Classifications

• • 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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
• • 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
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
• • 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
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • 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 containing a maleimide resin, a cyanate ester resin, and a benzoxazine resin, a cured product, a curable resin composition for semiconductor encapsulation, and a semiconductor encapsulation material.
• ECUs which electronically control automobile engines, transmissions, and other components, are traditionally manufactured by encasing an electronic circuit board equipped with semiconductors and other components in a metal case, pouring in a resin such as silicone, and then curing it.
• silicone resins have poor dimensional stability, which places a large thermal stress load on the solder joints under the chip, making them prone to cracking during temperature cycle tests (Non-Patent Documents 1-3).
• thermal stress in semiconductor packages is easily generated by the difference in linear expansion coefficients between the substrate and the encapsulant, causing concave warping on the encapsulant side at room temperature and convex warping on the encapsulant side at high temperatures.
• R 1 represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent
• p is an integer from 0 to 3.
• n is the average number of repetitions, and 1 ⁇ n ⁇ 10.
• * represents a bond to the benzene ring in formula (1).
• Plural R 2 s , q, m, and r s each exist independently, R 2 represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent, q is an integer of 0 to 4, m is an integer of 1 to 50, and r is an integer of 0 to 4.
• each of the multiple Ys, Rs , and ts is independently present, Y represents a direct bond, —CH 2 —, —CH(CH 3 )—, or —C(CH 3 ) 2 —, Rs represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and t is an integer of 0 to 4.
• the content of the cyanate ester resin (B) is 5% by mass or more and 50% by mass or less in the total amount of the maleimide resin (A), the cyanate ester resin (B), and the benzoxazine resin (C).
• the curable resin composition of the present invention produces a cured product that has excellent heat resistance, thermal decomposition properties, dimensional stability, high elasticity at room temperature, low elasticity at high temperatures, and low dielectric properties.
• the curable resin composition of this embodiment contains a maleimide resin (A) (hereinafter also simply referred to as the "maleimide resin (A)”) represented by the following formula (1), a bifunctional cyanate resin (B) (hereinafter also simply referred to as the “cyanate resin (B)”) represented by the following formula (3), and a benzoxazine resin (C).
• A maleimide resin
• B bifunctional cyanate resin
• C benzoxazine resin
• X represents any one of the structures represented by the following formulas (2-a) to (2-f).
• X is preferably represented by the following formula (2-b), (2-c), (2-e), or (2-f), and more preferably represented by the following formula (2-c) or (2-e).
• R 1 represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and p is an integer from 0 to 3.
• the value of n can be calculated from the number average molecular weight determined by gel permeation chromatography (GPC, detector: RI) of the maleimide resin (A) or from the area ratio of each separated peak.
• R 2 s represent an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent
• q s are integers from 0 to 4
• m s are integers from 1 to 50
• r s are integers from 0 to 4.
• maleimide resin (A) Since maleimide resin (A) has repeating units, it becomes a maleimide mixture with low crystallinity, low viscosity, low softening point, and excellent workability. It is preferable that the number of maleimide groups is more than 2 and less than 11.
• the method for producing maleimide resin (A) is not particularly limited, and any known method may be used.
• a specific preferred production method is, for example, the method described in JP 2009-001783 A.
• the content of maleimide resin (A) is preferably 40% by mass or more and 90% by mass or less, more preferably 45% by mass or more and 85% by mass or less, and even more preferably 50% by mass or more and 80% by mass or less, of the total amount of maleimide resin (A), cyanate resin (B), and benzoxazine resin (C).
• maleimide resin (A) is preferably 40% by mass or more and 90% by mass or less, more preferably 45% by mass or more and 85% by mass or less, and even more preferably 50% by mass or more and 80% by mass or less, of the total amount of maleimide resin (A), cyanate resin (B), and benzoxazine resin (C).
• Cyanate resin (B) is represented by the following formula (3).
• the plurality of Ys, Rs , and ts are each independently present, Y represents a direct bond, —CH 2 —, —CH(CH 3 )—, or —C(CH 3 ) 2 —, Rs represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and t is an integer of 0 to 4.
• Cyanate resin (B) can be used singly or in combination with multiple types. Furthermore, to reduce the stickiness of the resin and improve handling, a bifunctional cyanate resin may be prepolymerized before use. By mixing cyanate resin (B) with maleimide resin (A), the crystallinity of the maleimide resin composition can be reduced, and the softening point and ICI melt viscosity can be lowered. As cyanate resin (B), 1,1-bis(4-cyanatophenyl)ethane and 2,2-bis(4-cyanatophenyl)propane are preferred from the standpoint of low melt viscosity and low melting point, with 2,2-bis(4-cyanatophenyl)propane being even more preferred.
• the content of cyanate resin (B) is preferably 5% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 35% by mass or less, and even more preferably 20% by mass or more and 30% by mass or less, of the total amount of maleimide resin (A), cyanate resin (B), and benzoxazine resin (C).
• the cured product has excellent heat resistance, dimensional stability, low elasticity at high temperatures, and low dielectric properties.
• Phenol resins Polycondensates of phenols (phenol, alkyl-substituted phenols, aromatic-substituted phenols, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.), and polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes,
• divinylbenzene divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.
• polycondensation products of phenols and ketones acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.
• phenolic resins obtained by polycondensation of phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.), polycondensation products of bisphenols and various aldehydes, polyphenylene ether compounds, etc.
• Amine resins diaminodiphenylmethane, diaminodiphenyl sulfone, isophoronediamine, naphthalenediamine, aniline novolac, orthoethylaniline novolac, aniline resin obtained by reacting aniline with xylylene chloride, and aniline and substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl) or substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, and 1,4-bis(hydroxymethyl)benzene) as described in Japanese Patent No. 6,429,862.
• biphenyls such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-bipheny
• Aldehyde compounds examples include formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, and furfural.
• bifunctional benzoxazine resins represented by the following formula (4-1) are preferred because they have an excellent low elastic modulus at high temperatures.
• Z represents a direct bond, —CH 2 —, —CH(CH 3 )—, or —C(CH 3 ) 2 —.
• R 4 represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent, s is an integer from 0 to 3, and u is an integer from 0 to 5.
• a bifunctional benzoxazine resin represented by the following formula (4-2) may be used.
• Z represents a direct bond, —CH 2 —, —CH(CH 3 )—, or —C(CH 3 ) 2 —.
• R 4 represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent.
• p is an integer of 0 to 4
• v is an integer of 0 to 4.
• benzoxazine resin represented by the following formula (4-3) can also be used.
• X represents any one of the structures represented by the above formulas (2-a) to (2-f).
• R 4 represents an alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms which may have a substituent, p is an integer from 0 to 4, and v is an integer from 0 to 4.
• Benzoxazine resin (C) can have a melting point or softening point. If it has a melting point, it is preferably 200°C or lower, and if it has a softening point, it is preferably 150°C or lower. If the melting point or softening point is too high, it is not preferable because there is a high possibility of gelation during mixing.
• the benzoxazine resin (C) preferably accounts for 1% by mass or more and 40% by mass or less of the total amount of maleimide resin (A), cyanate resin (B), and benzoxazine resin (C), more preferably 5% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 20% by mass or less.
• the benzoxazine resin (C) undergoes copolymerization with the maleimide resin (A) and cyanate ester resin (B), and can be cured under specified conditions.
• the viscosity of the curable resin composition of this embodiment is preferably 0.001 to 0.9 Pa ⁇ s, more preferably 0.01 to 0.5 Pa ⁇ s, and particularly preferably 0.01 to 0.3 Pa ⁇ s. If the viscosity is lower than 0.001 Pa ⁇ s, dripping occurs during melt-kneading, making it difficult to maintain the molded body. On the other hand, if the viscosity is higher than 0.9 Pa ⁇ s, it is difficult to fill with filler, and the fluidity is poor, making it difficult to use as a sealant. Generally, sealants cannot be made with solvents, so the viscosity cannot be reduced by using a solvent.
• the softening point of the curable resin composition of this embodiment is preferably 40 to 110°C, more preferably 50 to 110°C, and particularly preferably 55 to 100°C. If the softening point is lower than 40°C, blocking of the resins occurs at room temperature, reducing workability and productivity. On the other hand, if the softening point is higher than 110°C, after the mixture is created by applying high heat during melt-kneading, the resin components aggregate and partially crystallize in the process of returning to room temperature, resulting in an inhomogeneous mixture and reduced quality and workability.
• the curable resin composition of this embodiment is preferably amorphous at room temperature (25°C).
• the curable resin composition can be easily prepared.
• the amorphous state can be confirmed by visually checking whether or not crystalline components are aggregated, but it can also be confirmed by DSC (differential scanning calorimetry) or XRD (X-ray diffraction) of the solid. Specifically, it is confirmed by DSC that there are no endothermic peaks due to the heat of fusion of the crystals, or by XRD that there are no peaks due to the repetition of the crystalline structure.
• the curable resin composition of this embodiment is self-curing (meaning that it can undergo ring-opening polymerization (curing) without other components such as a curing agent or polymerization catalyst). This means that no curing catalyst is required for curing, and no by-products are generated during the polymerization process, making it possible to obtain a void-free polymer (cured product) with high dimensional stability.
• the self-curing conditions are typically 180°C or higher, preferably 200°C or higher, and more preferably 220°C, for several tens of minutes to several hours.
• the curable resin composition of this embodiment may further contain at least one selected from the group consisting of a curing accelerator, a polymerization initiator, an epoxy resin, an active ester compound, a phenolic resin, a polyphenylene ether compound, an amine resin, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a polyimide resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, and polyethylene and modified products thereof.
• Polymerization initiators include olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, and radical polymerization initiators. Of these, it is preferable to use a radical polymerization initiator that has curability and appropriate stability.
• a radical polymerization initiator is a compound that generates radicals when exposed to ultraviolet or visible light or heat, and starts a chain polymerization reaction.
• Usable radical polymerization initiators include organic peroxides, azo compounds, and benzopinacols, with organic peroxides being preferred due to their ability to control the curing temperature, suppress outgassing, and have little effect on the electrical properties of decomposed products.
• epoxy resins examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins with an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins with a butadiene structure.
• solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, and examples of suitable solid epoxy resins include naphthol-type epoxy resins, bisphenol AF-type epoxy resins, naphthalene-type epoxy resins, and biphenyl-type epoxy resins.
• HP4032H manufactured by DIC Corporation, naphthalene-type epoxy resin
• HP-4700 manufactured by DIC Corporation, naphthalene-type tetrafunctional epoxy resin
• HP-4710 all manufactured by DIC Corporation, naphthalene-type tetrafunctional epoxy resin
• N-690 manufactured by DIC Corporation, cresol novolac-type epoxy resin
• N-695" manufactured by DIC Corporation, cresol novolac-type epoxy resin
• HP-7200 manufactured by DIC Corporation, dicyclopentadiene-type epoxy resin
• HP-7200 manufactured by DIC Corporation, dicyclopentadiene-type epoxy resin
• HP-7200 manufactured by DIC Corporation, dicyclopentadiene-type epoxy resin
• HP-7200 manufactured by DIC Corporation, dicyclopentadiene-type epoxy resin
• HP-7200 manufactured by DIC Corporation, dicyclopentadiene-type epoxy resin
• HP-7200 manufactured by DIC Corporation, dicyclopentadiene-type epoxy resin
• HP-7200 manufactured by
• active ester compounds include phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds.
• Phenol resins include the known compounds listed above.
• polyphenylene ether compounds examples include SA-9000 (manufactured by SABIC, a polyphenylene ether compound with a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Company, Inc., a polyphenylene ether compound with a styrene structure).
• Amine resins include the same known compounds as those mentioned above.
• Examples of compounds having an ethylenically unsaturated bond include reaction products of phenol resins with ethylenically unsaturated halogenated compounds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.), reaction products of ethylenically unsaturated phenols (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) with halogenated compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), reaction products of epoxy resins or alcohols with (meth)acrylic acids (acrylic acid, methacrylic acid
• isocyanate resin examples include aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more biuret compounds of isocyanate monomers or isocyanate compounds obtained by trimerizing the above diisocyanate compounds; and polyisocyanates
• maleimide compounds include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene), and Xylox-type maleimide compounds (anilix maleimide, manufactured by Mitsui Chemicals Fine Co., Ltd.), biphenylaralkyl-type maleimide compounds (solidified by distilling off the solvent under reduced pressure from a resin solution containing the maleimide compound
• MATERIAL STAGE Vol. 18, No. 12 2019 "Continued Epoxy Resin CAS Number Story - Curing Agent CAS Number Memorandum No. 31 Bismaleimide (1)”
• MATERIAL STAGE Vol. 19, No. 12 2019 Examples include the maleimide compounds described in "Continued Epoxy Resin CAS Number Story - Hardener CAS Number Memorandum No. 32 Bismaleimide (2)" published in 2019.
• polyamide resins examples include polyamide resins synthesized from dicyandiamide or a dimer of linolenic acid and ethylenediamine.
• Polyimide resins include those prepared by combining the above diamines with tetracarboxylic dianhydrides (4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, diphthalic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetrac
• Polybutadiene and its modified products, polystyrene and its modified products, polyethylene and its modified products include polybutadiene, hydroxyl-terminated polybutadiene, (meth)acrylate-terminated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, styrene-butadiene rubber, RICON-100, RICON-181, RICON-184 (all manufactured by Cray Valley Corporation), 1,2-SBS (manufactured by Nippon Soda Co., Ltd.), B-1000, B-2000, B-3000 (all manufactured by Nippon Soda Co., Ltd.); polystyrene, styrene-2-isopropenyl-2-oxazoline copolymer (Epocross RPS -1005, RP-61, all manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylene propylene copolymer: Sept
• benzoxazine compounds include benzoxazine P-d, Fa, and ALP-d (all manufactured by Shikoku Kasei Corporation), JBZ-BA100N, JBZ-FA100N, JBZ-DP100N, JBZ-OP100N, JBZ-OP100D, and JBZ-OP100I (all manufactured by JFE Chemical Corporation), and BTBz (manufactured by Japan Material Technology Co., Ltd.).
• the curable resin composition of this embodiment may contain, as needed, a curing catalyst (curing accelerator), binder resin, flame retardant, filler, additives, etc.
• a curing catalyst curing accelerator
• binder resin binder resin
• flame retardant filler
• additives additives
• curing catalyst there are no particular limitations on the curing catalyst, and known catalysts can be used. Specific examples include metal complex catalysts, phosphine compounds, compounds containing phosphonium salts, aromatic amine compounds, inorganic acids, inorganic bases, organic acids, and organic bases.
• metal complex catalysts can be used. Examples include metal naphthenates of cobalt, zinc, chromium, copper, iron, manganese, nickel, titanium, etc., acetylacetonates, salts of their derivatives, and organic acid salts such as various carboxylates and alkoxides. These may be used alone or in combination. Organic acid salts, chlorides, phosphates, phosphites, hypophosphites, nitrates, etc., alone or in combination, are also examples of metal complex catalysts.
• Phosphine compounds include alkyl phosphines such as ethylphosphine and propylphosphine, primary phosphines such as phenylphosphine; dialkyl phosphines such as dimethylphosphine and diethylphosphine, secondary phosphines such as diphenylphosphine, methylphenylphosphine, and ethylphenylphosphine; trialkyl phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine, and trioctylphosphine, and tertiary phosphines such as tricyclohexylphosphine, triphenylphosphine, alkyldiphenylphosphine, dialkylphenylphosphine, tribenzylphosphine, tritolylphosphine, tri-p-sty
• Examples of compounds containing phosphonium salts include compounds containing tetraphenylphosphonium salts, alkyltriphenylphosphonium salts, etc., and specific examples include tetraphenylphosphonium thiocyanate, tetraphenylphosphonium tetra-p-methylphenylborate, and butyltriphenylphosphonium thiocyanate.
• Aromatic amine compounds include tertiary amines and imidazoles, specifically 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole.
• 2-phenyl-4-methyl-5-hydroxymethylimidazole 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, diazabicycloundecene, histidine, etc.
• inorganic acids examples include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, sodium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, formic acid, acetic acid, citric acid, oxalic acid, p-toluenesulfonic acid, benzoic acid, phenol, allylphenol, methallylphenol, thiophenol, pyridine, trialkylamine, diazabicycloundecene, histidine, and imidazoles.
• Hydrochloric acid, p-toluenesulfonic acid, benzoic acid, phenol, and thiophenol are preferred, and p-toluenesulfonic acid and 2-ethyl-4-methylimidazole are more preferred.
• These additives may be used alone or in combination of two or more.
• the amount of these curing catalysts to be added can be appropriately selected depending on their type and effect, but is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and particularly preferably 0.05 to 3 parts by mass, per 100 parts by mass of the curable resin composition.
• fillers include various forms of organic or inorganic fillers such as fumed silica, calcined silica, precipitated silica, crushed silica, fused silica, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, pyrophyllite clay, kaolin clay, calcined clay, carbon black, polyamide resin, silicone resin, polytetrafluoroethylene, polybutadiene and modified products thereof, modified acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, and fluororesin. These fillers may be used alone or in combination of two or more types.
• surface treatment agents include silane coupling agents.
• reaction retarders include alcohol-based compounds
• antioxidants include hindered phenol-based compounds.
• antioxidants include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
• colorants include inorganic pigments such as titanium oxide, zinc oxide, ultramarine, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochlorides, and sulfates; and organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, quinonaphthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindoline pigments, and carbon black.
• organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, quinacridonequinone pigments, dioxazine pigments,
• Antistatic agents generally include quaternary ammonium salts, polyglycols, ethylene oxide derivatives, and other hydrophilic compounds.
• the curable resin composition of this embodiment may contain copolymer components such as epoxy resin, phenolic resin, melamine resin, unsaturated polyester resin, polyimide resin, polyamide resin, polyurethane resin, butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenolic resin, epoxy-NBR resin, and silicone resin.
• the amount of binder resin added is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is preferably 0.05 to 50 parts by mass, and more preferably 0.05 to 20 parts by mass, per 100 parts by mass of the total amount of resin components in the curable resin composition of this embodiment.
• copolymerization components it is preferable to blend epoxy resins or phenolic resins, which are reactive with phenolic hydroxyl groups generated in the resin composition upon heating, and it is particularly preferable to blend epoxy resins.
• the epoxy resins that can be blended are not particularly limited as long as they are compounds having at least one epoxy group, and examples include glycidyl ether types obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, cresol novolac, phenol novolac, tetrabromobisphenol A, trihydroxybiphenyl, bisresorcinol, bisphenol hexafluoroacetone, tetramethylbisphenol F, bixylenol, and dihydroxynaphthalene; polyglycidyl ether types obtained by reacting epichlorohydrin with aliphatic polyhydric alcohols such as glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, and
• glycidyl ether ester type obtained by reacting hydroxycarboxylic acid with epichlorohydrin; polyglycidyl ester type derived from polycarboxylic acid such as phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, polymerized fatty acid, etc.; glycidyl aminoglycidyl ether type derived from aminophenol, aminoalkylphenol, etc.; glycidyl aminoglycidyl ester type derived from aminobenzoic acid; glycidyl amine type derived from aniline, toluidine, tribromoaniline, xylylenediamine, diaminocyclohexane, bisaminomethylcyclohexane, 4,4'-di
• the curable resin composition of this embodiment can also be used as a varnish dissolved in a solvent. Forming it into a varnish is a preferred embodiment in that it makes the curable resin composition easier to handle.
• Solvents that can be used in the varnish include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dioxane, 1-propanol, 2-propanol, 1-butanol, 1,4-dioxane, ethylene glycol ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether, but any solvent that can dissolve the curable resin composition of this embodiment can be used without particular restrictions. Furthermore, the aforementioned additives and optional components may be blended as needed.
• the curable resin composition of this embodiment can contain various additives such as silane coupling agents, release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers, as well as various thermosetting resins.
• the curable resin composition of this embodiment may be prepolymerized.
• the maleimide resin mixture of this embodiment an epoxy resin, an amine compound, a maleimide-based compound, a cyanate ester compound, a phenolic resin, an acid anhydride compound, or other curing agent and other additives are added and prepolymerized by heating in the presence or absence of a solvent.
• the components can be mixed or prepolymerized using, for example, an extruder, kneader, or rolls in the absence of a solvent, or in a reaction vessel equipped with a stirrer in the presence of a solvent.
• a method for uniformly mixing without using solvents involves kneading the components at a temperature between 50 and 100°C using a device such as a kneader, roll, or planetary mixer to produce a uniform curable resin composition.
• the resulting curable resin composition can be pulverized and then molded into cylindrical tablets using a molding machine such as a tablet machine, or into a granular powder or powder-like molded product.
• these compositions can be melted on a surface support and molded into a sheet 0.05 mm to 10 mm thick to produce a molded curable resin composition.
• the resulting molded product is non-sticky at 0 to 20°C, and its fluidity and curability are hardly reduced even when stored at -25 to 0°C for more than one week.
• the resulting molded product can then be molded into a cured product using a transfer molding machine or compression molding machine.
• the curable resin composition of this embodiment can be obtained by uniformly mixing the above components in the specified ratios, pre-curing at 130-200°C for 30-500 seconds, and then post-curing at 150-250°C for 2-15 hours, allowing the curing reaction to proceed sufficiently and producing the cured product of this embodiment.
• the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent, etc., and then cured after removing the solvent.
• the curable resin composition of this embodiment obtained in this manner has cured products with heat resistance, thermal decomposition properties, dimensional stability, high elasticity at room temperature, low elasticity at high temperatures, and low dielectric properties, making it suitable for use in a wide range of fields.
• it is useful as a material for all kinds of electrical and electronic components, including insulating materials, laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), sealing materials, and resists. It can also be used in fields such as molding materials, composite materials, paint materials, adhesives, and 3D printing.
• a high modulus of elasticity at room temperature e.g., 2.6 GPa or more
• a low modulus of elasticity at high temperatures e.g., less than 1,000 MPa
• Semiconductor devices include those encapsulated with the curable resin composition of this embodiment.
• Examples of semiconductor devices include DIP (dual in-line package), QFP (quad flat package), BGA (ball grid array), CSP (chip size package), SOP (small outline package), TSOP (thin small outline package), and TQFP (thin quad flat package).
• softening points and melt viscosities in the synthesis examples were measured by the following methods.
• Softening point Measured according to JIS K-7234.
• Melt viscosity Viscosity at 150°C using the cone-plate method.
• aniline resin A-1 softening point 57°C, melt viscosity 0.035 Pa s, amine equivalent 196 g/eq
• Example 1 A maleimide resin, a cyanate ester resin, and a benzoxazine resin were blended in the proportions shown in Table 1 and cured at 220°C for 2 hours to obtain a cured product.
• Comparative Example 2 the compatibility between the resins was poor, and uniform test pieces could not be obtained.
• MI-3 Bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (K.I. Chemicals Co., Ltd., BMI-70)
• MI-4 4,4'-diphenylmethane bismaleimide (K.I. Chemical Co., Ltd., BMI)
• OCN-1 4,4'-isopropylidenediphenyl cyanate (manufactured by Mitsubishi Gas Chemical Company, Inc., CYTESTER (registered trademark) TA)
• BO-1 Benzoxazine P-d (manufactured by Shikoku Kasei Holdings Co., Ltd.)
• DMA Dynamic Viscoelasticity
• thermomechanical analysis (TMA)> The linear expansion coefficient ⁇ 1 at 60-90°C and the linear expansion coefficient ⁇ 2 at 260-290°C were measured using a thermomechanical analyzer (TMA).
• Measuring device Thermomechanical analyzer manufactured by TA-instruments, TMA Q400 Measurement temperature: 30-350°C Temperature increase rate: 2°C/min Sample size: width 4 mm x length 35 mm x thickness 0.25 mm
• ⁇ Dielectric property measurement> The dielectric constant (Dk) and dielectric loss tangent (Df) were measured by the cavity resonator perturbation method using a cavity resonator.
• the above results confirm that by incorporating maleimide resin, cyanate ester resin, and benzoxazine resin in the specified proportions, it is possible to obtain a uniformly cured product with high heat resistance without using a metal catalyst. Furthermore, in addition to a low linear expansion coefficient in the low temperature range (60-90°C), the material exhibits a high modulus of elasticity at room temperature and a low modulus of elasticity at high temperatures. This is expected to provide stress relaxation in heat cycle tests, which are primarily required for automotive semiconductor encapsulation, and prevent the formation of voids and cracks over the long term. Furthermore, the low dielectric properties are also favorable compared to conventional epoxy resin cured products, making the material useful for a wide range of applications in the communications field.
• the curable resin composition of the present invention produces cured products that have excellent heat resistance, thermal decomposition properties, dimensional stability, high elasticity at room temperature, low elasticity at high temperatures, and low dielectric properties, making it useful for insulating materials for electrical and electronic components, semiconductor encapsulation materials, laminates (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, adhesives, paints, etc.

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• 2025
  • 2025-03-17 WO PCT/JP2025/010237 patent/WO2025197852A1/ja active Pending
  • 2025-03-17 JP JP2025545830A patent/JP7804839B1/ja active Active
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