TW201109371A - Process for manufacturing flame-retardant and phosphorous-modified hardener - Google Patents

Abstract

Disclosed herein is a method for manufacturing a phosphorous-modified flame-retardant hardener with excellent flame-retardancy and heat resistance. The manufactured flame-retardant hardener exhibits excellent flame-retardancy, heat resistance and physical and chemical properties sufficient to use the hardener as an additive for polycarbonate or other engineering plastics such as ABS, HIPS, etc., and may also be used as a raw material for epoxy resin, cyanate resin and acrylate resin and/or as a hardener for epoxy resin. Especially, the flame-retardant hardener may be used in a variety of applications including, for example, insulating materials for highly reliable electrical/electronic components such as EMC, various composite materials such as PCB substrates and insulating plates that require excellent flame-retardancy and thermal stability, adhesives, coating agents, paints, and so forth.

Description

201109371 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a flame retardant and phosphorus-modified hardener. More specifically, it relates to a method for preparing a phosphorus-modified flame retardant hardener having excellent flame retardancy and heat. [Prior Art] Today's plastics are used in a wide range of industrial applications such as electronic equipment, conveyors, building materials, and the like. However, plastics containing carbon, oxygen, hydrogen, etc. are flammable, and it is necessary to improve the flame retardancy in consideration of the safety of fire. In general, fire requires fuel, oxygen, and energy, and if it does not meet any of these requirements, it does not catch fire. That is, the method of plastic flame retardancy can be achieved by eliminating at least one of these necessary factors. The flame retardant hardener means a substance which is chemically or physically added with a high flame retardant compound such as a halogen, a can and/or a nitrogen compound, a metal oxide or the like, which delays ignition or combustion and prevents combustion from spreading. Flame retardant hardeners are classified into various types in terms of their type and/or use, and are generally classified into a reactive hardener and an additive hardener. The reactive hardener contains a functional group capable of reacting in a molecule and is not affected by external conditions and thus maintains a flame retarding effect. On the other hand, the additive type hardener is physically mixed, added or dispersed in the plastic material: it causes a flame retardant effect and is generally used for a thermoplastic plastic material. In many technologies, the additive type or reactive flame retardant hardener has been widely used in the technology. 201109371 4 Additive type flame retardant hardener may include benzodiazepine wei §|, triphenyl _-f(tetra) phosphatic acid vinegar, formazan I know 锑, tetrabromobisphenol and so on. Further, the reactive flame retardant hardener is combined with the matrix structure and the polymer structure. Conversely, the chemical reaction, after which the permanent combustion material does not dissolve or branch with the polymer base, and the #m-reaction' is simply a fresh fly knife that is in the matrix and is therefore usually lost from the matrix. The technique of flame retardant of the second resin includes the addition of the compound of the compound to the epoxy resin composition when the synthetic epoxy resin is synthesized, and when the flammability is made, it is deteriorated during the combustion of the flame retardant hardener. Special r Γ 戴 戴 戴 或 n n n n n 或 或 或 或 n 毒性 毒性 毒性 毒性 毒性 毒性 毒性 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可Furthermore, in the case of _ series compounds, gases generated during combustion, such as HBr and HCl, are harmful to the human body and are rotted, so care must be taken when using the compound = as in the location of precision electronic equipment. Conversely, phosphorus-containing flame retardant hardener systems are preferred for use in comparison to pheromides, especially bromine-containing flame retardant hardener systems, depending on environmental considerations. However, the conventional non-halogen flame retardant hardener has a problem in that it is introduced into a quantity to impart a flame retardancy satisfactory to the structure of the epoxy molecule, because the molecular weight is increased and the gelation is reduced or the hardening density is reduced. . As a result, the hardened product 201109371 has disadvantages such as a strong decline in inherent physical properties such as heat, adhesion, and thermal stability. In other words, although the flame retardancy is sufficiently ensured by reacting a large amount of the phosphorus-containing raw material, a compound having a relatively large molecular structure is produced, resulting in a space barrier effect and a low hardening density. As a result, thermal properties and adhesive properties are degraded. However, due to environmental regulations such as RoHS, PoHS, etc., some materials (ie, erroneous, braided, hexavalent chromium) are used on conventional thermal insulation materials for printed circuit boards and other motor/electronic components and high reliability semiconductor packaging materials. Partially or completely restricted. Therefore, there is an increasing expectation today for suitable physical properties including flame retardant polymer materials such as high heat resistance, thermal stability, viscosity, and low absorbency. In particular, due to the increased soldering temperature during the manufacture of printed circuit boards, there is still a novel technique for synthesizing non-flame retarding binary compounds having unique properties such as high heat resistance, thermal stability, low moisture absorption, high viscosity, and the like. There is a demand, and there is still a need for efficient production of hydrazine compounds. In order to solve the above-mentioned conventional problems' and the first object of the present invention: it is possible to reduce the chemical properties, mechanical and chemical properties of the intermediate product, and to achieve excellent flame retardancy and adhesion to 7 The above-mentioned second-two, this: proposed: one: the preparation of burning hardener. The method of quality TM includes: 1) in:: tampering

C 6 201109371 reacting a phenol compound with an aldehyde compound to prepare a resol resin compound; and 2) directing dehydration of the prepared resol resin compound with a phosphorus-containing compound in a solvent to form a phosphorus-modified Flame retardant hardener. According to an exemplary embodiment of the present invention, the above phenol compound may comprise at least one compound selected from the group consisting of the following formulas 1 to 4: [Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

7 201109371 wherein each X is deuterium or substituted or unsubstituted C! to C1G alkyl, Y is each F, S, S02 or substituted or unsubstituted C! to C1G alkyl, and each is 1 to An integer of 10. According to a preferred embodiment of the present invention, the phenol compound and the aldehyde compound of the above step 1) may be reacted together with a relative molar ratio of from 1:1 to 1:5. According to another preferred embodiment of the present invention, the phenolic compound may comprise a phenolic compound selected from the group consisting of fragrant, fragrant, acetyl, diced, xinpan, benzene, cumene, methoxy, and ethoxy. At least one of the group consisting of naphthene, bis, A, bis, F, bisphenol, and bisphenol. According to another preferred embodiment of the present invention, the basic catalyst may comprise at least one selected from the group consisting of sodium hydroxide, hydrazine hydroxide, hydrazine hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, and amine. . According to another preferred embodiment of the present invention, the resol resin compound may be a di-acid polymer. According to another preferred embodiment of the present invention, the resol resin compound may comprise at least one compound selected from the group consisting of the following formulas 5 to 8: [Formula 5]

[Equation 6]

201109371 [Formula 7]

^x^H or substituted or substituted for Cl to Q alkyl, Y; SS〇2 or substituted or unsubstituted C! to C1G alkyl, ζ each * S, S 〇 2 or substituted or not Substituting (^ to CiG alkyl, each of the claws is 0 to 5, n. ^, and n is each an integer from 1 to 10. According to another preferred embodiment of the present invention, the solvent may comprise At least one of the group consisting of free benzene, toluene, diphenyl, dioxane, DMF, DMSO, methanol, ethanol, butanol, propanol, glycol, ether, and phenol. In a preferred embodiment, the phosphorus-containing compound may comprise at least one compound selected from the group consisting of the following formulas 9 and 10: [Equation 9] 〇Ri-Ρ-R〗 201109371 [Formula]

Wherein i and R2 are each independently hydrazine, substituted or unsubstituted alkyl, substituted or unsubstituted ^10 F cation Ci to CIG hybrid, substituted or unsubstituted 1 to ClG, substituted or non Substituting Q to Cl. Block group, substituted or unsubstituted, i substituted C, to c1G aryl compound, substituted or unsubstituted

a Cj to C]0 heteroaryl compound, a substituted or unsubstituted Cl to Q fluorenyl group, an alcohol, an alkoxy group, an ether, an ester, a ketone, a carboxyl group, a hydroxyl group or a thiol group. According to another preferred embodiment of the present invention, the phosphorus-containing compound may be 3,4,5,6-dibenzo-1,2-epoxyphosphonium-2_oxide (hereinafter referred to as "D〇p〇" ), dinonyl phosphite (hereinafter referred to as rDMpp), or diphenylphosphine oxide (hereinafter referred to as "DPPO"). According to another exemplary embodiment of the present invention, the step 2) may include: reacting the soluble resin compound with a solvent for 2 to 5 hours to obtain an alcohol-soluble soluble acid resin compound; The alcoholysis is soluble and hopes to react with the linden compound to produce a dish-modified flame retardant hardener. According to another preferred embodiment of the present invention, the above alcoholy-soluble phenol resin compound may be selected from the compounds represented by the following formulas 11 to 14: 201109371 [Formula 11] nh 〇Η

[Formula 12]

[Formula 14]

-ii. wherein X is each H or substituted or unsubstituted q to C1G alkyl, each Y is F, S, S02 or substituted or unsubstituted C! to C1() alkyl, each of which is deuterium or Substituted or unsubstituted C! to C1G alkyl, m is each from 0 to 5, 201109371 integer ' and n is each an integer from 1 to 10. According to another preferred embodiment of the present invention, the soluble resin compound may be reacted with the solvent in an amount of from 20 to 80 parts by weight based on the solvent of i (9) parts by weight (hereinafter referred to as "parts by weight"). (The phosphorus-containing compound may be in opposition to 1 to 1:1, the compound represented by the phosphorus-modified flame retardant W: according to another preferred embodiment of the present invention, the alcohol-soluble resol resin compound比例.5; ear ratio reaction. According to another preferred embodiment of the present invention, the hardener may comprise at least one selected from the group consisting of the following formula [15]

[Formula 16]

12 201109371 [Formula 18]

OH

Wherein each X is deuterium or substituted or unsubstituted C, to C1() alkyl, each Y is F, S, S02 or substituted or unsubstituted C, to C1 () alkyl, each of which is deuterium or Substituted or unsubstituted C! to C1G alkyl, Q is

0 —|—Ri , Ri and R 2 are each η, substituted or unsubstituted C! to C1G alkyl, substituted or unsubstituted q to C1G alkenyl, substituted or unsubstituted C! to C1G alkynyl , substituted or unsubstituted C! to C10 aryl compound, substituted or unsubstituted C, to C1G fluorenyl, alcohol, alkoxy, ether, ester, ketone, carboxyl, hydroxy or thiol group, m each An integer from 0 to 5, and each of η is an integer from 1 to 10. In order to accomplish the second object, the present invention provides a phosphorus-modified flame retardant hardener produced by the aforementioned method. Hereinafter, the terms used herein are succinctly explained. Unless otherwise indicated, the term "resin phenolic resin reaction" means the production of a compound via an addition reaction (first reaction) of phenol and formaldehyde under alkaline conditions of 13 201109371. The product of this soluble acid resin reaction is subjected to A (second reaction) during T% warm dehydration to produce a soluble phenolic resin. In the present invention, the addition reaction with formaldehyde is employed, and the product of the addition reaction (first reaction product) used can react the phenol with an excess of formaldehyde. The "resin phenol resin compound" is intended to include a compound produced by a reaction of a soluble brewing resin. Unless otherwise indicated, the term "substituted or unsubstituted" with a substituent is intended to include both substituted and unsubstituted substituents. When substituted, the substituent is at least one group selected from the group consisting of, but not limited to, alkyl, mercapto, cycloalkyl (including bicycloalkyl and tricycloalkyl), Haloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, alcohol (·〇Η), ketone, arylalkoxy, aryloxy, thiol, alkylthio, Arylthio, carbonyl, ether, ester, thiol, phosphorus, sulfur, phosphate, phosphite, hypophosphite, sulfate, disulfide and protective derivatives thereof. The substituents are generally concerned with the various substituents well known in the art and are not subject to their particular limitations. Optionally, such substituents may also be substituted or unsubstituted. As used herein, the term "aryl" relates to an aryl group having at least one ring containing a 71-electron system, and includes a carbocyclic aryl group (e.g., a stupid group) and a heterocyclic aryl group (e.g., a pyridine group). , furan, hydrazine, hydrazine). This term is intended to mean a group of mono- or fused-ring polycyclic (i.e., a ring of carbon atoms sharing a contiguous moiety). The term "heteroatom" refers to an atom other than carbon and hydrogen. The term "complex base" means that at least one carbon atom in a burnt group is replaced by another heterogeneous 201109371 atom. The term "heteroaryl" means an aryl group containing at least one heterocyclic ring, more specifically - any substituted aryl group having 5 or 6 atoms in each ring. The heteroaryl group preferably contains - or two oxogens +, - or disulfide', and / 3⁄4 to four nitrogen atoms in the ring, and may be bonded to the ring via a carbon atom or a hetero atom. other parts. Examples of the heteroaryl group may include a furyl group, a thienyl group, a pyridyl group, an oxazolyl group, an η-pyrrolyl group, a fluorenyl group, a quinolinyl group, and an isoquinolinyl group. Examples of the substituent may include at least one selected from the group consisting of a hydrocarbon group, a substituted hydrocarbon group, a ketone, a hydroxyl group, a protected hydroxyl group, a mercapto group, a decyloxy group, an alkoxy group, an alkenyloxy group, an aryloxy group, a thiol group. Base, shrinkage, shrinkage, ester and hydrazine. The term "heterocycle" means any of a monocyclic or bicyclic aryl group and a non-aryl group having at least one hetero atom (preferably five or six atoms) in each ring and optionally substituted 'Full saturated or unsaturated. The heterocyclic group may preferably have one or two oxygen atoms, one or two sulfur atoms and/or one to four nitrogen atoms' and is preferably bonded to the other part of the molecule via a carbon atom or a hetero atom. Examples of the heterocyclic group may include a furyl group, a thienyl group, a pyridyl group, a chelate group, a "pyrrolyl group, a fluorenyl group, a quinolyl group, and an isoquinolyl group. Examples of the substituent may include at least one member selected from the group consisting of a hydrocarbon group, a substituted hydrocarbon group, a ketone, a hydroxyl group, a guaranteed thiol group, a decyl group, a decyloxy group, an alkoxy group, a dilute oxy group, an alkyne group, an aryloxy group, and a sulfur group. Alcohol base, ketal, shrinkage, self-motivation and shouting. The term "alkyl" means an aliphatic hydrocarbon group, and the alkyl moiety may be "saturated alkyl", meaning that it does not contain an ene or a hydrocarbon moiety. The alkyl moiety can also be an "unsaturated alkyl" moiety, meaning that it contains at least one olefin or alkyne moiety. The term "olefin" means a group consisting of at least two carbon atoms and at least one carbon-carbon double bond 15 201109371, and "alkyne and one at least one carbon-carbon: bond:" έ: the word knife A group consisting of ν bonds of at least two carbon atoms. Whether saturated or unsaturated, the alkyl moiety can be a branch, a carbon atom, and more preferably a chain or a ring. The glare group preferably has from 1 to 20 q 1 to ίο carbon atoms. "The base of the brewing base" - the remaining residue of AH organic tannic acid (OOH-based removal of the residue of the base of the second family) and such as "calling, (4) money, shouting or plant aryljiyiji矣_, a homocyclic aryl group having from 2 to 2, preferably phenyl, naphthyl, substituted, early or bicyclic, such as phenyl, biphenyl and Replace the secret ride or replace the naphthyl group. "fe" and "smoke base" _ ιη矣 - compound or residue. The above residual two == = organic group, county, alkynyl and / or aryl, For example, the appearance of a radical substitution is otherwise indicated, and the residue is preferably a fluorenyl group, a aryl group and a aryl group. Other terms can be interpreted as having 20 carbon atoms with the present. The meaning of the solution is 4 (10) - the product of the == soluble -lipid compound prepared according to the process of the invention in weaving and which can reduce the side reaction, after which the yield is significantly improved", 'intermediately, prepared according to the method of the invention; The agent exhibits excellent flame retardancy, heat resistance and (10) physical and chemical properties of flame retardant hardening, which is enough to make 201109371 C T::: raw material 'and, this, this hair The hardener can be used for different applications, including, for example, insulating materials for high reliability motor/electronic components, for example, the following embodiments will be more clearly understood from the following detailed description. The conventional (four)-based flame retardant hardener for overcoming the problem of the _-based flame retardant hardener has the advantage of reducing environmental pollution. However, compared with the «hardener, the _-based hardener has a degraded flame retardant effect. And reduced physical and chemical properties. Accordingly, the present invention provides a method for preparing a phosphorus-modified flame retardant hardener which is modified by phosphorus compared to conventional non-halogen flame retardant hardeners. The flame retardant hardener has excellent flame retardant effect and physical properties without dentate. More specifically, the method for preparing the phosphorus modified flame retardant hardener comprises: 1) in the presence of an inert catalyst, The compound is reacted with an acid compound to prepare a soluble tannic acid resin compound, and 2) the prepared resol resin compound and the phosphorus-containing compound are dehydrated in a solvent to form a phosphorus-modified compound. First, in step 1), in the presence of a basic catalyst, the phenol compound 201109371 is reacted with a compound. More specifically, the test compound used herein may be selected from the conventional compounds commonly used in the art. It is not particularly limited, and preferably contains any one selected from the group consisting of the phenol compounds represented by Formulas 1 to 4. More preferably, the phenol compound represented by Formula 1 may be a phenol or an indophenol, and the Formula 2 represents The phenol compound may be bisphenol A, bisphenol F, bisphenol AD, bisphenol S, etc. Similarly, the phenol compound represented by the formula 3 may be a phenol novolac or a quinone acid/resin (cresol) Novolac), and the phenol compound represented by the formula 4 may be a bisphenol A phenol resin, a bisphenol F phenol resin, a bisphenol S phenol resin, a bisphenol AD phenol resin or the like. The above phenolic compounds have the advantages of improved flame retardant effect and physical properties. [Formula 1]

[Formula 2]

[Formula 3]

18 201109371 [Formula 4]

With respect to formulae 1 to 4, each X is deuterated or substituted or unsubstituted C! to C10 alkyl, each Y is F, S, S02 or substituted or unsubstituted C! to C10 alkyl, and each It is an integer from 1 to 10. The basic catalyst is not particularly limited as long as it is used for a reactive phenol resin reaction, and may preferably comprise a commercially available basic catalyst selected from sodium hydroxide, potassium hydroxide, lithium hydroxide or hydrogen. Magnesium oxide, sodium carbonate, potassium carbonate, calcium carbonate and amines. In order to guide the reaction of the resol phenol resin, the aldehyde compound is not particularly limited as long as it can react with the phenol compound, and may preferably contain any one selected from the group consisting of furfural, acetaldehyde, alkyl aldehyde, benzaldehyde, and alkyl group. Substituted aldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, furfural, and the like. Step 1) comprises reacting a desired compound with an acid compound in a specific reaction condition in the presence of an inert catalyst, wherein the compound is reacted with the acid compound in a relative molar ratio of 1:1 to 1:5. This reaction can be carried out at 30 to 100 ° C for 1 to 5 hours. 19 201109371

The soluble phenolic resin produced by reacting the surface of the phenolic resin compound surface I, and the phenolic resin can be produced by the reaction of the phenolic resin, and the soluble resin compound can be contained in any one selected from the group consisting of the formulas 5 to /f. Compound. More preferably, in view of achieving a flame retardant effect and an excellent (four) impurity, the soluble brittle tree compound represented by the formula 5 may be a versatile soluble phenol 25 resin compound. The dissolved acid resin compound may be a bisphenol A type resol resin compound. The resol resin compound represented by the formula 7 may be a phenol resin type soluble expectant resin compound, and the resol is represented by the formula 8. The resin compound may be a double-anticipation resin-based resol resin compound. [Formula 5]

OH

[Formula 7]

20 201109371 [Formula 8]

M-

〇Ηλ

-rX)

m

OH: -3⁄4 wherein X is each H or substituted or unsubstituted C! to C1G alkyl, each Y is F, S, S02 or substituted or unsubstituted q to C1G alkyl, each Z is hydrazine or Substituted or unsubstituted Q to C1G alkyl, m is each an integer from 0 to 5, and each of η is an integer from 1 to 10. Meanwhile, the soluble and acid resin compound can be obtained by reacting with an excess amount of acid in the presence of a basic catalyst, and in this case, an unreacted wake-up catalyst can be left. This residual unreacted awake may react with the phosphorus-containing compound without a catalyst, resulting in degradation of the flame retardant effect and physical properties. Furthermore, the residual basic catalyst can cause self-polymerization of the soluble resin compound during step 2). Due to the chlorination of the catalyst with the acid-containing compound, the catalyst does not participate in the reaction of the soluble acetal resin, which subsequently causes the polymerization of the final product (i.e., the phosphorus-modified compound) or reduces the phosphorus content thereof. Accordingly, the present invention may further comprise a method of removing both residual basic catalyst and residual aldehyde comprising using an appropriate acidic catalyst such as sulfuric acid, nitric acid or phosphoric acid in an aqueous solution to neutralize the residue and washing the neutralized residue. The product. However, the removal method and 21 201109371 are not specifically compared to the above method, and may be selected from any of the gastric separation techniques. Next, in the step 2), the phenolic phenol resin compound prepared in the step u is dehydrated together with the phosphorus-containing compound in the presence of a solvent to produce a phosphorus-modified flame retardant hardener. In particular, in order to impart flame retardancy, any reactive phosphorus-containing compound known and used in the art can be used. The phosphorus-containing compound may comprise any one selected from the group consisting of phosphorus-containing compounds represented by Formulas 9 and 1 , preferably 'D0P0 (represented by Formula )), Dpp〇 (represented by Formula 9), DMPP (by formula) 9)), etc., but there are no special restrictions. [Equation 9] 〇 R1--P-R2 Η

Wherein Ri and R 2 are each independently hydrazine, substituted or unsubstituted Ci to Ci fluorenyl, substituted or unsubstituted c] to CiQ minus, substituted or unsubstituted c! s Cl0 : ^, substituted or unsubstituted i alkynyl, substituted or unmodified (: fluorene to C1G aryl compound, substituted or unsubstituted broad 1 to C1G heteroaryl compound, substituted or unsubstituted ^ to thiol, alcohol, alkoxy, ether, vinegar, sulfhydryl, thiol or thiol. The resol phenolic resin is a very unstable substance that self-polymerizes at a low temperature of 22, 2011,093. In the presence of an S-progressive catalyst or an acidic catalyst, this self-polymerization reaction occurs rapidly in a side reaction. Therefore, in the case where the soluble secret resin compound is directly reacted with the compound, the acidity of the hybrid-containing compound The characteristic 'the soluble resin compound does not react with the phosphorus-containing compound' instead causes a self-dehydration reaction between the soluble secret resin compounds. The result 'because of the residual unreacted contained compound, leaving a relatively low obstructive lung, physical properties Target flame retardant hardener Rate and the like. Therefore, 'Step 2 of the present invention> includes first reacting a soluble resin compound with _ to prepare a lysible compound, and then, the alcohol-soluble phenol resin compound and The phosphorus compound reacts to produce a final product 'gp, a phosphorus modified flame retardant hardener. As a result of the above steps, the above side reaction is reduced, and a target flame retardant hardener having excellent flame retardancy and physical properties can be obtained in high yield. In this regard, the resol resin compound is preferably reacted with a solvent for 2 to 5 hours. If the reaction time is less than 2 hours, the alcoholysis is insufficient, and the resol resin compound is dehydrated and self-polymerized, thereby causing polymerization of the phosphorus-modified flame retardant hardener and its flame retardancy. 11 Degeneration of physical and physical properties. On the other hand, if the reaction time is more than 5 hours, the alcoholysis is sufficient to increase the yield of the target flame retardant hardener, but the reaction, the treatment time is prolonged, and then the productivity is considerably lowered. Further, it is preferred that the soluble secret resin compound is reacted with the solvent in an amount of from 2 to 8 parts by weight based on the parts by mass of the solvent. If less than 2 parts by weight of the acid tree compound is added, the rate of the homogeneous flame retardant hardener per batch is reduced, thereby considerably reducing the productivity. On the other hand, if 80,069,093 parts of the resol resin compound is added, the amount of the solvent for the alcoholysis is reduced, thereby causing dehydration and self-polymerization of the partially resol resin compound. As a result, it is necessary to withstand the problem of polymerization of, for example, a phosphorus-modified flame retardant hardener and/or degradation of its flame retardancy and physical properties. The solvent for use herein may comprise at least one selected from the group consisting of decyl alcohol, ethanol, butanol, propanol, glycols, ethers, and phenols. Benzene, toluene, dinonylbenzene, dioxane, DMF, DMSO, etc. may also be added to these alcohol compounds. However, in the case where a ketone is used as a solvent, this solvent may cause side reaction with the filler-containing compound, and thus is not preferable (see Table 1 below). The reaction between the above resole resin compound and a solvent can preferably produce the alcoholy-soluble resol resin compound represented by any of Formulas 11 to 14. [Formula 11]

[Formula 12]

[Formula 13]

24 201109371 [Formula 14]

Each is IS = H or substituted or unsubstituted Cl to Cl. A thiol group, Y Μ , 2 or substituted or unsubstituted to c1 () 炫, Ζ each is or, or substituted or unsubstituted Cl to Ci channel, m each is an integer from 0 to 5, and η Each is an integer from 1 to 10. The alcoholyzed hetero-lipid compound prepared according to the above method is reacted with any one of the Wei-containing compounds represented by Formula 9 and hydrazine to produce the filled flame retardant hardening of the present invention. Agent. In this regard, the phosphorus-containing compound and the alcohol-soluble resol resin compound are added in a relative molar ratio of from 0.5:1.0 to 1.0:1. If the molar ratio of the phosphorus-containing compound is less than 0.5, the non-reactive phenolic resin compound or the alcohol-soluble resol resin compound (ie, the unreacted resol resin compound) will be dehydrated or delisted. , causing the polymerization of the phosphorus-modified flame retardant hardener and the degradation of its flame retardancy and physical properties. On the other hand, if the molar ratio of the scaly compound exceeds 1.0, the amount of the dish-containing compound is excessively increased, and the remaining unreacted materials, such as thermal properties, heat 25 201109371 stability, moisture retention stability, and the like It is greatly deteriorated, although the phosphorus-modified flame retardant hardener has a high phosphorus content. The phosphorus-modified flame retardant hardener of the present invention may comprise any one of Formulas 15 to 18, and preferably, for the improvement of flame retardancy and physical properties, such as the flame retardant represented by Formula 15 Phosphorus-modified phenolic hardener of a hardener, phosphorus-modified bisphenol A hardener of a flame retardant hardener represented by Formula 16, and phosphorus-modified by a flame retardant hardener represented by Formula 17 The phosphorus-modified bisphenol A phenolic resin hardener of the phenolic resin hardener and/or the flame retardant hardener represented by Formula 18 can be advantageously obtained as a final product (see Table 1 for details). [Equation 15]

[Formula 16]

[formula]

26 201109371 [Formula 18]

OH

Wherein each X is deuterium or substituted or unsubstituted C! to C1G alkyl, each Y is F, S, S02 or substituted or unsubstituted C! to C1G alkyl, each of which is deuterated or substituted or non-substituted Substituting C to C1G alkyl, Q is

u

Rj-P^-R|, R and R2 are each deuterium, substituted or unsubstituted C! to C1G alkyl, substituted or unsubstituted C! to C1G alkenyl, substituted or unsubstituted Q to C1G Alkynyl, substituted or unsubstituted C! to C10 aryl compounds, substituted or unsubstituted Q to C1 G decyl, alcohol, alkoxy, ether, ester, ketone, carboxyl, hydroxy or thiol, m Each is an integer from 0 to 5, and η is each an integer from 1 to 10. With respect to Formulas 1 to 18, the substituted group may preferably include a group substituted with at least one selected from the group consisting of an alcohol, an alkoxy group, an ether, a vinegar, a ketone, a carboxyl group, a thiol group, and a thio group. group. The phosphorus content of the phosphorus-modified flame retardant hardener ranges from 1 to 15%, and is preferably from 5 to 11% compared to 27 201109371. If the content is less than 1%, the minimum flame retardant effect will be achieved. It is virtually impossible to modify the chemical structure because the content exceeds 15%. The balance between the mechanical properties of the improved and the improved flame retardant properties, the flame retardant hardener of the present invention prepared according to the above method can be added in an amount of (U s 5 G parts by weight) with respect to 100 parts by weight Preferably, the flame retardant hardener of the present invention exhibits excellent flame retardancy, heat resistance, and physical and chemical properties f, and is satisfactory for use of the hardener as a polycarbonate or, for example, ABS. , HIPS and other engineering plastics are added together and can also be used as a raw material for epoxy resin, cyanate resin and acrylic acid vinegar resin, and/or a hardener for epoxy resin. Therefore, the flame retardant of the present invention The modifier can be used in a variety of applications, including insulation materials such as EMC's highly reliable motor/electronic components, various composite materials such as pCB substrates, and insulating sheets, adhesives, and coatings that require excellent flame retardancy and thermal stability. A preferred embodiment of the present invention will be described in detail in accordance with the following examples. However, these examples are not intended to limit the scope of the invention, and are understood to provide The invention is understood. Example 1 An aqueous solution containing 228 g (l mole) of bisphenol A, 216 g (3 moles) of trioxane, 3 gram of water and 10 g of 50% sodium hydroxide was placed in a reaction bath, after which The mixture was reacted at 50 ° C for 5 hours under heating and stirring. Thereafter, after adding 1 〇〇 of water, neutralization was carried out using 5 g of N.1 N sulfuric acid. Then, using 1 〇〇g of water, the product was washed twice to Separating and obtaining a bisphenol A resol resin compound (304.3 g, yield 94.8%) by adding this resol resin compound to 28 201109371 610 g of sterol 'resin phenolic resin compound alcoholysis at 70 ° C (T) was carried out for 5 hours with stirring. Thereafter, 522.15 g (2.417 moles) of DOPO was added to the mixture and guided to de-alcolysis for 10 hours at 145 ° C (T) with heating and stirring. In addition to the sterol moiety, after completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thus obtaining 749 g of a phosphorus-modified bisphenol A flame retardant hardener compound having a phosphorus content of 9 3% (yield 91.9) 〇/〇). FT-IR Result: PCT-hydroxy: 3300〇111-1, ?=0: nOOcm-VuSOcm-1, PC-0 (aryl): 97 2cm-1, PC (aryl) 1424cm'1. Example 2 will contain 228g (l mole) bisphenol A, 〇 8.4g (1.5 moles) of paraformaldehyde, 30g of water and 5g of 50 ° / hydrogen An aqueous solution of sodium oxide was placed in the reaction bath, followed by a reaction at 50 ° C for 5 hours under heating and stirring. Thereafter, after adding 76 g of water, 'neutralization was carried out using 2.5 g of 0.1 N sulfuric acid. Then, using 76 g of water, The product was washed three times to separate and obtain a bisphenol A resol resin compound (260.6 g, yield 95%). The alcoholysis of the resol resin compound was carried out for 5 hours by adding the resol resin compound to 521 g of decyl alcohol at 70 ° C (T) with stirring. Thereafter, 261.6 g (l.211 mol) of DOPO was added to the mixture, and the alcoholysis was carried out at 145 ° C (T) under heating and stirring for 10 hours while removing the methanol portion. After completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thus obtaining 460 g of a phosphorus-modified bisphenol A flame retardant compound having a breaking content of 738% (yield 91.26%). FT-IR result: phenol-hydroxy group: 3300 Cm'Ρ=〇: 29 201109371 UOOcnrVnSOcm·1, PC-Ο (aryl): 972 cm-1, Ρ-C (aryl) 1424 cm'1. Example 3 228 g of bisphenol A, 288.4 g (4 moles) of trimeric acetal, 3 gram of water and 14 g of 50% aqueous sodium hydroxide were placed in a reaction bath, followed by 5 hours under heating and stirring for 5 hours. . Thereafter, after adding 116 g of water, neutralization was carried out using 6.7 g of 0.1 N sulfuric acid. Then, the product was washed three times with 丨丨24 water to separate and obtain a bisphenol A resol resin compound (323 g' yield 92%). The alcoholysis of the resol resin compound was carried out for 5 hours by adding this soluble acid-producing resin compound to 646 g of decyl alcohol at 70 ° C (T). Thereafter, 675 6 g (3 128 mTorr) of D〇p〇 was added to the mixture' and guided to decoupling for 1 hour at 145 ° C (T) with heating and stirring while removing the sterol moiety. After completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thus obtaining 883 g of a double-reacted a flame retardant hardener compound having a phosphorus content of 1 〇 43% (yield 87 42%). FT-IR results: phenol-hydroxy group: 3300 cm-1, p=〇: 1200 cm—VuSOcnT1, PC-0 (aryl): 972 cm·1, p_C (aryl) 1424 cm'1. Example 4 will contain 94.11g (l mole) phenol, 90.32g (1.25 moles) of trimeric acetal, 3 gram of water and 3.3g of 50% sodium hydroxide in an aqueous bath, produced / at 5 ° C, heating and The reaction was carried out for 5 hours with stirring. Thereafter, after adding 4^· of water, neutralization was carried out using 1.67 g of O.in sulfuric acid. Then, the product was washed three times with 5 g of water to separate and obtain phenol soluble novolacs 6g 201109371 (127.5 g, yield 96%). The alcoholysis of the resol resin was carried out for 5 hours by adding the resol resin compound to 255 g of decyl alcohol under stirring at 7 ° C (T). Thereafter, 207.36 g (0.96 mol) of DOPO was added to the mixture 'and decanted for 10 hours at Μ5° (:(Τ), under heating and stirring, while removing the methanol fraction. After completion of the reaction, under vacuum The remaining water and decyl alcohol were removed under reduced pressure, thus obtaining 291 g of a phosphorus-modified phenol flame retardant hardener compound having a phosphorus content of 9.59% (yield 90%). FT-IR result: phenol-based : 3300 cm-1, p=〇: nOOcm-VusOcm1, PC-0 (aryl): 972 cm·1, PC (aryl) 1424 cm'1. Example 5 will contain 108.14 g of indophenol, 90.32 g (1.25 mol) An aqueous solution of trimeric furfural, 30 g of water and 3.3 g of 50% sodium hydroxide was placed in a reaction bath, followed by reaction at 5 ° C for 5 hours under heating and stirring. Thereafter, after adding 45 g of water' Neutralization was carried out using 1.67 g of 〇.iN sulfuric acid. Then, using 45 g of water, the product was washed three times to separate and obtain a nonylphenol-soluble phenolic resin compound (139.5 g yield: 95%). The alcoholysis of the resol resin compound was carried out by stirring the resin compound to 279 g of decyl alcohol at 70 ° C (T) for 5 hours. Thereafter, 2 〇 7 36 g was added ( 96 mol) D〇p〇 to σ, and at 145 ° C (T), under heating and stirring to guide the de-alcolysis, 〇], while removing the methanol part. After completion of the reaction, in a vacuum or The remaining water and sterol were removed under reduced pressure, thus obtaining 299 g of a phosphorus-modified flame retardant hardening compound having a phosphorus content of 9.19% (yield 90%). FT_IR Result: phenol-hydroxy group: 3300 cm- 1, P = 〇: 201109371 nOOcm 'VuSOcnT1, PCO (aryl): 972cm-1, Ρ-C (aryl) 1424cm'1. Example 6 will contain 356g (l mole) phenolic resin, 216g (3 Mo An aqueous solution of trimeric furfural, 3 g of water and 10 g of 50% sodium hydroxide was placed in a reaction bath, followed by heating at 5 ° C for 5 hours under heating and stirring. Thereafter, after adding 13 g of water Neutralization was carried out using 5 g of N.1 N sulfuric acid. Then, 13 gram of water was used, and the product was washed three times to separate and obtain a phenol-soluble phenol resin compound (408 g, yield: 90.8%) by adding this soluble phenol aldehyde. Resin compound to 816g methanol in a '70 ° C (T) stirring for resol phenolic resin

Alcohol hydrolysis of the substance for 5 hours. Thereafter, 500.^8 (2.315 mol) of DOPO was added to the mixture' and de-alcoholization was carried out at 145 ° C (T) under heating and stirring for 10 hours while removing the sterol moiety. After completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thus obtaining 814 g of a phosphorus-modified phenolic resin flame retardant hardener compound' having a phosphorus content of 8.38% (yield 90.7%). FT-IR results: Classes and bases: 3300〇111-1,? =0 : • nOOcnfVnSOcm·1, PC-0 (aryl): 972CHT1, PC (aryl) 1424cm'1. Example 7 will contain 760g (l mole) bisphenol a phenolic resin, 216g (3 moles) An aqueous solution of tripolyformic acid, 30 g of water and 10 g of 50% sodium hydroxide was placed in a reaction bath, followed by a reaction at 50 ° C for 5 hours under heating and stirring. Thereafter, after adding 213 g of water, neutralization was carried out using 5 g of 0.1 N sulfuric acid. Then, the product was washed with 2i3g 32 201109371 water to separate and obtain (4) A soluble resin 1 (6 g yield 91.0 ° / 〇). The alcoholysis of the soluble secret tree was carried out for 5 hours by adding this soluble acid resin to i552 g of sterol under 'under T' and (d). Thereafter, 5 〇l 2g (2., mole): 〇# was added to the mixture, and at 145. India), in the addition and subtraction of the county, the solution is to remove the methanol portion. After completion of the reaction, the remaining water and decyl alcohol were removed under reduced pressure or reduced, thereby obtaining a % modified phenolic resin flame retardant hardening compound of HU having a phosphorus content of 5.88% (yield 86.24%). FT4R result: phenol-hydroxy group: 3300 cm·1, P=〇: i200 cm-i/1280 cm-i, PC-0 (aryl): 972 cm, 1, PC (aryl) 1424 cm-1. Example 8 228 g (1 mol) bisphenol A, 216 g (3 mol) trimeric furfural, 3 g water and 10 g 50% sodium hydroxide in an aqueous solution, followed by heating at 5 ° C The reaction was carried out for 5 hours with stirring. Thereafter, after adding i〇〇g water, neutralization was carried out using 5 g of 0.1 N sulfuric acid. Then, the product was washed three times with 1 〇〇 water to separate and obtain a bisphenol A resol resin compound (304.3 g, yield 94.8%). The alcoholysis of the resol resin compound was carried out for 5 hours by adding the resol resin compound to 61 g of methanol at 70 ° C (T) with stirring. Thereafter, 488 23 g (2 417 mol) of a base phosphine oxide was added to the mixture and de-alcoholization was carried out at 145 ° C (T) under heating and stirring for 10 hours while removing the sterol moiety. After completion of the reaction, the remaining water and methanol were removed under vacuum or reduced pressure, thus obtaining 728.9 g of a phosphorus-modified double-flavor A flame retardant compound having a filling content of 33 201109371 9.9% (yield 92%). FT-IR results: 酴-yl group: 3300 cm_1, P=〇: nOOcnrVnSOcm·1, PC-0 (aryl): 972 cm-1, PC (aryl) 1424 cm1. Example 9 will contain 228 g (1 mol) An aqueous solution of bisphenol a, 216 g (3 mol) of trimeric furfural, 30 g of water and 10 g of 50% sodium aroxide was placed in a reaction bath, followed by heating at 50 ° C for 5 hours under heating and stirring. Thereafter, after adding 100 g of water, neutralization was carried out using 5 g of 0.1 N sulfuric acid. Then, the product was washed three times using 1 () 〇 g of water to separate and obtain a bisphenol A resol phenol resin compound (304.3 g 'yield 94.8%). The alcoholysis of the resol resin compound was carried out by adding the resol resin compound to 610 g of decyl alcohol at 70 ° C (T) for 5 hours while stirring. Thereafter, 265.87 g (2.417 mol) of dinonyl phosphite was added to the mixture, and de-alcoholization was carried out at 145 ° C (T) under heating and stirring for 10 hours while removing the methanol portion. After completion of the reaction, the remaining water and decyl alcohol were removed under vacuum or reduced pressure, thereby obtaining 5 g of a phosphorus-modified bisphenol A flame retardant hardener compound having a phosphorus content of 14.22% (yield 89.3%). . FT-IR results: phenol-hydroxy group: 3300 CHT1, P=0: nOOcnrVnSOcuT1, PC-0 (aryl): 972 cm·1, PC (aryl) 1424 cm·1. Comparative Example 1 800 g of novolac epoxy resin, YDPN-638 (Kukdo Chemical (:〇.,!^1. Manufacture 3£\^:1808/call.), 20 (^00?0) and iodinated ethyltriphenyl scale (ETPPI) as catalyst 34 201109371 The mixture was polymerized at 160 ° C for 6 hours, thus preparing a phosphorus-modified epoxy resin (EEW: 29 〇g/eq., phosphorus content: 2.7%). Comparative Example 2 In addition to using water instead of decyl alcohol as a solvent Further, the procedure was repeated to produce a flame retardant compound. Comparative Example 3 The reaction was repeated except that the soluble acid resin compound was simultaneously reacted with methanol and D〇p〇 to replace the sequential reaction with these materials in sequence. 1 procedure to produce a flame retardant compound. Comparative Example 4 The procedure of the examples was repeated except that ethyl ketone was used instead of decyl alcohol to produce a flame retardant compound. Experimental Examples In order to evaluate the above examples and comparative examples Physical properties of the dish-modified flame retardant hardener compound prepared in accordance with The composition compositions shown in the following Table 1 were each mixed with the ingredients listed in the following Table 1. More specifically, according to the fact that these compounds were each mixed with the other components of the composition shown in Table 1 to prepare a varnish The varnish was poured into the glass fiber to form a prepreg. Then, the prepreg was heated at 175 ° C for 5 minutes to convert the prepreg into a semi-hardened state, and then an eight-folded sample was formed. The sample was pressed at 190 ° C and 25 kgf / cm 2 for 15 minutes and then pressed at 40 kgf / cm 2 for 12 minutes. The compressed sample was cooled using a cooler for 3 minutes. 35 201109371 The sample was tested according to the UL-94 standard method. Flame retardancy. The glass transition temperature of the sample was tested using a differential scanning calorimeter (DSC, 20/min). The peel strength of the sample was determined according to the GIS C-6471 standard method. [Table 1] Examples 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 YD-128 20 20 20 20 20 20 20 20 20 YD-011 30 30 30 30 30 30 30 30 30 BPA -phenolic epoxy resin 50 50 50 50 50 50 50 50 50 Resin obtained in the examples 70 87.9 57 52 58.22 75.6 145.79 64.4 42.5 BPA-phenolic resin hardener 30 9.8 38 13 10.27 32.4 25.7 27.6 28.3 2MI 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 MCs 200 197.7 195 165 168 208 271 192 170 Filling content 3.25 3.28 3.05 3.02 3.31 3.04 3.15 3.32 3.54 Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Glass transition temperature [°C] 165 155 160 130 140 155 160 163 158 Peel strength 1.35 1.30 1.30 1.20 1.10 1.20 1.25 1.35 1.25 36 201109371 [Table 1 - continued] Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 1 YD-128 20 20 20 Filled epoxy resin 100 YD-011 30 30 30 Dicy 434 BPA-phenolic epoxy resin 50 50 50 2MI 0.15 Resin obtained in the comparative example 70 70 70 MCs 100 BPA·phenolic resin Hardener 30 30 30 2MI 0.5 0.5 0.5 MCs 200 200 200 Fill content 3.28 3.05 3.02 Phosphorus content 2.7 Flame retardancy V-0 V-0 V-0 Flame retardancy (V-0) V-1 Glass transfer temperature [°C ] 145 155 120 Glass Transfer Temperature [°c] 150 Peel Strength 0.9 1.10 0.5 Strong Peeling 0.85 According to the above Table 1, D icy represents dicyanamide as a latent hardener, 2 ΜI represents 2-methylimidazole as a hardening accelerator, and MCs represents 2-methoxyethanol as a solvent. YDB-128 means having I86g /eq equivalent of bisphenol epoxy resin (Kukdo Chemical Co., Ltd.), and YD-011 means bisphenol epoxy resin (Kukd〇 Chemical c〇, Ltd.) having 475 g/eq equivalent. As shown in Table 1, it was found that the flame retardant compounds obtained in Examples 1 to 9 had excellent glass transition temperatures and peeling strengths as compared with those obtained in Comparative Examples 1 to 4. As apparent from the above description, the phosphorus-modified flame retardant hardener prepared according to the above method of the present invention can be used in various applications including, for example, various 37 201109371 composite materials, such as PCB substrates, and insulating sheets, adhesives, coatings. Cloth, paint, etc. [Simple description of the diagram] None. [Component Symbol Description] No 0 38

Claims (1)

201109371 VII. Patent Application Range: 1. A method for preparing a phosphorus-modified flame retardant hardener comprising: 1) reacting a desired compound with a waking compound in the presence of an inert catalyst to prepare a a phenolic resin compound; and 2) the prepared resol resin compound and a phosphorus-containing compound are dehydrated in a solvent to form the phosphorus-modified flame retardant hardener. 2. The method of claim 1, wherein the phenolic compound is selected from at least one of the compounds represented by Formulas 1 to 4: [Formula 1] [Formula 2] [Formula 3] 39 201109371 [Formula 4] Wherein each X is deuterium or substituted or unsubstituted heart to deuterium. The alkyl group, each of which is F, S, S02 or a substituted or unsubstituted C! to C1G alkyl group, and each of η is an integer of from 1 to 10. 3. The method of claim 1, wherein in the step 1), the phenol compound reacts with the aldehyde compound in a relative molar ratio of 1:1 to 1:5. The method, wherein the phenolic compound is selected from the group consisting of phenol, 甲, 乙, 丁, 辛, 苯盼, cumene, methoxy, ethoxy, naphthalene, double A, At least one of a group consisting of a pair of F, a pair of S, a pair of AD, and a bisphenol. 5. The method of claim 1, wherein the basic catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, and an amine. At least one of them. 6. The method of claim 1, wherein the resol resin compound is a pro-acid polymer. 7. The method of claim 6, wherein the resol phenolic compound 201109371 is selected from at least one of the compounds represented by Formulas 5 to 8: [Formula 5] [Formula 6] [Formula 7] Wherein each X is deuterium or substituted or unsubstituted C! to C1G alkyl, each Y is F, S, S02 or substituted or unsubstituted C! to C1 () alkyl, each Z is deuterium or substituted Or a non-substituted C! to C1G alkyl group, m each being an integer from 0 to 5, and each of η is an integer from 1 to 10. 41 201109371 wherein the solvent is at least one selected from the group consisting of benzene, methyl phenanthrene, dioxan, alcohol, butanol, propanol, diol dioxane, DMF, DMSO, hydrazine. Alcohol, B. And ether and a method of at least one of the group consisting of wherein the solvent further comprises at least one of the selected ones. The method of the first aspect of the invention, wherein the compound is selected from at least one of the compounds represented by the following formulas 9 and 10: [Formula 9] * 〇-R〇 R1-- Η [Formula 10] /, wherein Ri and R2 are each independently oxime, substituted or unsubstituted C, unsubstituted 1 to Cl°, substituted-substituted C, to decynyl, "substituted sulphate substituted C1 to C1G An aryl compound, taken or unsubstituted Cl to C]. Heteroaryl compound, substituted or unsubstituted C] to Q. Sulfhydryl, alcohol, silk, (iv), self-purpose, ketone, silk, warp group or thiol group. 42 201109371 11. The method of claim 2, wherein the phosphorus-containing compound is selected from the group consisting of 3'4,5,6-a benzoxan-1,5,6-phosphonium-2-oxide At least one of the group consisting of an ester and a diphenylphosphine oxide. 12. The method of claim 2, wherein the step 2) comprises: reacting the soluble raw resin compound with a solvent for 2 to 5 hours to obtain any one selected from the group consisting of the alcoholysis represented by the formulas 11 to 14. a resol resin compound; and reacting the alcoholy-soluble soluble resin compound with the filler-containing compound to produce a phosphorus-modified flame retardant hardener, [Equation 11] [Formula 12] [Formula 13] 43 201109371 [Formula 14] !n. wherein each X is deuterium or substituted or unsubstituted C! to C1G alkyl, Y is each F, S, S02 or substituted or unsubstituted Cj to C1G alkyl, each Z is deuterium or substituted Or a non-substituted C! to C1Q alkyl group, each m is an integer from 0 to 5, and each of η is an integer from 1 to 10. 13. The method of claim 12, wherein the soluble anti-awake resin compound is reacted with the solvent in an amount of from 20 to 80 parts by weight relative to 100 parts by weight of the solvent. 14. The method of claim 12, wherein the phosphorus-containing compound reacts with the alcohol-soluble resol resin compound in a relative molar ratio of from 0.5:1 to 1:1. 15. The method of claim 1, wherein the phosphorus-modified flame retardant hardener is at least one selected from the group consisting of compounds represented by Formulas 15 to 18: [Formula 15] 44 201109371 OH [Formula 16] X X [Formula π] [Equation 18] Wherein each X is deuterium or substituted or unsubstituted C! to C1G alkyl, each Y is F, S, S02 or substituted or unsubstituted C! to C1G alkyl, each Z is deuterated or substituted or non Substituted C! to C1G alkyl, Q is 45 201109371 =p_ο Rj-1—Ri • , Ri and R2 are each H, substituted or unsubstituted C! to C1G alkyl, substituted or unsubstituted C! to C1G alkenyl, substituted or unsubstituted C! to C1G Alkynyl, substituted or unsubstituted (^ to C1G aryl compound, substituted or unsubstituted (^ to C) G thiol, alcohol, alkoxy, ether, ester, ketone, carboxyl, hydroxy or thiol The bases, m are each an integer from 0 to 5, and η are each an integer from 1 to 10. 46 201109371 IV. Designation of the representative figure: (1) The representative figure of the case is: No. (2) The symbol of the component of the representative figure is simple. Note: None. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: No 0