WO2019083006A1 - Composition de résine durcissable, objet durci, agent adhésif, et film adhésif - Google Patents

Composition de résine durcissable, objet durci, agent adhésif, et film adhésif

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Publication number
WO2019083006A1
WO2019083006A1 PCT/JP2018/039833 JP2018039833W WO2019083006A1 WO 2019083006 A1 WO2019083006 A1 WO 2019083006A1 JP 2018039833 W JP2018039833 W JP 2018039833W WO 2019083006 A1 WO2019083006 A1 WO 2019083006A1
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WO
WIPO (PCT)
Prior art keywords
curable resin
resin composition
imide oligomer
weight
composition according
Prior art date
Application number
PCT/JP2018/039833
Other languages
English (en)
Japanese (ja)
Inventor
さやか 脇岡
新城　隆
悠太 大當
幸平 竹田
Original Assignee
積水化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN201880069199.XA priority Critical patent/CN111263782A/zh
Priority to KR1020207000233A priority patent/KR102692137B1/ko
Priority claimed from JP2018201451A external-priority patent/JP7132084B2/ja
Priority claimed from JP2018201452A external-priority patent/JP7171365B2/ja
Publication of WO2019083006A1 publication Critical patent/WO2019083006A1/fr

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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
    • 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
    • C08G59/40—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 curing agents 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
    • 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
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition

Definitions

  • the present invention relates to a curable resin composition excellent in flame retardancy, adhesiveness, high temperature long-term heat resistance, and moisture absorption reflow resistance, and having a low environmental impact.
  • the present invention relates to a cured product of the curable resin composition, and an adhesive and an adhesive film formed using the curable resin composition.
  • the present invention relates to a curable resin composition which is excellent in adhesiveness, high temperature long-term heat resistance, moisture absorption reflow resistance, plating resistance, and low bleeding and embedding during quick pressing.
  • the present invention relates to a cured product of the curable resin composition, and an adhesive and an adhesive film formed using the curable resin composition.
  • Patent Documents 1 and 2 disclose curable resin compositions containing an epoxy resin and an imide oligomer as a curing agent.
  • a flame retardant is blended in order to impart the flame retardancy required for in-vehicle use etc. to these curable resin compositions, there has been a problem that adhesiveness and high temperature long-term heat resistance decrease.
  • these curable resin compositions containing a large amount of flame retardant have a problem in that they are poor in moisture absorption reflow resistance. Therefore, the curable resin composition which has the further outstanding effect not only in heat resistance but also in adhesiveness, moisture absorption reflow tolerance, and plating tolerance was calculated
  • Patent Document 3 discloses a curable resin composition containing a modified polyamide epoxy resin, a maleimide oligomer, and a flame retardant.
  • the curable resin composition disclosed in Patent Document 3 is considered to be excellent in adhesiveness and high temperature long-term heat resistance while exhibiting flame retardancy.
  • halogen compounds are used as flame retardants, there are problems in terms of environmental impact etc.
  • adhesiveness and high temperature long-term heat resistance may not be sufficiently obtained. There was a problem that.
  • Patent Document 4 discloses a resin composition containing an inorganic filler having an average particle diameter of 1 nm or more and 500 nm or less.
  • the resin composition disclosed in Patent Document 4 is considered to be excellent in moisture absorption reflow resistance and low exudation property when heated and pressurized.
  • the resin composition disclosed in Patent Document 4 is insufficient in high temperature long-term heat resistance, or in a press method called quick press performed in the production or processing of FPC, the resin composition is sufficiently exuded. Problems that can not be suppressed.
  • JP 2007-91799 A Japanese Patent Application Laid-Open No. 61-270852 JP 10-130400 A JP 2007-204696 A
  • An object of the present invention is to provide a curable resin composition that is excellent in flame retardancy, adhesiveness, high temperature long-term heat resistance, and moisture absorption reflow resistance, and has a low environmental impact. Another object of the present invention is to provide a cured product of the curable resin composition, and an adhesive and an adhesive film formed using the curable resin composition. Another object of the present invention is to provide a curable resin composition which is excellent in adhesiveness, high temperature long-term heat resistance, moisture absorption reflow resistance, plating resistance, and low bleeding and embedding during quick pressing. Another object of the present invention is to provide a cured product of the curable resin composition, and an adhesive and an adhesive film formed using the curable resin composition.
  • the present invention 1 is a curable resin composition containing a curable resin, an imide oligomer, and a boehmite type aluminum hydroxide.
  • the present invention 1 will be described in detail below.
  • the present inventors examined blending a boehmite type aluminum hydroxide as a flame retardant further into a curable resin composition containing a curable resin and an imide oligomer. As a result, it has been found that a curable resin composition excellent in flame retardancy, adhesiveness, high temperature long-term heat resistance, and moisture absorption reflow resistance, and having a low environmental load can be obtained, resulting in completion of the first invention.
  • the curable resin composition of the first invention contains a curable resin.
  • An epoxy resin is preferably used as the curable resin. It is preferable that the said epoxy resin is a non-halogen-type epoxy resin manufactured without using a halogen compound as a raw material from an environmental load etc. viewpoint.
  • epoxy resin examples include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, 2,2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin Propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, naphthylene ether Epoxy resin, phenol novolac epoxy resin, ortho cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, bif Nirunoborakku type epoxy resins, naphthalene phenol novolac-type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, fluorene type epoxy resins, glycidyl ester compounds.
  • the viscosity is low and the processability at room temperature of the resulting curable resin composition can be easily adjusted, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, resorcinol epoxy resin, etc.
  • An epoxy resin which is liquid at normal temperature is preferred.
  • the epoxy resins may be used alone or in combination of two or more.
  • the curable resin composition of the first invention contains an imide oligomer.
  • the imide oligomer preferably has a reactive functional group capable of reacting with the curable resin.
  • the said reactive functional group is based also on the kind of curable resin to be used, when using an epoxy resin as curable resin, it is preferable that they are an acid anhydride group and / or phenolic hydroxyl group.
  • the imide oligomer preferably has the reactive functional group at the end of the main chain, and more preferably at both ends of the main chain.
  • the imide oligomer having an acid anhydride group as the reactive functional group is, for example, a segment derived from an acid dianhydride represented by the following formula (1) and a diamine represented by the following formula (2)
  • the imide oligomer etc. which have a segment are mentioned.
  • A is a tetravalent group represented by the following formula (3-1) or the following formula (3-2).
  • B is a divalent group represented by the following formula (4-1) or the following formula (4-2), and R 1 to R 4 are each independently a hydrogen atom or 1 Hydrocarbon group.
  • Y is a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, a bond A linear or branched divalent hydrocarbon group which may have an oxygen atom at a position, or a divalent group having an aromatic ring which may have an oxygen atom at a bonding position .
  • part or all of the hydrogen atoms may be substituted with a hydroxyl group or a monovalent hydrocarbon group.
  • an imide oligomer having an acid anhydride group as the reactive functional group for example, a reaction of an acid dianhydride represented by the above formula (1) and a diamine represented by the above formula (2) And the like.
  • the solvent is removed from the obtained amic acid oligomer solution by heating or reduced pressure or the like, or the solution is introduced into a poor solvent such as water, methanol, hexane and the like to reprecipitate to recover the amic acid oligomer, and
  • the imidation reaction is allowed to proceed by heating at 200 ° C. or more for 1 hour or more.
  • an imido oligomer having a phenolic hydroxyl group as the reactive functional group for example, a segment derived from the acid dianhydride represented by the formula (1) and a phenolic hydroxyl group represented by the following formula (5)
  • the imide oligomer etc. which have a segment derived from containing monoamine etc. are mentioned.
  • Ar is a divalent aromatic group which may be substituted, and R 5 and R 6 are each independently a hydrogen atom or a monovalent hydrocarbon group.
  • the following method etc. are mentioned, for example. That is, a method of reacting the acid dianhydride represented by the formula (1) with the phenolic hydroxyl group-containing monoamine represented by the formula (5), or the acid dianhydride represented by the formula (1) The method of making the phenolic hydroxyl group containing monoamine represented by said Formula (5), etc. be made to react, after making the diamine represented by said, and the said Formula (2) react.
  • the specific example of the method of making the acid dianhydride represented by said Formula (1) and the phenolic hydroxyl group containing monoamine represented with said Formula (5) is shown below.
  • the phenolic hydroxyl group-containing monoamine represented by the above formula (5) is dissolved in a solvent in which the amic acid oligomer obtained by the reaction is soluble (for example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc.)
  • the acid dianhydride represented by the above formula (1) is added to the obtained solution and reacted to obtain an amic acid oligomer solution.
  • the solvent is removed from the obtained amic acid oligomer solution by heating or reduced pressure or the like, or the solution is introduced into a poor solvent such as water, methanol, hexane and the like to reprecipitate to recover the amic acid oligomer, and
  • the imidation reaction is allowed to proceed by heating at 200 ° C. or more for 1 hour or more.
  • a method of reacting the acid dianhydride represented by the above formula (1) and the diamine represented by the above formula (2), and further reacting the phenolic hydroxyl group-containing monoamine represented by the above formula (5) Specific examples of are shown below.
  • a solution obtained by dissolving in advance a diamine represented by the above formula (2) in a solvent in which the amic acid oligomer obtained by the reaction is soluble eg, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc.
  • the acid dianhydride represented by the above-mentioned formula (1) is added to the mixture and reacted to obtain a solution of an amic acid oligomer (A) having an acid anhydride group at both ends.
  • the solvent is removed from the obtained solution of the amic acid oligomer (A) by heating or reduced pressure or the like, or the solution is introduced into a poor solvent such as water, methanol, hexane or the like to reprecipitate, thereby amic acid oligomer (A)
  • the reaction mixture is further heated at about 200.degree. C. or more for 1 hour or more to advance the imidation reaction.
  • the imide oligomer having an acid anhydride group as a reactive functional group at both terminals thus obtained is dissolved again in a solvent (eg, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc.)
  • a solvent eg, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc.
  • the phenolic hydroxyl group-containing monoamine represented by 5 is added and reacted to obtain a solution of an amic acid oligomer (B).
  • the solvent is removed from the obtained solution of the amic acid oligomer (B) by heating or reduced pressure or the like, or the solution is poured into a poor solvent such as water, methanol, hexane or the like to reprecipitate to recover the amic acid oligomer (B) Further, the imidization reaction is allowed to proceed by heating at about 200.degree.
  • the molar ratio between the acid dianhydride represented by the above formula (1), the diamine represented by the above formula (2) and the phenolic hydroxyl group-containing monoamine represented by the above formula (5), and the imidization conditions By adjusting, it is possible to obtain an imide oligomer having a desired number average molecular weight and having a phenolic hydroxyl group as a reactive functional group at both ends.
  • Examples of the acid dianhydride represented by the above formula (1) include pyromellitic dianhydride, 3,3′-oxydiphthalic dianhydride, 3,4′-oxydiphthalic dianhydride, 4,4 '-Oxydiphthalic acid dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride, 4,4'-bis (3,4-dicarboxylic phenoxy) diphenyl ether, p-phenylene bis (Trimellitate anhydride), 2,3,3 ', 4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-carbonyldiphthalic acid An acid dianhydride etc.
  • Examples of the diamine represented by the above formula (2) include 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl ether, 3,4 '-Diaminodiphenylether, 4,4'-diaminodiphenylether, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl Sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4) -Aminophenoxy) benzene, 1,
  • 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,2-phenylenediamine, 1 because they are excellent in control of softening point and solubility of imide oligomer, heat resistance and availability.
  • phenolic hydroxyl group-containing monoamines represented by the above formula (5) examples include 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, 4-amino-2 , 3-xylenol, 4-amino-2,5-xylenol, 4-amino-2,6-xylenol, 4-amino-1-naphthol, 5-amino-2-naphthol, 6-amino-1-naphthol, 4 And -amino-2,6-diphenylphenol and the like.
  • 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o- and the like because they are excellent in availability and storage stability and a cured product having a high glass transition temperature is obtained. Cresol is preferred.
  • the preferable lower limit of the imidation ratio of the imide oligomer is 70%.
  • the said imidation ratio being 70% or more, the hardened
  • a more preferable lower limit of the imidation ratio is 75%, and a still more preferable lower limit is 80%.
  • the preferable upper limit in particular of the imidation ratio of the said imide oligomer does not have it, a substantial upper limit is 98%.
  • the above “imidization ratio” can be determined by Fourier transform infrared spectroscopy (FT-IR).
  • the imide oligomers may be used alone or in combination of two or more.
  • the preferable lower limit of the number average molecular weight of the imide oligomer is 400, and the preferable upper limit is 5000.
  • the more preferable lower limit of the number average molecular weight of the imide oligomer is 500, and the more preferable upper limit is 4000.
  • the above-mentioned "number average molecular weight” is a value determined by gel permeation chromatography (GPC) and converted to polystyrene.
  • GPC gel permeation chromatography
  • JAIGEL-2H-A manufactured by Japan Analysis Industry Co., Ltd.
  • the preferable upper limit of the softening point of the imide oligomer is 250 ° C.
  • the softening point of the said imide oligomer being 250 degrees C or less, the hardened
  • a more preferable upper limit of the softening point of the imide oligomer is 200 ° C.
  • the substantial lower limit is 60.degree.
  • the softening point of the imide oligomer can be determined by the ring and ball method according to JIS K 2207.
  • the preferable upper limit of the melting point of the imide oligomer is 300 ° C.
  • the melting point of the imide oligomer is 300 ° C. or less, the resulting curable resin composition is excellent in adhesiveness and high temperature long-term heat resistance.
  • a more preferable upper limit of the melting point of the imide oligomer is 250 ° C.
  • the melting point of the imide oligomer can be determined by differential scanning calorimetry or a commercially available melting point measuring device.
  • the preferable lower limit of the content of the imide oligomer in the total 100 parts by weight of the curable resin and the imide oligomer is 10 parts by weight, and the preferable upper limit is 90 parts by weight.
  • the content of the imide oligomer is in this range, the cured product of the curable resin composition obtained is excellent in mechanical strength at high temperature, adhesiveness, and high temperature long-term heat resistance.
  • a more preferable lower limit of the content of the imide oligomer is 20 parts by weight, and a more preferable upper limit is 80 parts by weight.
  • the curable resin composition of the present invention 1 may contain other curing agent in addition to the imide oligomer as long as the object of the present invention is not impaired.
  • the other curing agent include phenol-based curing agents, thiol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, cyanate-based curing agents, active ester-based curing agents, and the like. Among them, phenolic curing agents, acid anhydride curing agents, cyanate curing agents, and active ester curing agents are preferable.
  • the upper limit of the content ratio of the other curing agent in the total 100 parts by weight of the imide oligomer and the other curing agent is preferably 70.
  • the upper limit is 50 parts by weight, more preferably 30 parts by weight.
  • the curable resin composition of the first invention contains a boehmite type aluminum hydroxide.
  • the curable resin composition of the present invention 1 has excellent flame retardancy without using a halogen compound etc. while maintaining excellent adhesiveness and high temperature long-term heat resistance. And moisture absorption reflow resistance.
  • the curable resin composition of this invention 2 also contains a boehmite type aluminum hydroxide so that it may mention later.
  • the preferable lower limit of the average particle diameter of the boehmite type aluminum hydroxide is 0.1 ⁇ m, and the preferable upper limit is 10 ⁇ m.
  • the average particle diameter of the boehmite type aluminum hydroxide is in this range, the dispersibility in the curable resin composition becomes excellent without deteriorating the coating property and the like, and the flame retardancy is improved. It becomes a thing.
  • the more preferable lower limit of the average particle diameter of the boehmite type aluminum hydroxide is 0.5 ⁇ m, and the more preferable upper limit is 8 ⁇ m.
  • the average particle diameter of the boehmite aluminum hydroxide can be measured by dispersing the boehmite aluminum hydroxide in a solvent (such as water or an organic solvent) using a particle size distribution analyzer.
  • a solvent such as water or an organic solvent
  • NICOMP 380ZLS made by PARTICLE SIZING SYSTEMS company
  • NICOMP 380ZLS made by PARTICLE SIZING SYSTEMS company
  • the lower limit of the content of the boehmite-type aluminum hydroxide is preferably 10 parts by weight and 150 parts by weight with respect to 100 parts by weight in total of the curable resin and the imide oligomer.
  • the content of the boehmite type aluminum hydroxide is 10 parts by weight or more, the resulting curable resin composition becomes excellent in flame retardancy.
  • the content of the boehmite type aluminum hydroxide is 150 parts by weight or less, the resulting curable resin composition becomes more excellent in adhesiveness.
  • a more preferable lower limit of the content of the boehmite type aluminum hydroxide is 20 parts by weight, and a more preferable upper limit is 100 parts by weight.
  • the curable resin composition of the first invention preferably contains a curing accelerator.
  • a curing accelerator By containing the said hardening accelerator, hardening time can be shortened and productivity can be improved.
  • the curing accelerator examples include imidazole curing accelerator, tertiary amine curing accelerator, phosphine curing accelerator, phosphorus curing accelerator, photo base generator, sulfonium salt curing accelerator and the like. .
  • an imidazole-based curing accelerator is preferable because of excellent storage stability.
  • the content of the curing accelerator is preferably 0.01 parts by weight with a preferable lower limit and 10 parts by weight with a preferable upper limit based on 100 parts by weight in total of the curable resin and the imide oligomer.
  • the curing time can be shortened while maintaining excellent adhesiveness and the like.
  • a more preferable lower limit of the content of the curing accelerator is 0.05 parts by weight, and a more preferable upper limit is 5 parts by weight.
  • the curable resin composition of the present invention 1 may contain an inorganic filler for the purpose of reducing the linear expansion coefficient after curing to reduce warpage, or further improving the adhesion reliability. .
  • inorganic filler examples include silica, barium sulfate, alumina, aluminum nitride, boron nitride, silicon nitride, aluminum hydroxide, magnesium hydroxide, glass powder, glass frit, glass fiber, carbon fiber, inorganic ion exchanger, etc. Can be mentioned.
  • the preferable lower limit of the content of the inorganic filler is 10 parts by weight and the preferable upper limit is 300 parts by weight with respect to 100 parts by weight in total of the curable resin and the imide oligomer.
  • the adhesive reliability can be improved by maintaining the excellent processability and the like.
  • a more preferable lower limit of the content of the inorganic filler is 20 parts by weight, and a more preferable upper limit is 200 parts by weight.
  • an inorganic filler can also be used as a flow control agent for the purpose of improving the coating property to an adherend in a short time, and a shape-retaining property.
  • inorganic filler used as a flow control agent examples include fumed silica such as aerosil and layered silicates.
  • the content of the inorganic filler used as the flow control agent is preferably 0.1 parts by weight with a preferable lower limit and 50 parts by weight with a preferable upper limit based on 100 parts by weight in total of the curable resin and the imide oligomer.
  • the content of the inorganic filler used as the flow control agent is in this range, the effect of improving the wettability and the shape retentivity in a short time to the adherend can be improved.
  • the more preferable lower limit of the content of the inorganic filler used as the flow control agent is 0.5 parts by weight, and the more preferable upper limit is 30 parts by weight.
  • the curable resin composition of the present invention 1 may contain an organic filler for the purpose of stress relaxation, toughness addition and the like.
  • organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, benzoguanamine particles, and core-shell particles thereof.
  • polyamide particles, polyamide imide particles and polyimide particles are preferable.
  • the upper limit of the content of the organic filler is preferably 300 parts by weight with respect to 100 parts by weight in total of the curable resin and the imide oligomer. When the content of the organic filler is in this range, the obtained cured product is excellent in toughness and the like while maintaining excellent adhesion and the like. A more preferable upper limit of the content of the organic filler is 200 parts by weight.
  • the curable resin composition of the present invention 1 may contain a polymer compound as long as the object of the present invention is not impaired.
  • the said high molecular compound plays a role of a film-forming component.
  • the polymer compound may have a reactive functional group.
  • examples of the reactive functional group that the polymer compound has include an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group and the like.
  • the curable resin composition of the present invention 1 may contain a reactive diluent as long as the object of the present invention is not impaired. From the viewpoint of adhesion reliability, a reactive diluent having two or more reactive functional groups in one molecule is preferable as the above-mentioned reactive diluent. As a reactive functional group which the said reactive diluent has, the thing similar to the reactive functional group which the high molecular compound mentioned above has is mentioned.
  • the curable resin composition of the present invention 1 may further contain additives such as a solvent, a coupling agent, a dispersant, a storage stabilizer, a bleed inhibitor, a flux agent, a leveling agent and the like.
  • additives such as a solvent, a coupling agent, a dispersant, a storage stabilizer, a bleed inhibitor, a flux agent, a leveling agent and the like.
  • Methyl ethyl ketone is preferably used as the solvent.
  • the curable resin composition of the first invention for example, a curable resin, an imide oligomer, and a boehmite aluminum hydroxide using a mixer such as a homodisper, a universal mixer, a Banbury mixer, a kneader, etc. And a method of mixing a curing accelerator, an inorganic filler and the like which are added as necessary.
  • a mixer such as a homodisper, a universal mixer, a Banbury mixer, a kneader, etc.
  • a method of mixing a curing accelerator, an inorganic filler and the like which are added as necessary.
  • the curable resin composition of this invention 1 can be used for a wide use, it can be used suitably for the electronic material use in which especially high heat resistance is calculated
  • it can be used as a die attach agent in aviation, in-vehicle electrical control unit (ECU) applications, power devices using SiC, GaN, and the like.
  • the cured product of the curable resin composition of the first invention is also one of the present invention.
  • An adhesive using the curable resin composition of the first invention (hereinafter also referred to as "the adhesive of the first invention") is also one of the present invention.
  • An adhesive film can be obtained by a method such as drying after coating the adhesive of the first invention on a film.
  • An adhesive film using the adhesive of the first invention is also one of the present invention.
  • the present invention 2 is a curable resin composition containing a curable resin, an imide oligomer, and an inorganic filler, and having a melt viscosity at 180 ° C. of 10 kPa ⁇ s or more and less than 1000 kPa ⁇ s.
  • the present invention 2 will be described in detail below.
  • the present inventors further studied that an inorganic filler was further added to a curable resin composition containing a curable resin and an imide oligomer, and that the melt viscosity of the entire composition was within a specific range. .
  • a curable resin composition excellent in adhesiveness, high temperature long-term heat resistance, moisture absorption reflow resistance, plating resistance, and low bleeding and embedding during quick pressing can be obtained, according to the present invention 2 It came to complete.
  • the curable resin composition of the second invention contains a curable resin.
  • An epoxy resin is preferably used as the curable resin.
  • epoxy resin examples include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, 2,2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin Propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, naphthylene ether Epoxy resin, phenol novolac epoxy resin, ortho cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, bif Nirunoborakku type epoxy resins, naphthalene phenol novolac-type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, fluorene type epoxy resins, glycidyl ester compounds.
  • the viscosity is low and the processability at room temperature of the resulting curable resin composition can be easily adjusted, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, resorcinol epoxy resin, etc.
  • An epoxy resin which is liquid at normal temperature is preferred.
  • the epoxy resins may be used alone or in combination of two or more.
  • the curable resin composition of the second invention contains an imide oligomer.
  • the imide oligomer preferably has a reactive functional group capable of reacting with the curable resin.
  • the said reactive functional group is based also on the kind of curable resin to be used, when using an epoxy resin as curable resin, it is preferable that they are an acid anhydride group and / or phenolic hydroxyl group.
  • the imide oligomer preferably has the reactive functional group at the end of the main chain, and more preferably at both ends of the main chain.
  • the imide oligomer having an acid anhydride group as the reactive functional group is, for example, a segment derived from an acid dianhydride represented by the following formula (6) and a diamine represented by the following formula (7)
  • the imide oligomer etc. which have a segment are mentioned.
  • A is a tetravalent group represented by the following formula (8-1) or the following formula (8-2).
  • B is a divalent group represented by the following formula (9-1) or the following formula (9-2), and R 7 to R 10 each independently represent a hydrogen atom or 1 Hydrocarbon group.
  • an imide oligomer having an acid anhydride group as the reactive functional group for example, a reaction of an acid dianhydride represented by the above formula (6) and a diamine represented by the above formula (7) And the like.
  • the solvent is removed from the obtained amic acid oligomer solution by heating or reduced pressure or the like, or the solution is introduced into a poor solvent such as water, methanol, hexane and the like to reprecipitate to recover the amic acid oligomer, and
  • the imidation reaction is allowed to proceed by heating at 200 ° C. or more for 1 hour or more.
  • an imido oligomer having a phenolic hydroxyl group as the reactive functional group for example, a segment derived from an acid dianhydride represented by the above formula (6) and a phenolic hydroxyl group represented by the following formula (10)
  • the imide oligomer etc. which have a segment derived from containing monoamine etc. are mentioned.
  • Ar is a divalent aromatic group which may be substituted, and R 11 and R 12 are each independently a hydrogen atom or a monovalent hydrocarbon group.
  • the following method etc. are mentioned, for example. That is, a method of reacting the acid dianhydride represented by the above formula (6) with the phenolic hydroxyl group-containing monoamine represented by the above formula (10), or the acid dianhydride represented by the above formula (6) And the diamine represented by the above formula (7), and then the method of reacting the phenolic hydroxyl group-containing monoamine represented by the above formula (10).
  • the specific example of the method of making the acid dianhydride represented by said Formula (6) and the phenolic hydroxyl group containing monoamine represented by said Formula (10) is shown below.
  • the phenolic hydroxyl group-containing monoamine represented by the above formula (10) is dissolved in a solvent in which the amic acid oligomer obtained by the reaction is soluble (for example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc.)
  • the acid dianhydride represented by the above formula (6) is added to the obtained solution and reacted to obtain an amic acid oligomer solution.
  • the solvent is removed from the obtained amic acid oligomer solution by heating or reduced pressure or the like, or the solution is introduced into a poor solvent such as water, methanol, hexane and the like to reprecipitate to recover the amic acid oligomer, and
  • the imidation reaction is allowed to proceed by heating at 200 ° C. or more for 1 hour or more.
  • a solution obtained by dissolving in advance a diamine represented by the above formula (7) in a solvent in which the amic acid oligomer obtained by the reaction is soluble eg, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc.
  • the acid dianhydride represented by the above formula (6) is added to the mixture and reacted to obtain a solution of an amic acid oligomer (A) having an acid anhydride group at both ends.
  • the solvent is removed from the obtained solution of the amic acid oligomer (A) by heating or reduced pressure or the like, or the solution is introduced into a poor solvent such as water, methanol, hexane or the like to reprecipitate, thereby amic acid oligomer (A)
  • the reaction mixture is further heated at about 200.degree. C. or more for 1 hour or more to advance the imidation reaction.
  • the imide oligomer having an acid anhydride group as a reactive functional group at both terminals thus obtained is dissolved again in a solvent (eg, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc.)
  • a solvent eg, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc.
  • the phenolic hydroxyl group-containing monoamine represented by 10 is added and reacted to obtain a solution of an amic acid oligomer (B).
  • the solvent is removed from the obtained solution of the amic acid oligomer (B) by heating or reduced pressure or the like, or the solution is poured into a poor solvent such as water, methanol, hexane or the like to reprecipitate to recover the amic acid oligomer (B) Further, the imidization reaction is allowed to proceed by heating at about 200 ° C. or more for one hour or more.
  • the molar ratio of the acid dianhydride represented by the above formula (6) to the diamine represented by the above formula (7) and the phenolic hydroxyl group-containing monoamine represented by the above formula (10), and the imidization conditions By adjusting, it is possible to obtain an imide oligomer having a desired number average molecular weight and having a phenolic hydroxyl group as a reactive functional group at both ends.
  • Examples of the acid dianhydride represented by the above formula (6) include pyromellitic dianhydride, 3,3′-oxydiphthalic dianhydride, 3,4′-oxydiphthalic dianhydride, 4,4 '-Oxydiphthalic acid dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride, 4,4'-bis (3,4-dicarboxylic phenoxy) diphenyl ether, p-phenylene bis (Trimellitate anhydride), 2,3,3 ', 4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-carbonyldiphthalic acid An acid dianhydride etc.
  • Examples of the diamine represented by the above formula (7) include 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenyl ether, and 3,4.
  • 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,2-phenylenediamine, 1 because they are excellent in control of softening point and solubility of imide oligomer, heat resistance and availability.
  • Examples of the phenolic hydroxyl group-containing monoamine represented by the above formula (10) include 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, 4-amino-2 , 3-xylenol, 4-amino-2,5-xylenol, 4-amino-2,6-xylenol, 4-amino-1-naphthol, 5-amino-2-naphthol, 6-amino-1-naphthol, 4 And -amino-2,6-diphenylphenol and the like.
  • 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o- and the like because they are excellent in availability and storage stability and a cured product having a high glass transition temperature is obtained. Cresol is preferred.
  • the preferable lower limit of the imidation ratio of the imide oligomer is 70%.
  • the said imidation ratio being 70% or more, the hardened
  • a more preferable lower limit of the imidation ratio is 75%, and a still more preferable lower limit is 80%.
  • the preferable upper limit in particular of the imidation ratio of the said imide oligomer does not have it, a substantial upper limit is 98%.
  • the above “imidization ratio” can be determined by Fourier transform infrared spectroscopy (FT-IR).
  • the imide oligomers may be used alone or in combination of two or more.
  • the preferable lower limit of the number average molecular weight of the imide oligomer is 400, and the preferable upper limit is 5000.
  • the more preferable lower limit of the number average molecular weight of the imide oligomer is 500, and the more preferable upper limit is 4000.
  • the above-mentioned "number average molecular weight” is a value determined by gel permeation chromatography (GPC) and converted to polystyrene.
  • GPC gel permeation chromatography
  • JAIGEL-2H-A manufactured by Japan Analysis Industry Co., Ltd.
  • the preferable upper limit of the softening point of the imide oligomer is 250 ° C.
  • the softening point of the said imide oligomer being 250 degrees C or less, the hardened
  • a more preferable upper limit of the softening point of the imide oligomer is 200 ° C.
  • the substantial lower limit is 60.degree.
  • the softening point of the imide oligomer can be determined by the ring and ball method according to JIS K 2207.
  • the preferable upper limit of the melting point of the imide oligomer is 300 ° C.
  • the melting point of the imide oligomer is 300 ° C. or less, the resulting curable resin composition is excellent in adhesiveness and high temperature long-term heat resistance.
  • a more preferable upper limit of the melting point of the imide oligomer is 250 ° C.
  • the melting point of the imide oligomer can be determined by differential scanning calorimetry or a commercially available melting point measuring device.
  • the preferable lower limit of the content of the imide oligomer in the total 100 parts by weight of the curable resin and the imide oligomer is 10 parts by weight, and the preferable upper limit is 90 parts by weight.
  • the content of the imide oligomer is in this range, the cured product of the curable resin composition obtained is excellent in mechanical strength at high temperature, adhesiveness, and high temperature long-term heat resistance.
  • a more preferable lower limit of the content of the imide oligomer is 20 parts by weight, and a more preferable upper limit is 80 parts by weight.
  • the curable resin composition of the present invention 2 may contain other curing agent in addition to the imide oligomer as long as the object of the present invention is not impaired.
  • the other curing agent include phenol-based curing agents, thiol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, cyanate-based curing agents, active ester-based curing agents, and the like. Among them, phenolic curing agents, acid anhydride curing agents, cyanate curing agents, and active ester curing agents are preferable.
  • the upper limit of the content ratio of the other curing agent in the total 100 parts by weight of the imide oligomer and the other curing agent is 70
  • the upper limit is 50 parts by weight, more preferably 30 parts by weight.
  • the curable resin composition of the present invention 2 contains an inorganic filler.
  • the curable resin composition of the present invention 2 is resistant to moisture absorption reflow, plating resistance and low stain at the time of quick pressing while maintaining excellent adhesiveness and high temperature long-term heat resistance. It is excellent in delivery properties.
  • the inorganic filler is preferably at least one of silica and barium sulfate.
  • the curable resin composition of the present invention 2 is excellent in moisture absorption reflow resistance, plating resistance, and low exudation property during quick pressing. It becomes.
  • Examples of the above-mentioned silica and other inorganic fillers other than the above-mentioned barium sulfate include alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, glass frit, glass fiber, carbon fiber, inorganic ion exchanger and the like.
  • the above inorganic fillers may be used alone or in combination of two or more.
  • the preferable upper limit of the average particle size of the inorganic filler is 4 ⁇ m.
  • the average particle diameter of the inorganic filler is 4 ⁇ m or less, the resulting curable resin composition becomes excellent due to the low bleeding property at the time of quick pressing.
  • a more preferable upper limit of the average particle size of the inorganic filler is 3 ⁇ m.
  • the preferable lower limit of the average particle diameter of the inorganic filler is 5 nm, and the more preferable lower limit is 10 nm.
  • the average particle diameter of the said inorganic filler and the flow control agent mentioned later disperses the said inorganic filler and flow control agent in solvent (water, organic solvent etc.), for example using a particle size distribution analyzer, and measures it. can do.
  • solvent water, organic solvent etc.
  • NICOMP 380ZLS made by PARTICLE SIZING SYSTEMS company
  • NICOMP 380ZLS made by PARTICLE SIZING SYSTEMS company
  • the preferable lower limit of the content of the inorganic filler is 10 parts by weight and the preferable upper limit is 150 parts by weight with respect to 100 parts by weight in total of the curable resin and the imide oligomer.
  • the resulting curable resin composition is excellent in moisture absorption reflow resistance, plating resistance, and low exudation property at the time of quick pressing.
  • the content of the inorganic filler is 150 parts by weight or less, the resulting curable resin composition is excellent in adhesiveness and embeddability at the time of quick pressing.
  • a more preferable lower limit of the content of the inorganic filler is 20 parts by weight.
  • the curable resin composition of the present invention 2 may contain a flow control agent, in addition to the above-mentioned inorganic filler, for the purpose of improving the wettability to an adherend in a short time and the shape retention. Good.
  • a flow control agent examples include fumed silica such as Aerosil and layered silicates.
  • fumed silica such as Aerosil and layered silicates.
  • said flow control agent that whose average particle diameter is less than 100 nm is used suitably.
  • a preferable lower limit is 0.1 parts by weight and a preferable upper limit is 50 parts by weight with respect to 100 parts by weight in total of the curable resin and the imide oligomer.
  • the content of the flow control agent is in this range, the effect of improving the wettability and the shape retention in a short time to the adherend can be improved.
  • the more preferable lower limit of the content of the flow control agent is 0.5 parts by weight, and the more preferable upper limit is 30 parts by weight.
  • the curable resin composition of the present invention 2 may contain an organic filler for the purpose of stress relaxation, toughness addition and the like.
  • organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, benzoguanamine particles, and core-shell particles thereof.
  • polyamide particles, polyamide imide particles and polyimide particles are preferable.
  • the upper limit of the content of the organic filler is preferably 300 parts by weight with respect to 100 parts by weight in total of the curable resin and the imide oligomer. When the content of the organic filler is in this range, the obtained cured product is excellent in toughness and the like while maintaining excellent adhesion and the like. A more preferable upper limit of the content of the organic filler is 200 parts by weight.
  • the curable resin composition of the present invention 2 may contain a flame retardant for the purpose of imparting flame retardancy.
  • a flame retardant for the purpose of imparting flame retardancy.
  • metal hydrates such as a boehmite type aluminum hydroxide, aluminum hydroxide, magnesium hydroxide, a halogen type compound, a phosphorus type compound, a nitrogen compound etc. are mentioned, for example.
  • boehmite type aluminum hydroxide is preferable.
  • the average particle size and the content of the boehmite type aluminum hydroxide are preferably in the same range as in the first invention.
  • the preferable lower limit is 5 parts by weight and the preferable upper limit is 200 parts by weight with respect to 100 parts by weight in total of the curable resin and the imide oligomer.
  • the content of the flame retardant is in this range, the resulting curable resin composition becomes excellent in flame retardancy while maintaining excellent adhesiveness and the like.
  • the more preferable lower limit of the content of the flame retardant is 10 parts by weight, and the more preferable upper limit is 150 parts by weight.
  • the curable resin composition of the second invention preferably contains a curing accelerator.
  • a curing accelerator By containing the said hardening accelerator, hardening time can be shortened and productivity can be improved.
  • the curing accelerator examples include imidazole curing accelerator, tertiary amine curing accelerator, phosphine curing accelerator, phosphorus curing accelerator, photo base generator, sulfonium salt curing accelerator and the like. .
  • an imidazole-based curing accelerator is preferable because of excellent storage stability.
  • the content of the curing accelerator is preferably 0.01 parts by weight with a preferable lower limit and 10 parts by weight with a preferable upper limit based on 100 parts by weight in total of the curable resin and the imide oligomer.
  • the curing time can be shortened while maintaining excellent adhesiveness and the like.
  • a more preferable lower limit of the content of the curing accelerator is 0.05 parts by weight, and a more preferable upper limit is 5 parts by weight.
  • the curable resin composition of the present invention 2 may contain a polymer compound as long as the object of the present invention is not impaired.
  • the said high molecular compound plays a role of a film-forming component.
  • the polymer compound may have a reactive functional group.
  • examples of the reactive functional group that the polymer compound has include an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group and the like.
  • the curable resin composition of the present invention 2 may contain a reactive diluent as long as the object of the present invention is not impaired. From the viewpoint of adhesion reliability, a reactive diluent having two or more reactive functional groups in one molecule is preferable as the above-mentioned reactive diluent. As a reactive functional group which the said reactive diluent has, the thing similar to the reactive functional group which the high molecular compound mentioned above has is mentioned.
  • the curable resin composition of the present invention 2 may further contain additives such as a solvent, a coupling agent, a dispersant, a storage stabilizer, a bleed inhibitor, a flux agent, and a leveling agent.
  • additives such as a solvent, a coupling agent, a dispersant, a storage stabilizer, a bleed inhibitor, a flux agent, and a leveling agent.
  • Methyl ethyl ketone is preferably used as the solvent.
  • a curable resin composition of the present invention for example, a curable resin, an imide oligomer, and an inorganic filler using a mixer such as a homodisper, a universal mixer, a Banbury mixer, a kneader, etc.
  • a mixer such as a homodisper, a universal mixer, a Banbury mixer, a kneader, etc.
  • examples thereof include a method of mixing with a curing accelerator, a flow control agent, and the like added as needed.
  • the curable resin composition of the present invention 2 has a melt viscosity at 180 ° C. of 10 kPa ⁇ s or more and less than 1000 kPa ⁇ s.
  • the melt viscosity at 180 ° C. is 10 kPa ⁇ s or more
  • the curable resin composition of the present invention 2 is excellent in moisture absorption reflow resistance, plating resistance, and low bleeding during quick pressing.
  • the melt viscosity at 180 ° C. is less than 1000 kPa ⁇ s
  • the curable resin composition of the present invention 2 is excellent in adhesiveness and embeddability at the time of quick pressing.
  • the melt viscosity at 180 ° C. is raised by using a rotary rheometer for the curable resin composition (curable resin composition film) in the B-stage state from which the solvent has been removed by a coating drying step or the like. It is determined as the viscosity at 180 ° C. when the viscosity is measured while heating at a temperature rate of 10 ° C./min.
  • melt viscosity in 180 degreeC of the curable resin composition of this invention 1 mentioned above is 10 kPa * s or more and less than 1000 kPa * s.
  • the curable resin composition of this invention 2 can be used for a wide use, it can be used suitably for the electronic material use which especially high heat resistance is calculated
  • it can be used as a die attach agent in aviation, in-vehicle electrical control unit (ECU) applications, power devices using SiC, GaN, and the like.
  • the cured product of the curable resin composition of the present invention 2 is also one of the present invention.
  • An adhesive using the curable resin composition of the present invention 2 (hereinafter also referred to as "the adhesive of the present invention 2") is also one of the present invention.
  • An adhesive film can be obtained by a method such as drying after coating the adhesive of the present invention 2 on a film.
  • An adhesive film using the adhesive of the present invention 2 is also one of the present invention.
  • curable resin composition which is excellent in a flame retardance, adhesiveness, high temperature long-term heat resistance, and moisture absorption reflow resistance, and has a low environmental impact can be provided. Further, according to the present invention, it is possible to provide a cured product of the curable resin composition, and an adhesive and an adhesive film formed using the curable resin composition. Further, according to the present invention, it is possible to provide a curable resin composition which is excellent in adhesiveness, high temperature long-term heat resistance, moisture absorption reflow resistance, plating resistance, and low bleeding and embedding during quick pressing. Further, according to the present invention, it is possible to provide a cured product of the curable resin composition, and an adhesive and an adhesive film formed using the curable resin composition.
  • Synthesis Example 1-1 Preparation of Imide Oligomer 1-A 17.2 parts by weight of 1,4-bis (2- (4-aminophenyl) -2-propyl) benzene were dissolved in 200 parts by weight of N-methylpyrrolidone.
  • 1,4-bis (2- (4-aminophenyl) -2-propyl) benzene bisaniline P (manufactured by Mitsui Chemicals Fine Inc.) is used, and as N-methylpyrrolidone, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The reagent was used.
  • the imide oligomer 1-A contains the imide oligomer represented by the following formula (11) as a main component. Further, the softening point of the imide oligomer 1-A was 155 ° C., and the melting point was 170 ° C.
  • Synthesis Example 1-2 (Preparation of Imide Oligomer 1-B) 21.8 parts by weight of 3-aminophenol were dissolved in 200 parts by weight of N-methylpyrrolidone. 17.2 parts by weight of 4,4 '-(4,4'-isopropylidenediphenoxy) diphthalic anhydride was added to the resulting solution, and the reaction was allowed to react at 25 ° C. for 2 hours with stirring to react with the amic acid oligomer solution Obtained. The N-methylpyrrolidone was removed under reduced pressure from the obtained amic acid oligomer solution, and then heated at 300 ° C. for 2 hours to obtain an imide oligomer 1-B (imidation ratio 96%).
  • the imide oligomer 1-B contains the imide oligomer represented by the following formula (12) as the main component.
  • the softening point of the imide oligomer 1-B was 134 ° C., and the melting point was 154 ° C.
  • Examples 1 to 13, Comparative Examples 1 to 4 Each material was stirred and mixed according to the compounding ratio described in Tables 1 and 2 to prepare each of the curable resin compositions of Examples 1 to 13 and Comparative Examples 1 to 4.
  • Each curable resin composition obtained in Examples 1 to 13 and Comparative Examples 1 to 4 is coated on a polyimide substrate (thickness 25 ⁇ m) to a thickness of about 20 ⁇ m and dried. , Obtained an adhesive film.
  • Kapton 100H manufactured by Toray Dupont
  • the obtained adhesive film was heated at 190 ° C. for 1 hour to obtain a cured film in which a cured product was formed on one side of the polyimide substrate.
  • the obtained cured film was cut into a size of 5 inches in length ⁇ 1/2 inches in width to prepare a test piece.
  • the obtained test pieces were evaluated for flame retardancy according to the vertical combustion test defined in UL-94 of US UL Standard.
  • thermogravimetric measurement device EXTEAR TG / DTA 6200 (manufactured by SII Nano Technology Inc.) was used.
  • Each curable resin composition obtained in Examples 1 to 13 and Comparative Examples 1 to 4 was coated on a release PET film so as to have a thickness of about 20 ⁇ m and dried to obtain an adhesive film. .
  • the PET film was peeled off from the obtained adhesive film, and a polyimide substrate (50 ⁇ m in thickness) was attached to both surfaces of the adhesive layer while heating to 80 ° C. using a laminator.
  • Kapton 200H manufactured by Toray Dupont was used as the polyimide substrate. After hot pressing under conditions of 190 ° C., 3 MPa and 1 hour to cure the adhesive layer, it was cut out into a width of 1 cm to obtain a test piece.
  • the obtained test piece was subjected to T-peel at a peeling rate of 20 mm / min with a tensile tester to measure adhesion.
  • UCT-500 manufactured by ORIENTEC was used as a tensile tester. If the adhesive strength is 3.4 N / cm or more, “ ⁇ ”, if 2.0 or more and less than 3.4 N / cm, if “ ⁇ ”, if less than 2.0 N / cm The adhesion was evaluated as "x".
  • Each curable resin composition obtained in Examples 1 to 13 and Comparative Examples 1 to 4 is coated on a polyimide substrate (thickness 25 ⁇ m) to a thickness of about 20 ⁇ m and dried.
  • An adhesive film was obtained.
  • Kapton 100H manufactured by Toray Dupont
  • L / S 100 ⁇ m / 100 ⁇ m and a thickness of 18 ⁇ m and a polyimide film of 50 ⁇ m thickness.
  • bonding was performed by hot press on the conditions of 190 degreeC, 3 Mpa, and 1 hour.
  • the obtained samples for FPC evaluation were plated at 80 ° C. to 90 ° C. under the conditions of 5 ⁇ m nickel and 0.05 ⁇ m gold using a commercially available electroless nickel plating bath and electroless gold plating bath.
  • the edge of the adhesive film at the opening is observed with an optical microscope, and when the leaching of the plating solution is not confirmed, " ⁇ ", and when the leaching of the plating solution is confirmed at the end, " ⁇ " evaluated.
  • Synthesis Example 2-1 Preparation of Imide Oligomer 2-A 17.2 parts by weight of 1,4-bis (2- (4-aminophenyl) -2-propyl) benzene were dissolved in 200 parts by weight of N-methylpyrrolidone.
  • 1,4-bis (2- (4-aminophenyl) -2-propyl) benzene bisaniline P (manufactured by Mitsui Chemicals Fine Inc.) is used, and as N-methylpyrrolidone, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The reagent was used.
  • the imide oligomer 2-A contains the imide oligomer represented by the following formula (13) as the main component.
  • the softening point of the imide oligomer 2-A was 155 ° C., and the melting point was 170 ° C.
  • the imide oligomer 2-B contains the imide oligomer represented by the following formula (14) as the main component.
  • the softening point of the imide oligomer 2-B was 134 ° C., and the melting point was 154 ° C.
  • Example 14 to 22, Comparative Examples 5 to 8 Each material was stirred and mixed according to the compounding ratio described in Table 3, and each curable resin composition of Examples 14 to 22 and Comparative Examples 5 to 8 was produced.
  • the obtained curable resin composition was coated on a release PET film so as to have a thickness of about 20 ⁇ m and dried to obtain a curable resin composition film.
  • Melt viscosity at 180 ° C when viscosity was measured while peeling the PET film from the obtained curable resin composition film and heating it under the conditions of a frequency of 1 Hz and a temperature rising rate of 10 ° C / min using a rotary rheometer was measured.
  • HAAKE MARS III manufactured by Thermo Fisher Scientific Co., Ltd.
  • the results are shown in Table 3.
  • Each curable resin composition obtained in Examples 14 to 22 and Comparative Examples 5 to 8 was coated on a release PET film to a thickness of about 20 ⁇ m and dried to obtain an adhesive film. .
  • the PET film was peeled off from the obtained adhesive film, and a polyimide substrate (50 ⁇ m in thickness) was attached to both surfaces of the adhesive layer while heating to 80 ° C. using a laminator.
  • Kapton 200H manufactured by Toray Dupont was used as the polyimide substrate. After hot pressing under conditions of 190 ° C., 3 MPa and 1 hour to cure the adhesive layer, it was cut out into a width of 1 cm to obtain a test piece.
  • the obtained test piece was subjected to T-peel at a peeling rate of 20 mm / min with a tensile tester to measure adhesion.
  • UCT-500 manufactured by ORIENTEC was used as a tensile tester. If the adhesive strength is 3.4 N / cm or more, “ ⁇ ”, if 2.0 or more and less than 3.4 N / cm, if “ ⁇ ”, if less than 2.0 N / cm The adhesion was evaluated as "x".
  • bonding was performed by the quick press system on 180 degreeC, the vacuum, and the conditions of 3 MPa of press pressures for 5 minutes using a slide-type vacuum heater press.
  • a slide type vacuum heater press MKP-3000V (manufactured by Mikado Technos Co., Ltd.) was used.
  • the adhesive film edge part of an opening part was observed with the optical microscope, and the amount of oozing out of the curable resin composition (the length of the part which exudeed most) was measured.
  • curable resin composition which is excellent in a flame retardance, adhesiveness, high temperature long-term heat resistance, and moisture absorption reflow resistance, and has a low environmental impact can be provided. Further, according to the present invention, it is possible to provide a cured product of the curable resin composition, and an adhesive and an adhesive film formed using the curable resin composition. Further, according to the present invention, it is possible to provide a curable resin composition which is excellent in adhesiveness, high temperature long-term heat resistance, moisture absorption reflow resistance, plating resistance, and low bleeding and embedding during quick pressing. Further, according to the present invention, it is possible to provide a cured product of the curable resin composition, and an adhesive and an adhesive film formed using the curable resin composition.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention a pour objet de fournit une composition de résine durcissable qui se révèle excellente en termes de propriétés ignifuges, propriétés adhésives, résistance à la chaleur à haute température et sur une longue durée, et de résistance à l'absorption d'humidité et refusion, et qui présente une faible charge environnementale. En outre, l'invention a pour objet de fournir un objet durci de cette composition de résine durcissable, et un agent adhésif ainsi qu'un film adhésif constitué à l'aide de cette composition de résine durcissable. Plus précisément, la composition de résine durcissable de l'invention comprend une résine durcissable, un oligomère imide et un hydroxyde d'aluminium de type boehmite.
PCT/JP2018/039833 2017-10-27 2018-10-26 Composition de résine durcissable, objet durci, agent adhésif, et film adhésif WO2019083006A1 (fr)

Priority Applications (2)

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CN201880069199.XA CN111263782A (zh) 2017-10-27 2018-10-26 固化性树脂组合物、固化物、粘接剂和粘接膜
KR1020207000233A KR102692137B1 (ko) 2017-10-27 2018-10-26 경화성 수지 조성물, 경화물, 접착제, 및, 접착 필름

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JP2017208212 2017-10-27
JP2017-208213 2017-10-27
JP2017208213 2017-10-27
JP2017-208212 2017-10-27
JP2018-201451 2018-10-26
JP2018-201452 2018-10-26
JP2018201451A JP7132084B2 (ja) 2017-10-27 2018-10-26 硬化性樹脂組成物、硬化物、接着剤、及び、接着フィルム
JP2018201452A JP7171365B2 (ja) 2017-10-27 2018-10-26 硬化性樹脂組成物、硬化物、接着剤、及び、接着フィルム

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2022220261A1 (fr) 2021-04-14 2022-10-20 積水化学工業株式会社 Feuille de résine isolante, corps multicouche et dispositif semi-conducteur

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JP2012220895A (ja) * 2011-04-13 2012-11-12 Kaneka Corp 新規な感光性樹脂組成物及びその利用
JP2013035980A (ja) * 2011-08-10 2013-02-21 Toray Ind Inc 難燃性熱可塑性ポリエステル樹脂組成物および成形品
WO2013084714A1 (fr) * 2011-12-06 2013-06-13 株式会社カネカ Composition de résine photosensible noire et son utilisation
JP2013199645A (ja) * 2012-02-24 2013-10-03 Arakawa Chem Ind Co Ltd ポリイミド系接着剤組成物、硬化物、接着シート、積層体、フレキシブルプリント基板
WO2013174791A1 (fr) * 2012-05-22 2013-11-28 Basf Se Phosphinyliminophosphoranes utilisés comme agents ignifugeants
JP2016040391A (ja) * 2010-04-08 2016-03-24 三菱瓦斯化学株式会社 樹脂組成物、プリプレグおよび積層板
JP2017179311A (ja) * 2016-03-31 2017-10-05 日立化成株式会社 樹脂組成物、プリプレグ、樹脂シート及び積層板

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Publication number Priority date Publication date Assignee Title
WO2010133570A1 (fr) * 2009-05-19 2010-11-25 Basf Se Compositions ignifuges de guanidine phénylphosphinate
JP2016040391A (ja) * 2010-04-08 2016-03-24 三菱瓦斯化学株式会社 樹脂組成物、プリプレグおよび積層板
JP2012220895A (ja) * 2011-04-13 2012-11-12 Kaneka Corp 新規な感光性樹脂組成物及びその利用
JP2013035980A (ja) * 2011-08-10 2013-02-21 Toray Ind Inc 難燃性熱可塑性ポリエステル樹脂組成物および成形品
WO2013084714A1 (fr) * 2011-12-06 2013-06-13 株式会社カネカ Composition de résine photosensible noire et son utilisation
JP2013199645A (ja) * 2012-02-24 2013-10-03 Arakawa Chem Ind Co Ltd ポリイミド系接着剤組成物、硬化物、接着シート、積層体、フレキシブルプリント基板
WO2013174791A1 (fr) * 2012-05-22 2013-11-28 Basf Se Phosphinyliminophosphoranes utilisés comme agents ignifugeants
JP2017179311A (ja) * 2016-03-31 2017-10-05 日立化成株式会社 樹脂組成物、プリプレグ、樹脂シート及び積層板

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022220261A1 (fr) 2021-04-14 2022-10-20 積水化学工業株式会社 Feuille de résine isolante, corps multicouche et dispositif semi-conducteur
KR20230170909A (ko) 2021-04-14 2023-12-19 세키스이가가쿠 고교가부시키가이샤 절연 수지 시트, 적층체, 및 반도체 장치

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