WO2015046626A1 - Composition de résine époxy contenant du phosphore et article durci - Google Patents

Composition de résine époxy contenant du phosphore et article durci Download PDF

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Publication number
WO2015046626A1
WO2015046626A1 PCT/JP2014/076481 JP2014076481W WO2015046626A1 WO 2015046626 A1 WO2015046626 A1 WO 2015046626A1 JP 2014076481 W JP2014076481 W JP 2014076481W WO 2015046626 A1 WO2015046626 A1 WO 2015046626A1
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Prior art keywords
phosphorus
epoxy resin
containing epoxy
resin composition
parts
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PCT/JP2014/076481
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English (en)
Japanese (ja)
Inventor
康幸 高尾
真也 河崎
司 後藤
一男 石原
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新日鉄住金化学株式会社
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Priority to CN201480053661.9A priority Critical patent/CN105555866B/zh
Priority to KR1020167007473A priority patent/KR102192792B1/ko
Priority to JP2015539481A priority patent/JP6596751B2/ja
Publication of WO2015046626A1 publication Critical patent/WO2015046626A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • 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
    • C08G59/3272—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
    • C08G59/1422—Polycondensates modified by chemical after-treatment with inorganic 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
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; 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
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/30—Environmental or health characteristics, e.g. energy consumption, recycling or safety issues

Definitions

  • the present invention relates to a phosphorus-containing epoxy resin composition having a flame retardancy composed of a phosphorus-containing epoxy resin and a phosphorus-containing phenol compound, and a cured product thereof.
  • Epoxy resins are widely used in industrial applications including the electric and electronic fields because of their excellent adhesiveness, heat resistance, and moldability.
  • flame retardancy is strongly demanded from the viewpoint of safety such as the purpose of preventing the occurrence of a fire when the device is used.
  • brominated flame retardants, nitrogen-based flame retardants, and phosphorus-based flame retardants alone or in combination as a method for imparting flame retardancy to laminates, and furthermore, a system using an inorganic flame retardant aid for the flame retardant Many have been applied.
  • Patent Documents 1 and 2 disclose 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA-HQ, manufactured by Sanko Co., Ltd.). Thermosetting resins and compositions obtained by reacting epoxy resins with epoxy resins at a predetermined molar ratio are disclosed.
  • Patent Document 3 discloses a phosphorus-containing epoxy resin obtained by reacting a resin having a bifunctional or higher functional epoxy group with diphenylphosphinylhydroquinone.
  • the phosphorus-containing epoxy resin obtained by the reaction between such a phosphorus compound and the epoxy resin has a high molecular weight as the phosphorus content increases, so that the resin varnish that provides sufficient flame retardancy has a high viscosity, There was a problem that workability in handling and impregnation into a substrate such as glass cloth deteriorated. Furthermore, since the molecular weight of the phosphorus-containing epoxy resin is increased, the crosslink density of the cured product is reduced, and thus it is difficult to obtain a high glass transition temperature.
  • Patent Document 4 discloses a method of reducing the molecular weight and decreasing the viscosity by using a phosphorus-containing epoxy resin that leaves a hydroxyl group derived from a phosphorus-containing phenol compound.
  • Patent Document 5 discloses a method for increasing the phosphorus content by dissolving a phosphorus compound in a phosphorus-containing epoxy resin varnish because sufficient flame retardancy cannot be obtained only by the phosphorus-containing epoxy resin.
  • Patent Document 6 discloses a method of dispersing HCA-HQ in a resin varnish by finely pulverizing HCA-HQ to an average particle size of 10 ⁇ m and a maximum particle size of 40 ⁇ m.
  • a phosphorus compound is dissolved using a high boiling point solvent. The viscosity is likely to be higher than that of the case, and there has been a problem that the curing conditions must be sufficiently examined in order to sufficiently perform the curing reaction.
  • Japanese Patent No. 3092009 JP-A-11-279258 Japanese Patent Laid-Open No. 5-214070 JP 2012-172079 A JP 2002-249540 A JP 2003-011269 A JP 60-126293 A JP-A-61-2236787
  • the phosphorus-containing epoxy resin or the phosphorus-containing epoxy resin composition that has been used so far, if the phosphorus content is increased in order to improve the flame retardancy, the solubility in the solvent becomes worse, and the viscosity is higher. Therefore, it was difficult to apply to a laminated board. Furthermore, the phosphorus-containing phenol compound has poor solubility in an organic solvent, and it has been difficult to apply it as a uniform resin varnish for use as a formulation for a substrate.
  • the present invention has been made in view of the above-described problems of the prior art, and has a low viscosity and good solubility in organic solvents while having sufficient flame retardancy by increasing the phosphorus content.
  • An epoxy resin composition having excellent workability such as impregnation into a fibrous base material is provided.
  • the present invention (1). It is represented by the following general formula (2) of 5 to 45 parts by mass with respect to 100 parts by mass of the phosphorus-containing epoxy resin having a phosphorus content having the structure of the following general formula (1) in the range of 2 to 7% by mass.
  • a phosphorus-containing epoxy resin composition that dissolves a phosphorus-containing phenol compound and has no precipitation at room temperature, (Wherein R 1 and R 2 represent a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different, and may be cyclic with a phosphorus atom.
  • I is 0 or 1) To express.) (Wherein R 3 and R 4 represent a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different and may be cyclic with a phosphorus atom. N is 0 or 1) A represents an arenetriyl group having 6 to 20 carbon atoms.) (2). A phosphorus-containing epoxy resin composition obtained by blending an epoxy resin (B) with the phosphorus-containing epoxy resin composition described in the item (1), (3). (2) A phosphorus-containing epoxy resin composition characterized in that the phosphorus content in the phosphorus-containing epoxy resin composition according to item (2) is 2% by mass or more, (4).
  • the phosphorus-containing epoxy resin composition of the present invention has been found out that a phosphorus-containing phenol compound, which has been difficult to dissolve in the past, can be dissolved in a specific phosphorus-containing epoxy resin, and has completed the present invention, and has a high phosphorus content It achieves both the flame retardancy due to and improved workability due to low resin viscosity. Since the phosphorus-containing epoxy resin composition of the present invention facilitates impregnation of fibrous materials such as glass cloth in the production of laminates and improves flame retardancy, printed wiring board materials and sealing materials in the electronic and electrical fields It is useful in fields requiring flame retardancy such as casting materials, adhesive materials, aerospace, and composite materials used in vehicles, bridges, windmills, and the like.
  • the phosphorus-containing epoxy resin used in the present invention is a phosphorus-containing epoxy resin having a chemical structure represented by the following general formula (1) in its molecule, for example, the following general formula (2) and / or the following general formula It can be synthesized by reacting the phosphorus compound shown in (3) with an epoxy resin.
  • R 1 and R 2 represent a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different, and may be cyclic with a phosphorus atom.
  • R 3 and R 4 represent a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different and may be cyclic with a phosphorus atom.
  • N is 0 or 1
  • A represents an arenetriyl group having 6 to 20 carbon atoms.
  • R 5 and R 6 represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and may be cyclic with a phosphorus atom.
  • Examples of the phosphorus compound represented by the general formula (2) or the general formula (3) include 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (Sanko) Product name HCA-HQ), 10- (1,4-dioxynaphthalene) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as HCA-NQ), diphenylphosphini Luhydroquinone (made by Hokuko Chemical Co., Ltd., trade name PPQ), diphenylphosphenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol (Nippon Chemical Industry Co., Ltd.) Manufactured, trade name CPHO-HQ), 1,5-cyclooctylenephosphinyl-1,4-phenyldio
  • the epoxy resin that reacts with the above-described phosphorus compound when synthesizing the phosphorus-containing epoxy resin has at least 1.5 epoxy groups in the molecule, and more preferably has two or more epoxy groups. good.
  • the phosphorus compound of general formula (3) it is preferable to use what has 3 or more as an epoxy group.
  • epoxy resins examples include Epototo YD-128, Epototo YD-8125 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type epoxy resin), Epototo YDF-170, Epototo YDF-8170 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol F) Type epoxy resin), YSLV-80XY (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., tetramethylbisphenol F type epoxy resin), Epototo YDC-1312 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroquinone type epoxy resin), jER YX-4000H (Mitsubishi Chemical) Co., Ltd., biphenyl type epoxy resin), Epototo YDPN-638, Epototo YDPN-63X (manufactured by Nippon Steel & Sumi
  • the reaction between the phosphorus compound of the general formula (2) and / or the general formula (3) and the epoxy resin is as follows.
  • Known and publicly known methods such as the advance method, which is a reaction method of a phenol compound and an epoxy resin, including the methods described in Patent Documents 1, 2, and 3 can be used.
  • the ratio of the phosphorus compound to the epoxy resin should be such that the phosphorus content of the phosphorus-containing epoxy resin obtained after the reaction is in the range of 2 to 7% by mass, more preferably in the range of 2.5 to 5% by mass. It is.
  • the solubility of the phosphorus-containing phenol compound and the phosphorus-containing epoxy resin used in the present invention may be deteriorated. If the phosphorus content is high, the viscosity of the phosphorus-containing epoxy resin will increase, It can be difficult to dissolve. In the reaction between the phosphorus compound and the epoxy resin, a reaction catalyst can be used as needed to promote the reaction.
  • Examples of the catalyst that can be used include phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, quaternary phosphonium salts such as n-butyltriphenylphosphonium bromide and ethyltriphenylphosphonium iodide, 2- Known and commonly used catalysts include imidazoles such as ethyl-4-methylimidazole and 2-phenylimidazole, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide, and tertiary amines such as triethylamine and benzyldimethylamine.
  • phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine
  • quaternary phosphonium salts such as n-butyltriphen
  • the amount used is preferably in the range of 0.002 to 2 parts by mass relative to 100 parts by mass of the total mass of the epoxy resin and the phosphorus compound. If the amount is large, the stability of the phosphorus-containing epoxy resin composition of the present invention may be adversely affected.
  • the phosphorus-containing phenol compound dissolved in the phosphorus-containing epoxy resin is a phosphorus-containing phenol compound having a structure represented by the general formula (2). Specific examples include phosphorus-containing phenols such as HCA-HQ, HCA-NQ, PPQ, diphenylphosphenyl-1,4-dioxynaphthalene, CPHO-HQ, and CPHO-HQ.
  • These phosphorus-containing phenol compounds can be used in combination of two or more.
  • These phosphorus-containing phenol compounds are compounds of the general formula (3), specifically, phosphorus compounds having an active hydrogen group directly connected to a phosphorus atom such as HCA and diphenylphosphine, 1,4-benzoquinone and 1 , 4-naphthoquinone and other quinones.
  • the synthesis methods are shown in Patent Document 7, Patent Document 8, and Non-Patent Document 1, but are not limited thereto.
  • a phosphorus-containing phenol compound may be synthesized in a phosphorus-containing epoxy resin.
  • the present invention is characterized in that a specific phosphorus-containing phenol compound is dissolved in a specific phosphorus-containing epoxy resin, but the state in which the phosphorus-containing phenol compound is dissolved in the phosphorus-containing epoxy resin is the state of the phosphorus-containing phenol resin at room temperature. It means that no solid is observed in the phosphorus-containing epoxy resin. Specifically, when the phosphorus-containing epoxy resin composition is solid, it is degassed by heat melting or the like, and when it is liquid, it is degassed as it is, and the phosphorus-containing phenol compound is used in a 23 ° C. atmosphere using a 20 ⁇ microscope. The state which has confirmed that the solid derived from this has not precipitated.
  • the solid derived from a phosphorus containing phenol compound does not precipitate by observing with a 20 time microscope as it is at room temperature.
  • the method for dissolving the phosphorus-containing phenol compound in the phosphorus-containing epoxy resin is not particularly specified, and a phosphorus-containing phenol compound synthesized in advance or commercially available may be mixed in the phosphorus-containing epoxy resin, or the phosphorus-containing epoxy
  • the target phosphorus-containing epoxy resin composition can also be obtained by synthesizing a phosphorus-containing phenol compound in the resin.
  • the remaining phosphorus compound can be dissolved while synthesizing the phosphorus-containing epoxy resin.
  • the phosphorus-containing phenol compound can be dissolved in the phosphorus-containing epoxy resin without solvent or in combination with a solvent, and can be dissolved by heating and stirring to such an extent that the reaction between the phosphorus-containing epoxy resin and the phosphorus-containing phenol compound does not occur. .
  • the phosphorus compound of the general formula (3) and the quinone compound can be charged and reacted in the phosphorus-containing epoxy resin.
  • a solvent is preferably used in combination.
  • an aprotic solvent is preferable, and examples thereof include toluene, xylene, methanol, ethanol, 2-butoxyethanol, dialkyl ether, glycol ether, propylene glycol monomethyl ether, dioxane and the like. These reaction solvents may be used alone or in combination of two or more.
  • the epoxy resin composition in which the phosphorus-containing phenol compound is dissolved in the phosphorus-containing epoxy resin can also be adjusted by adjusting the reaction ratio and reaction conditions when reacting the phosphorus-containing phenol compound with epihalohydrin.
  • Phosphorus-containing phenolic compounds are poorly soluble in organic solvents, so if any amount of solvent is used by any method, the phosphorus-containing phenolic compound will not dissolve in the phosphorus-containing epoxy resin and may precipitate.
  • the amount of the organic solvent is preferably 50% by mass or less based on the total mass of the phosphorus-containing epoxy resin composition.
  • the temperature at the time of dissolution is preferably 100 to 200 ° C, more preferably 120 to 160 ° C. If the dissolution temperature is low, the dissolution rate may be slow, and if the dissolution temperature is high, the reaction between the phenol group and the epoxy group occurs in parallel with the dissolution and the viscosity increases, which may make handling difficult.
  • the phosphorus-containing phenol compound used here needs to be 5 to 45 parts by mass with respect to 100 parts by mass of the phosphorus-containing epoxy resin, and it is flame retardant to be 10 to 45 parts by mass. Further desirable from the viewpoint of sex. If the phosphorus-containing phenol compound is less than 5 parts by mass, the phosphorus content of the phosphorus-containing epoxy resin must be increased in order to obtain flame retardancy, and it becomes difficult to dissolve the phosphorus-containing phenol resin because the resin viscosity increases. When the phosphorus content of the phosphorus-containing epoxy resin is low, dissolution is easy but flame retardancy is not obtained. When there are many phosphorus containing phenol compounds, there exists a possibility that it may become completely insoluble.
  • the phosphorus-containing epoxy resin composition of the present invention is a phosphorus-containing epoxy compound having a structure represented by the general formula (1) and a phosphorus-containing phenol compound represented by the general formula (2) unless otherwise specified.
  • a phosphorus-containing epoxy resin composition (c1) comprising (b), a phosphorus-containing epoxy resin having a structure of the general formula (1), a phosphorus-containing phenol compound represented by the general formula (2), and a curing agent (C);
  • a phosphorus-containing epoxy resin having a structure of the general formula (1), a phosphorus-containing phenol compound represented by the general formula (2), an epoxy resin (B), and a curing agent (C) It is used in the sense to include all of the epoxy resin composition (c2)
  • each phosphorus-containing epoxy resin composition when something is further blended in each phosphorus-containing epoxy resin composition, the total sum of each component constituting each phosphorus-containing epoxy resin composition is used as a reference. That is, when something is further blended in the phosphorus-containing epoxy resin composition (a), two components of the phosphorus-containing epoxy resin having the structure of the general formula (1) and the phosphorus-containing phenol compound represented by the general formula (2) In the case where something is further added to the phosphorus-containing epoxy resin composition (c2), the phosphorus-containing epoxy resin having the structure of the general formula (1) and the phosphorus-containing content represented by the general formula (2) The total amount of the four components of the phenol compound, the epoxy resin (B), and the curing agent (C) is a standard.
  • An epoxy resin (B) can be further added to the phosphorus-containing epoxy resin composition (a) of the present invention.
  • the method of mixing the epoxy resin (B) is not particularly defined, and can be performed using a generally used method. Moreover, when mixing by heating, it is desirable to carry out at 200 degrees C or less, and it is more desirable to carry out at 160 degrees C or less. When the mixing temperature is 200 ° C. or higher, the reaction of the epoxy group in the phosphorus-containing epoxy resin composition (b) occurs, the viscosity becomes high, and handling may be difficult.
  • the epoxy resin (B) used here has at least 1.5 epoxy groups in the molecule as in the epoxy resin used when synthesizing the phosphorus-containing epoxy resin, more preferably two or more.
  • the amount of the epoxy resin (B) is preferably 2% by mass or more of the total phosphorus-containing epoxy resin composition (b) added with the epoxy resin (B) from the viewpoint of flame retardancy. If the phosphorus content in the phosphorus-containing epoxy resin composition (b) is low, flame retardancy may not be exhibited.
  • the curing agent (C) that can be used in the phosphorus-containing epoxy resin composition [(a) or (b)] of the present invention known and publicly used ones used for epoxy resins can be used.
  • Hydroxybenzenes such as resorcinol and hydroquinone, binaphthols, biphenols, trisphenols, bisphenol A, bisphenol F, bisphenol S, trishydroxyphenylmethane, trishydroxyphenylethane, shounol BRG-555 (Phenol made by Showa Denko KK Novolak resin), cresol novolak resin, alkylphenol novolak resin, aralkylphenol novolak resin, triazine ring-containing phenol novolak resin, biphenylaralkylphenol resin, resin top TPM-10 (Gunei Chemical Industry Co., Ltd., trishydroxyphenylmethane type novolak resin), compounds having two or more phenolic hydroxyl groups in one molecule such as aralkyl naphthalene diol resin, hydrazides such as adipic acid dihydrazide and sebacic acid dihydrazide , Imidazole compounds and salts thereof, dic
  • the amount of the curing agent (C) used is the active hydrogen equivalent of the phosphorus-containing phenol compound contained in the phosphorus-containing epoxy resin composition from the epoxy group equivalent in the phosphorus-containing epoxy resin composition [(a) or (b)].
  • the functional group of the curing agent (C) is preferably in the range of 0.1 to 1.3 equivalent, more preferably 0.2 to 1.0 equivalent. If the functional group equivalent of the curing agent is small, the curing reaction of the epoxy group does not proceed sufficiently so that it cannot be obtained as a cured product. If it is large, unreacted curing agent remains, and the cured product has sufficient mechanical properties. There is a risk that you will not be able to get.
  • a diluent when adjusting fluidity, viscosity, etc., it is possible to use a diluent as long as the physical properties are not impaired.
  • the diluent is preferably a reactive diluent, but may be a non-reactive diluent.
  • monofunctional such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, bifunctional such as resorcinol glycidyl ether, neopentyl glycol glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol
  • polyfunctional glycidyl ethers such as polyglycidyl ether, trimethylolpropane polyglycidyl ether, and pentaerythritol polyglycidyl ether.
  • Non-reactive diluents include benzyl alcohol, butyl diglycol, pine oil and the like. These diluents are preferably 30 parts by mass or less with respect to 100 parts by mass of the phosphorus-containing epoxy resin composition. If the amount of diluent added is large, bleed out from the cured product may occur in the case of a non-reactive diluent, and in the case of a reactive diluent, the curing reaction may not sufficiently proceed to bleed out. . Moreover, it is possible to use a hardening accelerator as needed for the phosphorus-containing epoxy resin composition of the present invention.
  • phosphines for example, phosphines, quaternary phosphonium salts, tertiary amines, quaternary ammonium salts, imidazole compounds, boron trifluoride complexes, 3- (3,4-dichlorodiphenyl) -1,1-dimethylurea, 3 -(4-Chlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea and the like.
  • curing accelerators depend on the epoxy resin used, the type of epoxy resin curing agent used together, the molding method, the curing temperature, and other required characteristics, but 0.01 to 10 parts by mass with respect to 100 parts by mass of the phosphorus-containing epoxy resin composition.
  • the range of is preferable.
  • the phosphorus-containing epoxy resin composition of the present invention may be blended with other thermosetting resins and thermoplastic resins as long as the characteristics are not impaired.
  • thermosetting resins and thermoplastic resins for example, phenol resin, acrylic resin, petroleum resin, indene resin, coumarone indene resin, phenoxy resin, polyurethane, polyester, polyamide, polyimide, polyamideimide, polyetherimide, polyethersulfone, polysulfone, polyetheretherketone, polyphenylene sulfide, Examples thereof include, but are not limited to, polyvinyl formal and styrene maleic acid resin.
  • thermosetting resins and thermoplastic resins are desirably blended so as not to exceed 50 parts by mass with respect to 100 parts by mass of the phosphorus-containing epoxy resin composition. If the blending amount exceeds 50 parts by mass, the phosphorus content in the cured product will decrease, and sufficient flame retardancy may not be obtained.
  • the phosphorus containing epoxy resin composition of this invention can mix
  • fillers include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, talc, calcined talc, clay, kaolin, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium hydroxide, Magnesium carbonate, barium carbonate, barium sulfate, boron nitride, titanium oxide, glass powder, silica balloon, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, synthetic Examples thereof include fibers and ceramic fibers.
  • the fillers are preferably 1 to 80 parts by mass with respect to 100 parts by mass of the phosphorus-containing epoxy resin composition. If the amount is too small, the properties of the inorganic filler and the organic filler will not be exhibited. If the amount is too large, the material becomes brittle even after curing, and the cured product may not be able to obtain sufficient mechanical properties.
  • the phosphorus-containing epoxy resin composition of the present invention further includes various kinds of silane coupling agents, antioxidants, mold release agents, antifoaming agents, emulsifiers, thixotropic agents, smoothing agents, flame retardants, pigments and the like as necessary. Additives can be blended.
  • the phosphorus-containing epoxy resin composition of the present invention can be cured by the same method as known epoxy resin compositions to obtain a cured product.
  • the phenol compound dissolved in the phosphorus-containing epoxy resin causes a curing reaction with the epoxy group of the phosphorus-containing epoxy resin or the epoxy resin (B) and contributes to curing.
  • the curing method can be the same as that of a known epoxy resin composition, and the method unique to the resin composition of the present invention is unnecessary.
  • the phosphorus-containing epoxy resin composition of the present invention can make a prepreg used in a printed wiring board or the like by impregnating a fibrous base material.
  • the fibrous base material inorganic fibers such as glass, and woven or non-woven fabrics of organic fibers such as polyester, polyamine, polyacryl, polyimide, Kevlar, etc. can be used, but are not limited thereto.
  • the method for producing the prepreg from the phosphorus-containing epoxy resin composition of the present invention is not particularly limited.
  • the resin-varnish prepared by adjusting the viscosity of the phosphorus-containing epoxy resin composition with a solvent is impregnated. Thereafter, the resin component is obtained by heat-drying and semi-curing (B-stage).
  • the resin component can be heat-dried at 100 to 200 ° C. for 1 to 40 minutes.
  • the amount of resin in the prepreg is preferably 30 to 80% by mass.
  • the laminated board hardening method generally used when manufacturing a printed wiring board it is not limited to this.
  • the laminated board hardening method generally used when manufacturing a printed wiring board it is not limited to this.
  • the metal foil a single, alloy, or composite metal foil of copper, aluminum, brass, nickel or the like can be used.
  • the laminate prepared here can be heated under pressure to cure the prepreg to obtain a laminate.
  • the temperature is 160 to 220 ° C.
  • the pressure is 50 to 500 N / cm 2
  • the heating and pressing time is 40.
  • the target cured product can be obtained by setting it to ⁇ 240 minutes. If the heating temperature is low, the curing reaction does not proceed sufficiently, and if it is high, the phosphorus-containing epoxy resin composition may start to decompose. Moreover, when the pressurizing pressure is low, the resin flows, and a cured product having a desired thickness may not be obtained. Furthermore, if the heating and pressing time is short, the curing reaction may not proceed sufficiently, and if it is long, the phosphorus-containing epoxy resin composition in the prepreg may be thermally decomposed. Therefore, it is preferable to manage under the above conditions.
  • the phosphorus-containing epoxy resin composition of the present invention has excellent flame retardancy because it has a high phosphorus content, and because of its low viscosity, it has good impregnation into fibrous substrates such as glass cloth. Excellent workability. Phosphorus-containing epoxy resin cured products have good flame retardancy, heat resistance, and adhesiveness. Sealing materials used in electrical and electronic parts, copper-clad laminates, insulating paints, flame retardant paints, composite materials, insulating flame retardants It was found useful as a material for adhesives and the like.
  • the phenolic hydroxyl group was determined as the weight of the sample per equivalent of hydroxyl group.
  • Viscosity Measured at 25 ° C. using a B-type viscometer TVB-10H manufactured by Toki Sangyo Co., Ltd.
  • Phosphorus content Sulfuric acid, hydrochloric acid and perchloric acid were added to the sample and heated to wet ash to convert all phosphorus atoms to orthophosphoric acid. Metavanadate and molybdate were reacted in a sulfuric acid acidic solution, the absorbance at 420 nm of the resulting limpavande molybdate complex was measured, and the phosphorus atom content determined by a previously prepared calibration curve was expressed in%.
  • the phosphorus content of the laminate was expressed as the content relative to the resin content of the laminate.
  • Glass transition temperature Measured according to IPC-TM650 2.4.25c.
  • Flame retardancy Measurement was carried out according to UL (Underwriter Laboratories) standards. Evaluation was described by V-0, V-1, and V-2. Moreover, the sum total of 5 after-flame time was described as the after-flame time total.
  • Solubility In the case of a solid, it is degassed by heating and melting, and in the case of a liquid, it is degassed as it is, and a solid derived from a phosphorus-containing phenol compound is precipitated using a 20-fold microscope in an atmosphere at 23 ° C. Confirmed that there is no.
  • Example 1 57 A phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name Epototo YDPN-638) as an epoxy resin in a four-necked Separa brasso equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe. Put 72.3 parts and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA, manufactured by Sanko Co., Ltd.) as a phosphorus compound, and react at 160 ° C. for 5 hours.
  • HCA 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • a phosphorus-containing epoxy resin having an epoxy equivalent of 766 g / eq and a phosphorus content of 6.0% was obtained.
  • 10 parts of 10- (1,4-dioxynaphthalene) -10H-9-oxa-10-phosphaphenanthrene (manufactured by Sanko Co., Ltd., trade name HCA-NQ) is added as a phosphorus-containing phenol compound,
  • the desired phosphorus-containing epoxy resin composition was obtained by stirring for 2 hours.
  • the obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 6.2%.
  • the viscosity of the phosphorus-containing epoxy resin composition varnish obtained by diluting the phosphorus-containing epoxy resin composition with methyl ethyl ketone (hereinafter, MEK) to a solid content of 70% was 9800 mPa ⁇ s.
  • Example 2 66.2 parts YDPN-638 as an epoxy resin, 33.8 parts HCA as a phosphorus compound, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene as a phosphorus-containing phenol compound
  • a phosphorus-containing epoxy having an epoxy equivalent of 460 g / eq and a phosphorus content of 4.2%, except that 10-oxide (trade name HCA-HQ, manufactured by Sanko Co., Ltd.) was changed to 20 parts.
  • HCA-NQ was dissolved to obtain the intended phosphorus-containing epoxy resin composition.
  • the obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 5.6%.
  • Example 3 The viscosity of the phosphorus-containing epoxy resin composition varnish obtained by diluting this phosphorus-containing epoxy resin composition with MEK to a solid content of 70% was 1040 mPa ⁇ s.
  • Example 3 The same procedure as in Example 1 was carried out except that 71.8 parts of YDPN-638 was used as the epoxy resin, 28.2 parts of HCA was used as the phosphorus compound, and 45 parts of HCA-NQ was used as the phosphorus-containing phenol compound. After obtaining a phosphorus-containing epoxy resin having 363 g / eq and a phosphorus content of 4.0%, HCA-NQ was dissolved to obtain a target phosphorus-containing epoxy resin composition.
  • Example 4 The same procedure as in Example 1 was carried out except that 84.5 parts of YDPN-638 was used as the epoxy resin, 15.5 parts of HCA was used as the phosphorus compound, and 40 parts of HCA-NQ was used as the phosphorus-containing phenol compound.
  • Example 5 63.8 parts of YDPN-638 as epoxy resin, 10 parts of bisphenol F type liquid epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name Epototo YDF-170), 15.6 parts of HCA as phosphorus compound and HCA-HQ was changed to 10.6 parts, and the HCA-NQ was changed to 5 parts as a phosphorus-containing phenol compound, and the same operation as in Example 1 was carried out.
  • a phosphorus-containing epoxy resin having an epoxy equivalent of 355 g / eq and a phosphorus content of 3.2% After obtaining HCA-NQ, the intended phosphorus-containing epoxy resin composition was obtained.
  • the obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 3.5%.
  • the viscosity of the phosphorus-containing epoxy resin composition varnish obtained by diluting this phosphorus-containing epoxy resin composition with MEK to a solid content of 70% was 650 mPa ⁇ s.
  • Example 6 Orthocresol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name Epototo YDCN-700-7) as epoxy resin, 55.6 parts and YDF-170 as 20 parts, HCA as phosphorous compound as 16.4 parts and HCA A phosphorus-containing epoxy resin having an epoxy equivalent of 365 g / eq and a phosphorus content of 3.0%, except that -NQ was changed to 80 parts and the HCA-HQ was changed to 8 parts as a phosphorus-containing phenol compound. After obtaining HCA-NQ, the intended phosphorus-containing epoxy resin composition was obtained.
  • the obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 3.5%.
  • the viscosity of the phosphorus-containing epoxy resin composition varnish obtained by diluting this phosphorus-containing epoxy resin composition with MEK to a solid content of 70% was 600 mPa ⁇ s.
  • Comparative Example 1 100 parts of YDPN-638 and 28 parts of HCA-NQ were added into a four-necked separabrasco equipped with a stirrer, thermometer, cooling pipe and nitrogen gas introduction pipe, and stirring was carried out at 120 ° C. for 6 hours. It was not possible to completely dissolve even with stirring.
  • Comparative Example 2 The same operation as in Example 1 was carried out except that 88 parts of YDPN-638 as an epoxy resin, 12 parts of HCA as a phosphorus compound, and 4 parts of HCA-HQ as a phosphorus-containing phenol compound were used, and an epoxy equivalent of 226 g / eq, After obtaining a phosphorus-containing epoxy resin having a phosphorus content of 1.7%, HCA-NQ was dissolved to obtain a target phosphorus-containing epoxy resin composition. The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 2.0%.
  • the viscosity of the phosphorus-containing epoxy resin composition varnish obtained by diluting this phosphorus-containing epoxy resin composition with MEK to a solid content of 70% was 500 mPa ⁇ s.
  • Comparative Example 3 The same operation as in Example 1 was carried out except that 88 parts of YDPN-638 as the epoxy resin, 12 parts of HCA as the phosphorus compound, and 13 parts of HCA-HQ as the phosphorus-containing phenol compound were obtained, and an epoxy equivalent of 226 g / eq, After obtaining a phosphorus-containing epoxy resin having a phosphorus content of 1.7%, HCA-NQ crystals did not dissolve, and the intended phosphorus-containing epoxy resin composition could not be obtained.
  • Comparative Example 4 The same procedure as in Example 1 was carried out except that 49.3 parts of YDPN-638 was used as the epoxy resin, 50.7 parts of HCA was used as the phosphorus compound, and 8 parts of HCA-HQ was used as the phosphorus-containing phenol compound. After obtaining a phosphorus-containing epoxy resin having 2285 g / eq and a phosphorus content of 7.2%, HCA-NQ crystals did not dissolve, and the target phosphorus-containing epoxy resin composition could not be obtained.
  • the solubility of the phosphorus-containing epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 is shown in Table 1.
  • Example 7 75 parts of the phosphorus-containing epoxy resin composition obtained in Example 3 and 25 parts of trisphenylmethane type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name EPPN-501H) as an epoxy resin (B), curing agent (C) 25.6 parts of phenol novolac resin (manufactured by Showa Denko Co., Ltd., trade name Shonor BRG-557), 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., trade name Curazole 2E4MZ as a curing catalyst) ) was added, and a resin varnish was obtained using MEK so as to have a nonvolatile content of 50%.
  • trisphenylmethane type epoxy resin manufactured by Nippon Kayaku Co., Ltd., trade name EPPN-501H
  • epoxy resin (B) curing agent
  • C 25.6 parts of phenol novolac resin
  • a glass cloth (model number survey) was impregnated with the obtained resin varnish, followed by drying at 150 ° C. for 10 minutes to obtain a prepreg.
  • the obtained four prepregs and copper foil (made by Mitsui Mining & Smelting Co., Ltd., trade name 3EC-III, thickness 35 ⁇ m) are stacked and vacuum pressed at a pressure of 2 MPa under a temperature condition of 130 ° C. ⁇ 15 minutes + 190 ° C. ⁇ 80 minutes. To obtain a cured product of a 0.5 mm thick laminate.
  • Example 8 70 parts of the phosphorus-containing epoxy resin composition obtained in Example 3 and 30 parts of a styrene-modified phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name TX-1210-90) as the epoxy resin (B)
  • a cured product of a prepreg and a laminate was obtained in the same manner as in Example 7, except that 2.0 parts of dicyandiamide (DICY) was used as the curing agent (C) and 0.9 part of 2E4MZ was used as the curing catalyst.
  • DIX-1210-90 styrene-modified phenol novolac type epoxy resin
  • Example 9 70 parts of the phosphorus-containing epoxy resin composition obtained in Example 3, 30 parts of TX-1210-90 as epoxy resin (B), 19.9 parts of BRG-557 as curing agent (C), curing catalyst As a result, a cured product of a prepreg and a laminate was obtained in the same manner as in Example 7, except that 0.9 part of 2E4MZ was used.
  • Example 10 85 parts of the phosphorus-containing epoxy resin composition obtained in Example 3 and 15 parts of bisphenol A type solid epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name Epototo YD-903N) as the epoxy resin (B), cured A cured product of a prepreg and a laminate was obtained in the same manner as in Example 7, except that 1.3 parts of DICY was used as the agent (C) and 0.9 parts of 2E4MZ was used as the curing catalyst.
  • bisphenol A type solid epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name Epototo YD-903N
  • Comparative Example 5 70 parts of the phosphorus-containing epoxy resin composition obtained in Comparative Example 2, 30 parts of TX-1210-90 as the epoxy resin (B), 4.4 parts of DICY as the curing agent (C), and 2E4MZ as the curing catalyst A cured product of a prepreg and a laminate was obtained in the same manner as in Example 7 except that the content was 0.9 parts.
  • Comparative Example 6 Put 43.5 parts of HCA, 4.3 parts of 1,4-naphthoquinone, and 100 parts of toluene in a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction device. The mixture was stirred at 75 ° C.
  • TPP triphenylphosphine
  • Example 7 70 parts of the obtained phosphorus-containing epoxy resin, 30 parts of TX-1210-90 as the epoxy resin (B), 24.3 parts of BRG-557 as the curing agent (C), 0.92 of 2E4MZ as the curing catalyst A cured product of a prepreg and a laminate was obtained in the same manner as in Example 7 except that the parts were used.
  • Comparative Example 7 In a four-neck Separabrasco equipped with a stirrer, thermometer, cooling pipe, and nitrogen gas introduction pipe, 64.1 parts of YDPN-638 as an epoxy resin, 20.9 parts of HCA as a phosphorus compound, and HCA-HQ By putting 15 parts and reacting at 160 ° C.
  • a phosphorus-containing epoxy resin having an epoxy equivalent of 444 g / eq, a phenolic hydroxyl group equivalent of 1750 g / eq, and a phosphorus content of 3.0% was obtained.
  • the viscosity of the phosphorus-containing epoxy resin varnish obtained by diluting this phosphorus-containing epoxy resin with MEK to a solid content of 70% was 440 mPa ⁇ s.
  • Comparative Example 4 the phosphorus-containing epoxy resin was used to dissolve the phosphorus-containing phenol resin. However, since the phosphorus content in the phosphorus-containing epoxy resin composition exceeded 7%, the viscosity of the phosphorus-containing epoxy resin was increased. The contained phenol resin could not be dissolved. Comparative Example 6 was an evaluation using a laminate using the phosphorus-containing epoxy resin of Patent Document 2, but the flame retardancy was slightly worse and the heat resistance was also slightly worse.
  • Comparative Example 7 was an evaluation using a laminate using the phosphorus-containing epoxy resin of Patent Document 4, but the flame retardancy was slightly worse and the heat resistance was also slightly worse.
  • the specific phosphorus-containing epoxy compound was dissolved in the specific phosphorus-containing epoxy resin, and had low viscosity, excellent workability, and high flame retardancy. Further, it was found that the composition of the present invention can obtain flame retardancy even when an epoxy resin (B) that improves heat resistance, dielectric constant, and adhesive strength is blended, and particularly has low dielectric properties.

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Abstract

　La présente invention concerne une composition de résine époxy contenant du phosphore ayant une ininflammabilité adéquate qui est obtenue en augmentant la teneur en phosphore, tout en ayant une viscosité faible et une solubilité excellente dans des solvants organiques. Cette composition de résine époxy contenant du phosphore ne précipite pas à température ambiante, et est obtenue par dissolution de 5 à 45 parties en masse d'un composé phénolique contenant du phosphore représenté par la formule générale (2) dans 100 parties en masse d'une résine époxy contenant du phosphore représentée par la formule générale (1) et ayant une teneur en phosphore qui est dans la plage de 2 à 7 % en masse. [Composés représentés par la formule 1] (Dans la formule, R1 et R2 représentent des groupes hydrocarbonés en C1-6, qui peuvent être identiques ou différents, et peuvent former conjointement un cycle avec des atomes de phosphore. i représente 0 ou 1. [Composés représentés par la formule 2] (Dans la formule, R3 et R4 représentent des groupes hydrocarbonés en C1-6, qui peuvent être identiques ou différents, et peuvent former conjointement un cycle avec des atomes de phosphore. n représente 0 ou 1. A représente un groupe arène-triyle en C6-20).
PCT/JP2014/076481 2013-09-30 2014-09-26 Composition de résine époxy contenant du phosphore et article durci WO2015046626A1 (fr)

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