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WO2006004118A1 - Composition de résine thermodurcissable, résine novolaque contenant une structure de triazine modifiée par de l'acide borique et procédé servant à produire celle-ci - Google Patents

Composition de résine thermodurcissable, résine novolaque contenant une structure de triazine modifiée par de l'acide borique et procédé servant à produire celle-ci Download PDF

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Publication number
WO2006004118A1
WO2006004118A1 PCT/JP2005/012410 JP2005012410W WO2006004118A1 WO 2006004118 A1 WO2006004118 A1 WO 2006004118A1 JP 2005012410 W JP2005012410 W JP 2005012410W WO 2006004118 A1 WO2006004118 A1 WO 2006004118A1
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WIPO (PCT)
Prior art keywords
resin
boric acid
structural formula
epoxy resin
group
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PCT/JP2005/012410
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English (en)
Japanese (ja)
Inventor
Yasutoshi Nakajima
Masakazu Yoshizawa
Kenshi Miyazawa
Kazutoshi Haraguchi
Akira Ohbayashi
Original Assignee
Dainippon Ink And Chemicals, Inc.
Kawamura Institute Of Chemical Research
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Application filed by Dainippon Ink And Chemicals, Inc., Kawamura Institute Of Chemical Research filed Critical Dainippon Ink And Chemicals, Inc.
Publication of WO2006004118A1 publication Critical patent/WO2006004118A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions

Definitions

  • Thermosetting resin composition boric acid-modified triazine structure-containing novolak resin, and method for producing the same
  • the present invention relates to a thermosetting resin composition, a boric acid-modified triazine structure-containing novolak resin, and a method for producing the same. Specifically, it is useful for paints, adhesives, semiconductor encapsulation, and electrical laminates, and provides excellent moisture and solder resistance to laminates, especially as a varnish for electrical laminates such as printed wiring boards.
  • the present invention relates to a thermosetting resin composition to be obtained, a novolac resin containing a boric acid-modified triazine structure used in the composition, and a method for producing the same.
  • thermosetting resin composition using an epoxy resin has a laminated resin, a sealing material, a paint, an anticorrosive primer, an adhesive material, a molding material, and the like because of its high resin reactivity and excellent resin properties. It is used in a wide range of civil engineering materials. In recent years, due to problems associated with heat generation and lead-free soldering due to higher frequency of electronic equipment, it is a heat resistant material with higher glass transition temperature as a material used for laminates, adhesives, paints, and solders. Development of a thermosetting resin composition that yields a cured product is demanded.
  • boric acid or boric acid has been added to a partially cured product solution of epoxy resin and polyamine as a method for achieving a high glass transition point of a cured product of a thermosetting resin composition and improving heat resistance.
  • a technique is known in which an ester is added to uniformly and finely disperse a boron oxide or boric acid-modified compound produced from boric acid or a boric acid ester in an epoxy resin (see, for example, Patent Document 1). ).
  • boric acid partially forms a covalent bond with an epoxy resin hardener to improve heat resistance, but the strong borate ester bond is hydrolyzed very easily.
  • water resistance of the cured product must be low. Therefore, semiconductor sealing materials and products in the field of electronic components and electronic components described above. When used as a varnish for layer boards, it was inferior in solder resistance after moisture absorption (hereinafter abbreviated as “moisture and solder resistance”) due to low water resistance.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-338787
  • Patent Document 2 Japanese Patent Laid-Open No. 63-156814
  • the problem to be solved by the present invention is that the cured product of the composition combined with the epoxy resin exhibits excellent heat resistance and also has extremely good water resistance.
  • a thermosetting resin composition that improves the moisture resistance and solder resistance required in the field of electronic components, a boric acid-modified triazine structure-containing novolak resin that imparts such effects to the cured product, and a method for producing the same. There is.
  • the present inventors have found that a phenolic resin that can improve heat resistance and exhibits good hydrolysis resistance can be obtained, and the present invention has been completed.
  • the present invention is a thermosetting resin composition
  • phenol resin (A) and epoxy resin (B) as essential components wherein the phenol resin (A) has a triazine structure.
  • epoxy resin composition characterized by having a structure in which a plurality of aromatic nuclei present in a molecule are knotted by borate ester bonds.
  • thermosetting composition comprising phenolic resin (A) and epoxy resin (B) as essential components.
  • the fountain resin composition (A) is obtained by reacting a fountain resin composition containing a triazine structure with boric acid or a borate ester while performing dehydration. It is related with the epoxy resin composition characterized by being.
  • R and R are each independently an amino group, phenyl group, acetyl group, carbon
  • Ph represents an aromatic hydrocarbon group.
  • the present invention relates to a modified triazine structure-containing novolac resin.
  • the present invention provides a process for producing a boric acid-modified triazine structure-containing novolak resin, characterized by reacting phenolic resin containing a triazine structure with boric acid or boric acid ester while dehydrating. Regarding the method.
  • the cured product of the thermosetting resin composition can have both excellent heat resistance and extremely good water resistance, which is required in the electric component field or the electronic component field.
  • Thermosetting resin composition that exhibits high moisture and solder resistance, cures such effects
  • a boric acid-modified triazine structure-containing novolac resin to be imparted to the product and a method for producing the same can be provided.
  • thermosetting resin composition of the present invention is a sealing material or FRP, insulating board, printed wiring board, copper foil with adhesive, build-up material, film adhesive, interlayer insulating film, etc. It can be suitably used in the electric field such as various electric laminates.
  • Fig. 1 shows a novolac resin containing boric acid-modified triazine structure (A
  • the phenol resin (A) used in the present invention has a triazine ring in its molecular structure, and a phenol having a structure in which a plurality of aromatic nuclei present in the molecule are knotted by borate ester bonds. It is characterized by being greaves.
  • the cured product when the aromatic nucleus in the molecule is knotted by the borate ester bond, the cured product has a high glass transition point and good heat resistance, and can maintain a high elastic modulus at a high temperature. it can. Further, the synergistic action of the borate ester bond and the nitrogen atom forming the triazine structure increases the molecular rigidity, making the borate ester less susceptible to hydrolysis. Therefore, although the borate ester bond generally has the property of being easily hydrolyzed, the present invention can combine heat resistance with excellent water resistance. Furthermore, the phenol resin (A) exhibits excellent flame retardancy because it has a triazine structure.
  • the phenol resin (A) is specifically obtained by reacting a phenol resin containing a triazine structure with boric acid or a borate ester while performing dehydration.
  • a phenol resin containing the triazine structure has an amino group as a substituent in the triazine structure, a salt of the amino group and boric acid is further formed. Even so.
  • the triazine ring includes, for example, 1, 2, 3 triazine structure, 1, 2, 4 triazine.
  • Examples include 1,3,5 triazine structure, and 1,3,5 triazine structure is preferable from the viewpoint of good water resistance improvement effect of the present invention.
  • means for introducing a strong triazine ring into a phenol resin structure include, for example, phenols (a-1), amino group-containing triazine compounds (a-2) and aldehydes (a- 3) to form a phenol resin containing a triazine ring, or a phenol resin obtained by polycondensation of phenols (a-1) and aldehydes (a-3).
  • a method of reacting cyanuric acid or a triazine compound (a-2 ′) obtained by esterifying a part thereof is mentioned.
  • the former method is preferred because the effect of improving the water resistance of the final phenol resin (A) becomes remarkable, and thus the triazine ring is selected from phenols (a A triazine structure formed by the reaction of-1) with an amino group-containing triazine (a-2) and an aldehyde (a-3) is preferred.
  • the phenols (a-1) are not particularly limited, for example, Fueno monore, o Crezo monore, m-creso monore, p Crezo monore, o echeno leeno Nore, m-ethylphenol, p-ethylphenol, o-isopropylphenol, m-propyl phenolanol, p-propenolevenole, p-sec butinolevenole, p-tert-butinolephenol, p cyclohexylphenol, p Black mouth phenol, o bromophenol, m-bromophenol, p phenols such as bromophenol, ex naphthol, naphthols such as 13 naphthol, 2, 4 xylenol, 2, 5 xylenol, 2, 6 xylenol, etc.
  • Monovalent phenols such as xylenols, resorcinol, force tecohol, hydroquinone, 2, 2 bis (4 ' Hydroxyphenyl) propane, 1, 1 'bis (dihydroxyphenyl) methane, 1, 1'-bis (dihydroxynaphthyl) methane, tetramethylbienol, biphenol, hexamethylbiphenol, 1,2-dihydroxynaphthalene 1,3 dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5 dihydroxynaphthalene, 1,6 dihydroxynaphthalene, 1,7 dihydroxynaphthalene, 1,8 dihydroxynaphthalene, 2,3 dihydroxynaphthalene, 2,6 dihydroxy Examples thereof include divalent phenols such as naphthalene and naphthalenediols such as 2,7-dihydroxynaphthalene, and trivalent phenols such as trishydroxyphenol methane.
  • phenol, o-cresol, m-cresol, naphthols, 2 , 2 Bis (4'-hydroxyphenyl) propane, 2,6 xylenol, resorcin, hydroquinone, 1,5 dihydroxynaphthalene, 1,6 dihydroxynaphthalene, 2,7 dihydroxynaphthalene, etc. are economical and easy to manufacture Preferable from the point of view.
  • two or more of these phenols may be used in combination.
  • the amino group-containing triazines (a-2) include melamine or guanamines such as acetoguanamine, methyldaanamine, ethyldaanamine, i-propylguanamine, t-butyldiaanamin, cyclohexylguanamine, and benzoguanamine.
  • Examples of triazine compounds (a-2 ') obtained by esterifying cyanuric acid or a part thereof are cyanuric acid, monomethyl cyanurate, dimethyl cyanurate, monoethyl cyanurate, jetyl cyanurate, and And monoacetyl cyanurate.
  • the amino group-containing triazine compound (a-2) is particularly preferred from the viewpoint of heat resistance and water resistance. .
  • aldehydes (a-3) examples include formaldehyde, acetoaldehyde, benzaldehyde, hydroxyformaldehyde, furfural, and acrolein.
  • formaldehyde is preferable because it is easy to handle.
  • typical sources include formalin and paraformaldehyde.
  • the borate ester bond existing in the molecular structure of the phenolic resin (A) is specifically an ester bond having a structure in which the aromatic nucleus in the phenolic structure is esterified with orthoboric acid,
  • Examples include ester bonds with a structure in which the aromatic nucleus in the phenol structure is esterified with diboric acid, and ester bonds with a structure in which the aromatic nucleus in the phenol structure is esterified with metaboric acid trimer.
  • ester bonds with a structure in which the aromatic nucleus in the phenol structure is esterified with diboric acid and ester bonds with a structure in which the aromatic nucleus in the phenol structure is esterified with metaboric acid trimer.
  • a strong borate ester bond can be introduced into the phenolic resin (A) by reacting the above-described phenolic resin having a triazine ring with phenol or a boric acid ester under dehydrating conditions.
  • the boric acid or boric acid ester to be used includes, as boric acid, for example, orthophosphoric acid, metaboric acid, tetraboric acid and a mixture thereof.
  • boric acid esters include trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, trihexyl borate, trioctyl borate, tristearyl borate, triphenyl borate, and phosphoric acid.
  • Examples include tolylitol, trixyl borate, tribenzyl borate, tricresyl borate, trimethylboroxine, triethylboroxine, and trichloroboroxine.
  • boric acid, particularly orthoboric acid is particularly preferred because of its ability to efficiently and uniformly introduce boric acid ester bonds into phenolic resin (A) by dehydration.
  • the specific structure of the strong phenolic resin (A) includes the above-described phenols (a-1), the amino group-containing triazines (a-2), or the aldehydes (a-3), And various things are mentioned by the combination of boric acid or boric acid ester.
  • the phenol resin (A) may be a resol type containing a methylol group and / or a dimethylene ether group or a novolac type not containing them, but the storage stability is also a novolak type. More preferred.
  • the folic acid-modified triazine structure-containing novolak resin of the present invention is particularly preferable because of its excellent balance of heat resistance, water resistance, strength, and flame retardancy.
  • the boric acid-modified triazine structure-containing novolak resin of the present invention will be described in detail below.
  • the novolak resin has the following structural formula 1
  • An alkyl group having 1 to 6 carbon atoms such as a group, a phenyl group, a acetyl group, a methyl group, an ethyl group, an i-propyl group, a t-butyl group, a cyclohexyl group, or an imino methylene represented by NH It represents a group, and specifically, the following structure is preferable in terms of flame retardancy.
  • boric acid-modified triazine structure-containing novolac resin of the present invention further comprises the following structural formula 2
  • Ph represents an aromatic hydrocarbon group such as a benzene ring or a naphthalene ring
  • the aromatic hydrocarbon group includes those having a substituent of a methyl group or an ethyl group.
  • Specific examples of such a structure include the following.
  • the structural site represented by the structural formula 1 and the structural site represented by the structural formula 2 form a structure in which they are alternately bonded.
  • a structure in which a block having the structural unit represented by Structural Formula 1 as a repeating unit and a block having the structural unit represented by Structural Formula 2 as a repeating unit are combined is formed. Also good.
  • a structure is formed that binds to a group represented by NH of another structural site via a group acetylene bond represented by NH.
  • the group represented by NH in Structural Formula 1 and the aromatic hydrocarbon group in Structural Formula 2 are It forms a structure bonded through a methylene group.
  • the structural sites represented by Structural Formula 2 are bonded to each other, a structure in which the aromatic hydrocarbon group in Structural Formula 2 is bonded to the aromatic hydrocarbon group in another structural site via a methylene group.
  • the boric acid-modified triazine structure-containing novolak resin of the present invention further has a boric acid ester bond as a site for knotting a plurality of aromatic nuclei.
  • the ester bond of the structure in which the aromatic nucleus in the phenolic structure is esterified with orthoboric acid, the ester bond in the structure in which the aromatic nucleus in the phenolic structure is esterified with diboric acid, and the aromatic nucleus in the phenolic structure are metaboric acid. Examples include ester bonds having a structure esterified with a monomer.
  • the structure of Structural Formula 3-a or 3-b shown below is preferred from the standpoint that the effect of inhibiting hydrolysis appears more remarkably.
  • the structural moiety represented by Structural Formula 3-a or Structural Formula 3-b is bonded to the aromatic hydrocarbon group of the structural moiety represented by Structural Formula 2.
  • Structural Formula 3-a or Structural Formula 3-b is bonded to the aromatic hydrocarbon group of the structural moiety represented by Structural Formula 2.
  • heat resistance is dramatically improved, and it is generally known as a bond that is easily hydrolyzed. In spite of this, it exhibits hydrolysis resistance.
  • boric acid or a borate ester when boric acid or a borate ester is reacted with a phenolic resin having a triazine ring, the boric acid ester bond is naturally formed.
  • a phenolic hydroxyl group and boric acid or a borate ester, or a polymer thereof can form a hydrogen bond. Therefore, the boric acid-modified triazine structure-containing nopolac resin of the present invention may have strong hydrogen bonds formed.
  • the triazine structure-containing novolak resin (B) of the present invention has a good performance balance between heat resistance and water resistance as described above, when the boron atom content is in the range of 1 to 10% by mass. In particular, it is preferably 1 to 5% by mass from the point that this performance balance becomes more remarkable.
  • the content of boron atoms is determined by combusting the triazine structure-containing novolac resin (B) into ash, and the mass of the ash is regarded as the mass of B 2 O.
  • the mass force that is applied is calculated by calculating the mass of the boron atom.
  • the boric acid-modified triazine structure-containing novolak resin preferably has a glass transition point of 100 ° C to 200 ° C as determined by DSC thermal analysis, and also has excellent heat resistance and hydrolysis resistance.
  • the boric acid-modified triazine structure-containing novolak resin described in detail above is an unreacted triazine structure-containing novolak resin component, phenols (a-1) that has not been modified with boric acid or borate ester. ) And an aldehyde (a-3), an amino group-containing triazine compound (a-2) and an aldehyde (a 3), an unreacted amino group-containing triazine compound (a-2) ) Or unreacted phenols (a-1).
  • the unreacted phenols (a-1) are 3% by weight or less in the boric acid-modified triazine structure-containing novolac resin. This is preferable because of good properties and moisture resistance.
  • the method for producing the phenol resin (A) includes the phenols (a-1), the amino group-containing triazine compound (a-2), and the aldehydes (a- 3) to obtain a phenolic resin having a triazine structure, and then reacting this with boric acid or a borate ester (Method 1), and phenols ( a -1) and aldehydes.
  • the phenol resin obtained by reacting (a-3) is reacted with cyanuric acid or a triazine compound (a-2 ′) obtained by esterifying a part thereof, and this is then reacted with boric acid or boric acid ester.
  • the method 1 will be described in detail.
  • phenols (a-1), amino group-containing triazines (a-2), and aldehydes (a-3) are mixed.
  • the reaction system is reacted at a pH of 3.0 to 9.0.
  • phenols (a-1) and aldehydes (a-3) are first reacted to obtain the amino group-containing triazines (a-2), and vice versa.
  • the amino group-containing triazines (a-2) and aldehydes (a-3) may be reacted with the phenols (a-1).
  • all the raw materials may be added and reacted at the same time.
  • the molar ratio of the aldehydes (a-3) to the phenols (a-1) is not particularly limited, but preferably the aldehydes (a-3) and the phenols (a-1) It is preferable that the molar ratio of [aldehydes (a-3) Z phenols (a-1)] is 0.1 to 1.5, more preferably 0.2 to 0.8.
  • the molar ratio of amino group-containing triazines (a-2) to phenols (a-1) [(amino group-containing triazines (a-2)) / (phenols (a-1)) )] Is capable of obtaining a sufficient cross-linking density.
  • a part of the reaction system in which 0.05 or more is preferred is less likely to cause heterogeneity, and a uniform product can be obtained.
  • preferable 0.10-0.50 is particularly preferable.
  • it is preferable to make it react so that the content of the nitrogen atom contained in the phenol resin having the triazine structure to be generated may be 5 to 25% by weight.
  • the reaction reduces the residual amount of unreacted aldehydes and methylol groups as much as possible. Therefore, it is preferable to react under a temperature condition of 120 ° C or higher, preferably 150 to 200 ° C.
  • the reaction is usually performed in the presence of an organic solvent.
  • the organic solvent include lower alcohols having about 1 to 6 carbon atoms such as methanol, ethanol, and propanol, acetone, tetrahydrofuran, and methyl ethyl ketone.
  • the triazine structure-containing novolac resin thus obtained is as follows! Then, react with boric acid or fluoric acid ester.
  • the present invention is characterized in that a strong reaction is performed under dehydrating conditions. That is, by removing the water in the system generated by the reaction from the outside of the system, it is possible to dramatically improve the moisture resistance (water absorption rate) and moisture resistance and solder resistance when the molded product is finally produced.
  • moisture is removed under reduced pressure under a temperature condition of 100 ° C to 180 ° C, more preferably 120 to 150 ° C. Prefer to distill away.
  • the reaction time is 0.1 to 20 hours, more preferably 0.5 to 10 hours.
  • the reaction ratio between the triazine structure-containing novolak resin and boric acid or borate ester is such that uniform solubility can be obtained, so that 100 parts by weight of the triazine structure-containing novolak resin can be obtained. It is preferable to react with boric acid or boric acid ester in a proportion of 5 to 40 parts by weight.
  • examples of the organic solvent used in the above reaction include lower alcohols having about 1 to 6 carbon atoms such as methanol, ethanol, and propanol, acetone, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, Examples include cyclohexanone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methylethyl cellosolve, toluene, and xylene.
  • the boric acid-modified triazine structure-containing novolac resin produced in this way is usually obtained as a solution of the organic solvent used in the production thereof, and the hard solution is used as it is as a curing agent for epoxy resin. Can be used as Therefore, in order to produce the thermosetting resin composition of the present invention, the epoxy resin (B) may be added to the boric acid-modified triazine structure-containing novolac resin solution.
  • the epoxy resin (B) may be added to the boric acid-modified triazine structure-containing novolac resin solution.
  • triazine structure-containing novolac resin and boric acid or boric acid When solid content is precipitated in the reaction product solution with the ester, a uniform transparent resin solution can be obtained by adding a lower alcohol such as methanol or an amide solvent such as dimethylformamide.
  • epoxy resin (B) used in the present invention various epoxy resins can be used.
  • various epoxy resins can be used.
  • the phenol resin (A) has a triazine ring in the molecular structure. Therefore, as described above, an excellent flame retardant effect in the cured product. Is expressed. Therefore, when an epoxy resin having a structure having a higher flame retardant effect is selected, it is easy to obtain a non-halogen flame retardant cured product. From this point of view, it is desirable that the content of the aromatic ring skeleton or the condensed polycyclic skeleton in the epoxy resin structure is high.
  • bisphenol F type epoxy resin dihydroxynaphthalene type epoxy resin, biphenyl type Epoxy resin, tetramethylbiphenyl type epoxy resin, Nord novolak type epoxy resin, Cresol novolak type epoxy resin, Triphenyl methane type epoxy resin, Tetraphenol type epoxy resin, Phenolic aralkyl type Epoxy resin, Bi-Fuel aralkyl type epoxy resin, Naphthol novolak type Epoxy resin, naphthol aralkyl epoxy resin, naphthol monophenol co-condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, and biphenyl-modified novolac epoxy resin are preferable.
  • epoxy epoxy resin is an epoxidized product of 9, 10 dihydro-9 oxa 10 phosphaphenanthrene-10-oxide (hereinafter abbreviated as “HCA”), HCA and quinones.
  • Examples thereof include epoxy resin obtained by modification with phenol resin obtained.
  • the epoxy group equivalent of the epoxy resin (B) is less than 1, OOOgZ equivalent, especially 700gZ equivalent. In the following, it is particularly preferably 500 gZ equivalent or less.
  • thermosetting resin composition of the present invention comprises the above-described phenol resin (A) and epoxy resin (B) as essential components, and is an electric laminate material, particularly a printed circuit board. It is suitable as a varnish for use in a pre-preparing machine, or as an interlayer insulating material for copper-clad laminates and build-up printed circuit boards.
  • the epoxy resin (B) can be dissolved therein to easily adjust the composition of the present invention. it can. Accordingly, when used in an electric laminate varnish, it is preferable to add an organic solvent as necessary to adjust the insoluble content to 50 to 70% by mass.
  • organic solvents that can be used here include methanol, ethanol-isopropinoreanolenoconole, methinorecerosoreb, ethenorecerosonole.
  • non-alcoholic polar solvents such as alcoholic solvents such as alcohol, aromatic hydrocarbon solvents such as toluene and xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, etc.
  • C or lower solvents can be mentioned, and two or more mixed solvents can be used as appropriate.
  • thermosetting resin composition of the present invention when used in the varnish for an electrical laminate, in addition to the above-described components, other organic solvents, curing accelerators, inorganic fillers, phosphorus Various compounding agents such as a series flame retardant, other flame retardants, pigments, silane coupling agents, and mold release agents can be added.
  • Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. These may be used alone or in combination of two or more. Is possible.
  • Examples of the inorganic filler include hydroxides such as fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and magnesium hydroxide.
  • metal hydroxides such as hydroxide-aluminum or hydroxide-magnesium are preferred for imparting flame retardancy.
  • the blending amount of the metal hydroxide is increased in flame retardancy as the blending amount is increased, but on the other hand, the strength, heat resistance and moisture resistance of the cured product are lowered.
  • the thermosetting resin composition usually requires 35% by mass or more in the solid content to achieve the flame retardancy of “V-0” standard by UL94 vertical test method.
  • the inorganic filler is preferably used in the range of 20 to 35% by mass in the solid content.
  • fused silica can be used in either crushed or spherical shape, but in order to increase the amount of fused silica and to suppress the increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical one. .
  • a spherical one in order to increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica.
  • the filling rate depends on the application and desired characteristics. Although the preferred range is different, for example, when used for laminate applications, it is 40% by volume or more, preferably 50 to 90% by volume in the thermosetting resin composition.
  • the phosphorus compound examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethyl hexyl phosphate, tribubutoxy chinorephosphate, triphenylenophosphate, tricresinorephosphate, trixyleninore Phosphate, uddernoresiferous phosphate, xyleninoresiferous phosphate, 2-ethylhexyldiphosphate, tris (2,6 dimethylphenol) phosphate, resorcin diphosphate phosphate, polyphosphate
  • Examples include phosphorus atom-containing compounds such as condensed phosphate ester compounds such as acid ammonium, polyphosphate amide, red phosphorus, phosphate guanidine, and dialkylhydroxymethylphosphonate.
  • the varnish is made of paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth.
  • a prepreg which is a cured product is obtained by impregnating various reinforcing base materials such as glass mat and glass roving cloth and heating at a heating temperature corresponding to the solvent type used, preferably 50 to 180 ° C.
  • the weight ratio between the rosin composition and the reinforcing base material is not particularly limited, but it is usually preferable to adjust so that the rosin content in the prepreg is 20 to 60% by weight.
  • a copper-clad laminate is obtained by thermocompression bonding at 150 to 250 ° C for 10 minutes to 3 hours under the pressure of LOMPa. be able to.
  • the method for obtaining the interlayer insulating material for a varnish build-up substrate adjusted by blending each of the above-mentioned components is, for example, a build-up substrate adjusted appropriately by blending, for example, rubber, filler, etc.
  • Interlayer insulation material is obtained and applied to the wiring board on which the circuit is formed using a spray coating method, a curtain coating method, etc., and then cured, and then, if necessary, a predetermined through-hole portion, etc. After drilling, the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities, and a metal such as copper is applied, and such operations are sequentially repeated as desired.
  • a build-up substrate can be obtained by alternately building up a fat insulating layer and a conductor layer having a predetermined circuit pattern.
  • the thermosetting resin composition of the present invention can be used for electrical laminates, as well as for electronic component sealing materials, conductive pastes, resin casting materials, adhesives, and insulating paints. Coating materials such as
  • the resin composition for printed circuit boards the resin composition for sealing materials of an electronic component, and an electrically conductive paste, and is excellent in moisture resistance. It can be suitably used for adhesives. In addition, it has high functionality and can be suitably used for composite materials such as FRP or BMC.
  • a conductive filler such as silver powder or copper powder can also be used.
  • a method of preparing a paste resin composition for circuit connection that is liquid at room temperature or an anisotropic conductive adhesive is used.
  • thermosetting resin composition of the present invention is used as a resin composition for an adhesive, for example, other epoxy resins blended with the thermosetting resin composition as necessary. It can be obtained by uniformly mixing a fat, a curing agent, a curing accelerator, a solvent, an additive and the like at room temperature or under heating using a mixing mixer or the like.
  • a reinforcing base material is impregnated with the above-described varnish, heated by force tl to obtain a pre-preda, and then the direction of the fiber is changed.
  • thermosetting resin composition of the present invention further improves the flame retardancy depending on the use, and therefore it is difficult to use brominated aromatic flame retardants, metal hydroxides, antimony flame retardants and the like. You may add some fuel.
  • thermosetting resin composition of the present invention In order to cure the thermosetting resin composition of the present invention described in detail above, the thermosetting resin composition prepared for each application is heated at room temperature or 80 to 200 ° C. It only has to be cured.
  • a 20g sample is collected in a crucible, heated in an electric furnace from room temperature to 1000 ° C in 1 hour and 30 minutes, then treated at 1000 ° C for 3 hours to ash. After standing to cool, measure the mass of ash,
  • the glass transition point was measured using a solid dynamic viscoelasticity measuring device (“DMA 200” manufactured by Seiko Denshi Kogyo Co., Ltd.) at a measurement frequency of 1 ⁇ and a heating rate of 3 ° CZ.
  • the glass transition temperature (Tg) was tan ⁇ peak temperature (tan ⁇ ).
  • the lcm-wide copper foil (35 m copper foil) produced on the laminate was peeled off, and the peel strength in the 90-degree direction was determined.
  • the flame retardancy test was conducted according to UL94 vertical test method.
  • the laminate was forced to absorb moisture for 2 hours at a water pressure of 121 ° CZ2 atm with a pressure tacker tester, then immersed in a solder bath at 260 ° C for 30 seconds, and the appearance was visually checked.
  • a phenol resin containing a triazine structure which is a polycondensate of melamine, phenol and formalin (“Phenolite LA-1356” manufactured by Nippon Ink Chemical Co., Ltd.). ”, Nitrogen content 19%, hydroxyl equivalent 14 6.
  • boric acid-modified iminotriazine structure-containing nopolak resin (A-1) was obtained.
  • the resulting boric acid-modified iminotriazine structure-containing novolak rosin (A-1) solution had a nonvolatile content of 58%.
  • a phenol resin containing a triazine structure which is a polycondensate of melamine, phenol and formalin (“Phenolite LA-1356” manufactured by Nippon Ink Chemical Co., Ltd.).
  • Phenolite LA-1356 manufactured by Nippon Ink Chemical Co., Ltd.
  • ”Methylethylketone solution with nitrogen content of 19%, hydroxyl equivalent of 14 6 and non-volatile content of 60%) 100 parts of solid and 67 parts of cyclohexanone were added and dissolved uniformly with stirring at 100 to 125 ° C. I let you. Next, 16.2 parts of boric acid was added, and the mixture was stirred and dispersed uniformly at 100 ° C.
  • boric acid-modified iminotriazine structure-containing novolak resin (A-1) as a reaction product was obtained.
  • the obtained boric acid-modified iminotriazine structure-containing novolak rosin (A-1) solution had a non-volatile content of 58%.
  • the boron atom content of boric acid-modified iminotriazine structure-containing novolak resin (A-1) was 2.6% by mass, and the glass transition point by DSC thermal analysis was 128 ° C.
  • a phenol resin containing triazine structure which is a polycondensate of melamine, phenol and formalin (“Phenolite LA-1356” manufactured by Dainippon Ink & Chemicals, Inc., containing nitrogen)
  • Amount 19%, hydroxyl equivalent 146, non-volatile (60% methyl ethyl ketone solution) 87.5 parts of solid, 16.8 parts of boric acid, and 500 parts of xylene were charged and heated to 160 ° C while stirring. Subsequently, the reaction was carried out at 160 ° C for 6 hours while performing decanter dehydration.
  • Bisphenol A type epoxy resin (“EPICLON 850S” manufactured by Dainippon Ink and Chemicals, Epoxy equivalent l87gZ equivalent) 100 parts of the novolac resin (A-1) containing the boric acid modified triazine structure synthesized in Example 1
  • a varnish with a non-volatile content of 60% was prepared by blending 67 parts of the rosin solution and 64 parts of methanol.
  • the amount of boron atoms in the solid content of this varnish was 0.94%.
  • the produced varnish was impregnated with glass cloth (glass cloth for epoxy resin manufactured by Nitto Boseki Co., Ltd. “WEA 7628 30 S-236” thickness 180 / zm), and dried for 160 ° CZlO.
  • a predetermined prepreg was produced. Eight of the pre-predas were laminated and heat-molded at 150 ° C ZlOMPaZl time and further at 180 ° C ZlOMPaZ2 hour to produce a laminated plate.
  • the laminate was cut into a predetermined size to produce a test piece.
  • Phenolic novolak-type epoxy resin (“EPICLON N-770" manufactured by Dainippon Ink and Chemicals, Epoxy equivalent: 190gZ equivalent) Boric acid-modified tria synthesized in Example 1 in 100 parts
  • a varnish having a non-volatile content of 60% was prepared by blending 67 parts of a resin solution of gin structure-containing novolac resin (A-1) and further 64 parts of methanol. The amount of boron atoms in the solid content of this varnish was 0.92%.
  • a laminate was produced in the same manner as in Example 3 to produce a test piece.
  • Naphthalene-type epoxy resin (“EPICLON HP-4032" manufactured by Dainippon Ink and Chemicals, Epoxy equivalent: 150gZ equivalent) 100 parts of boric acid-modified triazine structure-containing novolac resin (A-1) synthesized in Example 1
  • a varnish having a non-volatile content of 60% was prepared by blending 85 parts of the rosin solution and 63 parts of methanol. The amount of boron atoms in the solid content of this varnish was 1.10%.
  • a laminate was produced in the same manner as in Example 1 to prepare a test piece.
  • Bisphenol A type epoxy resin (“EPICLON 850S” manufactured by Dainippon Ink and Chemicals, Epoxy equivalent l87gZ equivalent)
  • EPICLON 850S manufactured by Dainippon Ink and Chemicals, Epoxy equivalent l87gZ equivalent
  • a triazine structure-containing phenol resin “Dainippon, a polycondensate of melamine, phenol and formalin” “Phenolite LA-1356” manufactured by Ink Chemical Industry Co., Ltd., 65 parts of a methyl ethyl ketone solution having a nitrogen content of 19%, a hydroxyl equivalent of 146, and a non-volatile content of 60%), 67 parts of methyl ethyl ketone, accelerator 2 ethyl 4 methyl imidazole 0 1 part was blended to prepare a varnish having a nonvolatile content of 60%.
  • Example 4 a laminate was produced in the same manner as in Example 4 to produce a test piece.
  • the prepared varnish was impregnated with the glass cloth used in Example 3, and dried at 160 ° C. for 3 minutes to prepare a predetermined pre-preda. Eight of these pre-predas were laminated and heat-molded at 170 ° C / 2.9 MPaZl to produce a laminate. The laminate was cut into a predetermined size to produce a test piece.
  • Bisphenol F-type epoxy resin (“EPICLON 850S” manufactured by Dainippon Ink and Chemicals, Epoxy equivalent l70gZ equivalent) 100 parts
  • Polyamidoamine (“EPICLON B-053" manufactured by Dainippon Ink and Chemicals, active hydrogen equivalent 77g (Equivalent) 3. 2 parts were stirred and dissolved at 80 ° C., and 13.8 parts of boric acid, 31 parts of aluminum hydroxide and 95 parts of methanol were blended to prepare a varnish having a nonvolatile content of 60%.
  • the amount of boron (B) in the solid content of this varnish was 2.2% as a theoretical calculation value from the charged amount.
  • the glass cloth used in Example 3 was applied to the produced varnish. It was impregnated and dried at 160 ° C. for 10 minutes to produce a predetermined pre-preda.
  • pre-predas were stacked and heat-molded at 150 ° C / 10 MPa / l for another 180 ° C ZlOMPa Z for 2 hours to produce a laminate.
  • a test piece was produced by cutting the laminate into a predetermined size.
  • Bisphenol F-type epoxy resin (“EPICLON 830S” manufactured by Dainippon Ink and Chemicals, Epoxy equivalent: 70 gZ equivalent) 100 parts of the novolac resin (A-1) containing the boric acid-modified triazine structure synthesized in Example 1
  • a varnish having a non-volatile content of 60% was prepared by blending 148 parts of the resin solution, 80 parts of aluminum hydroxide, and 115 parts of methanol.
  • the prepared varnish was impregnated with the glass cloth used in Example 4 and dried at 160 ° C. for 10 minutes to prepare a predetermined pre-preda. Eight of the pre-predas were stacked and heated at 150 ° C ZlOMPaZl for a time to produce a laminate. Further, after-curing was performed in a dryer at 180 ° C / 1 hour. The laminate was cut into a predetermined size to produce a test piece.
  • Bisphenol F-type epoxy resin (“EPICLON 830S” manufactured by Dainippon Ink and Chemicals, Epoxy equivalent 170 g / equivalent) 100 parts, Nitrogen-containing phenol resin (Dainippon Ink and Chemicals) “Phenolite LA-1356” manufactured by Gaku Kogyo Co., Ltd., 72 parts of a methyl ethyl ketone solution with a nitrogen content of 19%, a hydroxyl equivalent of 146 and a non-volatile content of 60%, 61 parts of aluminum hydroxide, and 107 parts of methyl ethyl ketone Thus, a varnish having a nonvolatile content of 60% was prepared.
  • Example 3 the glass cloth used in Example 3 was impregnated into the produced varnish and dried at 160 ° C. for 3 minutes to produce a predetermined pre-preda. Eight of these pre-predas were stacked and thermoformed at 170 ° CZ2. 9 MPaZl time to produce a laminate. The laminate was cut into a predetermined size to produce a test piece.
  • Bisphenol F-type epoxy resin (“EPICLON 830S” manufactured by Dainippon Ink and Chemicals, epoxy equivalent 170 g / equivalent) 100 parts nitrogen-containing phenol resin (“Phenolite LA-1356” manufactured by Dainippon Ink & Chemicals, Inc.) 72 parts of a methyl ethyl ketone solution having a nitrogen content of 19%, a hydroxyl group equivalent of 146 and a nonvolatile content of 60%), 76 parts of aluminum hydroxide and 162 parts of methyl ethyl ketone were blended to prepare a varnish having a nonvolatile content of 60% . Next, the produced varnish was impregnated with the glass cloth used in Example 3, and dried at 160 ° C.
  • pre-preda for 3 minutes to produce a predetermined pre-preda. Eight of these pre-predas were stacked and thermoformed at 170 ° CZ2. 9 MPaZl time to produce a laminate. The laminate was cut into a predetermined size to produce a test piece.
  • the varnish was applied on clean aluminum foil, and after solvent casting for 12 hours, 50. C, 60 ° C, 70 ° C, 80 ° C, 90 ° C, dried for 1 hour each, and then heat treated at 150 ° C, 180 ° C for 2 hours each, and the thermosetting resin composition A cured product film was obtained. DMA measurement was performed using this film, and the obtained peak temperature (tan) of tan ⁇ was 230 ° C.
  • the present invention provides a thermosetting resin composition, a boric acid-modified triazine structure-containing novolak resin and a method for producing the same, and the cured product of the composition has excellent heat resistance and water resistance. Combined, it exhibits high moisture and solder resistance. Therefore, the thermosetting resin composition of the present invention is useful for applications such as paints, adhesives, semiconductor encapsulating and electrical laminates, and in particular, sealing materials, or FRP, insulating plates, printed wiring. It can be effectively used in the field of electrical components or electronic components such as various electrical laminates such as plates, copper foils with adhesives, build-up materials, film adhesives, and interlayer insulation films.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

Composition de résine thermodurcissable contenant pour l'essentiel une résine phénolique (A) et une résine époxyde (B). Une telle résine époxyde thermodurcissable est caractérisée en ce que la résine phénolique (A) a une structure de triazine et une structure dans laquelle une pluralité de noyaux aromatiques présents dans une molécule sont liés par une liaison ester de l'acide borique, ou en ce que la résine phénolique (A) est obtenue en faisant réagir une résine phénolique ayant une structure de triazine avec de l'acide borique ou un borate tout en effectuant la déshydratation. Il est également exposé une résine novolaque contenant une structure d'iminotriazine modifiée par de l'acide borique et un procédé servant à produire celle-ci.
PCT/JP2005/012410 2004-07-05 2005-07-05 Composition de résine thermodurcissable, résine novolaque contenant une structure de triazine modifiée par de l'acide borique et procédé servant à produire celle-ci WO2006004118A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8383738B2 (en) 2010-06-14 2013-02-26 Taiwan Union Technology Corporation Epoxy resin composition, and prepreg and printed circuit board using the same
US8748513B2 (en) 2010-04-20 2014-06-10 Taiwan Union Technology Corporation Epoxy resin composition, and prepreg and printed circuit board using the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102234408A (zh) * 2010-04-29 2011-11-09 台耀科技股份有限公司 环氧树脂组成物及其制成的预浸材和印刷电路板

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63156814A (ja) * 1986-12-22 1988-06-29 Gunei Kagaku Kogyo Kk 耐熱性フエノ−ル樹脂の製造方法
JPH09302228A (ja) * 1996-05-16 1997-11-25 Polyplastics Co ポリアリーレンサルファイド樹脂組成物
JP2001316564A (ja) * 2000-04-28 2001-11-16 Hitachi Chem Co Ltd 絶縁樹脂組成物、銅箔付き絶縁材及び銅張り積層板
JP2002047398A (ja) * 2000-08-01 2002-02-12 Sumitomo Bakelite Co Ltd 難燃性ポリエステル系樹脂組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63156814A (ja) * 1986-12-22 1988-06-29 Gunei Kagaku Kogyo Kk 耐熱性フエノ−ル樹脂の製造方法
JPH09302228A (ja) * 1996-05-16 1997-11-25 Polyplastics Co ポリアリーレンサルファイド樹脂組成物
JP2001316564A (ja) * 2000-04-28 2001-11-16 Hitachi Chem Co Ltd 絶縁樹脂組成物、銅箔付き絶縁材及び銅張り積層板
JP2002047398A (ja) * 2000-08-01 2002-02-12 Sumitomo Bakelite Co Ltd 難燃性ポリエステル系樹脂組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8748513B2 (en) 2010-04-20 2014-06-10 Taiwan Union Technology Corporation Epoxy resin composition, and prepreg and printed circuit board using the same
US8383738B2 (en) 2010-06-14 2013-02-26 Taiwan Union Technology Corporation Epoxy resin composition, and prepreg and printed circuit board using the same

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