KR101813527B1 - Phosphorus epoxy compound and method for preparing the same, epoxy composition comprising the same - Google Patents
Phosphorus epoxy compound and method for preparing the same, epoxy composition comprising the same Download PDFInfo
- Publication number
- KR101813527B1 KR101813527B1 KR1020150031200A KR20150031200A KR101813527B1 KR 101813527 B1 KR101813527 B1 KR 101813527B1 KR 1020150031200 A KR1020150031200 A KR 1020150031200A KR 20150031200 A KR20150031200 A KR 20150031200A KR 101813527 B1 KR101813527 B1 KR 101813527B1
- Authority
- KR
- South Korea
- Prior art keywords
- phosphorus
- based epoxy
- curing agent
- epoxy compound
- group
- Prior art date
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N c1ccccc1 Chemical compound c1ccccc1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
Classifications
-
- 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
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Epoxy Resins (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
Abstract
The present invention provides a novel structure of a phosphorus-based epoxy compound having a high heat resistance and low dielectric constant of a phosphorous (P) content, and a method of manufacturing a phosphorus-based epoxy resin by introducing an epoxy group into a phosphorus- P) content, and to provide a phosphorus-based epoxy composition containing the phosphorus-based epoxy composition.
Description
The present invention relates to a phosphorus-based epoxy compound, a method for producing the phosphorus-based epoxy compound, and a phosphorus-based epoxy composition containing the same. More particularly, the present invention relates to a phosphorus-based epoxy compound having a high phosphorus (P) content and high heat resistance and low dielectric properties, a process for producing the phosphorus-based epoxy compound, and an epoxy composition containing the same.
In general, a printed circuit board (PCB) is used to drive electronic products such as a computer, a camera, and a television. A printed circuit board is a circuit connection 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 parts.
In recent years, there has been a demand for high performance such as flame retardancy, heat resistance, moisture resistance, efficiency, and thermal conductivity of printed circuit boards in accordance with the trend of short and light electronic devices and environmentally friendly. CCL, Flexible Copper Clad Laminate (FCCL), and Metal Copper Clad Laminate (MCCL).
The copper clad laminate (CCL) is a laminated board obtained by heating and pressing multiple sheets of a sheet, which is a raw material of a printed circuit board and a compound of which is compounded with an insulating material such as paper or glass, as a laminate, and a copper foil is affixed on one side or both sides of the laminate , There has been a growing demand for lead-free insulating materials used in recent years in accordance with environmental regulations. As a result, there has been a demand for lead-free copper-clad laminated sheets requiring high- CCL) has been growing in recent years.
Copper clad laminates (CCL) are classified into glass-epoxy laminate for epoxy resin and glass-epoxy laminate for copper foil, paper-phenol copper clad laminate for mainly single-sided PCB, A high-frequency copper-clad laminate made of a material capable of responding to high-speed signal transmission, and a copper-clad laminate for a flexible printed circuit board (FPCB).
Epoxy compositions are widely used for electric and electronic parts due to their excellent properties, but there are many examples in which flame retardancy is imparted to ensure safety against fire. Conventionally, halogenated epoxy compounds such as brominated epoxy are generally used as the flame retardancy of the epoxy composition. The halogenated epoxy compound has excellent flame retardancy, but it has been pointed out that environmental problems such as generation of harmful halogen compounds such as hydrogen halide, polybrominated dibenzodioxins and furans by thermal decomposition are pointed out. For this reason, a phosphorus (P) compound has been studied as a flame retardant instead of a bromine-containing flame retardant.
However, the low phosphorus content of the conventional phosphorus (P) epoxy is a major impediment to achieving halogen-free and flame retardant UL-94 grade V-0, and the addition of additional flame retardant additive or phosphorus (P) Use has been added to affect physical, mechanical, and electrical properties.
In addition, conventional phosphorus (P) type epoxies have low heat resistance, which can be evaluated as a glass transition temperature (Tg) because of low crosslinking density, and secondary structure of secondary alcohol is additionally formed, There is a problem in that it is necessary to use other raw materials for use in the CCL.
In order to provide a phosphorus-based epoxy compound, DOPO (9,10-Dihydro-9-Oxa-10-Phosphaphenantrene-10-Oxide) or DOPO- HQ (10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phospha-phenantbrene-10-oxide) by indirect methods. However, (P) content is limited to the latter half of 2 wt% to 3 wt%, and there is a problem that excessive introduction of a phosphorus compound for the content of phosphorus is more than 5 wt% A phosphorus-based epoxy compound having a high heat resistance and low dielectric constant of phosphorus (P) content, a process for producing the phosphorus-based epoxy compound, and an epoxy composition containing the same.
The present invention provides a phosphorus-based epoxy composition comprising a phosphorus-based epoxy compound and a curing agent, wherein the phosphorus-based epoxy compound is a phosphorus-based epoxy compound represented by the following formula (1).
[Chemical Formula 1]
(wherein n is from 0 to 5 and R 1 and 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, (Selected from O, S, and N) and R 3 and R 4 are each independently a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group, or combinations thereof, R 5 and R 6 are each independently a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group, or may contain one or more heteroatoms selected from O, S, and N, And hetero atoms (selected from O, S and N) may be present in the structure, and R 7 is hydrogen, a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group, And a heteroatom (selected from O, S, and N) It can be.)
The present invention also provides a phosphorus-based epoxy composition wherein the phosphorus-based epoxy compound is a phosphorus-based epoxy compound represented by the following general formula (2).
(2)
(n is 0 to 5).
The present invention also provides a phosphorus-based epoxy composition wherein the content of the phosphorus-based epoxy compound in which n is 0 in the phosphorus-based epoxy compound is 30 to 99 wt%.
The present invention also provides a phosphorus-based epoxy composition comprising the phosphorus-based epoxy compound and the curing agent in an equivalent ratio of 1: 0.6 to 1.5.
The present invention also relates to a phosphorus-based epoxy composition wherein at least one selected from the group consisting of an amide type curing agent, a polyamine type curing agent, an acid anhydride curing agent, a phenol novolak type curing agent, a polymercaptan curing agent, a tertiary amine curing agent or an imidazole curing agent .
The present invention also relates to the aforementioned phosphorus-based epoxy composition further comprising a curing accelerator, wherein the curing accelerator is 2-methyl imidazole, 2-ethyl-4-methyl imidazole 1) selected from 1-benzyl-2-methyl imidazole, 2-heptadecyl imidazole and 2-undecyl imidazole. Imidazole compounds containing more than one species; Organic compounds containing triphenylphosphate; ETPPI (Ethyl Triphenyl Phosphonium Iodide); And 4-dimethylamino pyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,6-diamino Pyridine compounds containing at least one member selected from the group consisting of pyridine, 2-amino-6-methylpyridine, 3-amino-6-isopropylpyridine, 2,2-dipyridylamine and 4-pyrrolidinopyridine; ≪ / RTI > by weight based on the total weight of the composition.
The present invention also provides a phosphorus-based epoxy composition wherein the phosphorus (P) content relative to the total weight of the phosphorus-based epoxy composition is 2 to 7 wt%.
The present invention also provides a phosphorus-based epoxy composition characterized in that the cured product obtained from the phosphorus-based epoxy composition has a glass transition temperature (Tg) of 150 to 230 ° C.
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 present invention also provides a phosphorus-based epoxy compound represented by the following formula (1).
[Chemical Formula 1]
(wherein n is from 0 to 5 and R 1 and 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, (Selected from O, S, and N) and R 3 and R 4 are each independently a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group, or combinations thereof, R 5 and R 6 are each independently a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group, or may contain one or more heteroatoms selected from O, S, and N, And a heteroatom (selected from O, S, and N) may be present in the structure.
The present invention also provides a phosphorus-based epoxy compound represented by the following formula (2).
(2)
(n is 0 to 5).
Also, the present invention provides a phosphorus-based epoxy compound having a phosphorus (P) content of 6 to 8 wt% based on the total weight of the phosphorus-based epoxy compound.
The present invention also provides a phosphorus-based epoxy compound, which is produced by reacting a phosphorus-based hydroxy compound and an epoxy compound under an alkaline catalyst.
The present invention also provides a process for preparing a reaction product comprising a phosphorus-based hydroxy compound represented by the following formula (3), at least one epoxy compound selected from the following formula (4-1) and an epoxy compound represented by the following formula (4-2) A reaction mixture preparation step of charging the reaction mixture to obtain a reaction mixture; And reacting the reaction mixture to obtain an epoxy compound containing phosphorus.
(3)
[Formula 4-1]
[Formula 4-2]
(Wherein R 1 and 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 contain heteroatoms (O, S, and N And R 3 and R 4 are each independently a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group or a combination thereof and may contain a heteroatom (O, S, and N, and R 5 and R 6 are each independently a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group or a combination thereof, An element (selected from O, S and N) may be present and X is a halogen group, -OTs (O-Tosyl) or -OMs (O-Mesyl).
In the present invention, the reaction mixture preparation step may further comprise: 100 to 180 parts by weight of the phosphorus-containing hydroxy compound represented by Formula 3, 100 parts by weight of the first solvent, Wherein the epoxy compound to be displayed is mixed at 210 to 290 parts by weight.
The present invention also provides a laminate comprising the phosphorus-based epoxy composition.
The present invention relates to a novel phosphorus (P) content epoxy compound having a high heat resistance and low dielectric constant, which can achieve flame retardant UL-94 rating V-0 without containing halogen, It is possible to provide a phosphorus-based epoxy compound which does not require the use of additives and does not deteriorate physical, mechanical and electrical properties, and which is excellent in reliability, a method for producing the same, and a phosphorus-based epoxy composition containing the same.
Before describing the present invention in detail, it is to be 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 defined solely by 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 stated.
Throughout this specification and claims, the word "comprise", "comprises", "comprising" means including a stated article, step or group of articles, and steps, , Step, or group of objects, or a group of steps.
In addition, "C 1", "C 2", etc., for example, "C 1 -C 10 alkylene group" as meaning the number of carbon atoms refers to an alkylene group having a carbon number of 1-10.
On the contrary, the various embodiments of the present invention can be combined with any other embodiments as long as there is no clear counterpoint. Any feature that is specifically or advantageously indicated as being advantageous may be combined with any other feature or feature that is indicated as being preferred or advantageous. Hereinafter, embodiments of the present invention and effects thereof will be described with reference to the accompanying drawings.
The present invention provides a phosphorus-based epoxy compound represented by the following formula (1) as a phosphorus (P) phosphorus epoxy compound having a novel structure and high heat resistance and low dielectric constant.
[Chemical Formula 1]
n is 0-5. Also, the content of phosphorus-based epoxy compound having n = 0 in the phosphorus-based epoxy compound is 30 to 99 wt%. When the content of the phosphorus-based epoxy compound of n = 0 is less than 30 wt%, the curing rate is slow or uncured. When the content is more than 99 wt%, the mechanical strength may be lowered.
R 1 and 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 may contain a heteroatom (O, S, and N Selected) may be present.
R 3 and R 4 are each independently a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group or a combination thereof and wherein a heteroatom (selected from O, S, and N) Can exist. It is preferably a C 1 -C 20 aliphatic hydrocarbon group. More preferably a C 1 -C 10 alkylene group (-C n H 2n -). For example, a methylene group (-CH 2 -) or an ethylene group (-CH 2 CH 2 -).
R 5 and R 6 are each independently a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group or a combination thereof and the heteroatom (selected from O, S, and N) Can exist. It is preferably a C 6 -C 30 aromatic hydrocarbon group. More preferably, for example, an aryl group (Ar-R) containing a phenyl group, an anthracene group, an anthryl group, a phenanthryl group, a biphenyl group, ).
R 7 is independently hydrogen, a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group, or a combination thereof, wherein heteroatoms (selected from O, S, and N) have. It is preferably hydrogen.
The phosphorus-based epoxy compound, which is an embodiment of the present invention, may be represented by the following formula (2). Based epoxy compound represented by the formula (1), phosphorus based epoxy compounds 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) .
(2)
The phosphorus (P) content of the phosphorus-based epoxy compound according to the present invention is 5 to 10 wt%, more preferably 6 to 8 wt%, based on the total weight of the compound. When phosphorus (P) is contained in an amount of less than 5% by weight, it acts as a major obstacle to achieving flame retardant UL-94 rating V-0 in halogen free formulation, so that the use of additional flame retardant additive or phosphorus- Mechanical and electrical properties. When phosphorus (P) is contained in an amount exceeding 10% by weight, the synthesis itself is not easy due to the molecular structure, and even if synthesis is possible using a special phosphorus compound, , There is a problem that the overall heat resistance is lowered sharply. Therefore, it is preferable to contain phosphorus within the above range.
According to the phosphorus-based epoxy compound according to the present invention, the dielectric loss of high heat resistance is extremely low. The phosphorus-based epoxy compound according to the present invention has a phosphorus (P) content of 5 to 10 wt%, so that it is unnecessary to use an additional flame-retardant additive or phosphorus-containing curing agent for achieving flame retardant UL-94 Grade V-0, Mechanical, and electrical properties, and allows free formulations, thereby enhancing the possibility of compounding compositions that impart desired physical properties to other epoxy resins, curing agents, and the like. In addition, it has a high heat resistance, low dielectric property and low softening point due to the content of P (P) and functional groups in the structure, and is particularly suitable for use as a material of a laminated plate used for printed circuit boards. It is also useful as a material.
In another aspect of the present invention, the phosphorus-based epoxy compound is a phosphorus-based epoxy compound represented by the following formula (3), and an epoxy compound represented by the following formula (4-1) And at least one epoxy compound is dissolved in an organic solvent to obtain a phosphorus epoxy compound having a high heat resistance and low dielectric constant.
(3)
[Formula 4-1]
[Formula 4-2]
R 1 and 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 may contain a heteroatom (O, S, and N Selected) may be present. Preferably, it is, for example, a methylene group (-CH 2 -) or an ethylene group (-CH 2 CH 2 -). More preferably, it is not present.
R 3 and R 4 are each independently a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group or a combination thereof and wherein a heteroatom (selected from O, S, and N) Can exist. It is preferably a C 1 -C 20 aliphatic hydrocarbon group. More preferably a C 1 -C 10 alkylene group (-C n H 2n -). For example, a methylene group (-CH 2 -) or an ethylene group (-CH 2 CH 2 -).
R 5 and R 6 are each independently a C 1 -C 20 aliphatic hydrocarbon group or a C 6 -C 30 aromatic hydrocarbon group or a combination thereof and the heteroatom (selected from O, S, and N) Can exist. It is preferably a C 6 -C 30 aromatic hydrocarbon group. More preferably, for example, an aryl group (Ar-R) containing a phenyl group, an anthracene group, an anthryl group, a phenanthryl group, a biphenyl group, ).
X can be a good leaving group, for example a halogen group, -OTs (O-Tosyl), or -OMs (O-Mesyl). It is preferably a chlorine group (-Cl) or a bromine group (-Br).
The phosphorus-based epoxy compound according to the present invention may be prepared by reacting a phosphorus-based hydroxy compound represented by the formula (3) with at least one epoxy compound selected from the epoxy compounds represented by the formulas (4-1) and (4-2) As a method of reacting a mixed reaction mixture, the epoxy compound reacts with the hydroxy group (-OH) of the phosphorus-containing hydroxy compound to form a phosphorus-based epoxy compound represented by the formula (1).
The reaction mixture is prepared by mixing 80 to 250 parts by weight of the phosphorus-containing hydroxy compound represented by Formula 3 with respect to 100 parts by weight of the first solvent, and mixing at least one of the epoxy compounds represented by Formula 4-1 and Formula 4-2 And the epoxy compound is mixed at 210 to 290 parts by weight. More preferably, 100 to 220 parts by weight of the phosphorus-based hydroxy compound represented by Formula 3 is mixed with 100 parts by weight of the first solvent, and at least one of the epoxy compounds represented by Formula 4-1 and Formula 4-2 Or more of the epoxy compound is mixed in the amount of 230 to 270 parts by weight.
As an example of the method of reacting the reaction mixture, a method of reacting with an alkali catalyst can be used. As the alkali catalyst, for example, sodium hydroxide, lithium hydroxide, Hydroxides of alkali metals such as potassium hydroxide; Alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride, and potassium chloride; Alkaline metal alkoxides such as sodium methoxide and sodium ethoxide; Hydrides of alkali metals such as phenoxide, sodium hydride and lithium hydride of an alkali metal; Alkali metal salts of organic acids such as sodium nitrate, sodium stearate and the like can be used.
The first solvent may not be used, but when the solvent is used, the effect of improving the reactivity of the solvent is reduced to reduce the amount of the intermediate product during the reaction. Therefore, compared with the case where the solvent is not used, And excellent results can be obtained even in the final product compound color.
Examples of the first solvent include aromatic solvents including benzene, toluene, xylene and the like; Acetone, methylethylketone (MEK), methylisobutylketone (MIBK), diisobutyl ketone (DIBK), cyclohexanone, acetylacetone, dioxane dioxane) and the like; N-methylformamide, N-dimethylformamide (DMF), acetamide, N-methylacetamide, and the like. 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 monomethyl ether, Glycol ether type solvents including propylene glycol monobutyl ether and the like; Propanol, propanol, butyl alcohol, butanol, pentyl alcohol, pentanol, hexyl alcohol, and the like. , hexanol), isopropyl alcohol (IPA), isobutyl alcohol, and derivatives thereof; Etc. may be used.
As the first solvent, it is preferable to use isopropyl alcohol (IPA).
The synthesis reaction is carried out at a temperature of 30 to 200 캜. More preferably 45 to 170 ° C. The synthesis reaction is also carried out for 3 to 7 hours. More preferably 4 to 6 hours. The catalyst is added in an amount of 50 to 120 parts by weight based on 100 parts by weight of the first solvent.
(First purification) of removing the remaining epoxy compound represented by the above-mentioned formula (4-1) or (4-2) by raising the temperature after washing with water after completion of the synthesis reaction, and after the first purification (Second purification) using an alkali catalyst after the second solvent is added and dissolved.
The kind of the solvent which can be used as the second solvent is the same as the kind of the solvent which can be used as the first solvent. Preferably, methylisobutylketone (MIBK) is used.
The first purification step is a step of washing with water after completion of the synthesis reaction and then raising the temperature to 140 to 160 DEG C to remove the residual monomer. The second purification step is a step of removing the remaining monomer from the first purification step at 140 to 160 DEG C The solvent is gradually added to dissolve and the salt is removed from the reaction at 70 to 90 ° C for 1 hour to 1 hour and 30 minutes using an alkali catalyst.
In the first purification step, water is washed using 80 to 250 parts by weight of water with respect to 100 parts by weight of the first solvent. In the second purification step, 300 to 700 parts by weight of a second solvent And then the catalyst is added to the first solvent in an amount of 10 to 30 parts by weight based on 100 parts by weight of the first solvent.
In addition, after the second purification step, water is washed again using water, and vacuum degassing is performed at 140 to 160 ° C. to remove remaining water and solvent. Thus, a yellow phosphorus-based epoxy compound flake can be obtained.
The phosphorus-based epoxy composition according to another embodiment of the present invention comprises the phosphorus-based epoxy compound represented by the above formula (1) and a curing agent. If necessary, other components such as an epoxy compound and a curing accelerator, a diluent, a filler, and other additives may further be added and appropriately compounded. The phosphorus-based epoxy composition according to the present invention provides a cured product excellent in heat resistance and dielectric properties and satisfying the properties required according to the use.
The curing agent is a substance that contributes to the crosslinking reaction during curing of the epoxy composition, and even if it is sometimes called a curing accelerator, it can be regarded as a curing agent if it contributes to the crosslinking reaction. The equivalent ratio of the phosphorus-based epoxy compound to the curing agent is 1: 0.6 to 1.5. If the curing agent is contained in an amount less than 0.6 equivalents based on one equivalent of the phosphorus-containing epoxy compound, there may arise a problem of uncured or a very slow curing rate, and when the curing agent is contained in excess of 1.5 equivalents, the curing agent is excessively charged tacky and rheology control problems.
The curing agent may be at least one selected from the group consisting of an amide type curing agent, a polyamine type curing agent, an acid anhydride curing agent, a phenol novolak type curing agent, a polymercaptan curing agent, a tertiary amine curing agent and an imidazole curing agent. The phenol novolak type curing agent may be at least one selected from phenols such as phenol, cresol, xylenol, regenosol, catechol, bisphenol A, bisphenol F, bisphenol S, bisphenol Z, bisphenol AD and biphenol and / -Naphthols such as naphthol and dihydroxynaphthalene, compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde and an aldehyde group such as anthracene terpene, dicyclopentadiene and the like and condensation or cocondensation And the like.
Further, the phosphorus-based epoxy composition further includes a curing accelerator. Suitable curing accelerators include 2-methyl imidazole, 2-ethyl-4-methyl imidazole 1) selected from 1-benzyl-2-methyl imidazole, 2-heptadecyl imidazole and 2-undecyl imidazole. Imidazole compounds containing more than one species; Organic compounds containing triphenylphosphate; ETPPI (Ethyl Triphenyl Phosphonium Iodide); And 4-dimethylamino pyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,6-diamino Pyridine compounds containing at least one member selected from the group consisting of pyridine, 2-amino-6-methylpyridine, 3-amino-6-isopropylpyridine, 2,2-dipyridylamine and 4-pyrrolidinopyridine; It is preferable to use at least one selected from among them.
In addition, the phosphorus-based epoxy composition may further include an inorganic filler. Examples of suitable inorganic fillers include silica, alumina, barium sulfate, talc, mud, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, Magnesium, boron nitride, aluminum borate, barium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate.
The 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%. When the content is less than 2 wt%, the flame retardant property is deteriorated or not implemented at all. When the content exceeds 7 wt%, the heat resistance is deteriorated and the cured product is brittle and crumbled.
As a result of evaluating the properties of the cured product by the phosphorus-based epoxy composition according to the present invention, it has been found that the resultant cured product has excellent heat resistance and low dielectric properties, and is used as an encapsulating material, Adhesives, film materials, materials for electrical insulation paints, and the like.
In one embodiment, prepregs for the manufacture of laminated boards 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 are prepared and then used as one or more laminates, The outer layer can be integrated by heating and pressing to produce a laminate for a printed circuit board.
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments, but the present invention is not limited thereto.
Examples and Comparative Examples
(1) Examples 1 to 5 Synthesis of phosphorus-based epoxy compounds
Example 1
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 charged into a reactor equipped with a stirrer, a thermometer and a reflux condenser, purged with nitrogen for 30 minutes, Lt; RTI ID = 0.0 > 50 C. < / RTI >
After the dissolution was completed, 350 parts by weight of NaOH was gradually added thereto and reacted for 5 hours. After completion of the reaction, the reaction mixture was washed with 560 parts by weight of water and then heated to 150 DEG C to remove the remaining epoxy compound. 2100 parts by weight of Methyl Iso Butyl Ketone (MIBK) was slowly added and dissolved at 150 ° C., and the refinishing operation was performed for one hour at 80 ° C. by using 70 parts by weight of NaOH. After washing with water 560 parts by weight, the mixture was vacuum degassed to 160 deg. C to obtain 900 parts by weight of a yellow epoxy compound flake having an epoxy equivalent of 230.
Example 2
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 charged into a reactor equipped with a stirrer, a thermometer and a reflux condenser, purged with nitrogen for 30 minutes, Lt; RTI ID = 0.0 > 50 C. < / RTI >
After dissolution was completed, 400 parts by weight of NaOH was gradually added thereto and reacted for 5 hours. After completion of the reaction, the reaction mixture was washed with water by using 700 parts by weight of water, and then the temperature was raised to 150 DEG C to remove the remaining epoxy compound. After slowly dissolving 2500 parts by weight of Methyl Iso Butyl Ketone (MIBK) at 150 ° C., finishing was carried out for 1 hour at 80 ° C. using 100 parts by weight of NaOH. After washing with 700 parts by weight of water, the mixture was vacuum degassed to 160 DEG C to obtain 750 parts by weight of a yellow epoxy compound flake having an epoxy equivalent of 240.
Example 3
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 charged into a reactor equipped with a stirrer, a thermometer and a reflux condenser, purged with nitrogen for 30 minutes, Lt; RTI ID = 0.0 > 50 C. < / RTI >
After the dissolution was completed, 360 parts by weight of NaOH was gradually added thereto and reacted for 5 hours. After completion of the reaction, the reaction mixture was washed with 750 parts by weight of water and heated to 150 DEG C to remove the remaining epoxy compound. 2100 parts by weight of Methyl Iso Butyl Ketone (MIBK) was slowly added and dissolved at 150 DEG C, and finishing work was performed for one hour at 80 DEG C using 90 parts by weight of NaOH. Followed by washing with 750 parts by weight of water, followed by vacuum degassing to 160 deg. C to obtain 700 parts by weight of a yellow epoxy compound flake having an epoxy equivalent of 270.
Comparative Example 1
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 fed into a reactor equipped with a stirrer, a thermometer and a reflux condenser, Was purged for 30 minutes, and then the reaction temperature was raised to 100 DEG C and dissolved.
After the dissolution was completed, 0.02 part by weight of ETPPI was added, and the temperature was raised to 160 DEG C and reacted for 5 hours to obtain 880 parts by weight of a colorless epoxy compound flake having an epoxy equivalent of 310.
(2) Examples 4 to 6 and Comparative Example 2 - Preparation of phosphorus-based epoxy composition
Example 4
100 parts by weight of the phosphorus-containing epoxy compound of Example 1, 50 parts by weight of the phenol novolak type curing agent and 2 parts by weight of the C11Z (10% in MeOH) curing accelerator were blended to prepare a phosphorus-based epoxy composition.
Example 5
100 parts by weight of the phosphorus-based epoxy compound according to Example 2, 45 parts by weight of the phenol novolak type curing agent, and 3 parts by weight of the C11Z (10% in MeOH) curing accelerator were mixed to prepare a phosphorus-based epoxy composition.
Example 6
100 parts by weight of the phosphorus-based epoxy compound according to Example 3, 40 parts by weight of the phenol novolak type curing agent, and 1 part by weight of the C11Z (10% in MeOH) curing accelerator were mixed to prepare a phosphorus-based epoxy composition.
Comparative Example 2
100 parts by weight of the phosphorus-based epoxy compound of Comparative Example 1, 50 parts by weight of the phenol novolak type curing agent, and 2 parts by weight of the C11Z (10% in MeOH) curing accelerator were mixed to prepare a phosphorus-based epoxy composition.
(3) Examples 7 to 9 and Comparative Example 3 - Preparation of phosphorus-based epoxy cured product
The phosphorus-based epoxy compositions according to Examples 4 to 6 and Comparative Example 2 were precured in a 180-degree oven to a B-stage, and then fine powder was prepared. 5 g of powder was weighed in a standard frame of 4 cm in length and 1 to 2 mm in height, , And then cured at 200 占 폚 for 2 hours in a heating press to prepare a phosphorus-based epoxy cured product having a thickness of 1.5 mm.
Experimental Example
(1) Determination of phosphorus content
The phosphorus contents of the phosphorus-based epoxy compounds prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were measured and are shown in Table 1.
The phosphorus content of the phosphorus-containing epoxy compounds of Examples 1 to 3 was 7 wt% and the phosphorus content of the phosphorus-containing epoxy compositions of Examples 4 to 6 was 5 wt% (P) content as compared with Example 2.
(2) Heat resistance and dielectric property test
Tg, Td, Dk and Df were measured for the phosphorus-based epoxy cured products prepared in Examples 7 to 9 and Comparative Example 3, and the results are shown in Table 2 below. The dielectric constant (Dk) and the dissipation factor (Df) were determined by Agilent E4991A RF Impedance / Diffusion method according to JIS-C-6481 method. Tg was measured by differential scanning calorimetry (DSC, TA Instrument) Material Analyzer.
(-5% Loss)
As can be seen from Table 2, the Tg of the comparative example is 130 ° C or less and the thermal stability is very poor. On the other hand, when the epoxy according to the present invention is cured, the glass transition temperature (Tg) .
Also, in the implementation of electrical and electronic parts such as printed circuit boards, the lower the dielectric constant of the insulator, the lower the signal processing speed and the transmission loss, and the electrical characteristics of the phosphorus-based epoxy cured product according to the present invention are superior to those of the comparative example. .
The features, structures, effects, and the like illustrated in the above-described embodiments can be combined and modified in other embodiments by those skilled in the art to which the embodiments belong. Therefore, it should be understood that the present invention is not limited to these combinations and modifications.
Claims (17)
The phosphorus-based epoxy compound is a phosphorus-based epoxy compound represented by the following formula (1)
The phosphorus-based epoxy compound is a phosphorus-based epoxy compound having a phosphorus (P) content of 7 to 8% by weight based on the total weight of the phosphorus-
[Chemical Formula 1]
(n is 1 to 5,
R 1 and R 2 are each independently absent or a C1-C20 aliphatic hydrocarbon group or a C6-C30 aromatic hydrocarbon group, or a combination thereof, and a heteroatom (selected from O, S, and N) And,
R3 and R4 are each independently a C1-C20 aliphatic hydrocarbon group or a C6-C30 aromatic hydrocarbon group, or a combination thereof, and hetero elements (selected from O, S, and N)
R5 and R6 are each independently a C1-C20 divalent hydrocarbon group or a C6-C30 aromatic hydrocarbon group or a combination thereof, and a heteroatom (selected from O, S, and N) may be present in the structure,
R7 is hydrogen, a C1-C20 aliphatic hydrocarbon group or a C6-C30 aromatic hydrocarbon group, or a combination thereof, and a hetero element (selected from O, S, and N)
Wherein the phosphorus-based epoxy composition comprises the curing agent in an amount of 40 to 50 parts by weight based on 100 parts by weight of the phosphorus-based epoxy compound, the curing accelerator in an amount of 1 to 3 parts by weight,
The phosphorus obtained from the epoxy composition of the cured glass transition temperature (T g) is from 150 to 230 ℃, dielectric constant (D k) are turned over an epoxy composition for insulation of the copper-clad laminate board, characterized in that not more than 4.2.
Wherein the curing agent is at least one selected from the group consisting of an amide type curing agent, a polyamine type curing agent, an acid anhydride curing agent, a phenol novolak type curing agent, a polymercaptan curing agent, a tertiary amine curing agent or an imidazole curing agent, Epoxy composition.
The curing accelerator may be selected from the group consisting of 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 1-benzyl- Imidazole compounds containing at least one member selected from the group consisting of 2-methyl imidazole, 2-heptadecyl imidazole and 2-undecyl imidazole;
Organic compounds containing triphenylphosphate;
ETPPI (Ethyl Triphenyl Phosphonium Iodide); And
Examples of the amines include 4-dimethylamino pyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,5-diaminopyridine, Pyridine compounds containing at least one member selected from the group consisting of 2-amino-6-methylpyridine, 3-amino-6-isopropylpyridine, 2,2-dipyridylamine and 4-pyrrolidinopyridine; Wherein the epoxy group-containing epoxy resin is at least one selected from the group consisting of epoxy resin and epoxy resin.
Wherein the loss factor (D f ) of the cured product obtained from the phosphorus-based epoxy composition is 0.020 or less.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150031200A KR101813527B1 (en) | 2015-03-05 | 2015-03-05 | Phosphorus epoxy compound and method for preparing the same, epoxy composition comprising the same |
| CN201680000419.4A CN106132974B (en) | 2015-03-05 | 2016-02-24 | Phosphorus system epoxide and preparation method thereof includes its epoxy composite |
| PCT/KR2016/001813 WO2016140459A1 (en) | 2015-03-05 | 2016-02-24 | Phosphorus-based epoxy compound, preparation method therefor, and epoxy composition containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150031200A KR101813527B1 (en) | 2015-03-05 | 2015-03-05 | Phosphorus epoxy compound and method for preparing the same, epoxy composition comprising the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20160108721A KR20160108721A (en) | 2016-09-20 |
| KR101813527B1 true KR101813527B1 (en) | 2018-01-03 |
Family
ID=56848055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150031200A KR101813527B1 (en) | 2015-03-05 | 2015-03-05 | Phosphorus epoxy compound and method for preparing the same, epoxy composition comprising the same |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR101813527B1 (en) |
| CN (1) | CN106132974B (en) |
| WO (1) | WO2016140459A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192281B (en) * | 2017-12-27 | 2020-12-15 | 江西生益科技有限公司 | Halogen-free thermosetting resin composition, and prepreg, laminated board, metal foil-clad laminated board and printed circuit board using same |
| US10899871B2 (en) * | 2019-04-23 | 2021-01-26 | Chang Chun Plastics Co., Ltd. | Phosphorous containing epoxy resins and process for synthesis |
| CN112409572A (en) * | 2019-08-22 | 2021-02-26 | 苏州巨峰新材料科技有限公司 | Phosphorus-containing flame-retardant low-thermal-expansion-coefficient epoxy resin, preparation method thereof, related intermediate product and application |
| KR102600976B1 (en) | 2020-10-14 | 2023-11-10 | 주식회사 신아티앤씨 | Phosphorous compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0784509B2 (en) * | 1991-08-02 | 1995-09-13 | 北興化学工業株式会社 | Method for producing phosphorus-containing epoxy resin |
| KR100960679B1 (en) * | 2008-06-17 | 2010-05-31 | 주식회사 신아티앤씨 | Non-halogen type epoxy resin having high reflective index and method for preparing the same |
| US10307990B2 (en) * | 2009-03-26 | 2019-06-04 | Panasonic Intellectual Property Management Co., Ltd. | Epoxy resin composition, prepreg, resin-coated metal foil, resin sheet, laminate and multilayer board |
-
2015
- 2015-03-05 KR KR1020150031200A patent/KR101813527B1/en active IP Right Grant
-
2016
- 2016-02-24 CN CN201680000419.4A patent/CN106132974B/en active Active
- 2016-02-24 WO PCT/KR2016/001813 patent/WO2016140459A1/en active Application Filing
Non-Patent Citations (1)
| Title |
|---|
| Journal of Polymer Science: Part A: Polymer Chemistry. Wiley InterScience. 2007, Vol. 45, pp2142-2151* |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106132974A (en) | 2016-11-16 |
| KR20160108721A (en) | 2016-09-20 |
| CN106132974B (en) | 2018-10-12 |
| WO2016140459A1 (en) | 2016-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101914265B (en) | Non-halogen phosphorus-containing flame retardant high-frequency epoxy resin composition and application thereof to bonding sheet and copper-clad plate | |
| KR101141305B1 (en) | Phosphorus containing phenol novolac resin, hardener comprising the same and epoxy resin composition | |
| KR101613598B1 (en) | Epoxy resin, method for producing epoxy resin, epoxy resin composition, cured product thereof, and heat-dissipating resin material | |
| US8581107B2 (en) | Halogen-free flame-retardant epoxy resin composition, and prepreg and printed circuit board using the same | |
| JP6515255B1 (en) | Curable resin composition, varnish, prepreg, cured product, and laminate or copper-clad laminate | |
| KR101813527B1 (en) | Phosphorus epoxy compound and method for preparing the same, epoxy composition comprising the same | |
| CN110819279A (en) | Halogen-free environment-friendly thermosetting resin adhesive, method thereof and copper-clad plate | |
| KR102642644B1 (en) | Oxazine resin composition and cured product thereof | |
| EP2368930B1 (en) | Novel low dielectric resin varnish composition for laminates and the preparation thereof | |
| JP6946578B2 (en) | Resin composition and its manufacturing method | |
| JP5752574B2 (en) | Phenol novolac resin and epoxy resin composition using the same | |
| JP5866806B2 (en) | Epoxy resin composition, prepreg using this epoxy resin composition, resin film with support, metal foil-clad laminate and multilayer printed wiring board | |
| JP6863679B2 (en) | Solution, its manufacturing method, epoxy resin composition and laminate | |
| TWI388622B (en) | And a thermosetting resin composition having an acid anhydride hardening | |
| JP5880921B2 (en) | Curable resin composition, cured product thereof, printed wiring board | |
| JP2016104891A (en) | Epoxy resin composition, prepreg using the epoxy resin composition, resin film with supporter, metal foil-clad laminate and multilayer printed board | |
| EP2186816B1 (en) | Phosphorus compound and method for preparing the same | |
| JP7061944B2 (en) | Varnish and its manufacturing method | |
| CN112409572A (en) | Phosphorus-containing flame-retardant low-thermal-expansion-coefficient epoxy resin, preparation method thereof, related intermediate product and application | |
| KR20160051085A (en) | Non Halogen Flame Retardant Polymer and Method for Preparing the Same | |
| KR102587599B1 (en) | Phosphorus epoxy compound and method for preparing the same, epoxy composition comprising the same | |
| KR101598244B1 (en) | Non Halogen Flame Retardant Polymer and Composition Containing the Same | |
| WO2019092968A1 (en) | Resin composition | |
| EP2374828B1 (en) | Preparation of a low dielectric brominated resin with a symmetric or saturated heterocyclic aliphatic molecular structure and composition comprising said resin | |
| JP2011231134A (en) | Resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E90F | Notification of reason for final refusal | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |