Classifications

• • 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
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/16—Cyclic ethers having four or more ring atoms
  • C08G65/18—Oxetanes
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides
• • 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
  • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/071—Connecting or disconnecting
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials

Definitions

• the present invention relates to a curable resin composition, an adhesive, a sealing material, a cured product, a semiconductor device, and an electronic device.
• Patent Document 1 describes that in a thermally cationic polymerizable composition that can be used in fields such as adhesives, components that are not sufficiently cured volatilize as outgassing during heat resistance tests and contaminate the surroundings.
• Patent Document 1 discloses a thermally cationic polymerizable composition in which the amount of thermally cationic initiator added in the composition is adjusted to reduce the amount of outgassing.
• adherends to be bonded are components of precision equipment such as camera modules or sensor modules
• adhesives that can be cured at low temperatures are desirable.
• resin compositions used in adhesives it is desirable for the resin compositions used in adhesives to have good storage stability and an excellent pot life.
• the component (A) is The curable resin composition according to any one of the above [1] to [4], comprising at least one selected from the group consisting of (A1) an epoxy resin having an epoxy group equivalent of 100 g/eq to 1000 g/eq and having a ring skeleton in the molecule, and (A2) an oxetane resin.
• (A1) an epoxy resin having an epoxy group equivalent of 100 g/eq to 1000 g/eq and having a ring skeleton in the molecule
• A2 an oxetane resin.
• the amount of the component (C) is 0.1 to 10 parts by mass when the total amount is 100 parts by mass.
• the present invention provides a curable resin composition that can be cured by heating at a low temperature of 100°C or less, preferably 80°C or less, and has an excellent pot life, an adhesive, a sealant, a cured product obtained by curing these, and a semiconductor device and an electronic device that include the cured product.
• the curable resin composition, adhesive, encapsulant, cured product obtained by curing these, and semiconductor device and electronic component containing the cured product according to the present disclosure will be described based on the embodiments.
• the embodiments shown below are examples for embodying the technical idea of the present invention, and the present invention is not limited to the following curable resin composition, adhesive, encapsulant, cured product, semiconductor device and electronic component.
• the term "resin" which usually refers to a polymer (especially a synthetic polymer), may be used for the components that make up the curable resin composition before curing, even though the components are not polymers.
• functional group equivalents such as epoxy group equivalent and oxetane group equivalent refer to the molecular weight of a compound per functional group
• functional group equivalent numbers such as epoxy group equivalent number and oxetane group equivalent number refer to the number of functional groups (equivalent number) per compound mass (charge amount).
• Epoxy group equivalent or oxetane group equivalent can be measured in accordance with JIS K7236:2001 (corresponding to ISO3001:1999).
• the epoxy group equivalent of the epoxy resin of component (A1) may be 800 g/eq or less, 600 g/eq or less, 500 g/eq or less, 400 g/eq or less, 120 g/eq or more, 130 g/eq or more, 150 g/eq or more, 180 g/eq or more, preferably 200 g/eq or more, and may be 250 g/eq or more.
• oxetane resins include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (OXT-101 manufactured by Toagosei Co., Ltd., etc.), 2-ethylhexyloxetane (OXT-212 manufactured by Toagosei Co., Ltd., etc.), xylylene bisoxetane (OXT-121 manufactured by Toagosei Co., Ltd., etc.), 3-ethyl-3 ⁇ [(3-ethyloxetan-3-yl)methoxy]methyl ⁇ oxetane (OXT-221 manufactured by Toagosei Co., Ltd., etc.), oxetanyl silsesquioxetane (OXT-191 manufactured by Toagosei Co., Ltd., etc.), phenol novolac oxetane (PHOX manufactured by Toagosei Co.
• the oxetane group equivalent of the oxetane resin is preferably 100 g/eq to 500 g/eq, and may be 110 g/eq to 300 g/eq.
• component (A) contains oxetane resin of component (A2) if the oxetane group equivalent of component (A2) is 100 g/eq to 500 g/eq, a cured product can be obtained by heating at a low temperature of, for example, 100°C or less, preferably 80°C or less.
• the oxetane group equivalent of the oxetane resin may be 250 g/eq or less.
• the iodonium salt contained in the acid generator of component (B) is preferably an iodonium compound represented by the following formula (2).
• Ar 1 and Ar 2 each independently represent a substituted or unsubstituted aryl group, and Z ⁇ represents an anion.
• the aryl group represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group.
• Ar 1 and Ar 2 are each preferably independently a phenyl group or a naphthyl group.
• the aryl group may be unsubstituted or substituted with one or more optional substituents.
• Organic peroxides other than the peroxydicarbonate type, for example, alkyl peroxy ester type, are prone to generate oxygen radicals.
• the generated oxygen radical is prone to generate a stable alkyl radical due to self-cleavage or decarboxylation reaction.
• the stable alkyl radical has low reactivity and is considered to be more likely to cause oxygen inhibition reaction than electron transfer to an acid generator containing an iodonium salt. Due to this influence, the iodonium salt is less likely to be decomposed. This makes it difficult for acids (cations: H + ) to be generated, which is believed to make the polymerization reaction more likely to be inhibited.
• R 1 and R 2 are each independently an alkyl group having at least 10 carbon atoms, more preferably an alkyl group having at least 11 carbon atoms.
• R 1 and R 2 are each independently an alkyl group having at least 10 carbon atoms, preferably an alkyl group having at least 11 carbon atoms
• the organic peroxide is difficult to decompose even at room temperature, for example, 20 ° C to 40 ° C, which is lower than the heating temperature, or at a low temperature below 20 ° C
• the storage stability of the curable resin composition is good, and the pot life is excellent.
• R 1 and R 2 may each independently be an alkyl group having 30 or less carbon atoms.
• the curable resin composition may contain at least one selected from the group consisting of (D) a photosensitizer, (E) a photoradical generator, and (F) a filler (hereinafter also referred to as “component (D)", “component (E)", and “component (F)", respectively).
• the curable resin composition may further contain at least one selected from the group consisting of (G) a coupling agent, (H) an ion trapping agent, and (I) a coloring agent such as a pigment (hereinafter also referred to as “component (G)", “component (H)", and “component (I)", respectively).
• At least one component selected from the group consisting of (G) a coupling agent, (H) an ion trapping agent, and (I) a coloring agent may be included as an optional component.
• the filler is a component for improving the fluidity, injectability, coatability, adhesion, etc. of the curable resin composition.
• a cured product with good adhesion to the adherend can be obtained even when cured by heating at a low temperature of 100 ° C or less, preferably 80 ° C or less.
• the filler include known inorganic fillers or organic fillers. One type of filler may be used, or two or more types may be used in combination.
• silane coupling agents examples include vinyl groups, epoxy groups, styryl groups, methacryl groups, acrylic groups, amino groups, isocyanurate groups, ureido groups, mercapto groups, sulfide groups, and isocyanate groups.
• the colorant can be used for the purpose of coloring the curable resin composition.
• the colorant include pigments, dyes, and pigments. Known colorants such as red, blue, green, yellow, black, and white can be used as the colorant.
• the pigment include black colorants such as carbon black, graphite, iron oxide, titanium black, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, aniline, molybdenum sulfide, and bismuth sulfide.
• black colorants such as carbon black, graphite, iron oxide, titanium black, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, aniline, molybdenum sulfide, and bismuth sulfide.
• commercially available pigments include titanium black 13M, 13M-C, and 13M-T manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.
• the amount of component (B) in the curable resin is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1.0 to 5 parts by mass, per 100 parts by mass of component (A).
• C-2 Perkadox 26 (manufactured by Nouryon) dimyristyl peroxydicarbonate, having a molecular weight of 514.8, in which R 1 and R 2 in the formula (1) are each a tetradecane group having 14 carbon atoms (—(CH 2 ) 13 —CH 3 ).
• C-3) Perloyl TCP (manufactured by NOF Corporation), bis(4-tert-butylcyclohexyl) peroxydicarbonate, having a one-hour half-life temperature of 58° C., a molecular weight of 398.5, and being a solid (powder) at room temperature (about 20° C. to 25° C.).
• Component (C') Peroxydicarbonate-type organic peroxide represented by the formula (1), in which R 1 and R 2 are each an alkyl group having less than 10 carbon atoms.
• C'-1) Luperox 225 (manufactured by Arkema Yoshitomi Co., Ltd.), di(secondary butyl) peroxydicarbonate, having a one-hour half-life temperature of 69°C, a molecular weight of 234.2, and being liquid at room temperature (about 20°C to 25°C).
• E Photoradical generator (E-1): Omnirad (registered trademark) 184 (manufactured by IGM Resins), 1-hydroxycyclohexyl phenyl ketone
• F Filler
• F-1 SE5200SEE (manufactured by Admatechs Co., Ltd.), high purity synthetic spherical silica, average particle size at 50% cumulative in the volume-based particle size distribution determined by the laser diffraction scattering method is 1.5 ⁇ m (catalog value).
• F-2) Cabosil (registered trademark) TS720 (manufactured by Cabot Japan Co., Ltd.), hydrophobic silica, average particle size at cumulative 50% in the number-based particle size distribution determined by the laser diffraction scattering method is 0.012 ⁇ m (catalog value).
• H Ion trapping material (H-1): IXEPLAS-A1 (manufactured by Toagosei Co., Ltd.), a zirconium-magnesium based ion trapping material, with an average particle size of 0.5 ⁇ m (catalog value).
• Examples 1 to 11, Comparative Example 1 Curable resin compositions were prepared by mixing the respective amounts of each component using a three-roll mill according to the blending ratios shown in Tables 1 and 2.
• Tables 1 and 2 the numbers indicating the blending ratios of each component contained in the curable resin composition represent mass % relative to 100 mass % of the total amount of the curable resin composition, unless otherwise specified.
• each component is mainly described by the symbol of the product name or trade name.
• the symbol "-" indicates that the corresponding component is not included in the curable resin composition.
• a Teflon (registered trademark) sheet was attached to the surface of a 3 mm thick glass plate, and spacers (heat-resistant tape laminated thereon) were placed in two places so that the film thickness when cured would be 400 ⁇ 150 ⁇ m.
• the curable resin composition was applied between the spacers, sandwiched between another glass plate with a Teflon (registered trademark) sheet attached to the surface so as not to trap air bubbles, and heated and cured at 80°C for 60 minutes with a blower dryer.
• the cured products of the curable resin compositions of Examples 1 to 11 had good curability and could be cured by heating at low temperatures, for example, below 100°C, preferably below 80°C, and had an excellent pot life with a viscosity increase ratio of 1.0 up to 10 hours. After 24 hours, Example 10 had cured with a viscosity increase ratio of over 2.0. Furthermore, the Tg obtained in each of the Examples was within the range of 0°C to 200°C. Furthermore, the Tg obtained in each of the Examples, except for Examples 4, 7, and 8, was within the range of 0°C to 150°C.
• Comparative Example 1 can be cured at 80°C, but thickening was observed after 10 hours, impairing the pot life effect.
• the curable resin composition according to the present invention can be suitably used as an adhesive or sealant for fixing, joining or protecting components that constitute an electronic device.
• the resin composition according to the embodiment of the present invention, the adhesive or sealant containing the resin composition, the cured product obtained by curing the die attachment agent, and the electronic device containing the cured product can be used, for example, in mobile phones, smartphones, notebook computers, tablet terminals, camera modules, sensor modules, etc.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Epoxy Resins (AREA)
• Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
• Sealing Material Composition (AREA)
• Macromonomer-Based Addition Polymer (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=91717083

Family Applications (1)

Country Status (6)

Citations (3)

Family Cites Families (3)

• 2023
  • 2023-07-27 WO PCT/JP2023/027623 patent/WO2024142448A1/ja not_active Ceased
  • 2023-07-27 CN CN202380081676.5A patent/CN120265678A/zh active Pending
  • 2023-07-27 EP EP23911232.9A patent/EP4644458A4/en active Pending
  • 2023-07-27 JP JP2024567194A patent/JPWO2024142448A1/ja active Pending
  • 2023-07-27 KR KR1020257011209A patent/KR20250127046A/ko active Pending
  • 2023-08-08 TW TW112129675A patent/TW202426551A/zh unknown

Patent Citations (3)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events