether groups.
  • the hydroxyl value of the modified polydimethylsiloxane may be measured to confirm the presence of OH groups in the modified polydimethylsiloxane.
  • the modified polydimethylsiloxane has a hydroxyl value of 1 mg KOH/g or more.
  • the hydroxyl value can be measured, for example, by a method conforming to JIS K 0070 or by FT-NIR (near-infrared spectroscopy) conforming to JIS K 1557-6.
  • the organic substituent of the modified polydimethylsiloxane contains an OH group can also be confirmed by measuring the modified polydimethylsiloxane by Fourier transform infrared spectroscopy (FT-IR) and observing the presence or absence of an IR spectrum at about 1360 to 1340 cm ⁇ 1 due to the deformation vibration of alcoholic OH.
  • FT-IR Fourier transform infrared spectroscopy
  • the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the organic substituent can be determined from the structure of the modified polydimethylsiloxane disclosed in a catalog or the like. For example, if it is clear that the modified polydimethylsiloxane contains an OH group and an ether group but does not contain a polypropylene glycol repeating unit, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units will be 0, satisfying feature (b).
  • a specific structure is not disclosed, as described below with respect to feature (c), it can be calculated based on the 1H NMR spectrum of the modified polydimethylsiloxane measured in deuterated chloroform.
  • the value calculated using the following formula (1) based on the 1H NMR spectrum of the modified polydimethylsiloxane measured in deuterated chloroform can be considered to be the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units.
  • modified polydimethylsiloxanes do not disclose the detailed structure of the modifying group. Furthermore, some commercially available additives, such as surfactants, surface conditioners, leveling agents, antifoaming agents, wetting agents, and dispersants, are classified as modified polydimethylsiloxanes, even though they are not explicitly referred to as modified polydimethylsiloxanes or their structures are not disclosed.
  • the modified polydimethylsiloxanes of this embodiment are those that, in their 1H NMR spectrum measured in deuterated chloroform, have signals in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, have or do not have a signal in the range of 1.25 to 0.95 ppm, and have a signal in the range of 13 to 0 ppm that disappears upon addition of D2O , and for which the value calculated from the following formula (1) is less than 0.3 (the above-mentioned feature (c)).
  • first signal is a signal derived from a hydrogen atom (-Si(C H 3 ) 2 -) connected to a carbon atom adjacent to a Si atom.
  • the signal observed in the range of 4.4 to 3.2 ppm is a signal derived from a hydrogen atom connected to a carbon adjacent to an OH group or an oxygen atom of an ether (e.g., -O-C H 2 C H 2 -O-, -O-C H 2 C H (CH 3 )-O-, -C H 2 -OH).
  • the signal observed in the range of 1.25 to 0.95 ppm (hereinafter also referred to as "third signal”) is a signal derived from a hydrogen atom (-CH 2 CH(C H 3 )-O-) of a methyl group in a polypropylene glycol chain as a polyether modifying group.
  • the signal observed in the range of 13 to 0 ppm and disappearing upon addition of D 2 O (hereinafter also referred to as "fourth signal”) can be presumed to be a signal derived from the hydrogen atom of an OH group or an NH group.
  • Signals that disappear upon addition of D 2 O are usually observed in the range of 13 to 0 ppm. Among these, signals observed in the range of 3 to 2 ppm and that disappear upon addition of D 2 O can be presumed to be signals derived from hydrogen atoms of OH groups.
  • Whether the signal that disappears upon addition of D 2 O is a signal derived from a hydrogen atom of an OH group or an NH group can also be estimated by, for example, the following method.
  • Fourier transform infrared spectroscopy (FT-IR) measurement In addition to the above 1 H NMR measurement, the presence or absence of an IR spectrum at approximately 1360 to 1340 cm ⁇ 1 derived from the deformation vibration of alcoholic OH groups can be observed by Fourier transform infrared spectroscopy (FT-IR) measurement of the modified polydimethylsiloxane, and it can be assumed that the signal that disappears upon addition of D 2 O is a signal derived from the hydrogen atom of the OH group.
  • FT-IR Fourier transform infrared spectroscopy
  • measurement of the acidity of modified polydimethylsiloxane allows estimation of whether the signal that disappears upon addition of D2O is derived from the hydrogen atom of an OH group or an NH group.
  • 100 mg of a measurement sample of modified polydimethylsiloxane is dissolved in 200 uL of isopropyl alcohol, 200 uL of pure water is added, and the solution is shaken well, and the pH of the liquid is measured. If the pH is 3 to 7, the signal that disappears upon addition of D2O can be estimated to be derived from the hydrogen atom of an OH group. If the pH is 8 or higher, which is basic, the signal that disappears upon addition of D2O can be estimated to be derived from the hydrogen atom of an NH group.
  • the value calculated from formula (1) is less than 0.3, which roughly corresponds to the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the modified polydimethylsiloxane, as shown below.
  • the signal observed in the range of 0.3 to ⁇ 0.3 ppm (first signal) is attributed to the underlined hydrogen atom of the dimethylsiloxane repeating unit —O—Si(C H 3 ) 2 —.
  • the number of polypropylene glycol repeating units per dimethylsiloxane repeating unit can be calculated using the following formula (2): Equation (2): (integral value of the third signal)/3
  • the number of polyethylene glycol repeating units per dimethylsiloxane repeating unit can be calculated using the following formula (3): Equation (3): [(integral value of the second signal) - (integral value of the third signal)]/4
  • the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the modified polydimethylsiloxane can be calculated using formula (1).
  • modified polydimethylsiloxanes that satisfy characteristic (c) include products sold by Shin-Etsu Chemical Co., Ltd. under the product names KF-945 and X-22-4039, and products sold by Evonik Japan Co., Ltd. under the product names TEGO TWIN 4000 and TEGO TWIN 4100.
  • a modified polydimethylsiloxane in the polymerizable composition is thought to be, but is not limited to, the following: When a polymerizable composition containing a modified polydimethylsiloxane is applied to a substrate or the like, a portion of the modified polydimethylsiloxane migrates to the coating surface of the polymerizable composition due to the surface migration of the modified polydimethylsiloxane.
  • a small amount of the modified polydimethylsiloxane that has migrated to the coating surface migrates to a substrate that is not in contact with the polymerizable composition, before other unreacted components seep out of the coating of the polymerizable composition, and the modifying group of the modified polydimethylsiloxane adsorbs to the surface of the substrate. This is thought to form an adsorption film of modified polydimethylsiloxane on the substrate surface, resulting in water- and oil-repellent properties attributable to the polydimethylsiloxane portion and suppressing bleeding.
  • the organic substituent as the modifying group containing a COOH group or an OH group can provide a higher adsorption effect of the modified polydimethylsiloxane to the substrate. Furthermore, when the organic substituent as the modifying group contains an OH group, it is thought that the adsorption effect of the OH group to the substrate is not suppressed if the amount of polypropylene glycol groups contained in the organic substituent is below a certain amount.
  • a modified polydimethylsiloxane satisfying at least one of features (b) and (c) is one in which, in a 1 H NMR spectrum measured in deuterated chloroform, the integral of each signal (second signal) observed in the range of 4.4 to 3.2 ppm is preferably 0.3 to 19, and even more preferably 0.3 to 17, when the integral of the first signal corresponding to one dimethylsiloxane repeating unit is set to 6 and the integral of each signal is calculated.
  • 1H NMR measurements can be performed under normal conditions. For example, 100 mg of a measurement sample is dissolved in 500 ⁇ l of deuterated chloroform and placed in a 5 mm diameter 1H NMR sample tube, and measurements are performed under the following conditions. After the measurement, 50 ⁇ l of heavy water ( D2O ) is added to the sample tube, and measurements are performed again under the same conditions. The signal that disappears after the addition of heavy water is found to be a signal derived from active hydrogen bonded to a hydroxyl group or an amino group. Measurement frequency: 40-600 MHz Solvent: deuterated chloroform Measurement nuclide: 1 H Accumulation count: 4 to 80 times Measurement temperature: 15 to 50°C
  • the content of (C) modified polydimethylsiloxane is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, relative to the total mass of the polymerizable composition. It is also preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. In some embodiments, the content of (C) modified polydimethylsiloxane is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, and even more preferably 0.2 to 3% by mass, relative to the total mass of the polymerizable composition.
  • the polymerizable composition of this embodiment may contain optional components other than the above components (A) to (C), such as those described below, as needed.
  • the polymerizable composition of this embodiment may contain (D) filler (hereinafter also referred to as "component (D)”) within a range that does not impair the effects of the present invention.
  • component (D) filler
  • the linear expansion coefficient of the cured product obtained by curing the polymerizable composition can be reduced, and thermal cycle resistance can be improved.
  • the filler has a low elastic modulus, it can alleviate stress generated in the cured product, and long-term reliability can be improved.
  • (D) fillers are broadly classified into inorganic fillers and organic fillers.
  • the inorganic filler is not particularly limited as long as it is made of granular material and has the effect of lowering the linear expansion coefficient when added.
  • examples of inorganic materials that can be used include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. Any one of these inorganic fillers may be used alone, or two or more may be used in combination.
  • Silica filler is preferred as the inorganic filler, as it allows for a high loading.
  • Amorphous silica is preferred as the silica.
  • the surface of the inorganic filler be treated with a coupling agent such as a silane coupling agent. This allows the viscosity of the polymerizable composition to be within an appropriate range.
  • organic fillers examples include polytetrafluoroethylene (PTFE) filler, silicone filler, acrylic filler, styrene filler, etc.
  • PTFE polytetrafluoroethylene
  • silicone filler acrylic filler
  • styrene filler etc.
  • the organic filler may be surface-treated.
  • the glass transition point of the organic filler is preferably above 40°C.
  • the shape of the filler is not particularly limited and may be spherical, flaky, needle-like, irregular, etc.
  • the lower limit of the average particle size of the filler is not particularly limited, but from the viewpoint of the viscosity of the polymerizable composition, it is preferably 0.005 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
  • the average particle size of the filler is preferably 0.01 ⁇ m to 5.0 ⁇ m, more preferably 0.1 ⁇ m to 3.0 ⁇ m.
  • Fillers with different average particle sizes may be used in combination, for example, a filler with an average particle size of 0.005 ⁇ m or more and less than 0.1 ⁇ m may be used in combination with a filler with an average particle size of 0.1 ⁇ m to 5.0 ⁇ m.
  • the content of the filler (D) in the polymerizable composition of this embodiment is preferably 0.5 to 80% by mass, more preferably 1 to 70% by mass, and even more preferably 3 to 60% by mass, relative to the total mass of the polymerizable composition.
  • the polymerizable composition of this embodiment may contain a photosensitizer, if desired, within the range that does not impair the effects of the present invention.
  • the photosensitizer absorbs light energy and transmits it to the acid generator, thereby increasing the sensitivity of the acid generator to light.
  • photosensitizers include, but are not limited to, thioxanthone derivatives, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes.
  • the content of the photosensitizer is preferably 0.1 to 1000% by mass, and more preferably 1 to 500% by mass, relative to the total mass of the acid generator.
  • the polymerizable composition of this embodiment may contain a photoradical initiator, if desired, within the scope of not impairing the effects of the present invention.
  • the photoradical initiator absorbs light to generate radicals as active species, which can reductively decompose the acid generator and promote the generation of acid from the acid generator.
  • Examples of photoradical initiators include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, and compounds having a photosensitive moiety and a peroxide structure.
  • the polymerizable composition of this embodiment may contain a thermal radical initiator, if desired, within a range that does not impair the effects of the present invention.
  • the thermal radical initiator generates an active radical by cleavage at a predetermined temperature, which can reductively decompose the acid generator and promote the generation of an acid from the acid generator.
  • thermal radical initiators include organic peroxides, inorganic peroxides, and azo compounds.
  • thermal radical initiators Any one of the thermal radical initiators may be used, or two or more may be used in combination.
  • the content of the thermal radical initiator is preferably 1 to 200% by mass, and more preferably 10 to 150% by mass, relative to the total mass of the acid generator.
  • the polymerizable composition of this embodiment may contain a radically polymerizable compound to the extent that the effects of the present invention are not impaired.
  • active species radicals may also be generated, which causes radical polymerization of the radically polymerizable compound to proceed, imparting curability and adhesiveness to the polymerizable composition.
  • radically polymerizable compounds include, but are not limited to, compounds having an unsaturated double bond such as (meth)acrylate compounds, bismaleimide compounds, styrene compounds, and polybutadiene compounds, as well as mixtures of compounds having an unsaturated double bond and thiol compounds (mixtures capable of ene-thiol reaction). Any one type of radically polymerizable compound may be used, or two or more types may be used in combination.
  • the polymerizable composition may further contain other additives, such as a stabilizer, a coupling agent, carbon black, titanium black, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a thixotropic agent, a viscosity modifier, or a flame retardant, as needed, within the scope of the present embodiment.
  • additives such as a stabilizer, a coupling agent, carbon black, titanium black, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a thixotropic agent, a viscosity modifier, or a flame retardant, as needed, within the scope of the present embodiment.
  • the polymerizable composition of this embodiment preferably contains substantially no solvent, from the viewpoint of suppressing VOC emissions and shrinkage of the cured product.
  • the polymerizable composition contains substantially no solvent means that the content of solvent in the polymerizable composition is 1 mass % or less relative to the total mass of the polymerizable composition.
  • the viscosity of the polymerizable composition of this embodiment is preferably 0.5 to 100 Pa ⁇ s.
  • the viscosity can be adjusted appropriately depending on the intended use and application location of the polymerizable composition.
  • the viscosity of the composition is expressed as a value measured in accordance with Japanese Industrial Standard JIS K6833, unless otherwise specified. Specifically, it can be determined by measuring using an E-type viscometer at a rotation speed of 10 rpm. There are no particular restrictions on the equipment, rotor, or measurement range used.
  • each component may contain one or more components selected from the components (A) to (C) and other optional components as needed.
  • Components (A) to (C) may be contained in a single component, or a component may contain only the components (A) to (C) and/or other optional components as needed.
  • the separation may be as follows: liquid A: component (A), liquid B: component (B) and component (C), liquid A: component (A) and component (C), liquid B: component (B), liquid A: component (A) and component (C), liquid B: component (B) and component (C), liquid A: component (A), liquid B: component (B), component (C), and component (D), liquid A: component (A) and component (C), liquid B: component (B) and component (D), or liquid A: component (A) and component (D), liquid B: component (B) and component (C).
  • liquid A When components (A) to (C) are contained in liquid A and other components are contained in liquid B, only liquid A or a combination of liquid A and liquid B can be considered as the polymerizable composition of this embodiment.
  • components (A) to (C) when components (A) to (C) are contained in separate liquids, the liquids can be considered together to be the polymerizable composition of this embodiment.
  • An example of a case in which components (A) to (C) are contained in separate liquids is a polymerizable composition in which components (A) to (C) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of components (A) to (C).
  • the polymerizable composition of this embodiment can be used, for example, as an adhesive, sealant, or damming agent for fixing, adhering, or protecting components, as well as a raw material for these, and is suitable as a one-component type.
  • the damming agent is formed, for example, around the periphery of the substrate before sealing multiple semiconductor chips or the like on the substrate with a low-viscosity filler or the like. The formation of a dam by this damming agent can prevent the subsequent outflow of the low-viscosity filler that seals the multiple semiconductor chips.
  • adhesives containing the polymerizable composition of this embodiment enable good bonding to engineering plastics, ceramics, and metals.
  • the method for applying the polymerizable composition is not particularly limited, and for example, it can be applied to the desired portion of a component such as a substrate by a known printing method, dispensing method, or coating method.
  • Printing methods include, but are not limited to, inkjet printing, screen printing, lithographic printing, carton printing, metal printing, offset printing, gravure printing, and flexographic printing.
  • Dispensing methods include, but are not limited to, methods using a jet dispenser or air dispenser.
  • Coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, and spin coater coating.
  • the method for applying the polymerizable composition is preferably a method using an air dispenser.
  • the adhesive or sealant of this embodiment can be a one-component adhesive or sealant contained in a single container, or a two-component (or multi-component) adhesive or sealant separated into two or more containers.
  • a two-component (or multi-component) adhesive or sealant is used, the components (A) to (C) and other optional components as needed can be selected in the same way as for a one-component adhesive or sealant.
  • the components (A) to (C) and other optional components as needed can be separated into two or multiple components in any manner without particular restrictions.
  • each component may contain one or more components selected from the components (A) to (C) and other optional components as needed.
  • Components (A) to (C) may be contained in a single component, or a component may be a component consisting solely of the components (A) to (C) and/or other optional components as needed.
  • the division may be liquid A: component (A), liquid B: component (B) and component (C), or liquid A: component (A) and component (C), liquid B: component (B), or liquid A: component (A) and component (C), liquid B: component (B) and component (C), or liquid A: component (A), liquid B: component (B), component (C), and component (D), or liquid A: component (A) and component (C), liquid B: component (B) and component (D), or liquid A: component (A) and component (D), or liquid B: component (B) and component (C).
  • the cured product according to another embodiment of the present invention is a cured product obtained by curing the polymerizable composition according to the above embodiment or the adhesive or sealant according to the above embodiment. Bleeding is suppressed around an adherend to which the cured product is adhered.
  • a semiconductor device or electronic component according to one embodiment of the present invention includes the cured product according to the above-described embodiment.
  • semiconductor device refers to any device that can function by utilizing semiconductor properties, including electronic components, semiconductor circuits, modules incorporating these, and electronic devices. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, optical sensor modules, other semiconductor modules, and integrated circuits.
  • optical sensors include, but are not limited to, photodiodes, photo ICs, photomultiplier tubes (PMTs), phototubes, image sensors, spectroscopes/spectroscopic sensors, infrared sensors, ultraviolet/flame sensors, X-ray sensors, radiation sensors, electron/ion sensors, and distance/position sensors.
  • D Filler (Component (D))
  • D-1 Surface-treated silica filler (product name: SE5200SEE, average particle size 2 ⁇ m, manufactured by Admatechs Co., Ltd.)
  • D-2) Silica filler (product name: CAB-O-SIL (registered trademark) TS-720, polydimethylsiloxane surface-treated fumed silica, manufactured by Cabot Corporation)
  • E-1 Dicetyl peroxydicarbonate (product name: Perkadox 24L, manufactured by Kayaku Nouryon Co., Ltd., thermal radical initiator)
  • E-2) 2,4-diethylthioxanthone (DETX) (photosensitizer)
  • the polymerizable compositions of Examples 1 to 19 containing (C) a modified polydimethylsiloxane that satisfies at least one of characteristics (a), (b), and (c) showed significantly reduced bleeding under both Condition 1 and Condition 2, compared to the polymerizable compositions of Comparative Examples 1 and 7 to 11 that did not contain the (C) modified polydimethylsiloxane, and the polymerizable compositions of Comparative Examples 2 to 6 that contained (C') a modified polydimethylsiloxane other than component (C).
  • the present invention relates to a polymerizable composition that is at least photocurable or thermosetting and can suppress bleeding, and is particularly useful as an adhesive or sealant used to fix, bond, or protect components in miniaturized or highly integrated semiconductor modules.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'objet de la présente invention est de mettre à disposition au moins une composition polymérisable photodurcissable ou thermodurcissable et un adhésif capable de mettre fin à un phénomène de saignement.　L'invention concerne une composition polymérisable et un adhésif qui contiennent (A) un composé polymérisable par voie cationique, (B) un générateur d'acide, et (C) un polydiméthylsiloxane modifié qui satisfait au moins l'une des caractéristiques (a), (b) et (c) suivantes : (a) un substituant organique contenant un groupe COOH est lié au polydiméthylsiloxane directement ou via un lieur ; (b) un substituant organique contenant un groupe OH et optionnellement un groupe éther est lié au polydiméthylsiloxane directement ou via un lieur, et lorsque le substituant organique contient un groupe éther, le rapport du nombre de motifs répétés de polypropylène glycol au nombre de motifs répétés de polyéthylène glycol dans le substituant organique est inférieur à 0,3 ; et (c) le polydiméthylsiloxane modifié a un signal spécifique dans un spectre de RMN1H mesuré dans du chloroforme deutéré et satisfait une formule spécifique.
PCT/JP2025/011969 2024-03-29 2025-03-26 Composition polymérisable, adhésif, matériau d'étanchéité, produit durci, dispositif à semi-conducteur, et composant électronique Pending WO2025205910A1 (fr)

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PCT/JP2025/011969 Pending WO2025205910A1 (fr) 2024-03-29 2025-03-26 Composition polymérisable, adhésif, matériau d'étanchéité, produit durci, dispositif à semi-conducteur, et composant électronique

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