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WO2011078372A1 - Résine époxy, composition de résine époxy et produit durci correspondant - Google Patents

Résine époxy, composition de résine époxy et produit durci correspondant Download PDF

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Publication number
WO2011078372A1
WO2011078372A1 PCT/JP2010/073471 JP2010073471W WO2011078372A1 WO 2011078372 A1 WO2011078372 A1 WO 2011078372A1 JP 2010073471 W JP2010073471 W JP 2010073471W WO 2011078372 A1 WO2011078372 A1 WO 2011078372A1
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Prior art keywords
epoxy resin
phosphorus
formula
containing epoxy
general formula
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Japanese (ja)
Inventor
雅男 軍司
洋 佐藤
淳子 海東
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical Co Ltd
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Priority to JP2011547677A priority Critical patent/JP5793086B2/ja
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    • 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

Definitions

  • the present invention is excellent in low viscosity and as a cured product such as sealing of electrical and electronic parts typified by semiconductor elements that give excellent cured product having flame retardancy, coating material, laminated material, composite material, etc.
  • the present invention relates to a useful novel epoxy resin, an epoxy resin composition using the epoxy resin, and a cured product thereof, and is suitably used for an insulating material in the electric and electronic fields such as a printed wiring board and semiconductor encapsulation.
  • Epoxy resins have been used in a wide range of industrial applications, but their required performance has become increasingly sophisticated in recent years.
  • a semiconductor sealing material in a typical field of a resin composition mainly composed of an epoxy resin, but in recent years, as the integration degree of semiconductor elements has improved, the package size has become larger and thinner, and mounting The system is also shifting to surface mounting, and the development of materials with higher solder heat resistance is desired.
  • liquid materials have a drawback that they are less reliable than solid materials used for transfer molding. This is because the liquid material has a limit in viscosity, and there are restrictions on the resin, curing agent, filler, and the like to be used. Furthermore, in response to the recent halogen-free flame retardant, there is an increasing demand for flame retardant in these uses that were not required when using halogen-based flame retardants. In the field of composite materials, there is an increasing demand for halogen-free materials. However, since it is essential to reduce the viscosity while ensuring flame retardancy, satisfactory products have not been obtained.
  • the epoxy resin and the curing agent that are the main components are desired to have low viscosity, low moisture absorption, high heat resistance, and flame resistance.
  • the low-viscosity epoxy resin bisphenol A type epoxy resin, bisphenol F type epoxy resin and the like are generally widely known, but they are not sufficient in terms of low viscosity and do not have flame retardancy.
  • Patent Document 1 proposes an epoxy resin having an oxymethylene chain, but there is room for improvement in heat resistance and moisture resistance, and flame retardancy is completely considered.
  • Patent Document 2 proposes an epoxy resin having a bicyclohexyl ring, but no consideration is given to flame retardancy.
  • Patent Document 3 proposes a phosphorus-containing epoxy resin having flame retardancy, but is a phosphorus-containing epoxy resin obtained from a bifunctional epoxy resin having an aromatic skeleton and a phosphorus-containing phenol resin, and having a low viscosity. Then there was a problem.
  • Patent Document 4 mentions flame retardancy in a phosphorus-containing epoxy resin composition and describes that an aliphatic epoxy resin can also be used as a raw material for a phosphorus-containing epoxy resin. There is no description about the effect to be used. Furthermore, there is no description about the characteristics as a phosphorus-containing epoxy resin, and no consideration is given to the viscosity.
  • Patent Document 5 proposes a composition containing a phosphorus-containing monoepoxy resin, but the combined use of an aliphatic diluent is essential and cannot be used alone.
  • JP-A-4-359909 JP 2006-188606 A JP 2001-288247 A JP 2002-249540 A JP 2001-106766 A JP 61-268691 A
  • an object of the present invention is to provide an epoxy resin, an epoxy resin composition, and a cured product thereof that give a cured product having excellent low viscosity and flame retardancy.
  • the epoxy equivalent is 200 to 600 g / eq
  • the phosphorus content is 1 to 5% by weight
  • the total chlorine content is 0.2% by weight or less
  • the melt viscosity at 100 ° C. is 1,000 mPa ⁇ s.
  • the phosphorus containing epoxy resin shown by General formula (1) which is the following.
  • X is a monocyclic or heterocyclic ring which has at least one cyclohexane ring or aromatic ring and may contain an oxygen atom, a nitrogen atom, or a sulfur atom and has 6 to 31 carbon atoms
  • Y is a formula 2
  • Z represents hydrogen or any one of formulas (3) and (4)
  • n represents an integer of 0 to 10.
  • R1 and R2 represent hydrogen or a hydrocarbon group, and may be different or the same, and may be linear, branched, or cyclic. R1 and R2 may be combined to form a ring structure.
  • k represents an integer of 0 or 1.
  • Ar represents any one of benzene, biphenyl, naphthalene, anthracene, phenanthrene, and hydrocarbon substitutes thereof.
  • R3 and R4 represent hydrogen or a hydrocarbon group, and may be different or the same, and may be linear, branched or cyclic. R3 and R4 may be combined to form a ring structure.
  • m represents an integer of 0 or 1.
  • the phosphorus-containing epoxy resin of the present invention can provide a liquid epoxy resin having excellent low viscosity and flame retardancy, and molding obtained by using the epoxy resin composition of the present invention containing the epoxy resin As a result of evaluating the product, it is possible to obtain a cured product having flame retardancy and a relatively low water absorption rate as compared with the conventional low viscosity resin composition.
  • the epoxy resin composition and the cured product thereof are a resin composition for producing a copper-clad laminate used for an electronic circuit board and a sealing material, a molding material, a casting material, an adhesive, a film material, an electric material used for an electronic component. It was found to be useful as a material for insulating paints.
  • FIG. 1 is an infrared absorption spectrum of the phosphorus-containing epoxy resin (E-1) according to Example 1 of the present invention. It measured by the liquid film method (KBr) using the Fourier-transform infrared spectrophotometer (SpeckinOne by Perkin-Elmer).
  • FIG. 2 is a GPC chart of the phosphorus-containing epoxy resin (E-1) according to Example 1 of the present invention. The horizontal axis represents the elution time (minutes), the left axis represents mV, and the right axis represents the logarithm of the molecular weight (M) of the standard polystyrene calibration curve.
  • FIG. 3 is an infrared absorption spectrum of the phosphorus-containing epoxy resin (E-2) according to Example 2 of the present invention. It measured by the liquid film method (KBr) using the Fourier-transform infrared spectrophotometer (SpeckinOne by Perkin-Elmer).
  • FIG. 4 is a phosphorus-containing epoxy resin (E-2) GPC chart according to Example 2 of the present invention.
  • the horizontal axis represents the elution time (minutes), the left axis represents mV, and the right axis represents the logarithm of the molecular weight (M) of the standard polystyrene calibration curve. It measured with the gel permeation chromatography apparatus (HLC-8220GPC by Tosoh Corporation, elution solvent: tetrahydrofuran).
  • the phosphorus-containing epoxy resin of the present invention is represented by the general formula (1), n represents an integer of 0 to 10, and the average polymerization degree, which is the average value, is an oligomer in the range of 0.1 to 3.
  • the epoxy equivalent of the phosphorus-containing epoxy resin of the present invention must be controlled to 200 g / eq to 600 g / eq. When the epoxy equivalent is less than 200 g / eq, the adhesiveness is inferior, and when it exceeds 600 g / eq, the viscosity increases and the heat resistance of the resulting cured product is greatly impaired.
  • the phosphorus content of the phosphorus-containing epoxy resin of the present invention needs to be controlled to 1 to 5% by weight. From the standpoint of flame retardancy, a higher phosphorus content is preferable, but as the phosphorus content increases, the viscosity of the phosphorus-containing epoxy resin and the epoxy equivalent increase, and the heat resistance of the resulting cured product is greatly impaired. It is.
  • the total chlorine content of the phosphorus-containing epoxy resin of the present invention correlates with a decrease in the electrical reliability of the obtained cured product. If it is increased, the electrical reliability of the cured product is lowered, and if it is less, the electrical reliability is improved. To do.
  • the total chlorine content of the phosphorus-containing epoxy resin of the present invention is preferably 0.2% by weight or less, and more preferably 0. It is 09 weight% or less, More preferably, it is 0.05 weight% or less.
  • the phosphorus-containing epoxy resin represented by the general formula (1) of the present invention includes a bifunctional epoxy resin (A) represented by the general formula (5) and an organophosphorus compound (B1) represented by the general formula (6).
  • X is a hydrocarbon group having 6 to 31 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom and which has at least one cyclohexane ring or aromatic ring which may be monocyclic or heterocyclic.
  • R1 and R2 represent hydrogen or a hydrocarbon group, and may be different or the same, and may be linear, branched, or cyclic. R1 and R2 may be combined to form a ring structure.
  • k represents an integer of 0 or 1.
  • Ar represents any one of benzene, biphenyl, naphthalene, anthracene, phenanthrene, and hydrocarbon substitutes thereof.
  • R3 and R4 represent hydrogen or a hydrocarbon group, and may be different or the same, and may be linear, branched or cyclic. R3 and R4 may be combined to form a ring structure.
  • m represents an integer of 0 or 1.
  • the bifunctional epoxy resins (A) to be reacted with the organophosphorus compounds contain at least one cyclohexane ring or aromatic ring.
  • a cyclohexane ring or an aromatic ring helps to improve the flame retardancy of a phosphorus-containing epoxy resin, and an aliphatic epoxy resin that does not contain a cyclohexane ring or an aromatic ring cannot ensure the flame retardancy. That is, this bifunctional epoxy resin (A) is a glycidyl etherified product of a bifunctional primary alcohol having 8 to 33 carbon atoms containing at least one cyclohexane ring or aromatic ring in the skeleton.
  • the —O—CH 2 —X—CH 2 —O— structure is essential.
  • Bifunctional epoxy resins not having this structure do not provide the phosphorus-containing epoxy resin represented by the general formula 1, and the resulting phosphorus-containing epoxy resin is not sufficiently low in viscosity.
  • a reactive diluent such as an aliphatic epoxy resin
  • flame retardancy cannot be ensured.
  • reducing the amount of aliphatic epoxy resin used to ensure flame retardancy increases the viscosity of the epoxy resin composition, which is disadvantageous for lowering the viscosity.
  • the target low-viscosity phosphorus-containing epoxy resin composition I can't get anything.
  • glycidyl etherification derived from an alcoholic hydroxyl group tends to have a large amount of unreacted residual hydroxyl group because of poor reactivity.
  • the residual hydroxyl group in the raw material bifunctional epoxy resin (A) remains as it is without participating in the reaction with the phosphorus compound, and the purity of the terminal group of the phosphorus-containing epoxy resin is lowered, so that the raw material bifunctional epoxy resin (A)
  • the increase in the residual hydroxyl group in the same increases the hygroscopicity of the phosphorus-containing epoxy resin composition as it is, and causes a decrease in storage stability with respect to the acid anhydride curing agent and the microcapsule type latent curing agent.
  • the residual hydroxyl group concentration of the bifunctional epoxy resins (A) is preferably 200 meq / 100 g or less, more preferably 100 meq / 100 g or less, still more preferably 50 meq / 100 g or less. Further, when the reactivity is increased by adding a catalyst or the like in order to reduce the residual hydroxyl group concentration, the side reaction is increased in parallel to increase the total chlorine content.
  • the total chlorine content of the raw material bifunctional epoxy resins (A) is preferably 0.4% by weight or less, more preferably 0.2% by weight or less, and further preferably 0.1% by weight or less.
  • the total chlorine amount is 1% by weight or more in most cases, so it is necessary to reduce the total chlorine amount by an advanced purification reaction, distillation operation or extraction operation. Those methods are not particularly defined, and various methods devised at present can be used.
  • X in the formula of the bifunctional epoxy resins (A) represented by the general formula (5) are shown in the formula (8) group.
  • X may be an isomer of the general formula (8) group or may have a substituent.
  • X may be single or two or more.
  • each j independently represents an integer of 0 or 1.
  • each j independently represents an integer of 0 or 1.
  • each j independently represents an integer of 0 or 1.
  • the bifunctional epoxy resins (A) represented by the general formula (5) a glycidyl etherified product of cyclohexanedimethanol represented by the general formula (9) and a glycidyl paraxylene glycol represented by the general formula (10) Etherified products and glycidyl etherified products of oxymethylene biphenyl represented by the general formula (11) are preferred.
  • the organophosphorus compounds to be reacted with the bifunctional epoxy resins (A) are the organophosphorus compound (B1) represented by the general formula 6 or the organophosphorus compound (B2) represented by the general formula (7). May be used in combination.
  • the organophosphorus compound (B1) represented by the general formula (6) is an organophosphorus compound having two active hydrogens, and R1 and R2 in the formula represent hydrogen or a hydrocarbon group, which may be different or the same. It may be linear, branched or cyclic, and R1 and R2 may be combined to form a cyclic structure.
  • R1 and R2 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, Examples include tert-pentyl group, 1-methylbutyl group, 1-methylheptyl group, octyl group, nonyl group, dodecyl group, undecyl group, dodecyl group, benzyl group, phenyl group, toluyl group, xylyl group and the like.
  • R1 and R2 are bonded to form a cyclic structure
  • examples of those in which R1 and R2 are bonded to form a cyclic structure include, for example, tetramethylene, cyclopentylene, cyclohexylene, cyclohexylene, cyclooctylene, cyclodecylene, norbornylene, biphenylene, and the like.
  • Ar is an arylene group, and specific examples include a phenylene group, a toluylene group, a xylylene group, a naphthylene group, a biphenylene group, and the like.
  • the number of k is 0 or 1.
  • organophosphorus compounds (B1) can be easily obtained by reacting the organophosphorus compound (B2) of the general formula (7) with a monocyclic or polycyclic quinone compound (Patent Document 6).
  • a preferred organophosphorus compound used in the present invention is 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (hereinafter referred to as DOPO) which is an organophosphorus compound represented by the general formula (12).
  • DOPO-HQ 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide
  • a phosphorus-containing compound represented by the general formula (13) which is an addition reaction product of 1,4-benzoquinone (hereinafter abbreviated as DOPO-HQ) or an addition reaction product of DOPO and 1,4-naphthoquinone.
  • DOPO-NQ An organic phosphorus compound represented by a general formula (14) (hereinafter abbreviated as DOPO-NQ) can be given.
  • DOPO can be obtained under the trade name “HCA” (manufactured by Sanko Co., Ltd.), and DOPO-HQ can be obtained under the trade name “HCA-HQ” (manufactured by Sanko Co., Ltd.).
  • the organophosphorus compound (B2) represented by the general formula (7) is an organophosphorus compound having one active hydrogen, and R3 and R4 in the formula represent hydrogen or a hydrocarbon group, which are the same even if they are different. Alternatively, it may be linear, branched, or cyclic, and R3 and R4 may be bonded to form a cyclic structure.
  • R3 and R4 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, Examples include tert-pentyl group, 1-methylbutyl group, 1-methylheptyl group, octyl group, nonyl group, dodecyl group, undecyl group, dodecyl group, benzyl group, phenyl group, toluyl group, xylyl group and the like.
  • R3 and R4 are bonded to form a cyclic structure
  • examples of those in which R3 and R4 are bonded to form a cyclic structure include, for example, tetramethylene, cyclopentylene, cyclohexylene, cyclohexylene, cyclooctylene, cyclodecylene, norbornylene, biphenylene, and the like. Can be mentioned.
  • the number m is 0 or 1.
  • DOPO represented by the general formula (12) is preferable.
  • the organophosphorus compounds may be used by mixing the organophosphorus compound (B1) represented by the general formula (6) and the organophosphorus compound (B2) represented by the general formula (7) which are synthesized in advance.
  • the organophosphorus compound (B2) represented by the general formula (7) may be reacted with quinones before the reaction with the bifunctional epoxy resins (A). In that case, it is preferable that quinones react with less than 1 mol with respect to 1 mol of organophosphorus compound (B2) shown by General formula (7).
  • the reaction between the organophosphorus compounds used in the present invention and the bifunctional epoxy resins (A) can be carried out by a known method.
  • the reaction can be carried out with stirring at a temperature of 100 ° C. to 200 ° C., more preferably 120 ° C. to 180 ° C.
  • the reaction time can be determined by measuring the epoxy equivalent. Measurement can be performed by the method of JIS K-7236.
  • the epoxy equivalent is increased by the reaction between the bifunctional epoxy resins (A) and the organophosphorus compound, and the end point of the reaction can be determined by comparison with the theoretical epoxy equivalent. Further, when the reaction rate is slow, productivity can be improved by using a catalyst as necessary.
  • tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, ethyltriphenylphosphonium
  • phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine
  • catalysts such as phosphonium salts such as bromide and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used. You may mix
  • a higher phosphorus content is preferable from the viewpoint of flame retardancy, and a phosphorus content from the viewpoint of lowering the viscosity A lower rate is preferred. Therefore, in order to satisfy both, it is preferably 0.5 to 5% by weight, more preferably 1 to 4% by weight, and further preferably 2 to 3% by weight.
  • various polyhydric phenol resins and acid anhydrides typified by phenol novolac resins, amines typified by dicyandiamine and diethyldiaminodiphenylmethane, hydrazides, acidic polyesters, etc.
  • the epoxy resin curing agent used can be used, and these curing agents may be used alone or in combination of two or more.
  • a hardening accelerator can be used for this invention epoxy resin composition as needed.
  • curing accelerator examples include phosphines, quaternary phosphonium salts, tertiary amines, quaternary ammonium salts, imidazole compounds, boron trifluoride complexes, 3- (3,4-dichlorodiphenyl) -1,1- Examples include, but are not limited to, dimethylurea, 3- (4-chlorophenyl) -1,1-dimethylurea, and 3-phenyl-1,1-dimethylurea.
  • These curing accelerators depend on the epoxy resin used together, the type of epoxy resin curing agent used, the molding method, the curing temperature, and the required characteristics, but are preferably in the range of 0.01 to 20 parts by weight with respect to 100 parts of the epoxy resin.
  • the epoxy resin composition of this invention can mix
  • fillers include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon , Carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber and the like. These fillers are preferably 1 to 95% by weight in the epoxy resin composition.
  • the epoxy resin composition of the present invention further includes various additives such as a silane coupling agent, an antioxidant, a release agent, an antifoaming agent, an emulsifier, a thixotropic agent, a smoothing agent, a flame retardant, and a pigment as necessary. Can be blended. These additives are preferably in the range of 0.01 to 20% by weight based on the total amount of the epoxy resin composition.
  • the epoxy resin composition of the present invention can be molded and cured by the same method as known epoxy resin compositions to obtain a cured product.
  • the molding method and the curing method can be the same methods as known epoxy resin compositions, and the method unique to the epoxy resin composition of the present invention is unnecessary.
  • the cured epoxy resin of the present invention can take the form of a coating film, an adhesive layer, a molded product, a laminate, a film and the like.
  • Epoxy equivalent The method described in JIS K-7236. That is, dissolve a sample in 10 mL of chloroform, add 20 mL of acetic anhydride and 10 mL of 20% tetraethylammonium bromide solution, and perform titration with a 0.1 mol / L perchloric acid acetic acid standard solution using a potentiometric titrator.
  • the epoxy equivalent contained in the epoxy resin was measured from the concentration and addition amount of each reagent and the titration amount.
  • Total chlorine content The method described in JIS K-7243-3. That is, a sample is dissolved in 25 mL of diethylene glycol monobutyl ether, 25 mL of a 1-mol / L potassium hydroxide 1,2-propanediol solution is added, and the mixture is reacted on a hot plate for 10 minutes under heating and reflux. After cooling to room temperature, 50 mL of acetic anhydride is added, and titration is performed with a 0.01 mol / L silver nitrate solution using a potentiometric titrator.
  • Viscosity The method described in JIS K-7233. That is, 400 g of resin was weighed in a 500 mL cylindrical can, left in a constant temperature water bath at 25 ⁇ 0.2 ° C. for 5 hours, and the temperature was measured by immersing the rotor of a rotational viscometer in the resin.
  • Softening point The method described in JIS K-7234.
  • a sample was filled in a specified ring, supported horizontally in a glycerin bath, a specified ball was placed at the center of the sample, and the temperature was increased at 5 ° C./min.
  • Hydroxyl concentration To the amount of hydroxyl group contained in the epoxy resin, more than equivalent amount of phenyl isocyanate and dibutyltin maleate as a catalyst were added, and after sufficient reaction between the hydroxyl group and isocyanate, the equivalent of phenyl isocyanate used More dibutylamine was added to consume excess phenyl isocyanate, and finally titration was performed with perchloric acid, and the concentration of hydroxyl group contained in the epoxy resin was measured from the concentration and addition amount of each reagent and titration amount. .
  • Phosphorus content Sulfuric acid, hydrochloric acid and perchloric acid were added to the sample and heated to wet ash to convert all phosphorus atoms into normal phosphoric acid. Reaction of metavanadate and molybdate in a sulfuric acid acidic solution, the absorbance at 420 nm of the resulting limpavandemolybdate complex was measured, and the phosphorus atom content determined by a pre-prepared calibration curve was expressed in weight%. The phosphorus content contained in the resin was measured. Melt viscosity: Measurement at 100 ° C.
  • Moisture absorption A method according to JIS C-6481 5.13. That is, using a test piece cut to 50 mm ⁇ 50 mm, the dry weight after drying in an oven at 50 ° C. for 24 hours was measured, and subsequently stored in a treatment tank adjusted to 85 ° C./85% RH for 72 hours. The subsequent weight was measured, and the moisture absorption rate was measured based on the increase from the dry weight.
  • Heat resistance A method according to IPC-TM-650, 24.24.1. That is, the delamination time is measured by the TMA device.
  • TMA device is held at a constant temperature of 260 ° C. and the time until the test piece is repelled is 10 minutes or longer, the result is ⁇ , and the time is less than 10 minutes. X was marked.
  • the TMA apparatus used was TMA / SS120U manufactured by SII Nano Technology. Chlorine ion: After crushing the cured product and performing a pressure cooker test for 150 and 20 hours on a sample with a particle size of 2 mm pass and 1 mm on, the chlorine ion of the extracted water is measured by ion chromatography. It calculated
  • Example 1 Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling tube, Epototo ZX-1658 (Toto Kasei Co., Ltd.) as a bifunctional epoxy resin (A) of the general formula 5 Made by cyclohexanedimethanol diglycidyl ether resin, epoxy equivalent: 140 g / eq, total chlorine: 0.075 wt%, viscosity: 45 mPa ⁇ s, hydroxyl group concentration: 19 meq / 100 g) 632.0 g, DOPO-HQ as the organophosphorus compound (Sanko Co., Ltd., trade name: HCA-HQ, hydroxyl equivalent: 162 g / eq, phosphorus content: 9.5% by weight) 168.0 g was charged and heated to 130 ° C.
  • Epototo ZX-1658 Toto Kasei Co., Ltd.
  • A bifunctional epoxy
  • Example 2 Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling tube, Epototo TX-0929 (Toto Kasei Co., Ltd.) as a bifunctional epoxy resin (A) of the general formula 5 Made by para-alkylene glycol diglycidyl ether resin, epoxy equivalent: 144 g / eq, total chlorine: 0.11 wt%, viscosity: 50 mPa ⁇ s, hydroxyl group concentration: 39 meq / 100 g) 547.4 g, DOPO- as the organophosphorus compound 252.6 g of HQ (previously described) was charged and heated with stirring to 130 ° C.
  • Epototo TX-0929 Toto Kasei Co., Ltd.
  • A bifunctional epoxy resin (A) of the general formula 5 Made by para-alkylene glycol diglycidyl ether resin, epoxy equivalent: 144
  • Example 3 Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling tube, Epototo TX-0929 (described above) as a bifunctional epoxy resin (A) of the general formula (5) 602.5 g, DOPO-NQ (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 1,4-naphthoquinone adduct, hydroxyl equivalent: 187 g / eq, phosphorus content as an organic phosphorus compound : 8.1 wt%) 197.5 g was charged and heated to 130 ° C. with stirring with a mantle heater.
  • Epototo TX-0929 described above
  • DOPO-NQ 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 1,4-naphthoquinone adduct, hydroxyl equivalent:
  • Example 4 Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device and a cooling tube, Epototo TX-0934 (Toto Kasei Co., Ltd.) as a bifunctional epoxy resin (A) of the general formula 5 Manufactured by oxymethylene biphenyl diglycidyl ether resin, epoxy equivalent: 184 g / eq, total chlorine: 0.11% by weight, viscosity: 200 mPa ⁇ s, hydroxyl group concentration: 63 meq / 100 g) 608.7 g, DOPO-NQ as organophosphorus compound (Previously described) 116.3 g and DOPO (manufactured by Sanko Co., Ltd., trade name: HCA, phosphorus content: 14.2% by weight) 75.0 g were charged and heated to 130 ° C.
  • Epototo TX-0934 Toto Kasei Co., Ltd.
  • Example 5 Into a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction device, 168.0 g of DOPO (described above) and 400 g of toluene as an organophosphorus compound were charged and stirred in a nitrogen atmosphere.
  • Epototo TX-0917 manufactured by Tohto Kasei Co., Ltd., X of general formula 5 is a compound of formula 8-10, epoxy equivalent: 173 g / eq, total chlorine : 0.10 wt%, viscosity: 46 mPa ⁇ s, hydroxyl group concentration: 72 meq / 100 g) was charged with 563.0 g, stirred while introducing nitrogen gas, and heated to 130 ° C. to remove toluene out of the system. .
  • E-9 a phosphorus-containing epoxy resin
  • Table 2 shows the properties of the obtained phosphorus-containing epoxy resin (E-9).
  • Comparative Example 5 As an epoxy resin, Epototo ST-3000 (manufactured by Toto Kasei Co., Ltd., hydrogenated bisphenol A type diglycidyl) was added to a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling tube.
  • Ether resin epoxy equivalent: 230 g / eq, total chlorine: 5.0 wt%, viscosity: 3,200 mPa ⁇ s) 632.0 g
  • DOPO-NQ previously described 168.0 g as an organophosphorus compound
  • the mixture was heated to 130 ° C. with stirring, and when it reached 130 ° C., 0.17 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C.
  • Resin (E-10) 795g was obtained.
  • Table 2 shows properties of the obtained phosphorus-containing epoxy resin (E-10).
  • Epototo ZX-1658Z manufactured by Toto Kasei Co., Ltd., cyclohexanedimethanol diglycidyl ether resin, epoxy equivalent: 145 g / eq, total chlorine: 0.45 wt%, viscosity: 85 mPa ⁇ s, hydroxyl group Concentration: 150 meq / 100 g
  • 595.0 g stirred while introducing nitrogen gas, and heated to 130 ° C. to remove toluene out of the system.
  • 0.21 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 160 ° C.
  • a phosphorus-containing epoxy resin is dissolved in methyl ethyl ketone, and dicyandiamide (DICY, active hydrogen equivalent: 21.0 g / eq) as a curing agent previously dissolved in methyl cellosolve and dimethylformamide, and 2-ethyl 4-methylimidazole (as a curing accelerator)
  • the resin composition varnish was prepared so that the nonvolatile content was 50% by weight.
  • the obtained resin varnish was used to impregnate a glass cloth as a base material (WEA 116E 106S 136, thickness 100 ⁇ m, manufactured by Nitto Boseki Co., Ltd.), and the impregnated glass cloth was subjected to 8 in a hot air circulation oven at 150 ° C. Drying was performed for a minute to obtain a prepreg.
  • the obtained four prepregs were stacked and heated and pressurized under the conditions of 130 ° C. ⁇ 15 minutes and 170 ° C. ⁇ 2.0 MPa ⁇ 70 minutes to obtain a 0.5 mm thick laminate.
  • each physical property of a flame retardance, adhesiveness, and a hygroscopic rate was tested.
  • Comparative Example 8 uses an aliphatic phosphorus-containing epoxy resin, the adhesiveness is good, but the flame retardancy is poor and the moisture absorption resistance is also poor.
  • Comparative Example 9 is a phosphorus-containing epoxy resin of the general formula 1, but the flame retardancy is poor because the phosphorus content is as low as 0.5% by weight, and the adhesiveness is also poor because the epoxy equivalent is as small as 196 g / eq.
  • Comparative Example 10 is a phosphorus-containing epoxy resin of the general formula 1. However, since the phosphorus content is too large, 5.2% by weight, the epoxy equivalent is increased to 705 g / eq and the flame retardancy is good, but the adhesiveness is poor and the heat resistance is high. Is also bad.
  • Comparative Example 11 is a phosphorus-containing epoxy resin of the general formula 1, but the epoxy equivalent is as large as 880 g / eq and the melt viscosity is as large as 1,300 mPa ⁇ s. Therefore, the adhesiveness is good, but the heat resistance is poor. On the other hand, all the examples have good adhesiveness, moisture absorption resistance and heat resistance while ensuring sufficient flame retardancy. Examples 9-12, Comparative Examples 12-14 A phosphorus-containing epoxy resin, a curing agent, a curing accelerator, and the like were blended according to the blending formulation shown in Table 5.
  • Diethyldiaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayahard AA, active hydrogen equivalent: 63 g / eq, viscosity: 2,500 mPa ⁇ s) as a curing agent, and 2-ethyl 4-methylimidazole (as described above) as a curing accelerator.
  • the mixture was stirred and homogenized while heating to 50 ° C. to obtain an epoxy resin composition.
  • the obtained epoxy resin composition was defoamed and poured into a mold, and cured under a temperature condition of 150 ° C. ⁇ 120 minutes to obtain a cured product test piece having a thickness of 2 mm.
  • Comparative Example 12 uses an aliphatic phosphorus-containing epoxy resin having a very high total chlorine content of 3.8% by weight, the amount of chlorine ions is about 100 times that of the Examples. This indicates that the reliability is very poor.
  • Comparative Example 13 is a phosphorus-containing epoxy resin of the general formula (1), but the total chlorine is as high as 0.33% by weight, so the chlorine ion is about 5 to 7 times higher than in the examples. This indicates that the reliability becomes worse.
  • Comparative Example 14 is an epoxy resin composition in which a flame retardant is blended with a low-chlorine liquid resin that is generally used. However, even when the phosphorus content is combined with the examples, flame retardancy is poor and moisture absorption resistance is also poor. In contrast, all the examples have low chlorine ions and good moisture absorption resistance while ensuring sufficient flame retardancy. This indicates that the reliability is good.
  • Examples 13-14, Comparative Examples 15-17 A phosphorus-containing epoxy resin, a curing agent, a curing accelerator, and the like were blended according to the blending formulation shown in Table 7.
  • a curing agent triphenylmethane type phenol resin (manufactured by Gunei Chemical Industry Co., Ltd., trade name: TMP-100, hydroxyl group equivalent: 97.5 g / eq, softening point: 107 ° C.) is used while heating to 120 ° C. The mixture was stirred and homogenized to obtain an epoxy resin composition.
  • the obtained epoxy resin composition was defoamed and poured into a mold and cured under a temperature condition of 150 ° C. ⁇ 120 minutes + 180 ° C.
  • Example 13 Epototo ZX-1059 (described above) was used in combination as an epoxy resin other than the phosphorus-containing epoxy resin.
  • Example 17 Epototo ZX-1542 (Toto Kasei Co., Ltd.) was used as an epoxy resin other than the phosphorus-containing epoxy resin.
  • Comparative Example 15 uses an aliphatic phosphorus-containing epoxy resin, flame retardancy is poor and moisture absorption resistance is also poor.
  • Comparative Example 16 is a phosphorus-containing epoxy resin obtained by the manufacturing method disclosed in Patent Document 4, but is not a phosphorus-containing epoxy resin of the general formula 1, so that the viscosity of the epoxy resin composition is too high and mold molding is difficult. Therefore, a test piece necessary for the test could not be prepared.
  • Comparative Example 17 is an epoxy resin composition in which the viscosity is reduced by using a phosphorus-containing epoxy resin obtained by the production method disclosed in Patent Document 4 in combination with a diluent.
  • the moldability is improved, but the flame retardancy is improved. It deteriorates and the moisture resistance also deteriorates.
  • all the examples have good moldability and moisture absorption resistance while ensuring sufficient flame retardancy.
  • the present invention can be used as a flame retardant epoxy resin for electronic materials.

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

Abstract

La présente invention concerne une résine époxy contenant du phosphore représentée par la formule générale (1), qui possède un équivalent époxy de 200-600 g/éq., une teneur en phosphore de 1-5 % en poids, une teneur en chlore totale inférieure ou égale à 0,2 % en poids et une viscosité à l'état fondu à 100 °C inférieure ou égale à 1000 mPa.s, et qui présente d'excellentes caractéristiques de faible viscosité et une bonne résistance au feu. Dans la formule générale (1), X représente un groupe hydrocarboné en C6-31 comportant au moins un cycle cyclohexane ou noyau aromatique, qui peut être soit monocyclique soit hétérocyclique, et comportant éventuellement un atome d'oxygène, un atome d'azote ou un atome de soufre ; Y représente un groupe représenté par la formule (2) ; Z représente un hydrogène ou un groupe représenté par la formule (3) ou (4) ; et n représente un entier de 0 à 10. Dans la formule (2), R1 et R2 peuvent être identiques ou différents et chacun représente un hydrogène ou un groupe hydrocarboné linéaire, ramifié ou cyclique, ou R1 et R2 peuvent être liés ensemble pour former une structure cyclique ; k représente un entier valant 0 ou 1 ; et Ar représente un groupe benzène, biphényle, naphtalène, anthracène, phénanthrène ou un de leurs dérivés à substitution hydrocarbonée. Dans la formule (3), R3 et R4 peuvent être identiques ou différents et chacun représente un hydrogène ou un groupe hydrocarboné linéaire, ramifié ou cyclique, ou R3 et R4 peuvent être liés ensemble pour former une structure cyclique ; et m représente un entier valant 0 ou 1.
PCT/JP2010/073471 2009-12-25 2010-12-17 Résine époxy, composition de résine époxy et produit durci correspondant Ceased WO2011078372A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2019065552A1 (fr) * 2017-09-26 2019-04-04 日鉄ケミカル＆マテリアル株式会社 Résine phénoxy contenant du phosphore, composition de résine correspondante et produit durci

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5917227B2 (ja) * 2012-03-28 2016-05-11 新日鉄住金化学株式会社 リン含有エポキシ樹脂の製造方法
JP6452335B2 (ja) * 2013-08-09 2019-01-16 日鉄ケミカル＆マテリアル株式会社 エポキシ樹脂組成物及びその硬化物
TWI641628B (zh) * 2014-10-24 2018-11-21 新日鐵住金化學股份有限公司 環氧樹脂組成物及其硬化物
CN113801552B (zh) * 2021-10-18 2022-08-19 成都托展新材料股份有限公司 改性聚脲组合物及其制备方法和应用

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11199645A (ja) * 1998-01-16 1999-07-27 Mitsubishi Chemical Corp エポキシ樹脂組成物
JP2000309624A (ja) * 1999-02-23 2000-11-07 Dainippon Ink & Chem Inc 難燃性エポキシ樹脂組成物及び難燃性エポキシ樹脂の製造方法
JP2005097352A (ja) * 2003-09-22 2005-04-14 Dainippon Ink & Chem Inc エポキシ樹脂組成物、半導体封止材料及び半導体装置
JP2006036936A (ja) * 2004-07-27 2006-02-09 Matsushita Electric Works Ltd エポキシ樹脂組成物、プリプレグ、多層プリント配線板
JP2006160855A (ja) * 2004-12-06 2006-06-22 Hitachi Chem Co Ltd 封止用エポキシ樹脂組成物及び電子部品装置
JP2007177054A (ja) * 2005-12-27 2007-07-12 Toto Kasei Co Ltd 新規熱可塑性ポリヒドロキシポリエーテル樹脂、及び、それを配合した樹脂組成物
WO2008066101A1 (fr) * 2006-12-01 2008-06-05 Kyocera Chemical Corporation Composition de resine de type thermodurcissable photosensible et tableau de connexions imprime flexible
JP2008533236A (ja) * 2005-03-11 2008-08-21 株式会社 国都化▲学▼ ノンハロゲン系難燃性高耐熱リン変性エポキシ樹脂組成物
WO2008133246A1 (fr) * 2007-04-24 2008-11-06 Panasonic Electric Works Co., Ltd. Composition de résine époxyde, film de résine, préimprégné et carte de circuit imprimé multicouche
WO2009060987A1 (fr) * 2007-11-09 2009-05-14 Tohto Kasei Co., Ltd. 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
WO2009096235A1 (fr) * 2008-02-01 2009-08-06 Tohto Kasei Co., Ltd. Résine époxy contenant du phosphore, composition de résine époxy contenant du phosphore, procédé de fabrication d'une résine époxy contenant du phosphore, composition de résine durcissable utilisant la résine époxy et la composition de résine époxy, et produit durci
JP2010189466A (ja) * 2009-02-16 2010-09-02 Nippon Steel Chem Co Ltd 難燃性リン含有エポキシ樹脂組成物及びその硬化物

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11199645A (ja) * 1998-01-16 1999-07-27 Mitsubishi Chemical Corp エポキシ樹脂組成物
JP2000309624A (ja) * 1999-02-23 2000-11-07 Dainippon Ink & Chem Inc 難燃性エポキシ樹脂組成物及び難燃性エポキシ樹脂の製造方法
JP2005097352A (ja) * 2003-09-22 2005-04-14 Dainippon Ink & Chem Inc エポキシ樹脂組成物、半導体封止材料及び半導体装置
JP2006036936A (ja) * 2004-07-27 2006-02-09 Matsushita Electric Works Ltd エポキシ樹脂組成物、プリプレグ、多層プリント配線板
JP2006160855A (ja) * 2004-12-06 2006-06-22 Hitachi Chem Co Ltd 封止用エポキシ樹脂組成物及び電子部品装置
JP2008533236A (ja) * 2005-03-11 2008-08-21 株式会社 国都化▲学▼ ノンハロゲン系難燃性高耐熱リン変性エポキシ樹脂組成物
JP2007177054A (ja) * 2005-12-27 2007-07-12 Toto Kasei Co Ltd 新規熱可塑性ポリヒドロキシポリエーテル樹脂、及び、それを配合した樹脂組成物
WO2008066101A1 (fr) * 2006-12-01 2008-06-05 Kyocera Chemical Corporation Composition de resine de type thermodurcissable photosensible et tableau de connexions imprime flexible
WO2008133246A1 (fr) * 2007-04-24 2008-11-06 Panasonic Electric Works Co., Ltd. Composition de résine époxyde, film de résine, préimprégné et carte de circuit imprimé multicouche
WO2009060987A1 (fr) * 2007-11-09 2009-05-14 Tohto Kasei Co., Ltd. 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
WO2009096235A1 (fr) * 2008-02-01 2009-08-06 Tohto Kasei Co., Ltd. Résine époxy contenant du phosphore, composition de résine époxy contenant du phosphore, procédé de fabrication d'une résine époxy contenant du phosphore, composition de résine durcissable utilisant la résine époxy et la composition de résine époxy, et produit durci
JP2010189466A (ja) * 2009-02-16 2010-09-02 Nippon Steel Chem Co Ltd 難燃性リン含有エポキシ樹脂組成物及びその硬化物

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2019065552A1 (fr) * 2017-09-26 2019-04-04 日鉄ケミカル＆マテリアル株式会社 Résine phénoxy contenant du phosphore, composition de résine correspondante et produit durci
JPWO2019065552A1 (ja) * 2017-09-26 2020-10-15 日鉄ケミカル＆マテリアル株式会社 リン含有フェノキシ樹脂、その樹脂組成物、及び硬化物
JP7244427B2 (ja) 2017-09-26 2023-03-22 日鉄ケミカル＆マテリアル株式会社 リン含有フェノキシ樹脂、その樹脂組成物、及び硬化物

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