WO2016140459A1 - Phosphorus-based epoxy compound, preparation method therefor, and epoxy composition containing same - Google Patents

Phosphorus-based epoxy compound, preparation method therefor, and epoxy composition containing same Download PDF

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Publication number
WO2016140459A1
WO2016140459A1 PCT/KR2016/001813 KR2016001813W WO2016140459A1 WO 2016140459 A1 WO2016140459 A1 WO 2016140459A1 KR 2016001813 W KR2016001813 W KR 2016001813W WO 2016140459 A1 WO2016140459 A1 WO 2016140459A1
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Prior art keywords
phosphorus
hydrocarbon group
epoxy compound
formula
weight
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PCT/KR2016/001813
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French (fr)
Korean (ko)
Inventor
이은용
이지애
정병수
정용수
황재석
이귀항
백미정
정원호
최봉구
최호경
Original Assignee
주식회사 신아티앤씨
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Priority to CN201680000419.4A priority Critical patent/CN106132974B/en
Publication of WO2016140459A1 publication Critical patent/WO2016140459A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins

Definitions

  • the present invention relates to a phosphorus-based epoxy compound and a preparation method thereof, and a phosphorus-based epoxy composition comprising the same. More specifically, the present invention relates to a phosphorus-based epoxy compound having a high phosphorus (P) content, having high heat resistance and low dielectric properties, a method for preparing the same, and an epoxy composition comprising the same.
  • P phosphorus
  • a printed circuit board In general, a printed circuit board (PCB) is used to drive electronic products such as computers, cameras, and televisions.
  • a printed circuit board is a circuit connecting part that attaches a thin thin film such as copper to an insulating base film such as phenol or epoxy, and then patterns it in a desired shape to electrically connect and support the part.
  • Copper Clad Laminate is a raw material of a printed circuit board.
  • the insulating plate obtained by heat-pressing several layers of a sheet in which a compound is bonded to an insulating material such as paper or glass is called a laminate, and a copper foil is attached to one or both sides of the laminate.
  • the requirements for insulating materials used here have to be lead-free in accordance with recent environmental regulations. Accordingly, copper-clad laminates requiring an insulating material having high glass transition temperature characteristics have been increased. The demand for CCL is increasing considerably in recent years.
  • the type of copper clad laminate is a composite made by combining two or more kinds of reinforcement materials, such as a reinforcing material penetrating an epoxy compound into glass fiber, a glass epoxy copper clad laminate made of copper foil, and a paper phenolic copper clad laminate mainly used for manufacturing single-sided PCB.
  • reinforcement materials such as a reinforcing material penetrating an epoxy compound into glass fiber, a glass epoxy copper clad laminate made of copper foil, and a paper phenolic copper clad laminate mainly used for manufacturing single-sided PCB.
  • Epoxy compositions are widely used in electrical and electronic device parts due to their excellent properties, but in many cases flame retardancy is imparted to ensure safety against fire.
  • Flame retardance of epoxy compositions has conventionally used halogenated epoxy compounds such as brominated epoxy.
  • Halogenated epoxy compounds have excellent flame retardancy, but environmental problems have been pointed out by pyrolysis to produce harmful halogen compounds such as hydrogen halides and polybrominated dibenzodioxin and furan. For this reason, phosphorus (P) compounds have been studied as flame retardants to replace bromine-containing flame retardants.
  • the conventional phosphorus (P) -based epoxy has a low crosslinking density, low heat resistance that can be evaluated by the glass transition temperature (Tg), and the secondary structure (secondary alcohol) is added to the epoxy structure, the electrical properties (dielectric constant)
  • Tg glass transition temperature
  • secondary alcohol secondary structure
  • DOPO (9,10-Dihydro-9-Oxa-10-Phosphaphenantrene-10-Oxide) or DOPO- in a di-functional or multi-functional epoxy to provide a phosphorus-based epoxy compound.
  • Phosphorous compounds such as HQ (10- (2,5-dihydroxyphenyl) -10H-9 -oxa-10-phospha-phenantbrene-10-oxide) were prepared and used by modifying by indirect method, (P) content is limited to the latter 2wt% to ⁇ 3wt%, and there is a problem such that gelation occurs during the reaction when the phosphorus-based compound is introduced in excess for the phosphorus content, and more than 5wt%
  • the present invention provides a novel structure of a phosphorus-based epoxy compound having a high heat resistance, low dielectric properties, a high phosphorus (P) content, a manufacturing method, and an epoxy composition comprising the same.
  • the present invention provides a phosphorus epoxy composition
  • a phosphorus epoxy compound comprising a phosphorus epoxy compound and a curing agent, wherein the phosphorus epoxy compound is a phosphorus epoxy compound represented by the following formula (1).
  • R 1 , R 2 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof Or a hetero element (O, S, or N) in the structure
  • R 3 , R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 Are combinations thereof, and hetero elements (O, S, or N) may be present in the structure
  • R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon of C 6 -C 30 Or a combination thereof, and hetero elements (O, S, or N) may be present in the structure
  • each R 7 is independently hydrogen, an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon of C 6 -C 30 Group or a combination thereof, and heteroatoms (O, S, or N) may be present in the structure
  • the present invention provides a phosphorus-based epoxy composition is a phosphorus-based epoxy compound represented by the formula (2).
  • the present invention provides a phosphorus-based epoxy composition of the content of the phosphorus-based epoxy compound of n is 0 to 99wt% of the phosphorus-based epoxy compound.
  • the present invention provides a phosphorus-based epoxy composition
  • a phosphorus-based epoxy composition comprising the equivalent ratio of the phosphorus-based epoxy compound and the curing agent is 1: 0.6 to 1.5.
  • the curing agent is at least one phosphorus epoxy composition selected from the group consisting of amide curing agent, polyamine curing agent, acid anhydride curing agent, phenol novolak-type curing agent, polycapcaptan curing agent, tertiary amine curing agent or imidazole curing agent To provide.
  • the phosphorus-based epoxy composition further comprises a curing accelerator
  • the curing accelerator is 2-methyl imidazole, 2-ethyl-4-methyl imidazole (2-Ethyl-4-Methyl Imidazole ), 1-benzyl-2-methyl imidazole, 1 selected from 2-heptadecyl imidazole, and 2-undecyl imidazole.
  • Imidazole compounds containing more than one species Organic compounds containing triphenylphosphate; And trialkyl compounds such as Ethyl Triphenyl Phosphonium Iodide (ETPPI), 4-dimethylamino pyridine, 2-amino pyridine, 3-amino pyridine, 4-amino pyridine, 2,3-diamino pyridine, 2 ,, 5-diamino pyridine, 2,6-diamino pyridine, 2-amino-6-methyl pyridine, 3-amino-6-isopropyl pyridine, 2,2-dipyridyl amine and 4-pyrrolidino pyridine Pyridine compounds containing at least one selected; It provides a phosphorus-based epoxy composition comprising one or more selected from.
  • EPPI Ethyl Triphenyl Phosphonium Iodide
  • the present invention provides a phosphorus-based epoxy composition is 2 to 7% by weight relative to the total weight of the phosphorus-based epoxy composition.
  • the present invention also provides a phosphorus-based epoxy composition, wherein the glass transition temperature (Tg) of the cured product obtained from the phosphorus-based epoxy composition is 150 to 230.
  • Tg glass transition temperature
  • the present invention also provides a phosphorus-based epoxy composition, characterized in that the dielectric constant (D k ) of the cured product obtained from the phosphorus-based epoxy composition is 4.2 or less.
  • the present invention also provides a phosphorus-based epoxy composition, characterized in that the loss factor (D f ) of the cured product obtained from the phosphorus-based epoxy composition is 0.020 or less.
  • the phosphorus-based epoxy compound provides a phosphorus-based epoxy composition which is a phosphorus-based epoxy compound represented by the following formula (5).
  • the present invention provides a phosphorous epoxy compound represented by the formula (1).
  • the present invention provides a phosphorus-based epoxy compound represented by the formula (2) or (5).
  • the present invention provides a phosphorus-based epoxy compound of 6 to 8% by weight relative to the total weight of the phosphorus-based epoxy compound.
  • the present invention provides a phosphorus-based epoxy compound, characterized in that the phosphorus-based hydroxy compound and the epoxy compound is prepared by reacting under an alkali catalyst.
  • the present invention provides a reaction material comprising a phosphorus-based hydroxy compound represented by the following formula (3), at least one epoxy compound selected from the epoxy compounds represented by the following formula (4-1) and the formula (4-2), and a first solvent Preparing a reaction mixture to be added to a reactor to obtain a reaction mixture; And reacting the reaction mixture to obtain an epoxy compound containing phosphorus.
  • R 1 , R 2 are each independently, absent or a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group or a combination thereof and heteroatoms (O, S, or N in the structure) ) May be present, and R 3 and R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and a hetero element (O, S, Or N), R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and a hetero element (O, S, or N) may be present and X is a halogen group, -OTs (O-Tosyl), -OMs (O-Mesyl).)
  • the reaction mixture preparation step 100 to 180 parts by weight of the phosphorus-based hydroxy compound represented by the formula (3) with respect to 100 parts by weight of the first solvent, to the formula 4-1 and the formula 4-2
  • a method for producing a phosphorus-based epoxy compound characterized in that the epoxy compound is mixed in 210 to 290 parts by weight.
  • the present invention provides a laminate comprising the phosphorous epoxy composition.
  • the present invention is a high phosphorus (P) content phosphorus epoxy compound having a high heat resistance, low dielectric properties, and does not contain halogen, flame-retardant UL-94 grade V-0 can be achieved, further flame retardant in industrial use Since there is no need to use an additive, it is possible to provide a phosphorus-based epoxy compound having excellent reliability, a manufacturing method thereof, and a phosphorus-based epoxy composition including the same without reducing physical, mechanical, and electrical properties.
  • P phosphorus
  • C 1", C 2 ", etc. are as meaning the number of carbon atoms, for example," C 1 -C 10 alkylene group "means an alkylene group having a carbon number of 1-10.
  • the present invention is to provide a phosphorus-based epoxy compound represented by the following formula (1) as a high phosphorus (P) content phosphorus-based epoxy compound (Phosphorus Epoxy Compound) having a high heat resistance, low dielectric properties.
  • P phosphorus
  • R 1 , R 2 are each independently, absent or an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) in the structure May be present.
  • R 3 and R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure.
  • a hetero element O, S, or N
  • an aliphatic hydrocarbon group of C 1 -C 20 More preferably alkylene (alkylene) group (-C n H 2n -) of the C 1 -C 10 may be a.
  • R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) may be present in the structure. have. Preferably it is a C 6 -C 30 aromatic hydrocarbon group. More preferably, for example, an aryl group (Ar-) including a phenyl group, anthracene, anthryl group, phenanthryl group, and biphenyl group It is good to be).
  • R 7 is each independently hydrogen, an aliphatic hydrocarbon group of C 1 -C 20 , or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure. . Preferably it is hydrogen.
  • R 8 is each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, or a polymer (or prepolymer) having a weight average molecular weight of 500 to 5000, and a hetero element ( O, S, or N) may be present.
  • Phosphorus-based epoxy compound of one embodiment of the present invention may be represented by the following formula (2).
  • the phosphorus (P) content of the phosphorus epoxy compound according to the present invention is included in 5 to 10% by weight, more preferably 6 to 8% by weight relative to the total weight of the compound. If phosphorus (P) is present in less than 5% by weight, this is a major barrier to achieving flame retardant UL-94 grade V-0 in halogen-free formulations, preventing the use of additional flame retardant additives or phosphorus curing agents in industrial use.
  • the dielectric loss of high heat resistance has a very low characteristic.
  • Phosphorus-based epoxy compounds according to the present invention have a phosphorus (P) content of 5 to 10 wt%, which eliminates the need for the use of additional flame retardant additives or phosphorus curing agents to achieve flame retardant UL-94 grade V-0. ) It can give reliability for mechanical, electrical and electrical properties, and enables free formulation, increasing the possibility of blending compositions that give the required properties using other epoxy resins and hardeners.
  • the structure has high heat resistance, low dielectric properties and low softening point due to high phosphorus (P) content and functional groups in the structure, and is particularly suitable for being used as a material for laminated plates used in printed circuit boards. It is also useful as a material.
  • P phosphorus
  • Phosphorus-based epoxy compound of one embodiment of the present invention may be represented by the following formula (5).
  • the phosphorus-based epoxy compound according to one embodiment of the present invention is selected from a phosphorus-hydroxy compound represented by the following Formula 3 in the first solvent, and an epoxy compound represented by the following Formula 4-1 and the following Formula 4-2 Phosphorus Epoxy Compound having high heat resistance and low dielectric properties prepared by reacting a reaction mixture in which at least one epoxy compound is dissolved.
  • R 1 , R 2 are each independently, absent or an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) in the structure May be present.
  • hetero elements O, S, or N
  • ethylene (ethylene) group (-CH 2 CH 2- ) More preferably, it does not exist.
  • R 3 and R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure.
  • a hetero element O, S, or N
  • an aliphatic hydrocarbon group of C 1 -C 20 More preferably alkylene (alkylene) group (-C n H 2n -) of the C 1 -C 10 may be a.
  • R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) may be present in the structure. have. Preferably it is a C 6 -C 30 aromatic hydrocarbon group. More preferably, for example, an aryl group (Ar-) including a phenyl group, anthracene, anthryl group, phenanthryl group, and biphenyl group It is good to be).
  • X may be a kind of good leaving group, for example, a halogen group, -OTs (O-Tosyl), -OMs (O-Mesyl).
  • a halogen group for example, a halogen group, -OTs (O-Tosyl), -OMs (O-Mesyl).
  • -OTs O-Tosyl
  • -OMs O-Mesyl
  • it is a chlorine group (-Cl), bromine group (-Br).
  • More specific method for producing a phosphorus-based epoxy compound according to the present invention at least one epoxy compound selected from the epoxy compound represented by the formula (4-1) and the formula (4-2) to the phosphorus-hydroxy compound represented by the formula (3)
  • the epoxy compound is reacted with a hydroxy group (-OH) of the phosphorus hydroxy compound to form a phosphorus epoxy compound represented by Chemical Formula 1.
  • the reaction mixture is 80 to 250 parts by weight of the phosphorus hydroxy compound represented by the formula (3) relative to 100 parts by weight of the first solvent, at least one or more of the epoxy compounds represented by the formula (4-1) and (4-2)
  • the epoxy compound is mixed at 210 to 290 parts by weight. More preferably, the phosphorus hydroxy compound represented by Chemical Formula 3 is mixed in an amount of 100 to 220 parts by weight based on 100 parts by weight of the first solvent, and at least one of the epoxy compounds represented by Chemical Formulas 4-1 and 4-2. It is preferable that the above epoxy compound is mixed at 230 to 270 parts by weight.
  • a method of reacting using an alkali catalyst may be used.
  • the alkali catalyst for example, sodium hydroxide, lithium hydroxide, Alkali metal hydroxides such as potassium hydroxide; Alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride, and potassium chloride; Alkali metal alkoxides such as sodium methoxide and sodium ethoxide; Alkali metal hydrides such as phenoxide, sodium hydride, and lithium hydride of alkali metals; Alkali metal salts of organic acids, such as sodium acetate and sodium stearate, etc. can be used.
  • the first solvent may not be used, but when the solvent is used, the solvent gives an effect of improving the reactivity to reduce the amount of the intermediate product during the reaction, thus 10% in the product yield compared to the case where the solvent is not used.
  • the above results are improved, and excellent results can be obtained also in the color of the final product compound.
  • Aromatic solvent containing benzene, toluene, xylene, etc . Acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK) cyclohexanone, acetylacetone, dioxane ( ketone solvents such as dioxane); Formamide, N-methylformamide, N, N-dimethylformamide (N, N-dimethylformamide, DMF), acetamide, N-methylacetamide Amide solvents such as N, N-dimethylacetamide, 2-pyrrolidone, and N-methylpyrrolidone (NMP); Ethylene glycol monobutyl ether, propylene glycol methyl ether acetate, 1,4-dioxane, propylene glycol methyl ether, propylene Glycol ether solvents including
  • IPA isopropyl alcohol
  • the synthesis reaction takes place at a temperature of 30 to 200 ° C. More preferably, the reaction is carried out at a temperature of 45 to 170 ° C. In addition, the synthesis reaction takes place for 3 to 7 hours. More preferably, the reaction is carried out for 4 to 6 hours.
  • the catalyst is added in 50 to 120 parts by weight based on 100 parts by weight of the first solvent.
  • the method may further include a refining process (second purification) using an alkali catalyst.
  • the kind of solvent that can be used as the second solvent is the same as the kind of solvent that can be used as the first solvent described above.
  • methyl isobutyl ketone (MIBK) may be used.
  • the first purification step is a step of removing the remaining monomers by heating to 140 to 160 ° C after washing with water using water, and the second purification step is performed at 140 to 160 ° C after the first purification. After slowly adding the solvent to dissolve, it is a refining process of removing the salt generated during the reaction for 1 hour to 1 hour 30 minutes using an alkali catalyst at 70 to 90 ° C.
  • the first purification step is washed with water using 80 to 250 parts by weight of water based on 100 parts by weight of the first solvent
  • the second purification step is 300 to 700 parts by weight of a second solvent relative to 100 parts by weight of the first solvent
  • dissolving by adding to dissolve 10 to 30 parts by weight of catalyst based on 100 parts by weight of the first solvent.
  • the vacuum degassing is carried out to 140 to 160 °C to remove the remaining water and solvent to obtain a yellow phosphorous epoxy compound flake.
  • the method may further include modifying all or part of the obtained epoxy compound into a polyfunctional isocyanate compound. Upon modification, a compound having m of 1 to 3 may be obtained.
  • a catalyst for the modification reaction, a catalyst can be used, and specifically, a catalyst such as imidazole can be used.
  • the polyfunctional isocyanate compound may be a compound having 2 to 5 isocyanate groups per molecule, and may be an aromatic, aliphatic or alicyclic isocyanate compound, and may be used alone or in combination of two or more thereof. Specifically, hexamethylene diisocyanate, isophorone diisocyanate, methylene dicyclohexyl diisocyanate and cyclohexane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, tetramethylxylene diisocyanate, phenylene diisocyanate, tolidine diisocyanate, Methylene diphenyl diisocyanate (MDI), a polyisocyanate compound in the form of a polymer (or prepolymer).
  • MDI Methylene diphenyl diisocyanate
  • Polyisocyanates may include, in particular, isomeric mixtures of 4,4'-MDI and 4,4'-MDI, 2,4'-MDI and 2,2'-MDI, which are known in the art and are pure. Bayn Suprasec R MPR and 1306.
  • Carbodiimide and / or urethane modified modifications of the polyisocyanates are also possible and include those known in the art and commercially available, such as Huntsman's Suprasec R 2020.
  • polyisocyanates in the form of polymers (or prepolymers) produced by reacting with polyols having a weight average molecular weight of approximately 500 to 5000.
  • Polymer MDIs can also be used, examples include Huntsman's Suprasec R 2185, Suprasec R 5025 and Suprasec R DNR, and the prepolymer polyisocyanate is Huntsman's. Suprasec R 2054, Suprasec R 2061, and the like.
  • the phosphorus epoxy composition which concerns on another form of this invention contains the phosphorus epoxy compound represented by the said Formula (1), and a hardening
  • Phosphorus-based epoxy composition according to the present invention provides a cured product that is excellent in heat resistance and dielectric properties and meets the required physical properties according to the use.
  • the curing agent is a substance that contributes to the crosslinking reaction upon curing of the epoxy composition, and may be regarded as a curing agent as long as it is a substance that contributes to the crosslinking reaction, even if called a curing accelerator.
  • the equivalent ratio of the phosphorus epoxy compound and the curing agent is 1: 0.6 to 1.5.
  • the curing agent is contained in less than 0.6 equivalents to 1 equivalent of the phosphorus-based epoxy compound may cause uncured or very slow curing rate, and when included in excess of 1.5 equivalents, due to the remaining curing agent due to the excessive amount of the curing agent There are problems with tacky and rheological control.
  • the curing agent may be at least one selected from the group consisting of an amide curing agent, a polyamine curing agent, an acid anhydride curing agent, a phenol novolak-type curing agent, a polymercaptan curing agent, a third amine curing agent or an imidazole curing agent.
  • the phenol novolak-type curing agent is a phenol, such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, bisphenol Z, bisphenol AD, biphenol, and / or ⁇ -naphthol, ⁇ -Condensation or co-condensation of naphthols such as naphthol and dihydroxynaphthalene, anthracene terpenes and dicyclopentadienes, and compounds having an aldehyde group such as formaldehyde, acetaldehyde, prionaldehyde, benzaldehyde, salicylicaldehyde and the like under an acidic catalyst Novolak resin etc. obtained by making it cure are included.
  • phenol such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, bisphenol Z, bisphenol
  • the phosphorus-based epoxy composition further comprises a curing accelerator, suitable curing accelerators to be used 2-methyl imidazole, 2-ethyl-4-methyl imidazole (2-Ethyl-4-Methyl Imidazole ), 1-benzyl-2-methyl imidazole, 1 selected from 2-heptadecyl imidazole, and 2-undecyl imidazole.
  • a curing accelerator suitable curing accelerators to be used 2-methyl imidazole, 2-ethyl-4-methyl imidazole (2-Ethyl-4-Methyl Imidazole ), 1-benzyl-2-methyl imidazole, 1 selected from 2-heptadecyl imidazole, and 2-undecyl imidazole.
  • Imidazole compounds containing more than one species Organic compounds containing triphenylphosphate; And trialkyl compounds such as Ethyl Triphenyl Phosphonium Iodide (ETPPI), 4-dimethylamino pyridine, 2-amino pyridine, 3-amino pyridine, 4-amino pyridine, 2,3-diamino pyridine, 2 ,, 5-diamino pyridine, 2,6-diamino pyridine, 2-amino-6-methyl pyridine, 3-amino-6-isopropyl pyridine, 2,2-dipyridyl amine and 4-pyrrolidino pyridine Pyridine compounds containing at least one selected; It is good to use including 1 or more types selected from.
  • EPPI Ethyl Triphenyl Phosphonium Iodide
  • the phosphorus epoxy composition may further include an inorganic filler, and suitable inorganic fillers to be used include silica, alumina, barium sulfate, talc, mud, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, and oxides.
  • suitable inorganic fillers to be used include silica, alumina, barium sulfate, talc, mud, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, and oxides.
  • Phosphorus (P) content relative to the total weight of the phosphorus-based epoxy composition according to an embodiment of the present invention is 2 to 7 wt%. If it is less than 2wt% there is a problem that the flame retardant properties are not reduced or not implemented at all, if it is more than 7wt% there is a problem that the heat resistance is lowered and the cured product is brittle (brittle) to collapse.
  • the phosphorus-based epoxy composition according to the present invention As a result of evaluating the properties of the cured product by the phosphorus-based epoxy composition according to the present invention, it has excellent heat resistance and has a low dielectric property, and thus, an encapsulant, a molding material, a mold used in the compound composition for manufacturing a copper clad laminated board used in an electronic circuit board or an electronic part. It is useful as an ash, an adhesive agent, a film material, a material for electrically insulating paints, etc.
  • a prepreg for producing a laminate containing 30 to 70% by weight of the phosphorus-based epoxy composition of the present invention and 30 to 70% by weight of glass fibers is prepared, which is then used as one or more laminates, and copper foil located outside of the laminate.
  • the outer layer may be integrated by heat and pressure to manufacture a laminate for a printed circuit board.
  • 750 parts by weight of (2,5-Dihydroxyphenyl) diphenyl phosphine oxide, 750 parts by weight of Epichlorohydrin and 300 parts by weight of Isopropyl Alcohol (IPA) were added to a reactor equipped with a stirring device, a thermometer and a reflux condenser and purged with nitrogen for 30 minutes.
  • IPA Isopropyl Alcohol
  • Example 1 900 parts by weight of the flakes obtained in Example 1 were added to a reactor equipped with a stirring device, a thermometer and a reflux condenser, purged with nitrogen for 30 minutes, and the reaction temperature was raised to 120 ° C.
  • a phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Example 1, 50 parts by weight of a phenol novolak-type curing agent, and 2 parts by weight of a C11Z (10% in MeOH) curing accelerator.
  • a phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Example 2, 45 parts by weight of a phenol novolak type curing agent, and 3 parts by weight of a C11Z (10% in MeOH) curing accelerator.
  • a phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Example 3, 40 parts by weight of a phenol novolak type curing agent, and 1 part by weight of a C11Z (10% in MeOH) curing accelerator.
  • a phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Example 4, 30 parts by weight of a phenol novolak type curing agent, and 2 parts by weight of a C11Z (10% in MeOH) curing accelerator.
  • a phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Comparative Example 1, 50 parts by weight of a phenol novolak type curing agent, and 2 parts by weight of a C11Z (10% in MeOH) curing accelerator.
  • Phosphorus content of the phosphorus-based epoxy compounds of Examples 1 to 3 is 7 wt%
  • phosphorus content of the modified phosphorus-based epoxy compound of Example 4 is 6.57 wt%
  • the phosphorus content of the phosphorus-based epoxy composition of Examples 5 to 8 is 5 wt%, it can be seen that it has a high phosphorus (P) content compared to Comparative Example 2.
  • Tg, Td, Dk, and Df were measured for the phosphorus-based epoxy cured product prepared in Examples 9 to 12 and Comparative Example 3, and the results are shown in Table 2 below.
  • Tg was used by differential scanning calorimetry (DSC, TA instrument), and dielectric constant (Dk) and loss factor (Ds) were Agilent E4991A RF Impedance / by the JIS-C-6481 method. Measurement was made using a material analyzer.
  • glass transition temperature (Tg) is 170 to 180 °C excellent thermal stability It can be seen that.

Abstract

The present invention provides: a novel structure of a phosphorus-based epoxy compound having a high phosphorus (P) content and having high heat resistance and low dielectric characteristics; a method for preparing a phosphorus-based epoxy compound having a high phosphorus content and having high heat resistance and low dielectric characteristics through a preparation method in which an epoxy group is introduced into a phosphorus-based hydroxy compound by using an epoxy compound; and a phosphorus-based epoxy composition containing the same.

Description

인계 에폭시 화합물 및 이의 제조방법, 이를 포함하는 에폭시 조성물Phosphorus-based epoxy compound and preparation method thereof, epoxy composition comprising same
본 발명은 인계 에폭시 화합물 및 이의 제조방법, 이를 포함하는 인계 에폭시 조성물에 관한 것이다. 보다 구체적으로 본 발명은 고 인(P) 함량을 가지며, 고내열, 저유전 특성을 갖는 인계 에폭시 화합물 및 이의 제조방법, 이를 포함하는 에폭시 조성물에 관한 것이다. The present invention relates to a phosphorus-based epoxy compound and a preparation method thereof, and a phosphorus-based epoxy composition comprising the same. More specifically, the present invention relates to a phosphorus-based epoxy compound having a high phosphorus (P) content, having high heat resistance and low dielectric properties, a method for preparing the same, and an epoxy composition comprising the same.
일반적으로 컴퓨터, 카메라, 텔레비전 등의 전자 제품을 구동하기 위하여 인쇄회로기판(Printed Circuit Board; PCB)이 사용된다. 인쇄회로기판은 페놀이나 에폭시 등의 절연 베이스 필름에 구리 등과 같은 얇은 박막을 붙인 다음, 이를 원하는 형태로 패터닝하여 부품을 전기적으로 연결시켜주고 지지해주는 회로연결용 부품이다.In general, a printed circuit board (PCB) is used to drive electronic products such as computers, cameras, and televisions. A printed circuit board is a circuit connecting part that attaches a thin thin film such as copper to an insulating base film such as phenol or epoxy, and then patterns it in a desired shape to electrically connect and support the part.
최근 전자기기의 경박단소화 및 친환경 추세에 따라 인쇄회로기판에 대한 난연성, 내열성, 내습성, 효율성 및 열전도성 등 고성능화 요구가 증대되고 있어, 인쇄회로기판의 기초 소재인 동박적층판(Copper Clad Laminate, CCL), 연성동박적층판(Flexible Copper Clad Laminate, FCCL) 및 금속 동박적층판(Metal Copper Clad Laminate, MCCL) 등에 대해서도 고성능 구현이 요구되고 있다. Recently, the demand for high performance such as flame retardancy, heat resistance, moisture resistance, efficiency, and thermal conductivity of printed circuit boards is increasing according to the trend of thin and light reduction of electronic devices and eco-friendly trends, and thus, copper clad laminate, a basic material of printed circuit board, CCL), Flexible Copper Clad Laminate (FCCL), and Metal Copper Clad Laminate (MCCL) are also required for high performance.
동박적층판(CCL)은 인쇄회로기판의 원자재로써 종이 혹은 유리 등의 절연제에 화합물을 결합한 시트 여러 겹을 가열 가압 처리한 후 얻어진 절연판을 적층판이라 하고, 이러한 적층판의 한쪽 면이나 양면에 동박을 붙인 것으로서, 여기에 이용되는 절연 재료에는 최근의 환경 규제에 따라 납을 불포함(Lead-free)해야 하는 등의 요구 사항이 높아지게 되었고, 이에 따라, 높은 유리전이온도 특성을 가지는 절연재료를 요하는 동박적층판(CCL)에 대한 수요가 최근 상당히 높아지고 있는 추세이다.Copper Clad Laminate (CCL) is a raw material of a printed circuit board. The insulating plate obtained by heat-pressing several layers of a sheet in which a compound is bonded to an insulating material such as paper or glass is called a laminate, and a copper foil is attached to one or both sides of the laminate. In recent years, the requirements for insulating materials used here have to be lead-free in accordance with recent environmental regulations. Accordingly, copper-clad laminates requiring an insulating material having high glass transition temperature characteristics have been increased. The demand for CCL is increasing considerably in recent years.
동박적층판(CCL)의 종류에는 유리섬유에 에폭시 화합물을 침투시킨 보강기재와 동박으로 만들어지는 글래스에폭시 동박적층판과 주로 단면 PCB 제조에 사용되는 페이퍼페놀 동박적층판, 두 종류 이상의 보강기재를 복합해 만든 복합 동박적층판, 고속의 신호 전송에 대응할 수 있는 재질로 만든 고주파용 동박적층판, 연성인쇄회로기판(FPCB)용 동박적층판 등이 있다. The type of copper clad laminate (CCL) is a composite made by combining two or more kinds of reinforcement materials, such as a reinforcing material penetrating an epoxy compound into glass fiber, a glass epoxy copper clad laminate made of copper foil, and a paper phenolic copper clad laminate mainly used for manufacturing single-sided PCB. Copper foil laminates, high frequency copper foil laminates made of materials capable of high-speed signal transmission, and copper foil laminates for flexible printed circuit boards (FPCB).
에폭시 조성물은 그 뛰어난 특성에 기인하여 전기 및 전자 기기 부품 등에 널리 사용되고 있지만, 화재에 대한 안전성을 확보하기 위해 난연성이 부여되는 예가 많다. 에폭시 조성물의 난연성은 종래, 브롬화 에폭시 등의 할로겐화된 에폭시 화합물을 사용하는 것이 일반적이었다. 할로겐화된 에폭시 화합물은 뛰어난 난연성을 갖지만, 열분해에 의해 할로겐화 수소 등의 유해한 할로겐 화합물이나 폴리브롬화된 디벤조다이옥신 및 푸란을 생성한다는 환경문제가 지적되게 되었다. 이러한 이유에서, 브롬 함유 난연제를 대신하는 난연제로서 인(P) 화합물이 검토되고 있다.Epoxy compositions are widely used in electrical and electronic device parts due to their excellent properties, but in many cases flame retardancy is imparted to ensure safety against fire. Flame retardance of epoxy compositions has conventionally used halogenated epoxy compounds such as brominated epoxy. Halogenated epoxy compounds have excellent flame retardancy, but environmental problems have been pointed out by pyrolysis to produce harmful halogen compounds such as hydrogen halides and polybrominated dibenzodioxin and furan. For this reason, phosphorus (P) compounds have been studied as flame retardants to replace bromine-containing flame retardants.
그러나 종래의 인(P)계 에폭시의 낮은 인 함량은 할로겐 프리(Halogen free) 요구와 동시에 난연 UL-94 등급 V-0 달성에 큰 장애로 작용되어, 추가적인 난연 첨가제나 인(P)계 경화제의 사용이 부가되어 물리적(physical), 기계적(mechanical), 전기적(electrical) 물성을 저하시키는 영향을 끼치게 되었다.However, the low phosphorus content of conventional phosphorus (P) -based epoxy is a major obstacle to achieving flame retardant UL-94 grade V-0 simultaneously with the demand of halogen-free, so that additional flame retardant additives or phosphorus (P) Use has been added to affect physical, mechanical, and electrical properties.
또한 종래의 인(P)계 에폭시는 가교밀도가 낮아 유리 전이 온도(Tg)로 평가될 수 있는 내열성이 낮으며 에폭시 구조적으로 이차 알코올(secondary alcohol)의 생성이 부가적이어서 전기적 특성(유전율)이 떨어지는 단점이 있어 동박적층판(CCL)에 사용되기 위하여는 위한 다른 원자재의 사용이 필수적인 문제점이 있다.In addition, the conventional phosphorus (P) -based epoxy has a low crosslinking density, low heat resistance that can be evaluated by the glass transition temperature (Tg), and the secondary structure (secondary alcohol) is added to the epoxy structure, the electrical properties (dielectric constant) In order to be used in copper clad laminates (CCL), there is a disadvantage that it is necessary to use other raw materials.
인계 에폭시 화합물을 제공하기 위하여 이관능성 에폭시(Di-functional epoxy) 또는 다관능성 에폭시(Mult-functional epoxy)에 DOPO(9,10-Dihydro-9-Oxa -10-Phosphaphenantrene-10-Oxide)나 DOPO-HQ(10-(2,5-dihydroxyphenyl)-10H-9 -oxa-10-phospha-phenantbrene-10-oxide) 같은 인계 화합물을 간접법을 이용하여 모디파이(modify)하는 방식으로 제조 사용되었으나, 전체 인(P) 함량은 2wt% 대 ~ 3wt% 후반부에 국한되었으며 그 이상의 인 함량을 위해 인계 화합물을 과량 도입할 경우 반응 중 겔화물이 발생되는 등의 문제점이 존재하므로, 본 발명을 통해 특히 5wt% 이상의 고 인(P) 함량의 고내열, 저유전 특성을 갖는 인계 에폭시 화합물의 신규한 구조, 제조 방법 및 이를 포함하는 에폭시 조성물을 제공하고자 한다.DOPO (9,10-Dihydro-9-Oxa-10-Phosphaphenantrene-10-Oxide) or DOPO- in a di-functional or multi-functional epoxy to provide a phosphorus-based epoxy compound. Phosphorous compounds such as HQ (10- (2,5-dihydroxyphenyl) -10H-9 -oxa-10-phospha-phenantbrene-10-oxide) were prepared and used by modifying by indirect method, (P) content is limited to the latter 2wt% to ~ 3wt%, and there is a problem such that gelation occurs during the reaction when the phosphorus-based compound is introduced in excess for the phosphorus content, and more than 5wt% The present invention provides a novel structure of a phosphorus-based epoxy compound having a high heat resistance, low dielectric properties, a high phosphorus (P) content, a manufacturing method, and an epoxy composition comprising the same.
본 발명은 인계 에폭시 화합물 및 경화제를 포함하는 인계 에폭시 조성물로서, 상기 인계 에폭시 화합물은 하기 화학식 1로 표현되는 인계 에폭시 화합물인 인계 에폭시 조성물을 제공한다. The present invention provides a phosphorus epoxy composition comprising a phosphorus epoxy compound and a curing agent, wherein the phosphorus epoxy compound is a phosphorus epoxy compound represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2016001813-appb-I000001
Figure PCTKR2016001813-appb-I000001
(m은 0 내지 3이며, n은 0 내지 5이며, R1, R2는 각각 독립적으로, 존재하지 않거나 C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며, R3, R4는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며, R5, R6는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며, R7는 각각 독립적으로 수소, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며, R8은 각각 독립적으로 C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기 또는 이들의 조합이거나, 중량평균분자량 500 내지 5000의 고분자(또는 프리폴리머)이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있다.)(m is 0 to 3, n is 0 to 5, R 1 , R 2 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof Or a hetero element (O, S, or N) in the structure, R 3 , R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 Are combinations thereof, and hetero elements (O, S, or N) may be present in the structure, and R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon of C 6 -C 30 Or a combination thereof, and hetero elements (O, S, or N) may be present in the structure, and each R 7 is independently hydrogen, an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon of C 6 -C 30 Group or a combination thereof, and heteroatoms (O, S, or N) may be present in the structure , R 8 are each independently a C 1 -C aliphatic hydrocarbon group or aromatic hydrocarbon group, or a polymer (or prepolymer), or a combination thereof, the weight average molecular weight of 500 to 5000 of the C 6 -C 30 of 20, the hetero element in the structure (O, S, or N) may be present.)
또한 본 발명은 상기 인계 에폭시 화합물은 하기 화학식 2로 표현되는 인계 에폭시 화합물인 인계 에폭시 조성물을 제공한다. In another aspect, the present invention provides a phosphorus-based epoxy composition is a phosphorus-based epoxy compound represented by the formula (2).
[화학식 2][Formula 2]
Figure PCTKR2016001813-appb-I000002
Figure PCTKR2016001813-appb-I000002
(n은 0 내지 5이다.) (n is 0 to 5)
또한 본 발명은 상기 인계 에폭시 화합물 중 상기 n이 0인 인계 에폭시 화합물의 함량이 30 내지 99wt%인 인계 에폭시 조성물을 제공한다. In another aspect, the present invention provides a phosphorus-based epoxy composition of the content of the phosphorus-based epoxy compound of n is 0 to 99wt% of the phosphorus-based epoxy compound.
또한 본 발명은 상기 인계 에폭시 화합물과 상기 경화제의 당량비는 1 : 0.6 내지 1.5로 포함되는 인계 에폭시 조성물을 제공한다. In another aspect, the present invention provides a phosphorus-based epoxy composition comprising the equivalent ratio of the phosphorus-based epoxy compound and the curing agent is 1: 0.6 to 1.5.
또한 본 발명은 상기 경화제는 아마이드계 경화제, 폴리아민계 경화제, 산무수물 경화제, 페놀노볼락형 경화제, 폴리메르캅탄 경화제, 제3아민 경화제 또는 이미다졸 경화제로 이루어진 군으로부터 적어도 하나 이상 선택되는 인계 에폭시 조성물을 제공한다. In the present invention, the curing agent is at least one phosphorus epoxy composition selected from the group consisting of amide curing agent, polyamine curing agent, acid anhydride curing agent, phenol novolak-type curing agent, polycapcaptan curing agent, tertiary amine curing agent or imidazole curing agent To provide.
또한 본 발명은 상기 인계 에폭시 조성물은 경화촉진제를 더 포함하며, 상기 경화촉진제는 2-메틸 이미다졸(2-methyl Imidazole), 2-에틸-4-메틸 이미다졸(2-Ethyl-4-Methyl Imidazole), 1-벤질-2-메틸 이미다졸(1-Benzyl-2-Methyl Imidazole), 2-헵타데실 이미다졸(2-Heptadecyl Imidazole) 및 2-운데실 이미다졸(2-Undecyl Imidazole) 중에서 선택된 1종 이상을 함유한 이미다졸 화합물; 트리페닐포스페이트(Triphenylphosphate)를 함유한 유기화합물; 및 ETPPI(Ethyl Triphenyl Phosphonium Iodide) 등의 트리 알킬 화합물, 4-디메틸아미노피리딘(4-Dimethylamino Pyridine), 2-아미노 피리딘, 3-아미노 피리딘, 4-아미노 피리딘, 2,3-디아미노 피리딘, 2,5-디아미노 피리딘, 2,6-디아미노 피리딘, 2-아미노-6-메틸 피리딘, 3-아미노-6-이소프로필 피리딘, 2,2- 디피리딜 아민 및 4-피롤리디노 피리딘 중에서 선택된 1종 이상을 함유한 피리딘 화합물; 중에서 선택된 1종 이상을 포함하는 인계 에폭시 조성물을 제공한다. In addition, the present invention, the phosphorus-based epoxy composition further comprises a curing accelerator, the curing accelerator is 2-methyl imidazole, 2-ethyl-4-methyl imidazole (2-Ethyl-4-Methyl Imidazole ), 1-benzyl-2-methyl imidazole, 1 selected from 2-heptadecyl imidazole, and 2-undecyl imidazole. Imidazole compounds containing more than one species; Organic compounds containing triphenylphosphate; And trialkyl compounds such as Ethyl Triphenyl Phosphonium Iodide (ETPPI), 4-dimethylamino pyridine, 2-amino pyridine, 3-amino pyridine, 4-amino pyridine, 2,3-diamino pyridine, 2 ,, 5-diamino pyridine, 2,6-diamino pyridine, 2-amino-6-methyl pyridine, 3-amino-6-isopropyl pyridine, 2,2-dipyridyl amine and 4-pyrrolidino pyridine Pyridine compounds containing at least one selected; It provides a phosphorus-based epoxy composition comprising one or more selected from.
또한 본 발명은 상기 인계 에폭시 조성물의 전체 중량 대비 인(P) 함량은 2 내지 7 중량%인 인계 에폭시 조성물을 제공한다. In another aspect, the present invention provides a phosphorus-based epoxy composition is 2 to 7% by weight relative to the total weight of the phosphorus-based epoxy composition.
또한 본 발명은 상기 인계 에폭시 조성물로부터 얻어지는 경화물의 유리 전이 온도(Tg)가 150 내지 230 인 것을 특징으로 하는 인계 에폭시 조성물을 제공한다. The present invention also provides a phosphorus-based epoxy composition, wherein the glass transition temperature (Tg) of the cured product obtained from the phosphorus-based epoxy composition is 150 to 230.
또한 본 발명은 상기 인계 에폭시 조성물로부터 얻어지는 경화물의 유전상수(Dk)은 4.2 이하인 것을 특징으로 하는 인계 에폭시 조성물을 제공한다. The present invention also provides a phosphorus-based epoxy composition, characterized in that the dielectric constant (D k ) of the cured product obtained from the phosphorus-based epoxy composition is 4.2 or less.
또한 본 발명은 상기 인계 에폭시 조성물로부터 얻어지는 경화물의 손실인자(Df)는 0.020 이하인 것을 특징으로 하는 인계 에폭시 조성물을 제공한다. The present invention also provides a phosphorus-based epoxy composition, characterized in that the loss factor (D f ) of the cured product obtained from the phosphorus-based epoxy composition is 0.020 or less.
또한, 상기 인계 에폭시 화합물은 하기 화학식 5로 표현되는 인계 에폭시 화합물인 인계 에폭시 조성물을 제공한다.In addition, the phosphorus-based epoxy compound provides a phosphorus-based epoxy composition which is a phosphorus-based epoxy compound represented by the following formula (5).
[화학식 5][Formula 5]
Figure PCTKR2016001813-appb-I000003
Figure PCTKR2016001813-appb-I000003
(n, m, R8의 정의는 상기 화학식 1과 동일하다)(n, m, R 8 is the same as defined in Formula 1)
또한 본 발명은 상기 화학식 1로 표시되는 인계 에폭시 화합물을 제공한다. In another aspect, the present invention provides a phosphorous epoxy compound represented by the formula (1).
또한 본 발명은 상기의 화학식 2 또는 화학식 5로 표현되는 인계 에폭시 화합물을 제공한다. In another aspect, the present invention provides a phosphorus-based epoxy compound represented by the formula (2) or (5).
또한 본 발명은 상기 인계 에폭시 화합물의 전체 중량 대비 인(P) 함량은 6 내지 8 중량%인 인계 에폭시 화합물을 제공한다. In another aspect, the present invention provides a phosphorus-based epoxy compound of 6 to 8% by weight relative to the total weight of the phosphorus-based epoxy compound.
또한 본 발명은 상기 인계 에폭시 화합물은 인계 히드록시 화합물 및 에폭시 화합물을 알칼리 촉매 하에서 반응시켜 제조되는 것을 특징으로 하는 인계 에폭시 화합물을 제공한다. In another aspect, the present invention provides a phosphorus-based epoxy compound, characterized in that the phosphorus-based hydroxy compound and the epoxy compound is prepared by reacting under an alkali catalyst.
또한 본 발명은 하기 화학식 3으로 표시되는 인계 히드록시 화합물, 하기 화학식 4-1과 하기 화학식 4-2로 표시되는 에폭시 화합물 중 선택되는 적어도 하나 이상의 에폭시 화합물, 및 제1 용매를 포함하는 반응 물질들을 반응기에 투입하여 반응 혼합물을 얻는 반응 혼합물 준비단계; 및 상기 반응 혼합물을 반응시켜 인이 함유된 에폭시 화합물을 얻는 단계;를 포함하는 인계 에폭시 화합물 제조방법을 제공한다. In addition, the present invention provides a reaction material comprising a phosphorus-based hydroxy compound represented by the following formula (3), at least one epoxy compound selected from the epoxy compounds represented by the following formula (4-1) and the formula (4-2), and a first solvent Preparing a reaction mixture to be added to a reactor to obtain a reaction mixture; And reacting the reaction mixture to obtain an epoxy compound containing phosphorus.
[화학식 3][Formula 3]
Figure PCTKR2016001813-appb-I000004
Figure PCTKR2016001813-appb-I000004
[화학식 4-1][Formula 4-1]
Figure PCTKR2016001813-appb-I000005
Figure PCTKR2016001813-appb-I000005
[화학식 4-2][Formula 4-2]
Figure PCTKR2016001813-appb-I000006
Figure PCTKR2016001813-appb-I000006
(R1, R2는 각각 독립적으로, 존재하지 않거나 C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며, R3, R4는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며, R5, R6는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며, X는 할로겐기, -OTs(O-Tosyl), -OMs(O-Mesyl)이다.)(R 1 , R 2 are each independently, absent or a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group or a combination thereof and heteroatoms (O, S, or N in the structure) ) May be present, and R 3 and R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and a hetero element (O, S, Or N), R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and a hetero element (O, S, or N) may be present and X is a halogen group, -OTs (O-Tosyl), -OMs (O-Mesyl).)
또한 본 발명은 상기 반응 혼합물 준비단계는, 상기 제1 용매 100 중량부에 대하여, 상기 화학식 3으로 표시되는 인계 히드록시 화합물이 100 내지 180 중량부, 상기 화학식 4-1과 상기 화학식 4-2로 표시되는 에폭시 화합물이 210 내지 290 중량부로 혼합되는 것을 특징으로 하는 인계 에폭시 화합물 제조방법을 제공한다. In addition, the present invention, the reaction mixture preparation step, 100 to 180 parts by weight of the phosphorus-based hydroxy compound represented by the formula (3) with respect to 100 parts by weight of the first solvent, to the formula 4-1 and the formula 4-2 Provided is a method for producing a phosphorus-based epoxy compound, characterized in that the epoxy compound is mixed in 210 to 290 parts by weight.
또한, 상기 반응 혼합물을 반응시켜 인이 함유된 에폭시 화합물을 얻는 단계 이후에, 상기 얻어진 에폭시 화합물의 전부 또는 일부를 다관능 이소시아네이트 화합물로 변성시키는 단계를 더 포함하는 것을 특징으로 하는 인계 에폭시 화합물 제조방법을 제공한다.In addition, after the step of reacting the reaction mixture to obtain an epoxy compound containing phosphorus, further comprising the step of modifying all or part of the obtained epoxy compound to a polyfunctional isocyanate compound, characterized in that it further comprises To provide.
또한 본 발명은 상기 인계 에폭시 조성물을 포함하는 것을 특징으로 하는 적층판을 제공한다. In another aspect, the present invention provides a laminate comprising the phosphorous epoxy composition.
[유리한 효과][Favorable effect]
본 발명은 고내열, 저유전 특성을 갖는 신규한 구조의 고 인(P) 함량 인계 에폭시 화합물로서, 할로겐을 포함하지 않으면서도, 난연 UL-94 등급 V-0 달성이 가능하여 산업상 이용시 추가적인 난연 첨가제를 사용할 필요가 없어, 물리적, 기계적, 전기적 물성을 저하시키지 않아 신뢰성이 우수한 인계 에폭시 화합물, 이의 제조방법 및 이를 포함하는 인계 에폭시 조성물을 제공할 수 있다.The present invention is a high phosphorus (P) content phosphorus epoxy compound having a high heat resistance, low dielectric properties, and does not contain halogen, flame-retardant UL-94 grade V-0 can be achieved, further flame retardant in industrial use Since there is no need to use an additive, it is possible to provide a phosphorus-based epoxy compound having excellent reliability, a manufacturing method thereof, and a phosphorus-based epoxy composition including the same without reducing physical, mechanical, and electrical properties.
이하에 본 발명을 상세하게 설명하기에 앞서, 본 명세서에 사용된 용어는 특정의 실시예를 기술하기 위한 것일 뿐 첨부하는 특허청구의 범위에 의해서만 한정되는 본 발명의 범위를 한정하려는 것은 아님을 이해하여야 한다. 본 명세서에 사용되는 모든 기술용어 및 과학용어는 다른 언급이 없는 한은 기술적으로 통상의 기술을 가진 자에게 일반적으로 이해되는 것과 동일한 의미를 가진다.Prior to describing the present invention in detail below, it is understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is limited only by the scope of the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise indicated.
본 명세서 및 청구범위의 전반에 걸쳐, 다른 언급이 없는 한 포함(comprise, comprises, comprising)이라는 용어는 언급된 물건, 단계 또는 일군의 물건, 및 단계를 포함하는 것을 의미하고, 임의의 어떤 다른 물건, 단계 또는 일군의 물건 또는 일군의 단계를 배제하는 의미로 사용된 것은 아니다.Throughout this specification and claims, unless otherwise indicated, the termcomprise, constitutes, and configure means to include the referenced article, step, or group of articles, and step, and any other article It is not intended to exclude a stage or group of things or groups of stages.
또한 "C1", C2" 등은 탄소수를 의미하는 것으로서, 예를 들어 "C1-C10의 알킬렌기"는 탄소수 1 -10의 알킬렌기를 의미한다. In addition, "C 1", C 2 ", etc. are as meaning the number of carbon atoms, for example," C 1 -C 10 alkylene group "means an alkylene group having a carbon number of 1-10.
한편, 본 발명의 여러 가지 실시예들은 명확한 반대의 지적이 없는 한 그 외의 어떤 다른 실시예들과 결합될 수 있다. 특히 바람직하거나 유리하다고 지시하는 어떤 특징도 바람직하거나 유리하다고 지시한 그 외의 어떤 특징 및 특징들과 결합될 수 있다. 이하, 첨부된 도면을 참조하여 본 발명의 실시예 및 이에 따른 효과를 설명하기로 한다. On the other hand, various embodiments of the present invention can be combined with any other embodiment unless clearly indicated to the contrary. Any feature indicated as particularly preferred or advantageous may be combined with any other feature and features indicated as preferred or advantageous. Hereinafter, with reference to the accompanying drawings will be described an embodiment of the present invention and the effects thereof.
본 발명은 고내열, 저유전 특성을 갖는 신규한 구조의 고 인(P) 함량 인계 에폭시 화합물(Phosphorus Epoxy Compound)로서, 하기 화학식 1로 표시되는 인계 에폭시 화합물을 제공하고자 한다.The present invention is to provide a phosphorus-based epoxy compound represented by the following formula (1) as a high phosphorus (P) content phosphorus-based epoxy compound (Phosphorus Epoxy Compound) having a high heat resistance, low dielectric properties.
[화학식 1][Formula 1]
Figure PCTKR2016001813-appb-I000007
Figure PCTKR2016001813-appb-I000007
여기서, m은 0 내지 3이며, n은 0 내지 5이다. 또한 인계 에폭시 화합물 중 n=0인 인계 에폭시 화합물의 함량은 30 내지 99wt%이다. n=0인 인계 에폭시 화합물의 함량이 30wt% 미만인 경우 경화속도가 늦거나 미경화가 발생되는 문제점이 있고, 99wt% 초과인 경우 기계적 강도가 떨어지는 문제점이 있을 수 있다.Here m is 0-3 and n is 0-5. In addition, the content of the phosphorus-based epoxy compound of n = 0 in the phosphorus-based epoxy compound is 30 to 99wt%. When the content of the phosphorus-based epoxy compound of n = 0 is less than 30wt%, there is a problem that the curing rate is slow or uncured, and when the content is more than 99wt%, there may be a problem that the mechanical strength is lowered.
R1, R2는 각각 독립적으로, 존재하지 않거나 C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있다.R 1 , R 2 are each independently, absent or an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) in the structure May be present.
R3, R4는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있다. 바람직하게는 C1-C20의 지방족 탄화수소기인 것이 좋다. 더욱 바람직하게는 C1-C10의 알킬렌(alkylene)기(-CnH2n-)인 것이 좋다. 예를 들면, 메틸렌(methylene)기(-CH2-), 에틸렌(ethylene)기(-CH2CH2-)인 것이 좋다.R 3 and R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure. have. Preferably an aliphatic hydrocarbon group of C 1 -C 20. More preferably alkylene (alkylene) group (-C n H 2n -) of the C 1 -C 10 may be a. For example, methylene (methylene) group (-CH 2 -) - preferably in an ethylene (ethylene) group (-CH 2 CH 2).
R5, R6는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있다. 바람직하게는 C6-C30의 방향족 탄화수소기인 것이 좋다. 더욱 바람직하게는, 예를 들면, 페닐(phenyl)기, 안트라센(anthracene), 안트릴(anthryl)기, 페난트릴(phenanthryl)기, 비페닐(biphenyl)기를 포함하는 아릴(aryl)기(Ar-)인 것이 좋다. R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) may be present in the structure. have. Preferably it is a C 6 -C 30 aromatic hydrocarbon group. More preferably, for example, an aryl group (Ar-) including a phenyl group, anthracene, anthryl group, phenanthryl group, and biphenyl group It is good to be).
R7는 각각 독립적으로, 수소, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있다. 바람직하게는 수소인 것이 좋다.R 7 is each independently hydrogen, an aliphatic hydrocarbon group of C 1 -C 20 , or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure. . Preferably it is hydrogen.
R8은 각각 독립적으로 C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기 또는 이들의 조합이거나, 중량평균분자량 500 내지 5000의 고분자(또는 프리폴리머)이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있다.R 8 is each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, or a polymer (or prepolymer) having a weight average molecular weight of 500 to 5000, and a hetero element ( O, S, or N) may be present.
본 발명의 일실시예인 인계 에폭시 화합물은 하기 화학식 2로 표시되는 것일 수 있다. 화학식 1로 표시되는 인계 에폭시 화합물에 대하여 R3 및 R4가 각각 메틸렌(methylene)기(-CH2-)이며, R5 및 R6가 각각 페닐(phenyl)기(-Ph)인 인계 에폭시 화합물에 대응되며, m이 0인 경우이다. Phosphorus-based epoxy compound of one embodiment of the present invention may be represented by the following formula (2). Phosphorous epoxy compound wherein R 3 and R 4 are each a methylene group (-CH 2- ) and R 5 and R 6 are each a phenyl group (-Ph). Corresponding to, where m is zero.
[화학식 2] [Formula 2]
Figure PCTKR2016001813-appb-I000008
Figure PCTKR2016001813-appb-I000008
본 발명에 따른 인계 에폭시 화합물의 인(P) 함량은 화합물 전체 중량 대비 5 내지 10 중량%으로 포함되며, 더욱 바람직하게는 6 내지 8 중량%로 포함된다. 인(P)이 5 중량% 미만으로 포함되는 경우 할로겐 프리 포뮬레이션(Halogen free formulation)에서 난연 UL-94 등급 V-0 달성의 큰 장애로 작용되어 산업상 이용시 추가적인 난연 첨가제나 인계 경화제의 사용이 부가되어 물리적, 기계적, 전기적 물성을 저하시키는 문제점이 있으며, 인(P)이 10 중량%를 초과하여 포함되는 경우 분자구조상 합성 자체가 쉽지 않으며 특별한 인계 화합물을 이용하여 합성이 가능하더라도 아로마틱링의 배제가 필요하므로 전체적인 내열성의 급격한 저하가 초래되는 문제점이 있으므로, 상기 범위 내로 인을 함유하고 있는 것이 좋다.The phosphorus (P) content of the phosphorus epoxy compound according to the present invention is included in 5 to 10% by weight, more preferably 6 to 8% by weight relative to the total weight of the compound. If phosphorus (P) is present in less than 5% by weight, this is a major barrier to achieving flame retardant UL-94 grade V-0 in halogen-free formulations, preventing the use of additional flame retardant additives or phosphorus curing agents in industrial use. In addition, there is a problem of deteriorating physical, mechanical, and electrical properties, and if phosphorus (P) is included in excess of 10% by weight, the synthesis itself is not easy due to the molecular structure, and even if the synthesis is possible using a special phosphorus-based compound, the exclusion of aromatic ring Since it is necessary to have a problem of causing a sudden drop in overall heat resistance, it is preferable to contain phosphorus within the above range.
본 발명에 따른 인계 에폭시 화합물에 의하면, 고내열의 유전손실이 매우 낮은 특성을 갖는다. 본 발명에 따른 인계 에폭시 화합물은 5 내지 10 wt%의 인(P) 함량을 가져 난연 UL-94 등급 V-0 달성을 위한 추가적인 난연 첨가제나 인계 경화제의 사용이 불필요하여, 에폭시 화합물의 물리적(physical), 기계적(mechanical), 전기적(electrical) 물성에 대한 신뢰성을 부여할 수 있으며 자유로운 포뮬레이션을 가능케하여 다른 에폭시 수지, 경화제 등을 사용하여 필요로하는 물성을 부여하는 조성물 배합 가능성을 높여준다. 또한 고 인(P) 함량 및 구조 내의 작용기들로 인한 고내열, 저유전 특성, 저연화점을 가져, 특히 인쇄회로기판에 사용되는 적층판(laminated plate)의 소재로 사용되기에 매우 적합하며 복합재료의 소재로서도 유용하다.According to the phosphorus epoxy compound according to the present invention, the dielectric loss of high heat resistance has a very low characteristic. Phosphorus-based epoxy compounds according to the present invention have a phosphorus (P) content of 5 to 10 wt%, which eliminates the need for the use of additional flame retardant additives or phosphorus curing agents to achieve flame retardant UL-94 grade V-0. ) It can give reliability for mechanical, electrical and electrical properties, and enables free formulation, increasing the possibility of blending compositions that give the required properties using other epoxy resins and hardeners. In addition, it has high heat resistance, low dielectric properties and low softening point due to high phosphorus (P) content and functional groups in the structure, and is particularly suitable for being used as a material for laminated plates used in printed circuit boards. It is also useful as a material.
본 발명의 일실시예인 인계 에폭시 화합물은 하기 화학식 5로 표시되는 것일 수 있다. 화학식 1로 표시되는 인계 에폭시 화합물에 대하여 R3 및 R4가 각각 메틸렌(methylene)기(-CH2-)이며, R5 및 R6가 각각 페닐(phenyl)기(-Ph)인 인계 에폭시 화합물에 대응된다.Phosphorus-based epoxy compound of one embodiment of the present invention may be represented by the following formula (5). Phosphorous epoxy compound wherein R 3 and R 4 are each a methylene group (-CH 2- ) and R 5 and R 6 are each a phenyl group (-Ph). Corresponds to.
[화학식 5][Formula 5]
Figure PCTKR2016001813-appb-I000009
Figure PCTKR2016001813-appb-I000009
(n, m, R8의 정의는 상기 화학식 1과 동일하다)(n, m, R 8 is the same as defined in Formula 1)
또 다른 측면에서 본, 본 발명의 일실시예인 인계 에폭시 화합물은 제1 용매에 하기 화학식 3으로 표시되는 인계 히드록시 화합물, 및 하기 화학식 4-1과 하기 화학식 4-2로 표시되는 에폭시 화합물 중 선택되는 적어도 하나 이상의 에폭시 화합물을 용해시킨 반응 혼합물을 반응시켜 제조되는 고내열, 저유전 특성을 갖는 인계 에폭시 화합물(Phosphorus Epoxy Compound)이다. In another aspect, the phosphorus-based epoxy compound according to one embodiment of the present invention is selected from a phosphorus-hydroxy compound represented by the following Formula 3 in the first solvent, and an epoxy compound represented by the following Formula 4-1 and the following Formula 4-2 Phosphorus Epoxy Compound having high heat resistance and low dielectric properties prepared by reacting a reaction mixture in which at least one epoxy compound is dissolved.
[화학식 3][Formula 3]
Figure PCTKR2016001813-appb-I000010
Figure PCTKR2016001813-appb-I000010
[화학식 4-1][Formula 4-1]
Figure PCTKR2016001813-appb-I000011
Figure PCTKR2016001813-appb-I000011
[화학식 4-2][Formula 4-2]
Figure PCTKR2016001813-appb-I000012
Figure PCTKR2016001813-appb-I000012
R1, R2는 각각 독립적으로, 존재하지 않거나 C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있다. 바람직하게는, 예를 들면, 메틸렌(methylene)기(-CH2-), 에틸렌(ethylene)기(-CH2CH2-)인 것이 좋다. 더욱 바람직하게는 존재하지 않는 것이 좋다.R 1 , R 2 are each independently, absent or an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) in the structure May be present. Preferably, for example, methylene (methylene) group (-CH 2- ), ethylene (ethylene) group (-CH 2 CH 2- ). More preferably, it does not exist.
R3, R4는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있다. 바람직하게는 C1-C20의 지방족 탄화수소기인 것이 좋다. 더욱 바람직하게는 C1-C10의 알킬렌(alkylene)기(-CnH2n-)인 것이 좋다. 예를 들면, 메틸렌(methylene)기(-CH2-), 에틸렌(ethylene)기(-CH2CH2-)인 것이 좋다.R 3 and R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure. have. Preferably an aliphatic hydrocarbon group of C 1 -C 20. More preferably alkylene (alkylene) group (-C n H 2n -) of the C 1 -C 10 may be a. For example, methylene (methylene) group (-CH 2 -) - preferably in an ethylene (ethylene) group (-CH 2 CH 2).
R5, R6는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있다. 바람직하게는 C6-C30의 방향족 탄화수소기인 것이 좋다. 더욱 바람직하게는, 예를 들면, 페닐(phenyl)기, 안트라센(anthracene), 안트릴(anthryl)기, 페난트릴(phenanthryl)기, 비페닐(biphenyl)기를 포함하는 아릴(aryl)기(Ar-)인 것이 좋다. R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) may be present in the structure. have. Preferably it is a C 6 -C 30 aromatic hydrocarbon group. More preferably, for example, an aryl group (Ar-) including a phenyl group, anthracene, anthryl group, phenanthryl group, and biphenyl group It is good to be).
X는 일종의 우수한 이탈기(good leaving group), 예를 들면, 할로겐기, -OTs(O-Tosyl), -OMs(O-Mesyl) 일 수 있다. 바람직하게는 염소기(-Cl), 브롬기(-Br)인 것이 좋다. X may be a kind of good leaving group, for example, a halogen group, -OTs (O-Tosyl), -OMs (O-Mesyl). Preferably it is a chlorine group (-Cl), bromine group (-Br).
본 발명에 따른 인계 에폭시 화합물의 더욱 구체적인 제조방법은, 상기 화학식 3으로 표시되는 인계 히드록시 화합물에 상기 화학식 4-1과 상기 화학식 4-2로 표시되는 에폭시 화합물 중 선택되는 적어도 하나 이상의 에폭시 화합물이 혼합된 반응 혼합물을 반응시키는 방법으로서, 상기 에폭시 화합물은 상기 인계 히드록시 화합물의 하이드록시 그룹(-OH)과 반응하여 상기 화학식 1로 표현되는 인계 에폭시 화합물을 형성한다.More specific method for producing a phosphorus-based epoxy compound according to the present invention, at least one epoxy compound selected from the epoxy compound represented by the formula (4-1) and the formula (4-2) to the phosphorus-hydroxy compound represented by the formula (3) As a method of reacting the mixed reaction mixture, the epoxy compound is reacted with a hydroxy group (-OH) of the phosphorus hydroxy compound to form a phosphorus epoxy compound represented by Chemical Formula 1.
상기 반응 혼합물은 제1 용매 100 중량부에 대하여 상기 화학식 3으로 표시되는 인계 히드록시 화합물이 80 내지 250 중량부 혼합되며, 상기 화학식 4-1과 화학식 4-2로 표시되는 에폭시 화합물 중 적어도 하나 이상의 에폭시 화합물이 210 내지 290 중량부로 혼합된다. 더욱 바람직하게는 상기 제1 용매 100 중량부에 대하여 상기 화학식 3으로 표시되는 인계 히드록시 화합물이 100 내지 220 중량부로 혼합되며, 상기 화학식 4-1과 화학식 4-2로 표시되는 에폭시 화합물 중 적어도 하나 이상의 에폭시 화합물이 230 내지 270 중량부로 혼합되는 것이 좋다.The reaction mixture is 80 to 250 parts by weight of the phosphorus hydroxy compound represented by the formula (3) relative to 100 parts by weight of the first solvent, at least one or more of the epoxy compounds represented by the formula (4-1) and (4-2) The epoxy compound is mixed at 210 to 290 parts by weight. More preferably, the phosphorus hydroxy compound represented by Chemical Formula 3 is mixed in an amount of 100 to 220 parts by weight based on 100 parts by weight of the first solvent, and at least one of the epoxy compounds represented by Chemical Formulas 4-1 and 4-2. It is preferable that the above epoxy compound is mixed at 230 to 270 parts by weight.
상기 반응 혼합물을 반응시키는 방법의 일실시예로는 알칼리 촉매를 이용하여 반응시키는 방법을 사용할 수 있고, 상기 알칼리 촉매로는, 예를 들면, 수산화나트륨(sodium hydroxide), 수산화리튬(lithium hydroxide), 수산화칼륨(potassium hydroxide) 등의 알칼리 금속의 수산화물; 탄산나트륨(sodium carbonate), 중탄산나트륨(sodium bicarbonate), 염화나트륨(sodium chloride), 염화리튬(lithium chloride), 염화칼륨(potassium chloride) 등의 알칼리 금속염; 메톡시화나트륨(sodium methoxide), 에톡시화나트륨(sodium ethoxide) 등의 알칼리 금속 알콕시드(alkoxide); 알칼리 금속의 페녹시드(phenoxide), 수소화나트륨(sodium hydride), 수소화리튬(lithium hydride) 등의 알칼리 금속의 수소화물; 초산나트륨(sodium nitrate), 스테아린산 나트륨(sodium stearate) 등의 유기산의 알칼리 금속염 등을 사용할 수 있다. As an example of a method of reacting the reaction mixture, a method of reacting using an alkali catalyst may be used. As the alkali catalyst, for example, sodium hydroxide, lithium hydroxide, Alkali metal hydroxides such as potassium hydroxide; Alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride, and potassium chloride; Alkali metal alkoxides such as sodium methoxide and sodium ethoxide; Alkali metal hydrides such as phenoxide, sodium hydride, and lithium hydride of alkali metals; Alkali metal salts of organic acids, such as sodium acetate and sodium stearate, etc. can be used.
상기 제1 용매는 사용되지 않을 수 있으나, 용매를 사용할 경우 용매가 반응성을 향상시키는 효과를 주어 반응 시 중간 생성물의 양을 감소시킴에 따라 용매를 사용하지 않을 경우와 비교하여 제품 수율에 있어서 10% 이상 향상되고, 최종 제품 화합물 색상에 있어서도 우수한 결과를 얻을 수 있다. The first solvent may not be used, but when the solvent is used, the solvent gives an effect of improving the reactivity to reduce the amount of the intermediate product during the reaction, thus 10% in the product yield compared to the case where the solvent is not used. The above results are improved, and excellent results can be obtained also in the color of the final product compound.
사용되는 제1 용매로는, 예를 들면, 벤젠(benzene), 톨루엔(toluene), 크실렌(xylene) 등을 포함하는 방향족계 용매; 아세톤(acetone), 메틸에틸케톤(methylethylketone, MEK), 메틸이소부틸케톤(methylisobutylketone, MIBK), 디이소부틸케톤(diisobutyl ketone, DIBK) 시클로헥사논(cyclohexanone), 아세틸아세톤(acetylacetone), 디옥산(dioxane) 등을 포함하는 케톤계 용매; 포름아미드(formamide), N-메틸포름아미드(N-methylformamide), N,N-디메틸포름아미드(N,N-dimethylformamide, DMF), 아세트아미드(acetamide), N-메틸아세트아미드(N-methylacetamide), N,N-디메틸아세트아미드(N,N-dimethylacetamide), 2-피롤리돈(2-pyrrolidone), N-메틸피롤리돈(N-Methylpyrrolidone, NMP) 등의 아미드계 용매; 에틸렌글리콜모노부틸에테르(ethylene glycol monobutyl ether), 프로필렌글리콜메틸에테르아세테이트(propylene glycol methyl ether acetate), 1,4-다이옥산(1,4-dioxane), 프로필렌글리콜메틸에테르(Propylene Glycol Methyl Ether), 프로필렌글리콜모노부틸에테르(Propylene Glycol Monobutyl Ether) 등을 포함하는 글리콜 에테르계 용매; 메틸알콜(methyl alcohol, methanol), 에틸알콜(ethyl alcohol, ethanol), 프로필알콜(propyl alcohol, propanol), 부틸알콜(butyl alcohol, butanol), 펜틸알콜(pently alcohol, pentanol), 헥실알콜(hexyl alcohol, hexanol), 이소프로필알콜(isopropyl alcohol, IPA), 이소부틸알콜(isobutyl alcohol) 및 이들의 유도체 등을 포함하는 알콜계 용매; 등을 사용할 수 있다. As a 1st solvent used, For example, Aromatic solvent containing benzene, toluene, xylene, etc .; Acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK) cyclohexanone, acetylacetone, dioxane ( ketone solvents such as dioxane); Formamide, N-methylformamide, N, N-dimethylformamide (N, N-dimethylformamide, DMF), acetamide, N-methylacetamide Amide solvents such as N, N-dimethylacetamide, 2-pyrrolidone, and N-methylpyrrolidone (NMP); Ethylene glycol monobutyl ether, propylene glycol methyl ether acetate, 1,4-dioxane, propylene glycol methyl ether, propylene Glycol ether solvents including glycol monobutyl ether and the like; Methyl alcohol, methanol, ethyl alcohol, ethanol, propyl alcohol, propanol, butyl alcohol, butanol, pently alcohol, pentanol, hexyl alcohol alcohol solvents including hexanol), isopropyl alcohol (isoA), isobutyl alcohol and derivatives thereof; Etc. can be used.
제1 용매로는 바람직하게는 이소프로필알콜(isopropyl alcohol, IPA)을 사용하는 것이 좋다. As the first solvent, it is preferable to use isopropyl alcohol (IPA).
합성 반응은 30 내지 200℃의 온도에서 이루어진다. 더욱 바람직하게는 45 내지 170℃의 온도에서 반응시키는 것이 좋다. 또한 합성 반응은 3시간 내지 7시간 동안 이루어진다. 더욱 바람직하게는 4 내지 6시간 동안 반응시키는 것이 좋다. 촉매는 제1 용매 100중량부에 대하여 50 내지 120 중량부로 투입된다. The synthesis reaction takes place at a temperature of 30 to 200 ° C. More preferably, the reaction is carried out at a temperature of 45 to 170 ° C. In addition, the synthesis reaction takes place for 3 to 7 hours. More preferably, the reaction is carried out for 4 to 6 hours. The catalyst is added in 50 to 120 parts by weight based on 100 parts by weight of the first solvent.
합성 반응 종료 이후에, 물을 이용한 수세 후 승온하여 잔존하는 상기 화학식 4-1 또는 4-2로 표시되는 에폭시 화합물을 제거하는 공정(제1 정제)을 더 포함할 수 있으며, 제1 정제 이후에 제2 용매를 투입하여 용해시킨 후, 알칼리 촉매를 이용한 재정제 공정(제2 정제)을 더 포함할 수 있다. After the completion of the synthesis reaction, the step of increasing the temperature after washing with water to remove the remaining epoxy compound represented by the formula (4-1 or 4-2) (first purification), after the first purification After adding and dissolving the second solvent, the method may further include a refining process (second purification) using an alkali catalyst.
제2 용매로 사용될 수 있는 용매의 종류는 상술한 제1 용매로 사용될 수 있는 용매 종류와 동일하다. 바람직하게는 메틸이소부틸케톤(methylisobutylketone, MIBK)을 사용하는 것이 좋다. The kind of solvent that can be used as the second solvent is the same as the kind of solvent that can be used as the first solvent described above. Preferably, methyl isobutyl ketone (MIBK) may be used.
제1 정제 단계는, 합성 반응 종료 후 물을 이용하여 수세를 진행한 후 140 내지 160℃까지 승온하여 잔존 모노머를 제거하는 공정이며, 제2 정제 단계는 제1 정제 이후 140 내지 160℃에서 제2 용매를 서서히 투입하여 용해시킨 후 70 내지 90℃에서 알칼리 촉매를 이용하여 1시간 내지 1시간 30분간 반응 중 생성된 염을 제거하는 재정제 공정이다.After the completion of the synthesis reaction, the first purification step is a step of removing the remaining monomers by heating to 140 to 160 ° C after washing with water using water, and the second purification step is performed at 140 to 160 ° C after the first purification. After slowly adding the solvent to dissolve, it is a refining process of removing the salt generated during the reaction for 1 hour to 1 hour 30 minutes using an alkali catalyst at 70 to 90 ° C.
제1 정제 단계는 상기 제1 용매 100 중량부에 대하여 80 내지 250 중량부의 물을 이용하여 수세를 진행하고, 제2 정제 단계는 상기 제1 용매 100 중량부에 대하여 300 내지 700 중량부의 제2 용매를 투입하여 용해시킨 후 상기 제1 용매 100 중량부에 대하여 10 내지 30 중량부의 촉매를 투입하여 재정제한다.The first purification step is washed with water using 80 to 250 parts by weight of water based on 100 parts by weight of the first solvent, the second purification step is 300 to 700 parts by weight of a second solvent relative to 100 parts by weight of the first solvent After dissolving by adding to dissolve 10 to 30 parts by weight of catalyst based on 100 parts by weight of the first solvent.
또한 제2 정제단계 이후에 다시 물을 이용하여 수세를 진행한 후 140 내지 160℃까지 진공탈기를 실시하여 잔존하는 물과 용매를 제거하면 노란색의 인계 에폭시 화합물 플레이크를 얻을 수 있다.In addition, after washing with water again after the second purification step, the vacuum degassing is carried out to 140 to 160 ℃ to remove the remaining water and solvent to obtain a yellow phosphorous epoxy compound flake.
한편, 선택적으로, 상기 반응 혼합물을 반응시켜 인이 함유된 에폭시 화합물을 얻는 단계 이후에, 상기 얻어진 에폭시 화합물의 전부 또는 일부를 다관능 이소시아네이트 화합물로 변성시키는 단계를 더 포함할 수 있다. 변성시 화학식 1에서 m이 1 내지 3인 화합물이 얻어질 수 있다.Meanwhile, optionally, after the step of reacting the reaction mixture to obtain an epoxy compound containing phosphorus, the method may further include modifying all or part of the obtained epoxy compound into a polyfunctional isocyanate compound. Upon modification, a compound having m of 1 to 3 may be obtained.
변성 반응을 위해, 촉매를 사용할 수 있으며, 구체적으로는 이미다졸 등의 촉매를 사용할 수 있다.For the modification reaction, a catalyst can be used, and specifically, a catalyst such as imidazole can be used.
상기 다관능 이소시아네이트 화합물은 이소시아네이트기가 분자당 2 내지 5개가 존재하는 화합물을 사용할 수 있으며, 방향족, 지방족 또는 지환족 이소시아네이트 화합물일 수 있고, 1종 또는 2종 이상을 혼합하여 사용할 수 있다. 구체적으로는, 헥사메틸렌 디이소시아네이트, 이소포론 디이소시아네이트, 메틸렌 디시클로헥실 디이소시아네이트 및 시클로헥산 디이소시아네이트, 톨루엔 디이소시아네이트, 나프탈렌 디이소시아네이트, 테트라메틸크실렌 디이소시아네이트, 페닐렌 디이소시아네이트, 톨리딘 디이소시아네이트, 메틸렌 디페닐 디이소시아네이트(MDI), 폴리머(또는 프리폴리머) 형태의 폴리이소시아네이트 화합물일 수 있다. The polyfunctional isocyanate compound may be a compound having 2 to 5 isocyanate groups per molecule, and may be an aromatic, aliphatic or alicyclic isocyanate compound, and may be used alone or in combination of two or more thereof. Specifically, hexamethylene diisocyanate, isophorone diisocyanate, methylene dicyclohexyl diisocyanate and cyclohexane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, tetramethylxylene diisocyanate, phenylene diisocyanate, tolidine diisocyanate, Methylene diphenyl diisocyanate (MDI), a polyisocyanate compound in the form of a polymer (or prepolymer).
폴리이소시아네이트로는 구체적으로 당업계에 공지되고 순수한 4,4'-MDI 및 4,4'-MDI, 2,4'-MDI 및 2,2'-MDI의 이성질체 혼합물을 포함할 수 있으며, 예컨대 헌츠만의 수프라섹(Suprasec)R MPR 및 1306을 들 수 있다. Polyisocyanates may include, in particular, isomeric mixtures of 4,4'-MDI and 4,4'-MDI, 2,4'-MDI and 2,2'-MDI, which are known in the art and are pure. Bayn Suprasec R MPR and 1306.
또한, 폴리이소시아네이트의 카르보디이미드 및/또는 우레탄 개질된 변형물도 가능하며, 당업계에 공지되고 상업적으로 이용가능한, 예컨대, 헌츠만의 수프라섹(Suprasec)R 2020을 들 수 있다. Carbodiimide and / or urethane modified modifications of the polyisocyanates are also possible and include those known in the art and commercially available, such as Huntsman's Suprasec R 2020.
또한, 대략 500 내지 5000의 중량평균 분자량을 갖는 폴리올로 반응시켜 생성된 폴리머(또는 프리폴리머) 형태의 폴리이소시아네이트도 사용 가능하다.It is also possible to use polyisocyanates in the form of polymers (or prepolymers) produced by reacting with polyols having a weight average molecular weight of approximately 500 to 5000.
또한, 폴리머 MDI도 사용 가능하며, 예시는 헌츠만의 수프라섹(Suprasec)R 2185, 수프라섹(Suprasec)R 5025 및 수프라섹(Suprasec)R DNR 등을 들 수 있고, 프리폴리머 폴리이소시아네이트는 헌츠만의 수프라섹(Suprasec)R 2054, 수프라섹(Suprasec)R 2061 등을 들 수 있다.Polymer MDIs can also be used, examples include Huntsman's Suprasec R 2185, Suprasec R 5025 and Suprasec R DNR, and the prepolymer polyisocyanate is Huntsman's. Suprasec R 2054, Suprasec R 2061, and the like.
본 발명의 다른 일형태에 따른 인계 에폭시 조성물은 상기 화학식 1로 표시되는 인계 에폭시 화합물 및 경화제를 포함한다. 또한 필요에 따라 이외의 에폭시 화합물 및 경화촉진제, 희석제, 충진제, 기타 첨가제 등 그 밖의 성분을 더 포함하여 적절히 배합할 수 있다. 본 발명에 따른 인계 에폭시 조성물은 내열성, 유전 특성이 우수하고 용도에 따라 요구되는 물성을 충족하는 경화물을 제공한다. The phosphorus epoxy composition which concerns on another form of this invention contains the phosphorus epoxy compound represented by the said Formula (1), and a hardening | curing agent. Moreover, if necessary, other components, such as an epoxy compound, a hardening accelerator, a diluent, a filler, and other additives, can be further included suitably. Phosphorus-based epoxy composition according to the present invention provides a cured product that is excellent in heat resistance and dielectric properties and meets the required physical properties according to the use.
상기 경화제는 에폭시 조성물의 경화시 가교 반응에 기여하는 물질로서, 때에 따라 경화 촉진제라고 불리는 것이라도 상기 가교 반응에 기여하는 물질이라면 경화제로 간주할 수 있다. 상기 인계 에폭시 화합물과 상기 경화제의 당량비는 1 : 0.6 내지 1.5 이다. 경화제가 인계 에폭시 화합물 1 당량에 대하여 0.6 당량 미만으로 포함되는 경우 미경화가 발생되거나 경화속도가 매우 늦는 문제점이 발생될 수 있고, 1.5 당량 초과하여 포함되는 경우 경화제가 매우 과량 투입에 따라 잔존 경화제로 인하여 tacky의 발생과 레올로지 컨트롤의 문제점이 있다.The curing agent is a substance that contributes to the crosslinking reaction upon curing of the epoxy composition, and may be regarded as a curing agent as long as it is a substance that contributes to the crosslinking reaction, even if called a curing accelerator. The equivalent ratio of the phosphorus epoxy compound and the curing agent is 1: 0.6 to 1.5. When the curing agent is contained in less than 0.6 equivalents to 1 equivalent of the phosphorus-based epoxy compound may cause uncured or very slow curing rate, and when included in excess of 1.5 equivalents, due to the remaining curing agent due to the excessive amount of the curing agent There are problems with tacky and rheological control.
상기 경화제는 아마이드계 경화제, 폴리아민계 경화제, 산무수물 경화제, 페놀노볼락형 경화제, 폴리메르캅탄 경화제, 제3아민 경화제 또는 이미다졸 경화제로 이루어진 군으로부터 적어도 하나 이상 선택된 것을 사용할 수 있다. 상기 페놀노볼락형 경화제는 페놀, 크레졸, 크실레놀, 레조치놀, 카테콜, 비스페놀A, 비스페놀 F, 비스페놀 S, 비스페놀 Z, 비스페놀 AD, 비페놀 등의 페놀류 및/또는 α-나프톨, β-나프톨, 디히드록시나프탈렌 등의 나프톨류, 안트라센 테르펜, 디사이클로펜타디엔류 등과 포름알데히드, 아세트 알데히드, 프리피온알데히드, 벤즈알데히드, 살리실알데히드 등의 알데히드기를 갖는 화합물을 산성촉매 하에서 축합 또는 공축합시켜 얻어지는 노볼락 수지 등이 포함된다.The curing agent may be at least one selected from the group consisting of an amide curing agent, a polyamine curing agent, an acid anhydride curing agent, a phenol novolak-type curing agent, a polymercaptan curing agent, a third amine curing agent or an imidazole curing agent. The phenol novolak-type curing agent is a phenol, such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, bisphenol Z, bisphenol AD, biphenol, and / or α-naphthol, β -Condensation or co-condensation of naphthols such as naphthol and dihydroxynaphthalene, anthracene terpenes and dicyclopentadienes, and compounds having an aldehyde group such as formaldehyde, acetaldehyde, prionaldehyde, benzaldehyde, salicylicaldehyde and the like under an acidic catalyst Novolak resin etc. obtained by making it cure are included.
또한 상기 인계 에폭시 조성물은 경화촉진제를 더 포함하며, 사용되기 적합한 경화촉진제로는 2-메틸 이미다졸(2-methyl Imidazole), 2-에틸-4-메틸 이미다졸(2-Ethyl-4-Methyl Imidazole), 1-벤질-2-메틸 이미다졸(1-Benzyl-2-Methyl Imidazole), 2-헵타데실 이미다졸(2-Heptadecyl Imidazole) 및 2-운데실 이미다졸(2-Undecyl Imidazole) 중에서 선택된 1종 이상을 함유한 이미다졸 화합물; 트리페닐포스페이트(Triphenylphosphate)를 함유한 유기화합물; 및 ETPPI(Ethyl Triphenyl Phosphonium Iodide) 등의 트리 알킬 화합물, 4-디메틸아미노피리딘(4-Dimethylamino Pyridine), 2-아미노 피리딘, 3-아미노 피리딘, 4-아미노 피리딘, 2,3-디아미노 피리딘, 2,5-디아미노 피리딘, 2,6-디아미노 피리딘, 2-아미노-6-메틸 피리딘, 3-아미노-6-이소프로필 피리딘, 2,2- 디피리딜 아민 및 4-피롤리디노 피리딘 중에서 선택된 1종 이상을 함유한 피리딘 화합물; 중에서 선택된 1종 이상을 포함하여 사용하는 것이 좋다. In addition, the phosphorus-based epoxy composition further comprises a curing accelerator, suitable curing accelerators to be used 2-methyl imidazole, 2-ethyl-4-methyl imidazole (2-Ethyl-4-Methyl Imidazole ), 1-benzyl-2-methyl imidazole, 1 selected from 2-heptadecyl imidazole, and 2-undecyl imidazole. Imidazole compounds containing more than one species; Organic compounds containing triphenylphosphate; And trialkyl compounds such as Ethyl Triphenyl Phosphonium Iodide (ETPPI), 4-dimethylamino pyridine, 2-amino pyridine, 3-amino pyridine, 4-amino pyridine, 2,3-diamino pyridine, 2 ,, 5-diamino pyridine, 2,6-diamino pyridine, 2-amino-6-methyl pyridine, 3-amino-6-isopropyl pyridine, 2,2-dipyridyl amine and 4-pyrrolidino pyridine Pyridine compounds containing at least one selected; It is good to use including 1 or more types selected from.
또한, 상기 인계 에폭시 조성물은 무기충전제를 더 포함할 수 있으며, 사용되기 적합한 무기충전제로는 실리카, 알루미나, 황산바륨, 탈크, 진흙, 운모가루, 수산화알루미늄, 수산화마그네슘, 탄산칼슘, 탄산마그네슘, 산화마그네슘, 질화 붕소, 붕산 알루미늄, 티탄산바륨, 티탄산칼슘, 티탄산마그네슘, 티탄산비스머스, 산화 티탄, 지르콘산바륨, 및 지르콘산칼슘 등을 사용할 수 있다. In addition, the phosphorus epoxy composition may further include an inorganic filler, and suitable inorganic fillers to be used include silica, alumina, barium sulfate, talc, mud, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, and oxides. Magnesium, boron nitride, aluminum borate, barium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like.
본 발명의 일 실시예에 따른 인계 에폭시 조성물의 전체 중량 대비 인(P) 함량은 2 내지 7 wt%이다. 2wt% 미만인 경우 난연 특성의 저하되거나 전혀 구현되지 못하는 문제가 있으며, 7 wt% 초과인 경우 내열 특성이 저하되며 경화물이 브리틀(brittle)하여 바스러지는 문제가 있다. Phosphorus (P) content relative to the total weight of the phosphorus-based epoxy composition according to an embodiment of the present invention is 2 to 7 wt%. If it is less than 2wt% there is a problem that the flame retardant properties are not reduced or not implemented at all, if it is more than 7wt% there is a problem that the heat resistance is lowered and the cured product is brittle (brittle) to collapse.
본 발명에 따른 인계 에폭시 조성물에 의한 경화물의 특성 평가를 행한 결과 내열성이 우수하며 저유전 특성을 가져 전자회로기판에 사용되는 동장적층판의 제조용 화합물 조성물이나 전자부품에 사용되는 봉지재, 성형재, 주형재, 접착제, 필름재, 전기 절연 도료용 재료 등으로서 유용하다.As a result of evaluating the properties of the cured product by the phosphorus-based epoxy composition according to the present invention, it has excellent heat resistance and has a low dielectric property, and thus, an encapsulant, a molding material, a mold used in the compound composition for manufacturing a copper clad laminated board used in an electronic circuit board or an electronic part. It is useful as an ash, an adhesive agent, a film material, a material for electrically insulating paints, etc.
일 실시예로서, 본 발명의 인계 에폭시 조성물 30 내지 70 중량%와 유리 섬유 30 내지 70 중량%를 함유하는 적층판 제조용 프리프레그를 제조한 다음, 이를 하나 이상의 라미네이트로 하고, 상기 라미네이트의 외부에 위치한 동박 외부층을 가열 가압에 의해 일체화시켜 인쇄회로기판용 적층판을 제조할 수 있다. In one embodiment, a prepreg for producing a laminate containing 30 to 70% by weight of the phosphorus-based epoxy composition of the present invention and 30 to 70% by weight of glass fibers is prepared, which is then used as one or more laminates, and copper foil located outside of the laminate. The outer layer may be integrated by heat and pressure to manufacture a laminate for a printed circuit board.
이하, 바람직한 실시예를 들어 본 발명을 더욱 상세하게 설명하지만 본 발명이 이에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to preferred examples, but the present invention is not limited thereto.
실시예 및 비교예Examples and Comparative Examples
(1) 실시예 1 내지 4 및 비교예 1 - 인계 에폭시 화합물의 합성(1) Examples 1 to 4 and Comparative Example 1-Synthesis of phosphorus epoxy compound
실시예 1Example 1
(2,5-Dihydroxyphenyl) diphenyl phosphine oxide 560중량부, Epichlorohydrin 1470 중량부 및 Isopropyl Alcohol(IPA) 700중량부를 교반장치, 온도계, 환류냉각기가 부착된 반응기에 투입하고 질소를 30분간 퍼지한 후 반응온도를 50℃로 승온하여 용해시켰다.560 parts by weight of (2,5-Dihydroxyphenyl) diphenyl phosphine oxide, 1470 parts by weight of Epichlorohydrin and 700 parts by weight of Isopropyl Alcohol (IPA) were added to a reactor equipped with a stirring device, a thermometer and a reflux condenser and purged with nitrogen for 30 minutes. Was dissolved by heating to 50 ° C.
용해가 완료된 후 NaOH 350 중량부를 서서히 투입하여 5시간 동안 반응 시켰다. 반응 종료 후 물 560 중량부를 이용하여 수세를 진행한 후 150℃까지 승온하여 잔존 에폭시 화합물을 제거한다. 150에서 천천히 Methyl Iso Butyl Ketone(MIBK) 2100 중량부를 투입하여 용해시킨 후 80℃에서 NaOH 70 중량부를 이용하여 재정제 작업을 1시간 실시하였다. 물 560중량부로 수세작업을 실시 후 160℃까지 진공탈기를 실시하여 에폭시당량 230의 노란색의 에폭시 화합물 플레이크 900중량부를 얻었다.After dissolution was completed, 350 parts by weight of NaOH was slowly added and reacted for 5 hours. After the completion of the reaction, the water was washed with 560 parts by weight of water, and then heated to 150 ° C. to remove the remaining epoxy compound. After slowly dissolving 2100 parts by weight of Methyl Iso Butyl Ketone (MIBK) at 150 and dissolving at 70 ° C. with NaOH at 80 ° C. for 1 hour. After washing with water with 560 parts by weight of water, vacuum degassing was carried out to 160 ° C to obtain 900 parts by weight of a yellow epoxy compound flake having an epoxy equivalent of 230.
실시예 2Example 2
(2,5-Dihydroxyphenyl) diphenyl phosphine oxide 750중량부, Epichlorohydrin 1,150 중량부 및 Isopropyl Alcohol(IPA) 500중량부를 교반장치, 온도계, 환류냉각기가 부착된 반응기에 투입하고 질소를 30분간 퍼지한 후 반응온도를 50℃로 승온하여 용해시켰다.750 parts by weight of (2,5-Dihydroxyphenyl) diphenyl phosphine oxide, 1,150 parts by weight of Epichlorohydrin, and 500 parts by weight of Isopropyl Alcohol (IPA) were added to a reactor equipped with a stirring device, a thermometer, and a reflux condenser. Was dissolved by heating to 50 ° C.
용해가 완료된 후 NaOH 400 중량부를 서서히 투입하여 5시간 동안 반응 시켰다. 반응 종료 후 물 700 중량부를 이용하여 수세를 진행한 후 150℃까지 승온하여 잔존 에폭시 화합물을 제거한다. 150℃에서 천천히 Methyl Iso Butyl Ketone(MIBK) 2500 중량부를 투입하여 용해시킨 후 80℃에서 NaOH 100 중량부를 이용하여 재정제 작업을 1시간 실시하였다. 물 700중량부로 수세작업을 실시 후 160℃까지 진공탈기를 실시하여 에폭시당량 240의 노란색의 에폭시 화합물 플레이크 750중량부를 얻었다.After dissolution was completed, 400 parts by weight of NaOH was slowly added and reacted for 5 hours. After completion of the reaction, water washing was performed using 700 parts by weight of water, and then the temperature was raised to 150 ° C. to remove the remaining epoxy compound. After slowly dissolving 2500 parts by weight of Methyl Iso Butyl Ketone (MIBK) at 150 ° C and dissolving the same, refining was performed using 100 parts by weight of NaOH at 80 ° C for 1 hour. After washing with water by 700 parts by weight of water, vacuum degassing was carried out to 160 ° C to obtain 750 parts by weight of a yellow epoxy compound flake having an epoxy equivalent of 240.
실시예 3Example 3
(2,5-Dihydroxyphenyl) diphenyl phosphine oxide 750중량부, Epichlorohydrin 750 중량부 및 Isopropyl Alcohol(IPA) 300중량부를 교반장치, 온도계, 환류냉각기가 부착된 반응기에 투입하고 질소를 30분간 퍼지한 후 반응온도를 50℃로 승온하여 용해시켰다.750 parts by weight of (2,5-Dihydroxyphenyl) diphenyl phosphine oxide, 750 parts by weight of Epichlorohydrin and 300 parts by weight of Isopropyl Alcohol (IPA) were added to a reactor equipped with a stirring device, a thermometer and a reflux condenser and purged with nitrogen for 30 minutes. Was dissolved by heating to 50 ° C.
용해가 완료된 후 NaOH 360 중량부를 서서히 투입하여 5시간 동안 반응 시켰다. 반응 종료 후 물 750 중량부를 이용하여 수세를 진행한 후 150℃까지 승온하여 잔존 에폭시 화합물을 제거한다. 150℃에서 천천히 Methyl Iso Butyl Ketone(MIBK) 2100 중량부를 투입하여 용해시킨 후 80℃에서 NaOH 90 중량부를 이용하여 재정제 작업을 1시간 실시하였다. 물 750중량부로 수세작업을 실시 후 160℃까지 진공탈기를 실시하여 에폭시당량 270의 노란색의 에폭시 화합물 플레이크 700중량부를 얻었다.After dissolution was complete, 360 parts by weight of NaOH was slowly added and reacted for 5 hours. After completion of the reaction, the water was washed with 750 parts by weight of water, and then heated to 150 ° C. to remove the remaining epoxy compound. After slowly dissolving 2100 parts by weight of Methyl Iso Butyl Ketone (MIBK) at 150 ° C, the refinement operation was performed for 1 hour using 90 parts by weight of NaOH at 80 ° C. After washing with water at 750 parts by weight of water, vacuum degassing was carried out to 160 ° C to obtain 700 parts by weight of a yellow epoxy compound flake having an epoxy equivalent of 270.
실시예 4Example 4
실시예 1에서 획득한 플레이크 900중량부를 교반장치, 온도계, 환류냉각기가 부착된 반응기에 투입하고 질소를 30분간 퍼지한 후 반응온도를 120℃로 승온한다.900 parts by weight of the flakes obtained in Example 1 were added to a reactor equipped with a stirring device, a thermometer and a reflux condenser, purged with nitrogen for 30 minutes, and the reaction temperature was raised to 120 ° C.
이미다졸 촉매 0.2중량부를 투입하여 150℃까지 빠르게 승온하고, 150℃부터 Methylene diphenyl diisocyanate(MDI)를 100중량부 서서히 투입한다. 약 4시간동안 150℃를 유지하며 반응하여 에폭시당량 350의 노란색 에폭시 화합물 플레이크 1,000중량부를 얻었다.0.2 parts by weight of imidazole catalyst was rapidly heated up to 150 ° C, and 100 parts by weight of Methylene diphenyl diisocyanate (MDI) was gradually added from 150 ° C. The reaction was carried out at 150 ° C. for about 4 hours to obtain 1,000 parts by weight of a yellow epoxy compound flake having an epoxy equivalent of 350.
비교예 1Comparative Example 1
Diglycidyl ether of Phenol Novolac Resin 700중량부, DOPO(3,4,5,6-Dibenzo-1,2-oxaphosphane-2-oxide) 185중량부를 교반장치, 온도계, 환류냉각기가 부착된 반응기에 투입하고 질소를 30분간 퍼지한 후 반응온도를 100℃로 승온하여 용해시켰다.700 parts by weight of Diglycidyl ether of Phenol Novolac Resin and 185 parts by weight of DOPO (3,4,5,6-Dibenzo-1,2-oxaphosphane-2-oxide) were added to a reactor equipped with a stirring device, a thermometer, and a reflux condenser. After purging for 30 minutes, the reaction temperature was raised to 100 ° C and dissolved.
용해가 완료된 후 ETPPI 0.02 중량부를 투입한 후 160℃로 승온하여 5시간동안 반응하여 에폭시당량 310인 무색의 에폭시 화합물 플레이크 880중량부를 얻었다.After dissolution was completed, 0.02 parts by weight of ETPPI was added, and the reaction mixture was heated at 160 ° C. for 5 hours to obtain 880 parts by weight of a colorless epoxy compound flake having an epoxy equivalent of 310.
(2) 실시예 5 내지 8 및 비교예 2 - 인계 에폭시 조성물의 제조(2) Examples 5 to 8 and Comparative Example 2-Preparation of Phosphorous Epoxy Composition
실시예 5Example 5
실시예 1에서 따른 인계 에폭시 화합물 100 중량부, 페놀 노볼락형 경화제 50 중량부, C11Z(10% in MeOH) 경화촉진제 2중량부로 배합하여 인계 에폭시 조성물을 제조하였다.A phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Example 1, 50 parts by weight of a phenol novolak-type curing agent, and 2 parts by weight of a C11Z (10% in MeOH) curing accelerator.
실시예 6Example 6
실시예 2에서 따른 인계 에폭시 화합물 100 중량부, 페놀 노볼락형 경화제 45 중량부, C11Z(10% in MeOH) 경화촉진제 3중량부로 배합하여 인계 에폭시 조성물을 제조하였다.A phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Example 2, 45 parts by weight of a phenol novolak type curing agent, and 3 parts by weight of a C11Z (10% in MeOH) curing accelerator.
실시예 7Example 7
실시예 3에서 따른 인계 에폭시 화합물 100 중량부, 페놀 노볼락형 경화제 40 중량부, C11Z(10% in MeOH) 경화촉진제 1중량부로 배합하여 인계 에폭시 조성물을 제조하였다.A phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Example 3, 40 parts by weight of a phenol novolak type curing agent, and 1 part by weight of a C11Z (10% in MeOH) curing accelerator.
실시예 8Example 8
실시예 4에서 따른 인계 에폭시 화합물 100 중량부, 페놀 노볼락형 경화제 30 중량부, C11Z(10% in MeOH) 경화촉진제 2중량부로 배합하여 인계 에폭시 조성물을 제조하였다.A phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Example 4, 30 parts by weight of a phenol novolak type curing agent, and 2 parts by weight of a C11Z (10% in MeOH) curing accelerator.
비교예 2Comparative Example 2
비교예 1에서 따른 인계 에폭시 화합물 100 중량부, 페놀 노볼락형 경화제 50 중량부, C11Z(10% in MeOH) 경화촉진제 2중량부로 배합하여 인계 에폭시 조성물을 제조하였다.A phosphorus epoxy composition was prepared by mixing 100 parts by weight of the phosphorus epoxy compound according to Comparative Example 1, 50 parts by weight of a phenol novolak type curing agent, and 2 parts by weight of a C11Z (10% in MeOH) curing accelerator.
(3) 실시예 9 내지 12 및 비교예 3 - 인계 에폭시 경화물의 제조(3) Examples 9 to 12 and Comparative Example 3-Preparation of Phosphorous Epoxy Cured Product
실시예 5 내지 8 및 비교예 2 에 따른 인계 에폭시 조성물을 각각 180℃ 오븐에서 B-stage까지 Precure를 실시한 후 고운 파우더를 제조하여 가로 세로 4cm, 높이 1 내지 2mm의 규격틀에 파우더를 5그람 계량하여 감압하에 히팅프레스에서 200℃로 2시간 경화하여 두께 1.5mm의 인계 에폭시 경화물을 제조하였다(실시예 9 내지 실시예 12 및 비교예 3).Precure the phosphorus-based epoxy compositions according to Examples 5 to 8 and Comparative Example 2 to B-stage in an oven at 180 ° C., respectively, to prepare fine powder, and weigh 5 grams of powder in a standard frame of 4 cm and 1 to 2 mm in height. And cured at 200 ° C. for 2 hours in a heating press under reduced pressure to prepare a phosphorous epoxy cured product having a thickness of 1.5 mm (Examples 9 to 12 and Comparative Example 3).
실험예Experimental Example
(1) 인 함량 측정(1) determination of phosphorus content
실시예 1 내지 8 및 비교예 1 내지 2에 의해 제조된 인계 에폭시 화합물에 대하여 인 함량을 측정하여 표 1에 나타내었다. The phosphorus content of the phosphorus epoxy compounds prepared in Examples 1 to 8 and Comparative Examples 1 and 2 was measured and shown in Table 1.
구분division 인 함량(wt%)Phosphorus content (wt%)
실시예 1Example 1 7.37.3
실시예 2Example 2 7.37.3
실시예 3Example 3 7.37.3
실시예 4Example 4 6.576.57
실시예 5Example 5 5.045.04
실시예 6Example 6 5.105.10
실시예 7Example 7 5.295.29
실시예 8Example 8 5.005.00
비교예 1Comparative Example 1 3.03.0
비교예 2Comparative Example 2 2.262.26
실시예 1 내지 3의 인계 에폭시 화합물의 인함량은 7 wt% 대로, 실시예 4의 변성된 인계 에폭시 화합물의 인함량은 6.57 wt%로, 비교예 1 보다 4% 이상 고 인함량을 가지며(변성시 3.5% 이상), 실시예 5 내지 8의 인계 에폭시 조성물의 인함량은 5 wt% 대로, 비교예 2에 비하여 고 인(P)함량을 갖는 것을 알 수 있다. Phosphorus content of the phosphorus-based epoxy compounds of Examples 1 to 3 is 7 wt%, phosphorus content of the modified phosphorus-based epoxy compound of Example 4 is 6.57 wt%, and has a phosphorus content of at least 4% higher than that of Comparative Example 1 (modified 3.5% or more), the phosphorus content of the phosphorus-based epoxy composition of Examples 5 to 8 is 5 wt%, it can be seen that it has a high phosphorus (P) content compared to Comparative Example 2.
(2) 내열 및 유전 특성 테스트(2) heat and dielectric properties test
실시예 9 내지 12 및 비교예 3에 의해 제조된 인계 에폭시 경화물에 대하여 Tg, Td, Dk, Df를 측정하고, 그 결과를 하기 표 2에 나타내었다. Tg는 시차열분석기(Differential Scanning Calorimetry, DSC, TA Instrument)를 이용하였으며, 유전상수(Dielectric Constant, Dk) 및 손실인자(Dissipation Factor, Df)는 JIS-C-6481 방법에 의해 Agilent E4991A RF Impedance/Material Analyzer를 이용하여 측정하였다. Tg, Td, Dk, and Df were measured for the phosphorus-based epoxy cured product prepared in Examples 9 to 12 and Comparative Example 3, and the results are shown in Table 2 below. Tg was used by differential scanning calorimetry (DSC, TA instrument), and dielectric constant (Dk) and loss factor (Ds) were Agilent E4991A RF Impedance / by the JIS-C-6481 method. Measurement was made using a material analyzer.
구분division Tg()Tg () Td(℃)(-5% Loss)Td (℃) (-5% Loss) Dk[1GHz]Dk [1 GHz] Df[1GHz]Df [1 GHz]
실시예 9Example 9 175.8175.8 401.7401.7 3.2773.277 0.01290.0129
실시예 10Example 10 180.0180.0 404.5404.5 3.2403.240 0.01260.0126
실시예 11Example 11 172.8172.8 397.8397.8 3.2003.200 0.01500.0150
실시예 12Example 12 171.8171.8 401.5401.5 3.1503.150 0.01200.0120
비교예 3Comparative Example 3 129.0129.0 378.9378.9 3.3303.330 0.02500.0250
상기 표 2를 통해 알 수 있듯이, 비교예의 경우 Tg가 130℃ 이하로서 열 안정성이 매우 떨어지는데 반하여, 본 발명에 따른 에폭시를 경화시킨 경우 유리전이온도(Tg)가 170 내지 180℃으로서 열 안정성이 뛰어난 것을 알 수 있다.As can be seen from Table 2, in the case of the comparative example Tg is less than 130 ℃ thermal stability is very low, when curing the epoxy according to the present invention glass transition temperature (Tg) is 170 to 180 ℃ excellent thermal stability It can be seen that.
또한 인쇄회로기판 등의 전기전자 부품의 구현에 있어서 절연체의 유전상수가 낮을수록 신호의 처리 속도 및 전송손실이 줄어드는데, 본 발명에 의한 인계 에폭시 경화물의 전기적 특성이 비교예에 비해 우수한 것을 알 수 있다. In addition, in the implementation of electrical and electronic components such as printed circuit boards, the lower the dielectric constant of the insulator, the lower the processing speed and transmission loss of the signal. have.
전술한 각 실시예에서 예시된 특징, 구조, 효과 등은 실시예들이 속하는 분야의 통상의 지식을 가지는 자에 의하여 다른 실시예들에 대해서도 조합 또는 변형되어 실시 가능하다. 따라서 이러한 조합과 변형에 관계된 내용들은 본 발명의 범위에 포함되는 것으로 해석되어야 할 것이다.Features, structures, effects, and the like illustrated in the above-described embodiments may be combined or modified with respect to other embodiments by those skilled in the art to which the embodiments belong. Therefore, contents related to such combinations and modifications should be construed as being included in the scope of the present invention.

Claims (20)

  1. 인계 에폭시 화합물 및 경화제를 포함하는 인계 에폭시 조성물로서,As a phosphorus epoxy composition containing a phosphorus epoxy compound and a hardening | curing agent,
    상기 인계 에폭시 화합물은 하기 화학식 1로 표현되는 인계 에폭시 화합물인 인계 에폭시 조성물.The phosphorus epoxy compound is a phosphorus epoxy composition of the phosphorus epoxy compound represented by the following formula (1).
    [화학식 1][Formula 1]
    Figure PCTKR2016001813-appb-I000013
    Figure PCTKR2016001813-appb-I000013
    (m은 0 내지 3이며, n은 0 내지 5이며,(m is 0-3, n is 0-5,
    R1, R2는 각각 독립적으로, 존재하지 않거나 C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며,R 1 , R 2 are each independently, absent or an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) in the structure May exist,
    R3, R4는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며,R 3 and R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure. And
    R5, R6는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며,R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) may be present in the structure. And
    R7는 각각 독립적으로 수소, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며,Each R 7 is independently hydrogen, an aliphatic hydrocarbon group of C 1 -C 20 , or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure,
    R8은 각각 독립적으로 C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기 또는 이들의 조합이거나, 중량평균분자량 500 내지 5000의 고분자(또는 프리폴리머)이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있다.)R 8 is each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, or a polymer (or prepolymer) having a weight average molecular weight of 500 to 5000, and a hetero element ( O, S, or N) may be present.)
  2. 제1항에 있어서,The method of claim 1,
    상기 인계 에폭시 화합물은 하기 화학식 2로 표현되는 인계 에폭시 화합물인 인계 에폭시 조성물.The phosphorus epoxy compound is a phosphorus epoxy composition of the phosphorus epoxy compound represented by the following formula (2).
    [화학식 2][Formula 2]
    Figure PCTKR2016001813-appb-I000014
    Figure PCTKR2016001813-appb-I000014
    (n은 0 내지 5이다.) (n is 0 to 5)
  3. 제1항에 있어서,The method of claim 1,
    상기 인계 에폭시 화합물 중 상기 n이 0인 인계 에폭시 화합물의 함량이 30 내지 99wt%인 인계 에폭시 조성물.Phosphorus-based epoxy composition having a content of the phosphorus-based epoxy compound of n is 0 to 99wt% of the phosphorus-based epoxy compound.
  4. 제1항에 있어서,The method of claim 1,
    상기 인계 에폭시 화합물과 상기 경화제의 당량비는 1 : 0.6 내지 1.5로 포함되는 인계 에폭시 조성물.Phosphorus-based epoxy composition comprising the equivalent ratio of the phosphorus-based epoxy compound and the curing agent is 1: 0.6 to 1.5.
  5. 제1항에 있어서,The method of claim 1,
    상기 경화제는 아마이드계 경화제, 폴리아민계 경화제, 산무수물 경화제, 페놀노볼락형 경화제, 폴리메르캅탄 경화제, 제3아민 경화제 또는 이미다졸 경화제로 이루어진 군으로부터 적어도 하나 이상 선택되는 인계 에폭시 조성물. The curing agent is at least one selected from the group consisting of amide-based curing agent, polyamine-based curing agent, acid anhydride curing agent, phenol novolak-type curing agent, polymercaptan curing agent, tertiary amine curing agent or imidazole curing agent.
  6. 제1항에 있어서,The method of claim 1,
    상기 인계 에폭시 조성물은 경화촉진제를 더 포함하며,The phosphorous epoxy composition further includes a curing accelerator,
    상기 경화촉진제는 2-메틸 이미다졸(2-methyl Imidazole), 2-에틸-4-메틸 이미다졸(2-Ethyl-4-Methyl Imidazole), 1-벤질-2-메틸 이미다졸(1-Benzyl-2-Methyl Imidazole), 2-헵타데실 이미다졸(2-Heptadecyl Imidazole) 및 2-운데실 이미다졸(2-Undecyl Imidazole) 중에서 선택된 1종 이상을 함유한 이미다졸 화합물;The curing accelerator is 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 1-benzyl-2-methyl imidazole (1-benzyl- Imidazole compounds containing at least one selected from 2-Methyl Imidazole), 2-Heptadecyl Imidazole and 2-Undecyl Imidazole;
    트리페닐포스페이트(Triphenylphosphate)를 함유한 유기화합물; 및Organic compounds containing triphenylphosphate; And
    ETPPI(Ethyl Triphenyl Phosphonium Iodide) 등의 트리 알킬 화합물, 4-디메틸아미노피리딘(4-Dimethylamino Pyridine), 2-아미노 피리딘, 3-아미노 피리딘, 4-아미노 피리딘, 2,3-디아미노 피리딘, 2,5-디아미노 피리딘, 2,6-디아미노 피리딘, 2-아미노-6-메틸 피리딘, 3-아미노-6-이소프로필 피리딘, 2,2- 디피리딜 아민 및 4-피롤리디노 피리딘 중에서 선택된 1종 이상을 함유한 피리딘 화합물; 중에서 선택된 1종 이상을 포함하는 인계 에폭시 조성물.Trialkyl compounds such as ETPyl (Ethyl Triphenyl Phosphonium Iodide), 4-dimethylamino pyridine, 2-amino pyridine, 3-amino pyridine, 4-amino pyridine, 2,3-diamino pyridine, 2, 5-diamino pyridine, 2,6-diamino pyridine, 2-amino-6-methyl pyridine, 3-amino-6-isopropyl pyridine, 2,2-dipyridyl amine and 4-pyrrolidino pyridine Pyridine compounds containing at least one kind; Phosphorus-based epoxy composition comprising at least one selected from.
  7. 제1항에 있어서,The method of claim 1,
    상기 인계 에폭시 조성물의 전체 중량 대비 인(P) 함량은 2 내지 7 중량%인 인계 에폭시 조성물.Phosphorus (P) content relative to the total weight of the phosphorus-based epoxy composition is 2 to 7% by weight phosphorus-based epoxy composition.
  8. 제1항에 있어서,The method of claim 1,
    상기 인계 에폭시 조성물로부터 얻어지는 경화물의 유리 전이 온도(Tg)가 150 내지 230℃ 인 것을 특징으로 하는 인계 에폭시 조성물. The glass transition temperature (Tg) of the hardened | cured material obtained from the said phosphorus epoxy composition is 150-230 degreeC, The phosphorus epoxy composition characterized by the above-mentioned.
  9. 제1항에 있어서,The method of claim 1,
    상기 인계 에폭시 조성물로부터 얻어지는 경화물의 유전상수(Dk)은 4.2 이하인 것을 특징으로 하는 인계 에폭시 조성물. The dielectric constant (D k ) of the cured product obtained from the phosphorus-based epoxy composition is 4.2 or less.
  10. 제1항에 있어서,The method of claim 1,
    상기 인계 에폭시 조성물로부터 얻어지는 경화물의 손실인자(Df)는 0.020 이하인 것을 특징으로 하는 인계 에폭시 조성물. The loss factor (D f ) of the hardened | cured material obtained from the said phosphorus epoxy composition is 0.020 or less, The phosphorus epoxy composition characterized by the above-mentioned.
  11. 제1항에 있어서,The method of claim 1,
    상기 인계 에폭시 화합물은 하기 화학식 5로 표현되는 인계 에폭시 화합물인 인계 에폭시 조성물.The phosphorus epoxy compound is a phosphorus epoxy composition of the phosphorus epoxy compound represented by the formula (5).
    [화학식 5][Formula 5]
    Figure PCTKR2016001813-appb-I000015
    Figure PCTKR2016001813-appb-I000015
    (n, m, R8의 정의는 상기 화학식 1과 동일하다)(n, m, R 8 is the same as defined in Formula 1)
  12. 하기 화학식 1로 표시되는 인계 에폭시 화합물.Phosphorus-based epoxy compound represented by the following formula (1).
    [화학식 1][Formula 1]
    Figure PCTKR2016001813-appb-I000016
    Figure PCTKR2016001813-appb-I000016
    (m은 0 내지 3이며, n은 0 내지 5이며,(m is 0-3, n is 0-5,
    R1, R2는 각각 독립적으로, 존재하지 않거나 C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며,R 1 , R 2 are each independently, absent or an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) in the structure May exist,
    R3, R4는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며,R 3 and R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure. And
    R5, R6는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며,R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) may be present in the structure. And
    R7는 각각 독립적으로 수소, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며,Each R 7 is independently hydrogen, an aliphatic hydrocarbon group of C 1 -C 20 , or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure,
    R8은 각각 독립적으로 C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기 또는 이들의 조합이거나, 중량평균분자량 500 내지 5000의 고분자(또는 프리폴리머)이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있다.)R 8 is each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, or a polymer (or prepolymer) having a weight average molecular weight of 500 to 5000, and a hetero element ( O, S, or N) may be present.)
  13. 제12항에 있어서,The method of claim 12,
    하기의 화학식 2로 표현되는 인계 에폭시 화합물.Phosphorus-based epoxy compound represented by the following formula (2).
    [화학식 2][Formula 2]
    Figure PCTKR2016001813-appb-I000017
    Figure PCTKR2016001813-appb-I000017
    (n은 0 내지 5이다.)(n is 0 to 5)
  14. 제12항에 있어서,The method of claim 12,
    하기의 화학식 5로 표현되는 인계 에폭시 화합물.Phosphorus-based epoxy compound represented by the following formula (5).
    [화학식 5][Formula 5]
    Figure PCTKR2016001813-appb-I000018
    Figure PCTKR2016001813-appb-I000018
    (n, m, R8의 정의는 상기 화학식 1과 동일하다)(n, m, R 8 is the same as defined in Formula 1)
  15. 제12항에 있어서, The method of claim 12,
    상기 인계 에폭시 화합물의 전체 중량 대비 인(P) 함량은 6 내지 8 중량%인 인계 에폭시 화합물.Phosphorus (P) content relative to the total weight of the phosphorus-based epoxy compound is 6 to 8% by weight phosphorus-based epoxy compound.
  16. 제12항에 있어서, The method of claim 12,
    상기 인계 에폭시 화합물은 인계 히드록시 화합물 및 에폭시 화합물을 알칼리 촉매 하에서 반응시켜 제조되는 것을 특징으로 하는 인계 에폭시 화합물.The phosphorus epoxy compound is produced by reacting a phosphorus hydroxy compound and an epoxy compound under an alkali catalyst.
  17. 하기 화학식 3으로 표시되는 인계 히드록시 화합물, 하기 화학식 4-1과 하기 화학식 4-2로 표시되는 에폭시 화합물 중 선택되는 적어도 하나 이상의 에폭시 화합물, 및 제1 용매를 포함하는 반응 물질들을 반응기에 투입하여 반응 혼합물을 얻는 반응 혼합물 준비단계; 및A reaction material comprising a phosphorus hydroxy compound represented by the following Chemical Formula 3, at least one epoxy compound selected from the epoxy compounds represented by the following Chemical Formula 4-1 and the following Chemical Formula 4-2, and a first solvent is added to the reactor. Preparing a reaction mixture to obtain a reaction mixture; And
    상기 반응 혼합물을 반응시켜 인이 함유된 에폭시 화합물을 얻는 단계;를 포함하는 인계 에폭시 화합물 제조방법.Reacting the reaction mixture to obtain an epoxy compound containing phosphorus; Phosphorus-based epoxy compound manufacturing method comprising a.
    [화학식 3][Formula 3]
    Figure PCTKR2016001813-appb-I000019
    Figure PCTKR2016001813-appb-I000019
    [화학식 4-1][Formula 4-1]
    Figure PCTKR2016001813-appb-I000020
    Figure PCTKR2016001813-appb-I000020
    [화학식 4-2][Formula 4-2]
    Figure PCTKR2016001813-appb-I000021
    Figure PCTKR2016001813-appb-I000021
    (R1, R2는 각각 독립적으로, 존재하지 않거나 C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며,(R 1 , R 2 are each independently, absent or a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group or a combination thereof and heteroatoms (O, S, or N in the structure) ) May exist,
    R3, R4는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며,R 3 and R 4 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 , or a combination thereof, and a hetero element (O, S, or N) may be present in the structure. And
    R5, R6는 각각 독립적으로, C1-C20의 지방족 탄화수소기 또는 C6-C30의 방향족 탄화수소기이거나 이들의 조합이며, 구조 내에 헤테로 원소(O, S, 또는 N)가 존재할 수 있으며,R 5 and R 6 are each independently an aliphatic hydrocarbon group of C 1 -C 20 or an aromatic hydrocarbon group of C 6 -C 30 or a combination thereof, and hetero elements (O, S, or N) may be present in the structure. And
    X는 할로겐기, -OTs(O-Tosyl), -OMs(O-Mesyl)이다.)X is a halogen group, -OTs (O-Tosyl), -OMs (O-Mesyl).)
  18. 제17항에 있어서,The method of claim 17,
    상기 반응 혼합물 준비단계는, The reaction mixture preparation step,
    상기 제1 용매 100 중량부에 대하여, 상기 화학식 3으로 표시되는 인계 히드록시 화합물이 100 내지 180 중량부, 상기 화학식 4-1과 상기 화학식 4-2로 표시되는 에폭시 화합물이 210 내지 290 중량부로 혼합되는 것을 특징으로 하는 인계 에폭시 화합물 제조방법.100 to 180 parts by weight of the phosphorus hydroxy compound represented by Formula 3, and 210 to 290 parts by weight of the epoxy compound represented by Formula 4-1 and Formula 4-2, based on 100 parts by weight of the first solvent Phosphorus-based epoxy compound production method characterized in that.
  19. 제17항에 있어서,The method of claim 17,
    상기 반응 혼합물을 반응시켜 인이 함유된 에폭시 화합물을 얻는 단계 이후에, 상기 얻어진 에폭시 화합물의 전부 또는 일부를 다관능 이소시아네이트 화합물로 변성시키는 단계를 더 포함하는 것을 특징으로 하는 인계 에폭시 화합물 제조방법.And after the step of reacting the reaction mixture to obtain an epoxy compound containing phosphorus, modifying all or part of the obtained epoxy compound into a polyfunctional isocyanate compound.
  20. 제1항의 인계 에폭시 조성물을 포함하는 것을 특징으로 하는 적층판.A laminate comprising the phosphorus-based epoxy composition of claim 1.
PCT/KR2016/001813 2015-03-05 2016-02-24 Phosphorus-based epoxy compound, preparation method therefor, and epoxy composition containing same WO2016140459A1 (en)

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