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WO2009060987A1 - Résine époxy contenant du phosphore et composition de résine époxy contenant du phosphore, leur procédé de fabrication et composition de résine durcissable et objet durci contenant chacun ou obtenus chacun à partir de la résine et de la composition de résine - Google Patents

Résine époxy contenant du phosphore et composition de résine époxy contenant du phosphore, leur procédé de fabrication et composition de résine durcissable et objet durci contenant chacun ou obtenus chacun à partir de la résine et de la composition de résine Download PDF

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Publication number
WO2009060987A1
WO2009060987A1 PCT/JP2008/070622 JP2008070622W WO2009060987A1 WO 2009060987 A1 WO2009060987 A1 WO 2009060987A1 JP 2008070622 W JP2008070622 W JP 2008070622W WO 2009060987 A1 WO2009060987 A1 WO 2009060987A1
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WO
WIPO (PCT)
Prior art keywords
phosphorus
epoxy resin
resin composition
general formula
containing epoxy
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2008/070622
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English (en)
Japanese (ja)
Inventor
Tetsuya Nakanishi
Kazuo Ishihara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tohto Kasei Co Ltd
Original Assignee
Tohto Kasei Co Ltd
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 Tohto Kasei Co Ltd filed Critical Tohto Kasei Co Ltd
Priority to JP2009540114A priority Critical patent/JP5632163B2/ja
Priority to CN2008801152610A priority patent/CN101883806B/zh
Publication of WO2009060987A1 publication Critical patent/WO2009060987A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • 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

Definitions

  • the present invention relates to an epoxy resin composition for producing a copper-clad laminate, a film material, a resin-coated copper foil, etc. used for an electronic circuit board, and a sealing material, a molding material, a casting material, an adhesive, an electrical insulation used for an electronic component.
  • the present invention relates to a phosphorus-containing epoxy resin and a phosphorus-containing epoxy resin composition useful as a coating material, a production method thereof, a curable resin composition using the resin, and a cured product.
  • Epoxy resins are widely used in electronic parts, electrical equipment, automotive parts, FRP, sports equipment, etc. due to their excellent adhesion, heat resistance, and moldability.
  • copper-clad laminates and encapsulants used in electronic parts and electrical equipment are strongly required to have safety such as fire prevention and delay.
  • Epoxy resin is used.
  • the specific gravity is large, flame retardancy is imparted by introducing halogen, particularly bromine, into the epoxy resin, and the epoxy group has ⁇ reactivity and excellent curability is obtained.
  • Brominated epoxy resins are positioned as useful electronic and electrical materials.
  • Patent Document 1 includes HCA—HQ (manufactured by Sanko Co., Ltd.
  • thermosetting flame retardant resin obtained by reacting dihydro 9-oxa 1 10-phosphaphenanthrene 1 10-oxide)) and epoxy resins at a predetermined molar ratio is disclosed.
  • Patent Document 2 discloses a phosphorus-containing epoxy resin obtained by reacting an epoxy compound having at least two epoxy groups with diphenylphosphine hydroquinone.
  • Patent Document 3 discloses a method for producing a flame-retardant epoxy resin characterized by reacting an epoxy resin, a phosphine compound having an aromatic group on a phosphorus atom, and a quinone compound in the presence of an organic solvent. Yes.
  • Patent Document 4 discloses a phosphorus-containing epoxy resin and a phosphorus-containing flame-retardant epoxy resin composition obtained by reacting a phosphorus-containing polyvalent phenol compound represented by the general formula (2) with an epoxy resin.
  • Patent Document 5 9, 10-dihydro-9-oxa 1 10-phosphaphenanthrene 1 10-oxide and 1,4 monobenzoquinone and / or 1,4 mononaphthoquinone are reacted.
  • the total water content in the system is used 9, 1 0-dihydrazide chondroitinase 9 Okisa one 1 0 phosphine Afuenantoren one 1 0 Okishido 0.3 mass 0/0 controlled to be below the total amount in the reaction Step 1 to obtain a reaction composition by reacting, and Step 2 to react with bisphenol A type epoxy resin and / or bisphenol F type epoxy resin without purifying the reaction composition obtained in step 1
  • a method for producing a phosphorus-containing flame-retardant bisphenol type epoxy resin is disclosed.
  • Patent Document 1 JP 04-1 1 6 6 2
  • Patent Document 2 Japanese Patent Laid-Open No. 05-214040
  • Patent Document 3 JP 2000-3 09 6 24
  • Patent Document 4 JP 2002-2 6 5 5 6 2
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2006-342 2 1 7
  • Patent Document 6 discloses a monofunctional compound including structural formula 4, which is a compound represented by the general formula (1).
  • organophosphorus compounds “In order to form a so-called pendant in the resin by reacting with an epoxy group, the crosslinking density of the epoxy resin is reduced, the curing speed is delayed, the heat resistance is lowered, or the mechanical It is difficult to use an amount that is sufficient to exhibit sufficient flame retardancy, such as a decrease in strength, and it is difficult to use a monofunctional organic compound as a reactive organic phosphorus compound. It is stated that the use of phosphorus compounds with sufficient flame retardancy (generally, dozens to dozens of percent) reduces crosslink density and causes problems such as slowing of the curing rate. It is.
  • Patent Document 6 Japanese Patent Application Laid-Open No. 2 0 00-1 5 4 2 3 4 Disclosure of Invention
  • the present inventor has found that there is a significant difference in reactivity depending on the obtained phosphorus-containing epoxy resin. If the gel time, which is an indicator of the reactivity of the epoxy resin, is long, for example, the resin flows too much during curing during lamination bonding, and the resulting laminate has insufficient adhesion, resulting in reduced adhesion and migration. This may cause problems such as blistering and blistering during solder immersion. In addition, when the gel time is adjusted by increasing the blending amount of the curing catalyst, there is a problem that the storage stability of the pre-preda is deteriorated and long-term storage cannot be performed.
  • the present inventor has found that the compound represented by the general formula (1) has a content exceeding 2.5% by weight among monofunctional organophosphorus compounds.
  • a compound represented by a general formula (2) it was found that the curing reactivity of the resulting phosphorus-containing epoxy resin was significantly impaired, and the phosphorus-containing epoxy resin of the present invention was completed.
  • Means for solving this problem are as follows, which are described in the claims.
  • n 0 or 1
  • R 1 and R 2 represent hydrogen or a hydrocarbon group, and each may be different or the same, and may be linear, branched or cyclic. R 1 and R 2 may be bonded to form a cyclic structure.
  • B represents any one of benzene, biphenylenole, naphthalene, anthracene, phenanthrene, and hydrocarbon substitutes thereof.
  • the content of the compound represented by the general formula (1) is 2.5% by weight or less, and the compound represented by the general formula (2) is reacted with an epoxy resin.
  • a phosphorus-containing bull ester resin characterized by using the phosphorus-containing epoxy resin according to any one of (1) to (2).
  • a phosphorus-containing epoxy resin composition comprising the phosphorus-containing epoxy resin according to any one of (1) to (2) as an essential component and a curing agent.
  • a radical polymerizable resin composition comprising the phosphorus-containing bull ester resin of (3) as an essential component and a radical polymerization initiator and / or curing agent.
  • the phosphorus-containing epoxy resin of the present invention is obtained by reacting an epoxy resin with a compound represented by the general formula (2), and is represented by the general formula (1) present in the compound represented by the general formula (2).
  • the compound shown is not more than 2.5% by weight, preferably not more than 1.0% by weight, more preferably not more than 0.5% by weight.
  • the compound represented by the general formula (2) used in the present invention is, for example, Non-Patent Document 1, Non-Patent Document 2, which is a general magazine in Russia, Patent Document 7, Patent Document 8, Patent Document 9. It is obtained by the method shown in item 10.
  • HCA 10-dihydro 9-oxa 1 10-phosphaphenanthrene 1 10-oxide
  • the reaction is described in the state, and it is described that the reaction solvent is used as a washing solvent after the reaction. This is intended to remove excess phosphorus compounds.
  • Non-Patent Document 1 ' ⁇ I. tr. M. Campbell and I. D. R. Stevens, Chemical Communications pp. 505-506 (1 9 6 6)
  • Non-Patent Document 2 (Zh.0bshch.Khim.), 42 (11), pp. 2415-2418 (1 9 7 2)
  • Patent Document 7 Japanese Patent Application Laid-Open No. 60-0 1 2 6 2 93
  • Patent Document 8 Japanese Patent Laid-Open No. Sho 6 1-2-3 6 7 8 7
  • Patent Document 9 Japanese Patent Laid-Open No. 5-3 3 1 1 7 9
  • Patent Document 10 Japanese Patent Laid-Open No. 05_3 9 3 4 5
  • reaction formula 1 illustrates the formation of the compound represented by general formula (2) and the compound represented by general formula (1), but the compound represented by general formula (3) represented by reaction formula 1 remains. is there.
  • R 1 and R 2 represent hydrogen or a hydrocarbon group, and each may be different or the same, and may be linear, branched, or cyclic. R 1 and R 2 may be bonded to form a cyclic structure.
  • B represents any one of benzene, biphenyl / ale, naphthalene, anthracene, phenanthrene, and hydrocarbon substitutes thereof.
  • the present inventor found that the epoxy resin obtained by using the compound represented by the general formula (2) containing the compound represented by the general formula (1) as an impurity component is not so large as to reduce the crosslinking density. Even when the content of the compound represented by the general formula (1) is small, it was found that the reaction rate was remarkably delayed, and this has been achieved. This is not possible with conventional monofunctional phenols. It was found that the influence of the delay effect on the reaction rate of the epoxy resin was particularly large. Therefore, in addition to purifying the compound represented by the general formula (2) at a higher production cost to obtain a high purity, the management of the components of the compound represented by the general formula (1) It can solve problems when used as a sealing material or casting material.
  • the use of the compound represented by the general formula (2) in which the content of the compound represented by the general formula (1) is 2.5% by weight or less has little effect on the reactivity between the epoxy resin and the curing agent. Absent. That is, the compound represented by the general formula (2) having a content of the compound represented by the general formula (1) of 2.5% by weight or less, preferably 2.0% by weight or less is used.
  • the preferred content of the compound represented by the general formula (1) contained in the compound represented by the general formula (2) is 2% by weight or less. A more preferable content is 1% by weight or less, and desirably 0.5% or less.
  • the phosphorus-containing epoxy resin obtained by reacting the compound represented by the general formula (2) and the epoxy resin containing the compound represented by the general formula (1) in an amount exceeding 2.5% by weight it is cured. Since the reactivity with the agent is significantly delayed, the practicality is inferior.
  • the compound represented by the general formula (2) used in the present invention can be produced by the methods disclosed in Non-Patent Documents 1 and 2, and Patent Documents 7 to 10, and extraction, washing,
  • the compound represented by the general formula (1) is 2 to 5 weight by refining operation such as recrystallization and distillation. / 0 or less.
  • the compound represented by the general formula (1) may be 2.5% by weight or less depending on the reaction conditions of the compound represented by the general formula (2) regardless of these methods.
  • HC A—HQ manufactured by Sanko Co., Ltd.
  • HC A-NQ represented by structural formula 2 (1 0-(2,7-dihydroxynaphthyl)-1 0 H—dihydro 1-9— Oxaxa 1 0—phosphaphenanthrene _ 1 0—oxide
  • PPQ diphenylphosphini / rehydroquinone
  • diphenylphosphinenaphthoquinone C PHO_HQ (six made by Nippon Chemical Industry Co., Ltd.) 1), 4-benzenediol, and naphthylene phosphinyl 1,4, naphthalene diene, phosphorus disclosed in JP-A-2002-2 6 5 5 6 2
  • the epoxy resin that reacts with the compound represented by the general formula (2) whose content of the compound represented by the general formula (1) is 2.5% by weight or less has a daricidyl ether group.
  • Epototo YDC— 1 3 1 2, ZX— 1 0 2 7 (Hydroquinone type epoxy resin manufactured by Toto Kasei Co., Ltd.), Z X- 1 2 5 1 (Biphenol type epoxy resin manufactured by Toto Kasei Co., Ltd.)
  • Epototo YD— 1 27, epototo YD— 1 2 8, epototo YD— 8 1 2 5, epototo YD— 8 2 5 GS, epototo YD— 0 1 1, epototo YD— 9 0 0, epototo YD— 9 0 1 (BPA type epoxy resin manufactured by Toto Kasei Co., Ltd.)
  • the content of the compound represented by the general formula (1) is 2.5% by weight or less in the same manner as the reaction of ordinary polyfunctional phenols and epoxy resins.
  • a compound represented by the general formula (2) and an epoxy resin are charged and heated to melt and react. The reaction is performed at a reaction temperature of 100 ° C. to 200 ° C., more preferably 120 ° C. to 180 ° C. with stirring. This reaction can improve productivity by using a catalyst if necessary.
  • catalysts include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, triphenylphosphine, tris (2,6-dimethoxyphenyl). / Le) Various catalysts such as phosphines such as phosphine, phosphonium salts such as ethyltriphenylphosphonium bromide, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used. Depending on the viscosity during the reaction, a reaction solvent may be used. Specific examples include benzene, toluene, xylene, cyclopentanone, and cyclohexanone, but are not limited to these, and two or more types may be used.
  • denaturing agents include bisphenol, bisphenol F, bisphenol AD, and tetraptyl bisphenol.
  • the phosphorus content of the phosphorus-containing epoxy resin of the present invention is preferably 0.3 to 5% by weight, more preferably 0.5 to 3.6% by weight, and still more preferably 1.0 to 3.1% by weight.
  • the phosphorus content in the organic component in the phosphorus-containing epoxy resin composition comprising the phosphorus-containing epoxy resin is preferably 0.2 to 4% by weight, more preferably 0.4 to 3.5% by weight. Further, it is preferably 0.6 to 3% by weight. If the content of phosphorus in the organic component in the epoxy resin composition containing phosphorus is 0.2% by weight or less, it becomes difficult to ensure flame retardancy, and if it exceeds 5% by weight, the heat resistance may be adversely affected. Yes, adjust from 0.2% to 5% by weight It is desirable.
  • the epoxy equivalent of the phosphorus-containing epoxy resin used in the present invention is preferably 2 0 0 to 15 500 g / eq, more preferably 2 5 0 to 1 0 0 0 ⁇ 6 (1, more preferably 3 0 0 ⁇ 8 0 0 g / eq If the epoxy equivalent is less than 2 00 g / eq, the adhesion is inferior, and if it exceeds 1 500 g / eq, the heat resistance is adversely affected. It is desirable to adjust to ⁇ 1500 g / eq.
  • epoxy resin curing agents such as various phenol resins, acid anhydrides, amines, hydrazides, and acidic polyesters are used. These curing agents may be used alone or in combination of two or more.
  • the phosphorus-containing epoxy resin composition of the present invention may contain a curing accelerator such as a tertiary amine, a quaternary ammonium salt, a phosphine, and an imidazole, if necessary.
  • a curing accelerator such as a tertiary amine, a quaternary ammonium salt, a phosphine, and an imidazole
  • an organic solvent can also be used for viscosity adjustment.
  • organic solvents include amides such as N, N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methylethylketone, methanol, and ethanol.
  • examples include alcohols, benzene, and aromatic hydrocarbons such as toluene, but are not limited to these.
  • One or more of these solvents may be used.
  • the epoxy resin concentration can be blended in the range of 30 to 80% by weight.
  • the filler that can be used in the phosphorus-containing epoxy resin composition of the present invention includes aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, glass powder, fine powder silica, molten
  • examples include inorganic fillers such as silica, crystalline silica, and silica palon, but pigments may be blended.
  • the reason for using a general inorganic filler is an improvement in impact resistance.
  • a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is used, it acts as a flame retardant aid, and flame retardancy can be ensured even with a low phosphorus content. In particular, if the blending amount is not more than 10%, Impact effect is small.
  • the blending amount exceeds 1550%, the adhesiveness, which is a necessary item for laminated board applications, is lowered.
  • fibrous fillers such as silica, glass fiber, pulp fiber, synthetic fiber, and ceramic fiber, and organic fillers such as fine particle rubber and thermoplastic elastomer can also be contained in the resin composition.
  • Examples of the electronic circuit board material obtained from the phosphorus-containing epoxy resin composition include a resin sheet, a resin-attached metal foil, a pre-preda, and a laminate.
  • the method for producing the resin sheet is not particularly limited.
  • a phosphorus-containing epoxy resin composition as described above is preferably used for a carrier film that does not dissolve in an epoxy resin composition such as a polyester film or a polyimide film. After being applied to a thickness of 5 to 100 m, it can be heated and dried at 100 to 200 ° C. for 1 to 40 minutes to form a sheet.
  • a resin sheet is generally formed by a method called a casting method. At this time, if the sheet to which the phosphorus-containing epoxy resin composition is applied is previously surface treated with a release agent, the molded resin sheet can be easily peeled off.
  • the thickness of the resin sheet is preferably 5 to 80 ⁇ m.
  • the resin-coated metal foil obtained from the phosphorus-containing epoxy resin composition will be described.
  • the metal foil copper, aluminum, brass, nickel or the like, an alloy, or a composite metal foil can be used. It is preferable to use a metal foil having a thickness of 9 to 70 ⁇ m.
  • a method for producing a resin-coated metal foil from a flame-retardant resin composition containing a phosphorus-containing epoxy resin and a metal foil is not particularly limited.
  • the above-mentioned phosphorus-containing epoxy resin is provided on one surface of the metal foil.
  • the resin component can be obtained by applying a resin varnish whose viscosity has been adjusted with a solvent using a mouth coater, etc., and then drying by heating to semi-cure (B-stage) the resin component to form a resin layer.
  • semi-curing the resin component for example, it can be dried by heating at 100 to 200 ° C. for 1 to 40 minutes.
  • the thickness of the resin portion of the metal foil with resin is preferably 5 to 110 / m.
  • the sheet-like base material examples include inorganic fibers such as glass, polyester, etc.
  • a woven or non-woven fabric of organic fibers such as polyethylene, polyacryl, polyimide, and Kepler can be used, but is not limited thereto.
  • the method for producing the pre-preda from the phosphorus-containing epoxy resin composition and the base material is not particularly limited.
  • the base material is impregnated by immersing the base material in a resin varnish whose viscosity is adjusted with a solvent.
  • the resin component is obtained by semi-curing (B-stage) by heating and drying.
  • the amount of resin in the prepreg is preferably 30 to 80% by weight.
  • a multilayer board can be produced using the thus obtained single-layer laminated board as an inner layer material.
  • circuit formation is performed on the laminated board by an additive method, a subtractive method, or the like, and the formed circuit surface is treated with an acid solution and blackened to obtain an inner layer material.
  • An insulating layer is formed on one or both sides of this inner layer material with a resin sheet, a metal foil with resin, or a pre-preda, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board.
  • a laminate is formed by arranging resin-attached sheets on the circuit forming surfaces of a plurality of inner layer materials.
  • a laminate is formed by placing a resin sheet between the circuit formation surface of the inner layer material and the metal foil. Then, this laminate is heated and pressed and integrally molded, thereby forming a cured product of the resin sheet as an insulating layer.
  • multiple layers of inner layer material are formed.
  • the inner layer material and the metal foil as the conductor layer are formed by using a cured product of the resin sheet as an insulating layer.
  • a metal foil the thing similar to what was used for the laminated board used as an inner layer material can also be used.
  • the heat and pressure molding can be performed under the same conditions as the formation of the inner layer material.
  • the outermost circuit-forming surface resin of the inner layer material is a phosphorus-containing epoxy resin composition or a flame-retardant epoxy resin composition containing a phosphorus-containing epoxy resin.
  • it is applied to a thickness of 5 to 100 / zm, and then dried by heating at 100 to 200 ° C.
  • a printed wiring board can be formed by applying a via hole or a circuit to the surface of the multilayer laminated board thus formed by an additive method or a subtractive method. Furthermore, by repeating the above-described construction method using this printed wiring board as a glazing layer material, a multilayered board having more layers can be formed.
  • the insulating layer is formed of a resin-coated metal foil
  • the resin-coated metal foil is layered on the circuit forming surface of the inner layer material so that the resin layer of the resin-coated metal foil faces the circuit forming surface of the inner layer material. To form a laminate.
  • the laminate is heated and pressed to be integrally formed, whereby a cured product of the resin layer of the resin-coated metal foil is formed as an insulating layer, and the outer metal foil is formed as a conductor layer.
  • the heat and pressure molding can be performed under the same conditions as the formation of the inner layer material.
  • the insulating layer is formed by a pre-predder
  • a laminate of one or a plurality of pre-predators is placed on the circuit forming surface of the inner layer material, and a metal foil is placed on the outer side to form a laminate. To do.
  • the laminate is heated and pressed and integrally formed, whereby the hardened material of the pre-preda is formed as an insulating layer and the outer metal foil is formed as a conductor layer.
  • the metal foil the same metal foil as that used for the laminated plate used as the inner layer plate can be used.
  • the heat and pressure molding can be performed under the same conditions as the formation of the inner layer material.
  • Via holes and circuits are further formed on the surface of the multilayer laminate thus formed by the subtractive method using the additive method.
  • a wiring board can be formed. Furthermore, by repeating the above method using this printed wiring board as an inner layer material, a multilayer board can be formed.
  • the phosphorus-containing bull ester resin of the present invention can be obtained by adding an ethylenically unsaturated monobasic acid to the phosphorus-containing epoxy resin of the present invention.
  • Ethylene unsaturated monobasic acids include unsaturated monocarboxylic acids such as (meth) acrylic acid, polybasic acid anhydrides and at least one (meth) acrylic double bond per molecule.
  • Polybasic acid anhydrides used in the above reaction include aliphatic anhydrides such as maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and aromatic dicarboxylic anhydrides. Thing etc. are mentioned.
  • Examples of compounds having both (meth) acrylic double bond and alcoholic OH group include hydroxychetyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic And a reaction product of an acid and a polyhydric alcohol. Of these, (meth) acrylic acid is preferred.
  • the reaction between the phosphorus-containing epoxy resin and the ethylenically unsaturated monobasic acid can be performed by a known method. For example, in the presence of a polymerization inhibitor such as hydroquinone, tertiary amines such as benzyldimethylamine and phosphorus compounds such as triphenylphosphine are used as catalysts at 80 to 15 ° C for about 1 to 20 hours. By reacting, the desired bull ester resin can be obtained.
  • the reaction between the epoxy group and the carboxy group in the bull esterification reaction may be a reaction with the same equivalent ratio, but it can also be produced under conditions where the epoxy group is excessive or the carboxyl group is excessive.
  • a diluent in advance during the reaction.
  • a diluent any known organic solvent, inert diluent, that is, an inert solvent sealed with an epoxy group or a carboxyl group can be used without any particular limitation.
  • diluents include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, and cello soap acetate, polyethylene glycol monomethyl ether acetate, canolebitol acetate, butyl Acetic esters such as diethylene glycol monovinyl ether ethers such as canolebitono alcoholate, propylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl etherate acetates , Ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers such as methylol carbitol, ethyl carbitol, ptyl carbitol, triethylene glycol dialkyl ethers, propylene glycol dialkyl ethers, diethylene ether Propylene glycol dialkyl ethers, ethers such as 1,4-dioxane, tetrahydro
  • the resulting phosphorus-containing butyl ester is further blended with radically polymerizable monomers such as styrene dialyl phthalate, radical polymerization initiators, hardeners, and other fillers as necessary, to obtain radically polymerizable resin compositions.
  • This radical polymerizable resin composition has high flame retardancy without containing halogens such as bromine and chlorine.
  • the content of the compound represented by the general formula (1) is 2.5% by weight or less.
  • the epoxy resin containing phosphorus obtained by reacting the compound represented by the general formula (2) with epoxy resins is highly reactive with the curing agent, and the resin flow and curing balance during curing.
  • the pre-preda and the laminate obtained by heat-curing the pre-preda were flame retardant without containing a halide and were a resin composition with excellent solder heat resistance.
  • the peel strength of the copper foil was measured according to JIS C 64 8 15.7, and the interlayer adhesion was measured by peeling between one pre-preda and the remaining three sheets according to JIS C 6 48 1 5.7.
  • Solder heat resistance was measured at 280 according to JIS C 64 8 15.5, and the presence or absence of blistering or peeling was visually marked as ⁇ , and the one having no blistering or peeling as X.
  • the glass transition temperature and the heat generation amount of the cured product were measured by using an Exster DSC 6200 manufactured by Seiko Instruments Inc.
  • Curing calorific value retention rate is the percentage of the total curing calorific value of the pre-preda after storage for 72 hours at 60 ° C, assuming that the total curing calorific value of the pre-prepare immediately after creation is 100%. The smaller the number, the worse the storage stability.
  • HPLC of HCA—HQ represented by the structural formula 1 was measured. Elution time The peak components from 12.8 minutes to 13.2 minutes were collected, and the delayed components of the curing reaction were taken out and measured by FD-MASS, FTIR, and Proton NMR.
  • the MAS S measurement results showed a molecular weight of 3 24, and the FT IR results were compared with HCA-HQ.
  • a decrease in phenolic hydroxyl groups, a decrease in benzene 3-substitutions, and an increase in benzene 2-substitutions were observed. . From the NMR results, it was confirmed that only one of the two chemical shifts was twice as strong as the other.
  • HCA—HQ 3 1.72 parts by weight and YDF— 1 as a compound represented by the general formula (2) 70 (BPF type epoxy resin, manufactured by Tohto Kasei Co., Ltd.) 6 8. 2 8 parts by weight were charged, heated to 120 ° C under a nitrogen atmosphere, and held there for 1 hour.
  • As a catalyst 0.31 part by weight of trifurphosphine was added and reacted at 160 ° C. for 4 hours.
  • the purity of HC A—HQ was 99.5%.
  • the content of the compound represented by the structural formula 3 contained in H C A—H Q was 0.01% by weight.
  • the epoxy equivalent of the obtained epoxy resin was 48 0. O g / e q, and the phosphorus content was 3.0% by weight.
  • the content of the compound represented by Structural Formula 3 is 0.65 wt.
  • the same operation as in Synthesis Example 1 was performed except that HC A—HQ, which was / 0 , was used.
  • the purity of HC A—HQ was 98.7%.
  • the epoxy equivalent of the obtained epoxy resin was 48.83 g / e.
  • the phosphorus content was 3.0% by weight.
  • the content of the compound represented by Structural Formula 3 is 0.95 weight.
  • the same operation as in Synthesis Example 1 was performed except that HC A—HQ, which was / 0 , was used.
  • the purity of HC A—HQ was 98.2%.
  • the epoxy equivalent of the obtained epoxy resin was 4 8 7.7 g / eq, and the phosphorus content was 3.0% by weight.
  • Synthesis Example 7 In the same apparatus as in Synthesis Example 1, add HCA (9, 10—dihydr 9 mono-oxa 1 0—phosphaphenanthrene 1 0-oxide) 2 1.1 5 parts by weight and toluene 5 0 parts by weight was charged and dissolved in a nitrogen atmosphere by heating to 75 ° C. 3 parabenzoquinones here A portion of 10 0.47 parts by weight was charged over a period of 0 minutes, held at 85 for 30 minutes, heated up, and reacted at the reflux temperature for 3 hours.
  • the compound represented by the general formula (2) produced (specifically, the compound represented by the general formula (1) included in the HCA—HQ represented by the structural formula 1), specifically represented by the structural formula 3.
  • the compound content was 2.40% by weight.
  • the purity of the compound represented by the general formula (2) was 95.0% by weight.
  • 68.39 parts by weight of YDF-1700 was charged and heated to 1550 to remove toluene by refluxing.
  • Triphenylphosphine 0.32 part by weight was added and reacted at 160 ° C. for 4 hours.
  • the epoxy equivalent of the obtained epoxy resin was 470.2 gZeq, and the phosphorus content was 3.0% by weight.
  • the content of the compound represented by the general formula (1), specifically the compound represented by the structural formula 3, is 0.01 wt%.
  • the same operation as in Preparation 1 and Synthesis Example 1 was performed.
  • the purity of the 4 ⁇ compound represented by the general formula (2) is 97.3 wt. With respect to the total of HCA and HCA—HQ charged. /. Met.
  • the epoxy equivalent of the obtained epoxy resin was 4 8 0.3 g / e q, and the phosphorus content was 3.0% by weight.
  • the compound represented by the general formula (1) specifically the compound represented by the general formula (2) in which the content of the compound represented by the structural formula 4 is 0.15% by weight (specifically, the structural formula 2
  • the same operation as in Synthesis Example 1 was carried out except that 26.86 parts by weight of HCA—NQ) and 73.14 parts by weight of YDF—8 1 70 were used.
  • the purity of the compound represented by the general formula (2) was 90.1% by weight.
  • the epoxy equivalent of the obtained epoxy resin was 3 2 1.8 g / eq, and the phosphorus content was 2.2% by weight.
  • the content of the compound represented by the structural formula 3 using a 3. 1 0 weight 0/0 HC A- HQ The same operation as in Synthesis Example 1 was performed except that.
  • the purity of HC A—HQ was 93.0%.
  • the epoxy equivalent of the obtained epoxy resin was 47.lg / eq, and the phosphorus content was 3.0% by weight.
  • the content of the compound represented by the structural formula 3 contained in the compound represented by the general formula (2) (specifically, HCA—HQ represented by the structural formula 1) is 3.50 weight. /. Met.
  • the purity of the compound represented by the general formula (2) was 69.4% by weight.
  • the epoxy resin thus obtained had an epoxy equivalent of 444.4 g / eq and a phosphorus content of 3.0% by weight.
  • Table 1 the epoxy resin, dicyanamide curing agent, and imidazole curing accelerator obtained in each synthesis example were blended and dissolved in a solvent to evaluate the laminate.
  • Tables 1 and 2 summarize the results of Examples 1 to 9 and Comparative Examples 1 to 3.
  • a phenol novolak resin curing agent and an imidazole curing accelerator were blended, dissolved in a solvent, and evaluated for reactivity by gel time.
  • Table 3 summarizes the results of Examples 10 to 12 and Comparative Example 4.
  • Table 4 summarizes the results of the storage stability evaluation when the amount of catalyst was adjusted in Example 13 and Comparative Example 5 to match the gel time in the same manner as the heat generation amount retention rate (o / 0 ).
  • the adhesion time, migration resistance It is possible to provide a phosphorus-containing epoxy resin and an electronic circuit board material excellent in solder immersion resistance and storage stability in a pre-preda.

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Abstract

Selon l'invention, un composé de phénol contenant du phosphore représenté par la formule générale (2), dans laquelle la teneur d'un composé représenté par la formule générale (1) est de 2,5 % en poids ou moins, est utilisé pour obtenir une résine époxy contenant du phosphore ayant une aptitude élevée au durcissement. Cette résine époxy contenant du phosphore hautement réactive et une composition de résine époxy contenant du phosphore contenant la résine sont appropriées à être utilisées dans des applications telles qu'une matière de scellement, une matière de moulage, une matière d'empotage, un adhésif, une matière pour des revêtements d'isolation électrique, une feuille d'isolation électrique, une feuille de cuivre revêtue de résine, un préimprégné, un stratifié électrique, entre autres, ces applications étant destinées à être utilisées dans la production de stratifiés cuivrés pour des cartes à circuit électronique dans la production de pièces électroniques. L'invention concerne également une composition de résine durcissable contenant soit la résine soit la composition de résine ; et un objet durci obtenu à partir de la résine ou de la composition de résine. Formule générale (1) (1) le symbole n représente 0 ou 1. R1 et R2 représentent chacun un atome d'hydrogène ou un groupe hydrocarboné, peuvent être identiques ou différents et peuvent être linéaires, ramifiés ou cycliques. R1 et R2 peuvent être liés l'un à l'autre pour former une structure cyclique. B représente l'un quelconque parmi benzène, biphényle, naphtalène, anthracène, phénanthrène et les formes substituées de ces hydrocarbures. Formule générale (2) (2) le symbole n représente 0 ou 1. R1 et R2 représentent chacun un atome d'hydrogène ou un groupe hydrocarboné, peuvent être identiques ou différents et peuvent être linéaires, ramifiés ou cycliques. R1 et R2 peuvent être liés entre eux pour former une structure cyclique. B représente l'un quelconque parmi benzène, biphényle, naphtalène, anthracène, phénanthrène et les formes substituées de ces hydrocarbures.
PCT/JP2008/070622 2007-11-09 2008-11-06 Résine époxy contenant du phosphore et composition de résine époxy contenant du phosphore, leur procédé de fabrication et composition de résine durcissable et objet durci contenant chacun ou obtenus chacun à partir de la résine et de la composition de résine Ceased WO2009060987A1 (fr)

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JP2010070470A (ja) * 2008-09-16 2010-04-02 Toto Kasei Co Ltd リン含有フェノール化合物およびその製造方法、該化合物を用いた硬化性樹脂組成物および硬化物
WO2011055850A1 (fr) * 2009-11-05 2011-05-12 新日鐵化学株式会社 Résine époxy contenant du phosphore, composition de résine et produit durci résistant au feu à base de celle-ci
WO2011078372A1 (fr) * 2009-12-25 2011-06-30 新日鐵化学株式会社 Résine époxy, composition de résine époxy et produit durci correspondant
WO2011096588A1 (fr) * 2010-02-08 2011-08-11 新日鐵化学株式会社 Procédé de production d'une résine époxyde contenant du phosphore, composition de résine époxyde et produit traité correspondant
JP2013043910A (ja) * 2011-08-23 2013-03-04 Sanko Kk 高融点難燃剤結晶とその製造方法、該難燃剤含有エポキシ樹脂組成物、該組成物を用いたプリプレグ及び難燃性積層板
CN108314774A (zh) * 2012-06-15 2018-07-24 新日铁住金化学株式会社 含磷的环氧树脂和以该环氧树脂作为必须成分的组合物、固化物
WO2018180267A1 (fr) 2017-03-29 2018-10-04 新日鉄住金化学株式会社 Composé phénolique contenant du phosphore, résine époxy contenant du phosphore, composition de résine durcissable associée, ou composition de résine époxy et produit durci correspondant

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CN102757547B (zh) * 2011-04-27 2016-07-06 新日铁住金化学株式会社 含磷和氮的环氧树脂
CN104356360B (zh) * 2014-11-06 2017-06-30 济南圣泉集团股份有限公司 高Tg无卤阻燃环氧树脂的制备方法
CN107383337A (zh) * 2017-07-31 2017-11-24 镇江利德尔复合材料有限公司 一种无卤素阻燃乙烯基酯树脂及其制备方法

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JP2010070470A (ja) * 2008-09-16 2010-04-02 Toto Kasei Co Ltd リン含有フェノール化合物およびその製造方法、該化合物を用いた硬化性樹脂組成物および硬化物
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WO2011055850A1 (fr) * 2009-11-05 2011-05-12 新日鐵化学株式会社 Résine époxy contenant du phosphore, composition de résine et produit durci résistant au feu à base de celle-ci
JP5793086B2 (ja) * 2009-12-25 2015-10-14 新日鉄住金化学株式会社 エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
WO2011078372A1 (fr) * 2009-12-25 2011-06-30 新日鐵化学株式会社 Résine époxy, composition de résine époxy et produit durci correspondant
WO2011096588A1 (fr) * 2010-02-08 2011-08-11 新日鐵化学株式会社 Procédé de production d'une résine époxyde contenant du phosphore, composition de résine époxyde et produit traité correspondant
JP2011162621A (ja) * 2010-02-08 2011-08-25 Nippon Steel Chem Co Ltd リン含有エポキシ樹脂の製造方法、エポキシ樹脂組成物及びその硬化物
CN102741314A (zh) * 2010-02-08 2012-10-17 新日铁化学株式会社 含磷环氧树脂的制备方法、环氧树脂组合物及其固化物
JP2013043910A (ja) * 2011-08-23 2013-03-04 Sanko Kk 高融点難燃剤結晶とその製造方法、該難燃剤含有エポキシ樹脂組成物、該組成物を用いたプリプレグ及び難燃性積層板
CN108314774A (zh) * 2012-06-15 2018-07-24 新日铁住金化学株式会社 含磷的环氧树脂和以该环氧树脂作为必须成分的组合物、固化物
CN108314774B (zh) * 2012-06-15 2021-02-12 日铁化学材料株式会社 含磷的环氧树脂和以该环氧树脂作为必须成分的组合物、固化物
WO2018180267A1 (fr) 2017-03-29 2018-10-04 新日鉄住金化学株式会社 Composé phénolique contenant du phosphore, résine époxy contenant du phosphore, composition de résine durcissable associée, ou composition de résine époxy et produit durci correspondant
KR20190132662A (ko) 2017-03-29 2019-11-28 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 인 함유 페놀 화합물, 인 함유 에폭시 수지, 그 경화성 수지 조성물 또는 에폭시 수지 조성물 및 그 경화물

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