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WO2015083585A1 - Composé, composition de résine thermodurcissable, et feuille thermodurcissable - Google Patents

Composé, composition de résine thermodurcissable, et feuille thermodurcissable Download PDF

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Publication number
WO2015083585A1
WO2015083585A1 PCT/JP2014/081161 JP2014081161W WO2015083585A1 WO 2015083585 A1 WO2015083585 A1 WO 2015083585A1 JP 2014081161 W JP2014081161 W JP 2014081161W WO 2015083585 A1 WO2015083585 A1 WO 2015083585A1
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WIPO (PCT)
Prior art keywords
group
general formula
carbon atoms
resin composition
ammonium salt
Prior art date
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PCT/JP2014/081161
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English (en)
Japanese (ja)
Inventor
健 西尾
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Dexerials Corp
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Dexerials Corp
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Priority to KR1020167017393A priority Critical patent/KR102239537B1/ko
Priority to CN201480066345.5A priority patent/CN105814090B/zh
Publication of WO2015083585A1 publication Critical patent/WO2015083585A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/64—Quaternary ammonium compounds having quaternised nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C215/90—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with quaternised amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds

Definitions

  • the present invention relates to a thermosetting resin composition, a thermosetting sheet, a novel compound usable for them, and a precursor thereof.
  • Patent Document 3 a technique for generating a tertiary amine by UV irradiation has been disclosed (see Patent Document 3).
  • a tertiary amine is generated by UV irradiation using a quaternary ammonium salt derivative.
  • the means using UV irradiation is always required to be shielded during storage, and the work environment also requires UV cut.
  • the infrastructure for UV irradiation must be improved, which is disadvantageous in terms of cost.
  • sufficient adhesive strength cannot be obtained without UV irradiation, and curing cannot be performed with heat alone. Therefore, it can be said that a technique that can be cured at a low temperature in a short time and that can ensure storage stability before curing is still insufficient.
  • thermosetting resin composition that can be cured at a low temperature and in a short time, and that can ensure storage stability before curing, a thermosetting sheet, a novel compound that can be used for them, and a precursor thereof. Is currently required.
  • JP 2004-224819 A JP-A-2-281018 Japanese Patent No. 4967276 JP 2013-1654 A JP-A-4-222879 JP-A-8-283657 Japanese Patent No. 3218345
  • thermosetting resin composition that can be cured at a low temperature and in a short time, and that can ensure storage stability before curing, a thermosetting sheet, a novel compound that can be used for them, and a An object is to provide a precursor.
  • thermosetting resin composition containing a radical polymerization component, a thermal polymerization initiator, and an ammonium salt
  • the thermosetting resin composition is characterized in that the thermal dissociation start temperature of the ammonium salt is 60 ° C to 140 ° C.
  • the ammonium salt is a compound represented by the following general formula (1).
  • R 1 to R 4 each independently represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted aryl group, and It represents either a substituted or unsubstituted aralkyl group.
  • X ⁇ represents an anion.
  • R 1 and R 2 each independently represents an alkyl group having 1 to 4 carbon atoms
  • R 3 represents a substituted or unsubstituted aryl group
  • R 4 represents The thermosetting resin composition according to ⁇ 3>, which represents a substituted or unsubstituted aralkyl group.
  • R 5 represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 6 represents an alkyl group having 1 to 4 carbon atoms.
  • m represents 0-3.
  • n represents 0 to 3.
  • m + n is 0 to 5.
  • R 5 may be different.
  • n is 2 or 3, R 6 may be different.
  • X ⁇ in the general formula (1) is a carboxylic acid anion.
  • thermosetting resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the thermal polymerization initiator is an organic peroxide thermal polymerization initiator.
  • the organic peroxide thermal polymerization initiator contains at least one of diacyl peroxide and peroxydicarbonate.
  • thermosetting sheet comprising the thermosetting resin composition according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 11> A compound represented by the following general formula (1).
  • R 1 and R 2 each independently represents an alkyl group having 1 to 4 carbon atoms
  • R 3 represents a substituted aryl group
  • R 4 represents a substituted or Represents an unsubstituted aralkyl group.
  • X ⁇ represents an anion.
  • R 3 is the compound according to the above ⁇ 11>, which is a group represented by the following general formula (2).
  • R 5 represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 6 represents an alkyl group having 1 to 4 carbon atoms.
  • m represents 0-3.
  • n represents 0 to 3.
  • m + n is 1 to 5.
  • R 5 may be different.
  • n is 2 or 3, R 6 may be different.
  • X ⁇ in the general formula (1) is any one of a halogen anion, an anion of naphthalenecarboxylic acids, a diphenylacetic acid anion, and a 1-adamantanecarboxylic acid anion The described compounds.
  • ⁇ 14> A compound represented by the following general formula (1).
  • R 1 and R 2 each independently represents an alkyl group having 1 to 4 carbon atoms
  • R 3 represents a substituted or unsubstituted aryl group
  • R 4 represents Represents a substituted or unsubstituted aralkyl group.
  • X ⁇ represents a halogen anion.
  • R 3 is a compound according to the above ⁇ 14>, which is a group represented by the following general formula (2).
  • R 5 represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 6 represents an alkyl group having 1 to 4 carbon atoms.
  • m represents 0-3.
  • n represents 0 to 3.
  • m + n is 0 to 5. When m is 2 or 3, R 5 may be different. When n is 2 or 3, R 6 may be different.
  • thermosetting resin composition that can solve the above-described problems and can achieve the above-described object, can be cured at a low temperature in a short time, and can ensure storage stability before curing.
  • thermosetting sheet, and a novel compound usable in them, and a precursor thereof can be provided.
  • thermosetting resin composition contains at least a radical polymerization component, a thermopolymerization initiator, and an ammonium salt, preferably contains a film-forming resin, and further contains other components as necessary. To do.
  • the radical polymerization component is not particularly limited as long as it is a component that undergoes radical polymerization by the action of the thermal polymerization initiator, and can be appropriately selected according to the purpose.
  • (meth) acrylates, vinyl ester resins , Unsaturated polyester resin, diallyl phthalate, vinyl ethers, dicyclopentadiene, and the like may be used individually by 1 type and may use 2 or more types together.
  • Examples of the (meth) acrylates include monofunctional (meth) acrylates and polyfunctional (meth) acrylates.
  • (meth) acrylate means acrylate and methacrylate.
  • Examples of the monofunctional (meth) acrylates include alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, and aromatics. And monofunctional (meth) acrylates having a ring.
  • alkyl (meth) acrylates examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2- Examples include ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like.
  • Examples of the hydroxyalkyl (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
  • Examples of the monofunctional (meth) acrylates having an aromatic ring include benzyl (meth) acrylate, (meth) acrylate of p-cumylphenol alkylene oxide adduct, and (meth) acrylate of o-phenylphenol alkylene oxide adduct.
  • Acrylate (meth) acrylate of phenol alkylene oxide adduct, (meth) acrylate of nonylphenol alkylene oxide adduct, and the like.
  • examples of the alkylene oxide include ethylene oxide (EO) and propylene oxide (PO).
  • Examples of the polyfunctional (meth) acrylates include di (meth) acrylates of alkylene glycol, di (meth) acrylate having an alicyclic ring ( And (meth) acrylates and di (meth) acrylates having an aromatic ring.
  • Examples of the di (meth) acrylates of alkylene glycol include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, pentanediol di (meth) acrylate, and hexanediol di (meth) acrylate.
  • di (meth) acrylate having an alicyclic ring examples include tricyclodecane dimethylol di (meth) acrylate, 1,4-cyclohexane dimethylol di (meth) acrylate, and norbornane dimethylol di (meth) acrylate. And di (meth) acrylate of hydrogenated bisphenol A.
  • di (meth) acrylate having an aromatic ring examples include di (meth) acrylate of a bisphenol A alkylene oxide adduct, di (meth) acrylate of bisphenol A diglycidyl ether, and the like.
  • the (meth) acrylates for example, isocyanuric acid ethylene oxide (EO) modified polyfunctional (meth) acrylate, pentaerythritol triacrylate and the like can be used.
  • isocyanuric acid EO-modified polyfunctional (meth) acrylate include isocyanuric acid EO-modified di- and triacrylate (for example, Aronix M-315 manufactured by Toagosei Co., Ltd.).
  • (meth) acrylates for example, urethane (meth) acrylate can be used.
  • the (meth) acrylates may be used alone or in combination of two or more.
  • thermosetting resin composition There is no restriction
  • the thermal polymerization initiator is not particularly limited as long as it is decomposed by heat to radically polymerize the radical polymerization component, and can be appropriately selected according to the purpose.
  • an azo thermal polymerization initiator And organic peroxide thermal polymerization initiators are examples of organic peroxide thermal polymerization initiators.
  • an organic peroxide thermal polymerization initiator is preferable in terms of excellent low-temperature curability.
  • the organic peroxide thermal polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose.
  • diacyl peroxide and peroxydioxide are preferred because they can easily enjoy the decomposition promoting effect of the ammonium salt. Carbonate is preferred.
  • diacyl peroxide include diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinic acid peroxide, dibenzoyl peroxide, and di (4-methylbenzoyl). ) Peroxide.
  • peroxydicarbonate examples include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di (4 -T-butylcyclohexyl) peroxydicarbonate and the like.
  • the content of the thermal polymerization initiator in the thermosetting resin composition is not particularly limited and may be appropriately selected depending on the intended purpose, but with respect to the nonvolatile content of the thermosetting resin composition, 0.5% by mass to 20% by mass is preferable, and 1% by mass to 15% by mass is more preferable.
  • the ammonium salt is not particularly limited as long as the thermal dissociation start temperature is 60 ° C. to 140 ° C., and can be appropriately selected according to the purpose.
  • the thermal dissociation start temperature is less than 60 ° C., the low temperature curability is excellent, but the storage stability is insufficient, and when it exceeds 140 ° C., the low temperature curability is insufficient.
  • the thermal dissociation start temperature is a temperature at which thermal dissociation starts when a sufficiently dried ammonium salt is heated, and specifically, N using a differential thermothermal gravimetric simultaneous measurement device (TG / DTA).
  • TG / DTA differential thermothermal gravimetric simultaneous measurement device
  • the ammonium salt is preferably an ammonium salt having a pKa of 3 or more at 25 ° C. in the water of the conjugate acid of the anion in the ammonium salt in that the thermal dissociation starting temperature is easily adjusted to 60 ° C. to 140 ° C. If the pKa is less than 3, the thermal dissociation start temperature may increase, and the thermosetting acceleration effect may be reduced.
  • the said pKa has 7 or less preferable.
  • Examples of the conjugate acid having a pKa of 3 or more include p. Of Electrochemical Handbook 5th Edition (Electrical Society of Japan: Maruzen). 102-p. The pKa data in water can be referred to from 104 or the following URL address. http: // www. chem. wsc. edu / areas / organic / index-chem. htm
  • a carboxylic acid anion is preferable from the viewpoint of easy availability of raw materials and easy synthesis.
  • the ammonium salt is preferably a compound represented by the following general formula (1) in terms of easy availability of raw materials and ease of synthesis.
  • R 1 to R 4 each independently represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted aryl group, and It represents either a substituted or unsubstituted aralkyl group.
  • X ⁇ represents an anion.
  • Examples of the alkyl group having 1 to 4 carbon atoms of R 1 to R 4 in the general formula (1) include, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert- A butyl group etc. are mentioned. Among these, a methyl group and an ethyl group are preferable from the viewpoint of thermal stability and ease of synthesis.
  • the thermal dissociation start temperature of the ammonium salt may be excessively lowered, and the thermal stability may be lowered.
  • the steric hindrance increases, the synthesis of the ammonium salt may be difficult.
  • Examples of the cycloalkyl group having 3 to 8 carbon atoms of R 1 to R 4 in the general formula (1) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Can be mentioned. Among these, a cyclohexyl group is preferable from the viewpoint of easy availability of raw materials.
  • Examples of the substituted or unsubstituted aryl group of R 1 to R 4 in the general formula (1) include an unsubstituted aromatic hydrocarbon group and a substituted aromatic hydrocarbon group.
  • Examples of the unsubstituted aromatic hydrocarbon group include a phenyl group and a naphthyl group.
  • Examples of the substituted aromatic hydrocarbon group include a substituted phenyl group and a substituted naphthyl group.
  • Examples of the substituted phenyl group include an alkyl-substituted phenyl group, a hydroxy-substituted phenyl group, and an alkoxy-substituted phenyl group.
  • Examples of the alkyl substituent in the alkyl-substituted phenyl group include an alkyl group having 1 to 4 carbon atoms.
  • Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a tert-butyl group.
  • Examples of the substituted or unsubstituted aralkyl group of R 1 to R 4 in the general formula (1) include an aralkyl group having 7 to 15 carbon atoms.
  • Examples of the aryl group in the aralkyl group include an aromatic hydrocarbon group.
  • Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group.
  • Examples of the substituent include an alkyl group having 1 to 4 carbon atoms.
  • Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a tert-butyl group.
  • Examples of the alkylene group in the aralkyl group include a methylene group and an ethylene group.
  • Examples of the aralkyl group include benzyl group, o-methylbenzyl group, p-methylbenzyl group, 2,5-dimethylbenzyl group, (1-naphthyl) methyl group, and phenethyl group.
  • R 1 and R 2 each independently represents an alkyl group having 1 to 4 carbon atoms
  • R 3 represents a substituted or unsubstituted aryl group
  • R 4 represents a substituted group. Or it preferably represents an unsubstituted aralkyl group.
  • R 3 is preferably a group represented by the following general formula (2) from the viewpoint that the thermal dissociation start temperature is easily adjusted and the synthesized product is easily crystallized.
  • R 5 represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 6 represents an alkyl group having 1 to 4 carbon atoms.
  • m represents 0-3.
  • n represents 0 to 3.
  • m + n is 0 to 5.
  • R 5 may be different.
  • R 6 may be different.
  • m + n is preferably 1 to 5.
  • R 5 is preferably a hydrogen atom.
  • R 6 is preferably a methyl group.
  • Examples of the cation of the ammonium salt represented by the general formula (1) include cations represented by the following structural formulas (1-1) to (1-12).
  • X - - X ⁇ in the general formula (1) is an anion.
  • the anion an anion having a pKa of 3 or more at 25 ° C. in water of the conjugate acid is preferable.
  • X ⁇ is preferably a carboxylate anion from the viewpoint of easy availability of raw materials and easy synthesis.
  • Examples of the carboxylate anion include anions represented by the following general formula (3).
  • R 21 represents a hydrocarbon group.
  • the hydrocarbon group may have a halogen atom.
  • the halogen atom include a fluorine atom and a chlorine atom.
  • hydrocarbon group examples include a hydrocarbon group having a cyclic structure.
  • hydrocarbon group having a cyclic structure examples include an aromatic hydrocarbon group and a hydrocarbon group having an alicyclic structure.
  • the number of carbon atoms of the hydrocarbon group is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15, and more preferably 6 to 13.
  • carboxylic acid examples include saturated fatty acids, unsaturated fatty acids, carboxylic acids having an aromatic ring, carboxylic acids having an alicyclic structure, acrylic acid, and trifluoroacetic acid.
  • Examples of the saturated fatty acid include acetic acid, propionic acid, decanoic acid, myristic acid, stearic acid, 2-ethylhexanoic acid and the like.
  • Examples of the unsaturated fatty acid include oleic acid and linoleic acid.
  • Examples of the carboxylic acid having an alicyclic structure include 1-adamantane carboxylic acid and cyclohexane carboxylic acid.
  • Examples of the carboxylic acid having an aromatic ring include substitution of benzoic acid, 2-methylbenzenecarboxylic acid, 2-phenylbenzenecarboxylic acid, 2,6-dimethylbenzenecarboxylic acid, 2-hydroxybenzenecarboxylic acid, and the like.
  • Substituted benzoic acid (benzoic acid optionally having substituent); 1-naphthalene carboxylic acid, 2-naphthalene carboxylic acid, 2-hydroxy-1-naphthalene carboxylic acid, 3-hydroxy-2-naphthalene carboxylic acid, etc.
  • carboxylic acid anion naphthalenecarboxylic acid anions, diphenylacetic acid anions, and 1-adamantanecarboxylic acid anions are preferable from the viewpoint that crystals are easily obtained.
  • ammonium salt examples include the following ammonium salts.
  • thermosetting resin composition There is no restriction
  • the film-forming resin is not particularly limited and can be appropriately selected depending on the purpose.
  • polyacrylic resin, phenoxy resin, polyester resin, polyurethane resin, polyester urethane resin, polyvinyl butyral resin, polyvinyl formal resin examples thereof include polyamide resin and polyimide resin. These may be used individually by 1 type and may use 2 or more types together. Among these, a phenoxy resin is particularly preferable from the viewpoint of film formability and processability.
  • phenoxy resin examples include those obtained by reacting a bifunctional phenol with epichlorohydrin to increase the molecular weight, or a resin obtained by polyaddition of a bifunctional epoxy resin and a bifunctional phenol.
  • the bifunctional epoxy resin used include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, biphenyl diglycidyl ether, and methyl-substituted biphenyl diglycidyl ether. It is done.
  • bifunctional phenols examples include hydroquinones, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, bisphenol fluorene, methyl-substituted bisphenol fluorene, bisphenols such as dihydroxybiphenyl and methyl-substituted dihydroxybiphenyl.
  • thermosetting resin composition there is no restriction
  • % By mass to 90% by mass is preferable, 20% by mass to 80% by mass is more preferable, and 30% by mass to 60% by mass is particularly preferable.
  • the other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include thixotropic agents, fillers, leveling agents, antioxidants, colorants, conductivity-imparting agents, and adhesion-imparting agents. Is mentioned.
  • thermosetting sheet The said thermosetting sheet
  • the thermosetting sheet is formed, for example, by forming a thermosetting adhesive layer made of the thermosetting resin composition on a base film (peeling base).
  • the base film include a polyethylene terephthalate film and a polyimide film.
  • the thermosetting sheet is obtained by applying the thermosetting resin composition to a base film that is peel-treated with silicone or the like as necessary for a polyethylene terephthalate film, a polyimide film, or the like.
  • the thermosetting adhesive layer is preferably formed with an average thickness of 10 ⁇ m to 50 ⁇ m.
  • thermosetting resin composition and the thermosetting sheet can be preferably applied to the electronic component field.
  • the thermosetting sheet adhesively fixes a terminal portion of a flexible printed wiring board and a reinforcing sheet having a thickness of 50 ⁇ m to 2 mm such as polyethylene terephthalate, polyimide, glass epoxy, stainless steel, and aluminum for lining it.
  • the terminal portion of the flexible printed wiring board and the reinforcing sheet can be bonded with the thermosetting material of the thermosetting adhesive layer excluding the base film of the thermosetting sheet of the present invention.
  • a reinforced flexible printed wiring board that is fixed is obtained.
  • the compound of the present invention (first compound) is represented by the following general formula (1).
  • the compound is useful as a curing accelerator or a precursor thereof that promotes low temperature curing by the thermal polymerization initiator while maintaining the storage stability of the thermosetting resin composition.
  • R 1 and R 2 each independently represents an alkyl group having 1 to 4 carbon atoms
  • R 3 represents a substituted aryl group
  • R 4 represents a substituted or Represents an unsubstituted aralkyl group.
  • X ⁇ represents an anion.
  • Examples of the alkyl group having 1 to 4 carbon atoms of R 1 and R 2 in the general formula (1) of the compound (first compound) include, for example, a methyl group, an ethyl group, an n-propyl group, and iso-propyl. Group, n-butyl group, tert-butyl group and the like. Among these, a methyl group and an ethyl group are preferable from the viewpoint of thermal stability and ease of synthesis.
  • the alkyl group has 3 or more carbon atoms, the thermal dissociation start temperature of the ammonium salt may be excessively lowered, and the thermal stability may be lowered. In addition, since the steric hindrance increases, the synthesis of the ammonium salt may be difficult.
  • Examples of the substituted aryl group of R 3 in the general formula (1) of the compound (first compound) include a substituted aromatic hydrocarbon group.
  • Examples of the substituted aromatic hydrocarbon group include a substituted phenyl group and a substituted naphthyl group.
  • Examples of the substituted phenyl group include an alkyl-substituted phenyl group, a hydroxy-substituted phenyl group, and an alkoxy-substituted phenyl group.
  • Examples of the alkyl substituent in the alkyl-substituted phenyl group include an alkyl group having 1 to 4 carbon atoms.
  • alkyl group having 1 to 4 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a tert-butyl group.
  • Examples of the substituted or unsubstituted aralkyl group of R 4 in the general formula (1) of the compound (first compound) include an aralkyl group having 7 to 15 carbon atoms.
  • Examples of the aryl group in the aralkyl group include an aromatic hydrocarbon group.
  • Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group.
  • the substituent include an alkyl group having 1 to 4 carbon atoms.
  • Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a tert-butyl group.
  • Examples of the alkylene group in the aralkyl group include a methylene group and an ethylene group.
  • Examples of the aralkyl group include benzyl group, o-methylbenzyl group, p-methylbenzyl group, 2,5-dimethylbenzyl group, (1-naphthyl) methyl group, and phenethyl group.
  • the R 3 is a group represented by the following general formula (2), and it is easy to adjust the thermal dissociation start temperature, and synthesis It is preferable from the point that an object tends to become a crystal.
  • R 5 represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 6 represents an alkyl group having 1 to 4 carbon atoms.
  • m represents 0-3.
  • n represents 0 to 3.
  • m + n is 1 to 5. When m is 2 or 3, R 5 may be different. When n is 2 or 3, R 6 may be different.
  • R 5 is preferably a hydrogen atom.
  • R 6 is preferably a methyl group.
  • Examples of the cation of the compound represented by the general formula (1) include cations represented by the following structural formulas (1-3) to (1-12).
  • X - >> X ⁇ in the general formula (1) of the compound (first compound) is an anion.
  • the anion is preferably a halogen anion or an anion having a pKa of 3 or more of its conjugate acid at 25 ° C. in water.
  • the anion is an anion having a pKa of 3 or more at 25 ° C. in water of the conjugate acid
  • the compound depends on the thermal polymerization initiator while maintaining the storage stability of the thermosetting resin composition. It is useful as a curing accelerator that promotes low temperature curing.
  • the compound is useful as a precursor of the curing accelerator.
  • the upper limit of the pKa is not particularly limited and may be appropriately selected depending on the intended purpose. However, the pKa is preferably 7 or less.
  • halogen anion examples include chlorine ion, fluorine ion, bromine ion and iodine ion.
  • X ⁇ is preferably a carboxylate anion from the viewpoint of easy availability of raw materials and easy synthesis.
  • Examples of the carboxylate anion include anions represented by the following general formula (3).
  • R 21 represents a hydrocarbon group.
  • the hydrocarbon group may have a halogen atom.
  • the halogen atom include a fluorine atom and a chlorine atom.
  • hydrocarbon group examples include a hydrocarbon group having a cyclic structure.
  • hydrocarbon group having a cyclic structure examples include an aromatic hydrocarbon group and a hydrocarbon group having an alicyclic structure.
  • the number of carbon atoms of the hydrocarbon group is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15, and more preferably 6 to 13.
  • carboxylic acid examples include saturated fatty acids, unsaturated fatty acids, carboxylic acids having an aromatic ring, carboxylic acids having an alicyclic structure, acrylic acid, and trifluoroacetic acid.
  • Examples of the saturated fatty acid include acetic acid, propionic acid, decanoic acid, myristic acid, stearic acid, 2-ethylhexanoic acid and the like.
  • Examples of the unsaturated fatty acid include oleic acid and linoleic acid.
  • Examples of the carboxylic acid having an alicyclic structure include 1-adamantane carboxylic acid and cyclohexane carboxylic acid.
  • Examples of the carboxylic acid having an aromatic ring include substitution of benzoic acid, 2-methylbenzenecarboxylic acid, 2-phenylbenzenecarboxylic acid, 2,6-dimethylbenzenecarboxylic acid, 2-hydroxybenzenecarboxylic acid, and the like.
  • Substituted benzoic acid (benzoic acid optionally having substituent); 1-naphthalene carboxylic acid, 2-naphthalene carboxylic acid, 2-hydroxy-1-naphthalene carboxylic acid, 3-hydroxy-2-naphthalene carboxylic acid, etc.
  • carboxylic acid anion naphthalenecarboxylic acid anions, diphenylacetic acid anions, and 1-adamantanecarboxylic acid anions are preferable from the viewpoint that crystals are easily obtained.
  • Examples of the compound (first compound) include the following compounds.
  • the compound of the present invention (second compound) is represented by the following general formula (1).
  • the said compound is useful as a precursor for synthesize
  • R 1 and R 2 each independently represents an alkyl group having 1 to 4 carbon atoms
  • R 3 represents a substituted or unsubstituted aryl group
  • R 4 represents Represents a substituted or unsubstituted aralkyl group.
  • X ⁇ represents a halogen anion.
  • This tertiary amine contributes to the promotion of decomposition of the thermal polymerization initiator (for example, organic peroxide thermal polymerization initiator), and effectively enhances the curing of the radical polymerization component.
  • the thermal polymerization initiator for example, organic peroxide thermal polymerization initiator
  • Examples of the alkyl group having 1 to 4 carbon atoms of R 1 and R 2 in the general formula (1) of the compound (second compound) include a methyl group, an ethyl group, an n-propyl group, and iso-propyl. Group, n-butyl group, tert-butyl group and the like. Among these, a methyl group and an ethyl group are preferable from the viewpoint of thermal stability and ease of synthesis.
  • the alkyl group has 3 or more carbon atoms, the thermal dissociation start temperature of the ammonium salt may be excessively lowered, and the thermal stability may be lowered. In addition, since the steric hindrance increases, the synthesis of the ammonium salt may be difficult.
  • Examples of the substituted aryl group of R 3 in the general formula (1) of the compound (second compound) include a substituted aromatic hydrocarbon group.
  • Examples of the substituted aromatic hydrocarbon group include a substituted phenyl group and a substituted naphthyl group.
  • Examples of the substituted phenyl group include an alkyl-substituted phenyl group, a hydroxy-substituted phenyl group, and an alkoxy-substituted phenyl group.
  • Examples of the alkyl substituent in the alkyl-substituted phenyl group include an alkyl group having 1 to 4 carbon atoms.
  • alkyl group having 1 to 4 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a tert-butyl group.
  • Examples of the substituted or unsubstituted aralkyl group of R 4 in the general formula (1) of the compound (second compound) include an aralkyl group having 7 to 15 carbon atoms.
  • Examples of the aryl group in the aralkyl group include an aromatic hydrocarbon group.
  • Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group.
  • the substituent include an alkyl group having 1 to 4 carbon atoms.
  • Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a tert-butyl group.
  • Examples of the alkylene group in the aralkyl group include a methylene group and an ethylene group.
  • Examples of the aralkyl group include benzyl group, o-methylbenzyl group, p-methylbenzyl group, 2,5-dimethylbenzyl group, (1-naphthyl) methyl group, and phenethyl group.
  • the R 3 is a group represented by the following general formula (2), and it is easy to adjust the thermal dissociation start temperature, and synthesis It is preferable from the point that an object tends to become a crystal.
  • R 5 represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 6 represents an alkyl group having 1 to 4 carbon atoms.
  • m represents 0-3.
  • n represents 0 to 3.
  • m + n is 0 to 5. When m is 2 or 3, R 5 may be different. When n is 2 or 3, R 6 may be different.
  • m + n is preferably 1 to 5.
  • R 5 is preferably a hydrogen atom.
  • R 6 is preferably a methyl group.
  • Examples of the cation of the compound represented by the general formula (1) include cations represented by the following structural formulas (1-1) to (1-12).
  • halogen anion examples include chlorine ion, fluorine ion, bromine ion and iodine ion. Among these, chlorine ions are preferable.
  • Examples of the compound (second compound) include the following compounds.
  • Example A2 ⁇ Synthesis of ammonium salt A2>
  • Example A1 was the same as Example A1 except that N, N-dimethylaniline was changed to 5.58 g (0.0413 mol) of N, N-dimethyl-p-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.). As a result, 9.82 g (yield: 86.2%) of white crystals of ammonium salt A2 represented by the following structural formula (A2) were obtained.
  • Example A3 ⁇ Synthesis of ammonium salt A3> Except that ⁇ -chloro-o-xylene was changed to 5.23 g (0.0413 mol) of benzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in Example A2, the following structural formula (A3 9.03 g (yield 83.5%) of ammonium salt A3 represented by the following formula:
  • Example A4 ⁇ Synthesis of ammonium salt A4>
  • 10.0 g (0.0740 mol) 1- (chloromethyl) N, N-dimethyl-p-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) Naphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) 13.07 g (0.0740 mol) and 60 g of methanol were added, and the mixture was reacted at 50 ° C. for 8 hours with stirring. After cooling, the methanol was distilled off under reduced pressure to precipitate crystals.
  • Example A5 ⁇ Synthesis of ammonium salt A5> In the same manner as in Example A2, except that ⁇ -chloro-o-xylene was changed to 6.39 g (0.0413 mol) of 2,5-dimethylbenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in Example A2. 8.99 g (yield 75.2%) of white crystals of ammonium salt A5 represented by the following structural formula (A5) was obtained.
  • Example A6 ⁇ Synthesis of ammonium salt A6> In the same manner as in Example A2, except that ⁇ -chloro-o-xylene was changed to 5.81 g (0.0431 mol) of ⁇ -chloro-p-xylene (manufactured by Tokyo Chemical Industry Co., Ltd.) in Example A2. 8.91 g (yield 78.2%) of white crystals of ammonium salt A6 represented by the following structural formula (A6) were obtained.
  • Example A7 ⁇ Synthesis of ammonium salt (stabilizer) A7>
  • Example A5 was the same as Example A5 except that N, N-dimethyl-p-toluidine was changed to 5.91 g (0.0431 mol) of 3- (dimethylamino) phenol (manufactured by Tokyo Chemical Industry Co., Ltd.). Thus, 7.64 g (yield 62.1%) of reddish brown crystals of ammonium salt A7 represented by the following structural formula (A7) was obtained.
  • Example B1 ⁇ Synthesis of ammonium salt B1> While keeping a 100 mL three-necked flask equipped with a stirrer in a light-shielded state, 2.42 g (0.0076 mol) of silver diphenylacetate synthesized in Synthesis Example 1 and 10 g of acetonitrile were put into the suspension state by stirring at room temperature. A solution prepared by dissolving 2.00 g (0.0076 mol) of the ammonium salt A1 synthesized in A1 in 20 g of acetonitrile and 2 g of methanol was added.
  • Example B2 ⁇ Synthesis of ammonium salt B2>
  • the ammonium salt A1 was changed to 2.10 g (0.0076 mol) of the ammonium salt A2 synthesized in Example A2, it is represented by the following structural formula (B2) in the same manner as in Example B1. 3.04 g (yield 88.5%) of white crystals of ammonium salt B2 was obtained.
  • Example B3 ⁇ Synthesis of ammonium salt B3>
  • the ammonium salt A1 was changed to 1.99 g (0.0076 mol) of the ammonium salt A3 synthesized in Example A3, it was represented by the following structural formula (B3) in the same manner as in Example B1. 3.07 g (yield 92.3%) of white crystals of ammonium salt B3 was obtained.
  • Example B4 ⁇ Synthesis of ammonium salt B4>
  • the ammonium salt A1 was changed to 2.37 g (0.0076 mol) of the ammonium salt A4 synthesized in Example A4, it was represented by the following structural formula (B4) in the same manner as in Example B1. 3.53 g (yield 95.3%) of white crystals of ammonium salt B4 were obtained.
  • Example B5 ⁇ Synthesis of ammonium salt B5>
  • the ammonium salt A1 was changed to 2.20 g (0.0076 mol) of the ammonium salt A5 synthesized in Example A5, it was represented by the following structural formula (B5) in the same manner as in Example B1. 3.23 g (yield 91.2%) of white crystals of ammonium salt B5 were obtained.
  • Example B6 ⁇ Synthesis of ammonium salt B6>
  • the ammonium salt A1 was changed to 2.10 g (0.0076 mol) of the ammonium salt A6 synthesized in Example A6, it was represented by the following structural formula (B6) in the same manner as in Example B1. 2.99 g (yield 87.1%) of white crystals of ammonium salt B6 was obtained.
  • Example B7 ⁇ Synthesis of ammonium salt B7>
  • ammonium salt A1 was changed to 2.22 g (0.0076 mol) of ammonium salt A7 synthesized in Example A7, it was represented by the following structural formula (B7) in the same manner as in Example B1. 3.02 g (yield 85.1%) of white crystals of ammonium salt B7 was obtained.
  • Example B8 ⁇ Synthesis of ammonium salt B8>
  • ammonium salt A1 was changed to 2.20 g (0.0076 mol) of ammonium salt A8 synthesized in Example A8, it was represented by the following structural formula (B8) in the same manner as in Example B1. 2.49 g (yield 70.3%) of white crystals of ammonium salt B8 were obtained.
  • Example B9 ⁇ Synthesis of ammonium salt B9>
  • silver diphenylacetate was changed to 2.18 g (0.0076 mol) of silver 1-adamantanecarboxylate synthesized in Synthesis Example 2, the following structural formula (B9) was used. 1.39 g (yield 42.3%) of white crystals of the ammonium salt B9 represented were obtained.
  • Example B10 ⁇ Synthesis of ammonium salt B10>
  • silver diphenylacetate was changed to 2.18 g (0.0076 mol) of silver 1-adamantanecarboxylate synthesized in Synthesis Example 2, the following structural formula (B10) was used. 2.50 g (yield 72.1%) of white crystals of ammonium salt B10 represented were obtained.
  • Example B11 ⁇ Synthesis of ammonium salt B11>
  • silver diphenyl acetate was changed to 1.74 g (0.0076 mol) of silver benzoate synthesized in Synthesis Example 3, it was represented by the following structural formula (B11) in the same manner as in Example B4. 2.15 g (yield 71.1%) of white crystals of ammonium salt B11 was obtained.
  • Tables 1-1 and 1-2 show the pKa values at 25 ° C. in water of conjugate acids of ammonium salts B1 to B12 anions.
  • Thermal dissociation start temperature of ammonium salts B1 to B13 Thermal dissociation of ammonium salts B1 to B13 is started using a TG / DTA6200 differential thermal thermogravimetric simultaneous measurement device manufactured by SII Nanotechnology Co., Ltd. under a nitrogen gas atmosphere at a heating rate of 10 ° C./min and 200 mL / min. The temperature was evaluated. The results are shown in Table 2-1 and Table 2-2. In addition, since the peak of DTA accompanying the thermal dissociation start was obtained except ammonium salt B7, the peak temperature was made into thermal dissociation start temperature.
  • thermosetting resin compositions were prepared according to the formulations shown in Table 3-1 and Table 3-2.
  • the prepared thermosetting resin composition is coated on release PET (polyethylene terephthalate) that has been subjected to silicone-based mold release treatment, and is dried in a hot-air circulating oven set at 60 ° C. for 5 minutes, thereby thermosetting with an average thickness of 15 ⁇ m. Sheet was prepared.
  • the blending of phenoxy resin in Table 3-1 and Table 3-2 is the blending amount excluding the solvent, and the unit is parts by mass.
  • the radical polymerization component, the thermal polymerization initiator, and the ammonium salt are also compounded in amounts excluding the solvent, and the unit is parts by mass.
  • each material in Table 3 is as follows.
  • YP70 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • bisphenol A / bisphenol F copolymerized phenoxy resin FX-316 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • bisphenol F-type phenoxy resin Aronix M-315 manufactured by Toagosei Co., Ltd.
  • Isocyanuric acid EO modified di and triacrylate NK ester A-TMM-3L Shin-Nakamura Chemical Co., Ltd., pentaerythritol triacrylate Art Resin UN-5500: Negami Kogyo Co., Ltd., urethane acrylate oligomer Parroyl L: NOF Corporation Manufactured by Organic peroxide NIPPER BW: NOF Corporation, Organic peroxide
  • YP70 and FX-316 used a 45 mass% solid content solution of methyl ethyl ketone.
  • Aronix M-315 used a 50% by mass solid solution of toluene
  • NK ester A-TMM-3L used the stock solution as it was.
  • Art Resin UN-5500 was a 50% by weight solid solution of methyl ethyl ketone.
  • Parroyl L was a 20% by weight solid solution of toluene.
  • Nyper BW used a 20% by weight solid solution of acetone.
  • ammonium salts B1 to B13 those dissolved in methanol to a solid content of 10% by mass were used.
  • Niper BW 3.04 parts by mass and Parroyl L5 parts by mass are equimolar amounts.
  • the ammonium salt was blended so as to be 30 mol% with respect to Parroyl L or Nyper BW.
  • thermosetting sheets of Examples 1 to 16 and Comparative Examples 1 to 5 The initial low temperature curability and storage stability of the produced thermosetting sheets of Examples 1 to 16 and Comparative Examples 1 to 5 (average thickness: 15 ⁇ m) were determined by using a differential scanning calorimeter DSC6200 manufactured by SII NanoTechnology. It was evaluated by. Storage stability was evaluated by calculating the rate of decrease from the calorific value change in DSC before and after standing for 2 weeks in a dark environment of 25 ° C./65% Rh.
  • the exothermic behavior by differential scanning calorimetry reflects the curing reaction behavior of the radical polymerization component. Therefore, it can be said that the lower the curing start temperature and the curing end temperature, the lower the curability of the composition.
  • the low temperature curability was evaluated using as an index the temperature at which 2% of the total heat generation in the DSC chart reaches the curing start temperature and the temperature at which the curing end temperature reaches 98% of the total heat generation in the DSC chart. In either case, the lower temperature has low-temperature curing activity, but the exothermic (curing) end temperature, which is an indicator of the completion of the reaction, is a more important indicator.
  • the amount of change in the total calorific value before and after being left reflects the amount of progress of the reaction during being left. It can be said that the smaller the change in calorific value before and after being left, the higher the storage stability. Specifically, the function as an adhesive sheet can be maintained by suppressing the decrease to 10% or less.
  • thermosetting sheets of Examples 1 to 16 of the present invention both the curing start temperature and the curing end temperature can be lowered compared to Comparative Examples 1 and 2 in which no ammonium salt is added.
  • Comparative Examples 1 and 2 in which no ammonium salt is added.
  • Comparative Examples 3 to 5 to which an ammonium salt having a high thermal dissociation start temperature was added had almost no difference from those to which no ammonium salt was added (Comparative Examples 1 and 2), and no effect was observed. This result proved the usefulness of the present invention.
  • thermosetting resin composition of the present invention can be cured at a low temperature in a short time and can ensure storage stability before curing, it can be suitably used as an adhesive for joining electronic components.

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Abstract

Cette composition de résine thermodurcissable contient un composant de polymérisation radicalaire, un initiateur de thermopolymérisation, et un sel d'ammonium, la température de déclenchement de dissociation thermique du sel d'ammonium étant de 60 à 140° c
PCT/JP2014/081161 2013-12-05 2014-11-26 Composé, composition de résine thermodurcissable, et feuille thermodurcissable Ceased WO2015083585A1 (fr)

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