KR101044656B1 - Flame retardant compound - Google Patents

Abstract

The flame retardant compound according to the present invention has superior peeling strength, glass transition temperature, heat resistance, adhesion, and flame retardancy compared to conventional flame retardant compounds.

Description

Flame retardant compound

The present invention relates to a flame retardant compound, and more particularly to a flame retardant compound having excellent heat-resistance characteristics excellent adhesion, flame retardancy and compatibility with the polymer.

Currently, plastics are widely used in various industrial fields such as electrical equipment, transportation equipment, and building materials, but most of them need to be flame-retardant in consideration of safety in case of fire due to the characteristics of being easily burned with organic materials such as carbon, oxygen, and hydrogen. This is constantly increasing. Generally, fuel, oxygen and energy are necessary for a fire to occur. If any of these conditions are not met, a fire cannot occur. In other words, one method of flame retardant plastics can be implemented by eliminating one or more of the three factors that cause fire. A flame retardant is a substance that slows the ignition and prevents the expansion of combustion by chemically or physically adding a compound having a high flame retardancy effect such as halogen-based, phosphorus-based, nitrogen-based or metal products to a polymer material having a property of easy combustion. .

Flame retardants are divided into various types according to the end use, and can be divided into reactive and additive types. Reactive flame retardant is a type that reacts chemically with functional groups in the molecule. It is a flame retardant that keeps flame retardant effect without being greatly influenced by external conditions. Used in thermoplastics.

There are various types of additives or reactive flame retardants known to date. Examples of additive flame retardants include tricresyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tributyl phosphate, tris (bromo chloropropyl) phosphate, and tris (dichloropropyl). Phosphate, etc., and reactive flame retardants include bromo phenyl allyl ether including bromophenol, vinyl chloroacetate, antimony glycol, tetrabromobisphenol A, and the like.

Reactive flame retardants are chemically reacted with the substrate, so they are permanently mixed into the polymer structure, but additive flame retardant systems do not cause chemical reactions with the flame retardant and polymeric substrates, so the added flame retardant is simply dispersed in the substrate. Or dissolve and are often lost from the substrate.

On the other hand, as a technique for imparting flame retardancy to epoxy resins, halogen-containing compounds (eg, tetrabromobisphenol-A) are reacted together during the synthesis of epoxy resins, or halogen-containing compounds are added in the epoxy resin composition. When the flame retardant is imparted to the epoxy resin composition using the halogen-based flame-retardant curing paper, toxic carcinogens such as polyhalogenated aromatic dioxin or dibenzofuran are generated during combustion of the flame-retardant curing agent. Particularly in the case of polybrominated flame-retardant paper, a problem occurs that toxic carcinogens such as decabromo phenyldioxide and octabromophenylether are generated. In addition, the halogen-based compound is harmful to the human body due to the gas such as HBr and HCl generated during combustion, there is a problem that must be used in places where precision electronic equipment is installed due to the problem of corrosion of metal. Phosphorus-containing flame retardant hardener systems are therefore preferred over halogens, in particular bromine-containing flame retardant systems.

However, the conventional non-halogen flame-retardant curing agent by injecting a large amount of phosphorus-based raw material to give sufficient flame retardant properties to the epoxy molecular structure, even if the gelation phenomenon due to the increase in molecular weight or the gelation phenomenon does not occur, the curing density due to the molecular weight increase There is a disadvantage that the heat resistance properties, adhesive properties, heat stability properties that are inherent in the cured product is significantly lowered. In other words, by reacting a large amount of phosphorus-based raw material can have sufficient flame retardancy characteristics, but has a relatively large compound molecular structure, thermal properties and adhesive properties are deteriorated due to steric hindrance and low curing density during the curing reaction. Recently, due to environmental regulations such as RoHS, PoHS, etc. on printed circuit boards, various electrical / electronic parts insulation materials, and high reliability semiconductor encapsulant materials, the use of certain materials (lead, cadmium, hexavalent chromium, etc.) is partially or entirely restricted. Expectations such as high heat resistance, heat stability, adhesion, and low water absorption, which are required properties of flame retardant polymer materials, are rising. In particular, the development of a technology for a flame retardant compound having characteristics such as high heat resistance, thermal stability, low hygroscopicity, and high adhesion due to an increase in soldering temperature during printed circuit board manufacture was required.

The present invention has been made to solve the above-described problems, the present invention relates to a flame retardant compound, and more particularly to provide a flame retardant compound having excellent adhesion, flame retardancy and heat resistance excellent in compatibility with the polymer.

The present invention provides a flame retardant compound represented by the following formula (3) to solve the above problems.

(3)

n is each independently an integer of 0 or 1, and m is 1.

According to a preferred embodiment of the present invention, at least one or more of n in the general formula (3) may be 1.

According to another preferred embodiment of the present invention, a resin composition for a printed circuit board comprising 1 to 50% by weight of the flame retardant compound with respect to 100% by weight of the total resin composition.

According to one preferred embodiment of the invention, (1) reacting a compound represented by the formula (1) with an aldehyde-based compound under an alkali catalyst to replace the terminal of the compound represented by the formula (1) with a methol group; (2) adding an amine compound to remove the unreacted aldehyde compound; (3) reacting the solvent containing the compound substituted with the methiol group with an alcohol; And (4) preparing a flame retardant compound by reacting the compound substituted with the methiol group with a compound represented by the following Chemical Formula 2.

According to another preferred embodiment of the present invention, the aldehyde-based compound alone formaldehyde, acetaldehyde, alkyl aldehyde, benz aldehyde, alkyl substituted aldehyde, hydroxy benz aldehyde, naphtho aldehyde, glutar aldehyde, futal aldehyde and the like Or it can mix and use.

According to another preferred embodiment of the present invention, the amine compound may be a primary amine or a secondary amine, preferably a primary amine.

According to another preferred embodiment of the present invention, the alcohol may be butanol.

According to another preferred embodiment of the present invention, the compound represented by the formula (2) in the step (3) and the compound substituted with a methol group may be added in a molar ratio of 0.5: 1.0 ~ 1.0: 1.0.

According to another preferred embodiment of the present invention, step (3) may be performed at 150 ~ 220 ℃.

The flame retardant compound according to the present invention has superior peeling strength, glass transition temperature, heat resistance, adhesion, and flame retardancy compared to conventional flame retardant compounds.

In addition, the aldehyde compounds inevitably remaining in the manufacturing process of the present invention can be removed with amine compounds to suppress side reactions with the flame retardant compounds of Phosphine, and more fundamentally, the self-contained phenol terminal methol substituents are intermediates in the reaction process. By suppressing side reactions of the dehydration condensation reaction, the physical properties of the flame retardant compound can be significantly improved.

Furthermore, the flame retardant compound prepared by the above-described method has excellent flame retardancy, heat resistance and physical and chemical properties as an additive of engineering plastics such as polycarbonate, ABS, HIPS, and is a raw material of epoxy resin, cyanate resin and acrylate resin. And flame retardant compounds of epoxy resins. Through this, it can be widely applied to a variety of composite materials, adhesives, coatings, paints, such as insulating materials of high reliability electrical and electronic components, PCB substrates and insulating plates requiring excellent flame retardancy and thermal stability.

1 is a GPC graph according to a preferred embodiment of the present invention.
2 is a GPC graph according to another preferred embodiment of the present invention.
3 is a GPC graph according to another preferred embodiment of the present invention.
4 is a GPC graph according to another preferred embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

As described above, in order to overcome the disadvantages of the halogen flame retardant compound, the non-halogen-based flame retardant compound disclosed in the related art has an advantage of reducing environmental pollution. There was a problem of poor physical and chemical properties.

Accordingly, the present invention provides a flame retardant compound having excellent adhesion, excellent flame retardant effect, excellent heat resistance, and compatibility with a polymer compared to a conventional flame retardant compound.

Specifically, according to a preferred embodiment of the present invention, the method for producing a flame retardant compound of the present invention (1) reacting a compound represented by the formula (1) with an aldehyde-based compound under an alkali catalyst to the terminal of the compound represented by the formula (1) Replacing with a methiol group; (2) adding an amine compound to remove the unreacted aldehyde compound; (3) reacting the solvent containing the compound substituted with the methiol group with an alcohol; And (4) reacting the compound substituted with the methiol group with a compound represented by the following Chemical Formula 2 to prepare a flame retardant compound. Through this, it is possible to minimize yield reduction in the manufacturing process and to produce a flame retardant compound having excellent physical properties.

[Formula 1]

Provided that each X is independently H or an unsubstituted C1 alkyl group.

[Formula 2]

First, as a step (1), the compound represented by the following Chemical Formula 1 is reacted with an aldehyde compound under an alkali catalyst to replace the terminal of the compound represented by the Chemical Formula 1 with a methol group.

According to a preferred embodiment of the present invention, by reacting the compound represented by the formula (1) and the aldehyde-based compound in the molar ratio of 1: 1 to 1: 5, the reaction temperature of 30 to 100 ℃ under an alkali catalyst for 1 to 10 hours The terminal of the compound represented by Formula 1 may be substituted with a methiol group.

Meanwhile, the aldehyde-based compound which can be used in the present invention can be used without limitation as long as the terminal of the compound represented by the formula (1) can be substituted by the reaction of the compound of the formula (1) with a methiol group, preferably formaldehyde, acet Aldehydes, alkyl aldehydes, benzaldehydes, alkyl substituted aldehydes, hydroxy benzaldehydes, naphtho aldehydes, glutar aldehydes and futalaldehydes may be used alone or in combination, more preferably formaldehyde may be used.

 In addition, according to a preferred embodiment of the invention, the alkali catalyst may be any one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate and amine.

On the other hand, the remaining alkali catalyst does not participate in the reaction due to the chloride with the flame-retardant compound represented by the formula (2) having acidic characteristics, and thus exists in the form of polymerized or additive flame-retardant compound of the final flame-retardant compound. This may be a major cause of deterioration in physical properties such as poor compatibility. In addition, the remaining alkali catalyst may provide a cause of causing self-polymerization between compounds substituted with a methiol group. Accordingly, the present invention may perform a process of removing the residual alkali catalyst and the remaining aldehydes through neutralization and a plurality of washing processes using an aqueous solution of sulfuric acid, nitric acid, and phosphoric acid as acidic catalysts, but is not limited thereto. Can be.

Next, an amine compound is added as step (2) to remove the unreacted aldehyde compound.

Specifically, the compound in which the terminal of the compound of Formula 1 is substituted with a methiol group through step (1) may be obtained through the reaction of a rather excess aldehyde compound with the compound of Formula 1 under an alkali catalyst. A class may inevitably exist. Since the remaining unreacted aldehydes are easily added to the flame retardant compound represented by the formula (2), which is added afterwards, without reaction, the flame retardant compound itself is present in the form of an additional flame retardant, resulting in low flame retardant effect, low adhesion, and compatibility with polymers. It is the main cause of deterioration of physical properties such as poor properties.

In the present invention, after the step (1) is added to the amine compound to remove the unreacted aldehyde compound.

Specifically, in the step, the amine compound may use primary amine or secondary amine, but meta-phenylene diamine, benzoquanamine, trimethyl hexamethylene diamine, Isophorone diamine, etc. may be used as the primary amine, and N-Ethylbenzylamine as the secondary amine. , Bis (2-ethylhexy) amine, Dipropylamine, etc. can be used. The use of primary amine may be effective to remove aldehyde compounds. At this time, the amine compound is preferably added in 0.5 mol or less compared to the aldehyde compound. Generally, aldehyde compounds are reacted with primary or secondary amines to proceed with urea reactions.Unreacted aldehyde compounds with urea compounds produced by reactions with primary or secondary amines are easily dissolved in water and are removed from the reaction system. Is easy. In this case, when the addition molar ratio of the amine compound to the aldehyde compound is more than 0.5 moles, there is a possibility of remaining of the amine compound in the final flame retardant compound, which may cause problems such as reduced heat resistance.

In the next step (3), a solvent containing the compound substituted with the methiol group and an alcohol is reacted. Specifically, the compound substituted with the methiol group has a strong self-polymerization property at room temperature and high temperature, and therefore, a reaction must first be performed with an alcohol solvent serving as a buffer. Compounds substituted with a methiol group at the terminal of Chemical Formula 1 are highly unstable substances in which self polymerization occurs at a low temperature, and particularly, there is a problem that autopolymerization is rapidly performed as a side reaction under a basic catalyst or an acid catalyst. Therefore, under the solvent conditions, the compound substituted with a methol group at the end of the compound of Formula 1 and the flame retardant compound represented by the following Formula 2 are added at the same time or sequentially added within 2 hours to react the acidic phosphine structure (Phosphine) structure Due to the properties of the flame retardant compound represented by the formula (2) having a compound substituted with a thiol group at the end of the formula (1) compound and a flame retardant compound having a phosphine structure, the compound substituted a methiol group at the terminal of the formula (1) compound The liver will undergo a self-dehydration condensation reaction. As a result, there is a problem in that physical properties such as flame retardant properties, adhesive strength, etc. due to the remaining of the flame retardant compound represented by the unreacted formula (2), and the yield of the target flame retardant compound are significantly decreased.

The first reaction of the compound substituted with the methiol group and the alcohol containing alcohol may have the effect of inhibiting the self-polymerization of the methiol group through the alcohol decomposition decomposition reaction of the methiol group. In this case, the compound substituted with the methiol group and the solvent are preferably reacted for 2 hours to 5 hours. If the reaction is less than 2 hours, sufficient reaction does not occur, which may result in a problem of poor polymerization and flame retardant properties and physical properties of the final target flame retardant compound due to dehydration autopolymerization between the compounds substituted with methol groups. Although it is possible to increase the yield of the target flame retardant compound having excellent flame retardant properties and physical properties, the productivity may be remarkably reduced due to the extension of the reaction process time. Also preferably, it is advantageous to react 20 to 80 parts by weight of the compound substituted with a methiol group based on 100 parts by weight of the solvent. If the compound substituted with the methiol group is added in less than 20 parts by weight of the target flame retardant compound per batch (batch) may be a problem that the productivity is significantly lowered, if exceeding 80 parts by weight, the amount of solvent is small Due to the dehydration self-polymerization of the compound substituted with a methiol group, there may be a problem in that the polymerization of the target flame retardant compound and the flame retardant properties and physical properties are inferior.

     Meanwhile, according to another preferred embodiment of the present invention, the alcohol solvent is selected from the group consisting of methanol, ethanol, butanol, propanol, glycol, 2 methoxy ethanol, propylene glycol monomethyl ether, ether and phenol It may be any one or more, and most preferably using butanol is very advantageous in terms of physical properties (see Table 1, 2).

Benzene, toluene, xylene, dioxane, DMF, DMSO and the like can be used in combination with the alcohol solvent. However, when ketones are used as a solvent, side reactions occur with phosphorus compounds, so it is preferable not to use them (see Tables 1 and 2 below).

As a next (4) step, to prepare a flame retardant compound comprising the step of reacting the compound represented by the formula (2) to the compound substituted with the methiol group. At this time, the compound represented by the formula (2) and the compound substituted with a methol group is added at a molar ratio of 0.5: 1.0 ~ 1.0: 1.0 and dehydrogenation (dehydration) at a reaction temperature of 100 ~ 250 degrees, preferably 150-220 degrees As the reaction occurs, it proceeds. If the molar ratio of the compound represented by the formula (2) is less than 0.5, the compound substituted with the methiol group, which does not participate in the reaction, may be polymerized by dehydration reaction at a high temperature, resulting in gelation or flame retardant properties and physical properties. If the molar ratio exceeds 1.0, the flame retardant compound represented by the formula (2) remains unreacted in the final flame retardant compound and the physical properties such as thermal properties, thermal stability, stability due to moisture absorption, etc. Problems that can fall significantly can occur.

Flame retardant compound prepared through the preferred embodiment of the present invention described above is a compound represented by the following formula (3).

(3)

n is each independently an integer of 0 or 1, and m is 1. On the other hand, more preferably, when at least one of the n is 1, the effect of improving physical properties can be maximized (see Tables 1 and 2).

The flame retardant compound represented by Chemical Formula 3 of the present invention has excellent peel strength, heat resistance, adhesive strength, and flame retardancy as compared with the conventional flame retardant compound.

The phosphorus content of the final flame retardant compound prepared by the above-mentioned method is preferably 1 to 15%, preferably 5 to 15%. If the phosphorus content is less than 1%, the flame retardant effect is insignificant, and if the content exceeds 15%, there is a problem in that chemical modification is impossible.

The flame retardant compound of the present invention prepared by the above-described method is 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight of the flame retardant compound with respect to 100 parts by weight of the resin component in consideration of the balance between mechanical properties and flame retardant performance improvement Can be added. In this case, it is an additive of engineering plastics such as polycarbonate, ABS, HIPS, and has excellent flame retardancy, heat resistance, physical and chemical properties, and can be used as a raw material of epoxy resin, cyanate resin and acrylate resin, and as a curing agent of epoxy resin. . Through this, it can be widely applied to various composite materials, adhesives, coatings, paints such as PCB boards and insulating plates which require excellent flame retardancy and thermal stability as insulation materials of halogen, high reliability electrical and electronic components such as EMC.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are not intended to limit the scope of the present invention, which will be construed as to help the understanding of the present invention.

≪ Example 1 >

228 g (1 mole) of 4,4-dihydroxy-2,2-diphenyl propane, aqueous solution of methyl aldehyde (41.5%) 216 g ( 3 mole), 30 g of water, and 10 g of a 50% sodium hydroxide aqueous solution were added to the reactor, and the reaction was performed at 75 ° C. for 5 hours while heating and stirring. Then, 100 g of water was added to the reaction tank and neutralized with 0.1 N 5 g of phosphoric acid. After removing the upper water, 100 g of water and 95.34 g (0.7 mole) of meta-xylenediamine were added again. Into the reactor to remove the unreacted methyl aldehyde. Thereafter, the purification process was further performed three times using 100 g of water. Thereafter, the mixture was added to 610 g of butanol as a buffer, followed by an alcoholic reaction at T = 105 ° C. for 5 hours, followed by 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide (3,4 , 5,6-Dibenzo-1,2-oxaphosphane-2-oxide) (hereinafter referred to as HCA) After the addition of 522.15 g (2.417 mole) of butanol recovered under heating and stirring, the dehydration reaction was carried out. = It progressed for about 10 hours at 180 degreeC. After the reaction was completed, the remaining water and butanol were removed under reduced pressure to obtain 749 g (yield 91.9%) of a flame retardant compound having a phosphorus content of 9.3% and Mw 780 g / mol (FIG. 1). (FT-IR results: Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic))

<Example 2>

228 g (1 mole) of 4,4-Dihydroxy-2,2-diphenyl propane, aqueous solution of methyl aldehyde (41.5%) 108.4 g (1.5 mole), 30 g of water, and 5 g of 50% aqueous sodium hydroxide solution were added to the reactor and heated and stirred. The reaction was carried out at 75 ° C. for 5 hours. Thereafter, 76 g of water was added to the reaction tank and neutralized with 0.1 N 2.5 g of phosphoric acid. After removing the water at the upper part, 100 g of water and 47.67 g (0.35 mole) of meta-xylenediamine were added to the reaction tank. Remove aldehyde. Thereafter, the purification process was further performed three times using 76 g of water. Thereafter, the mixture was added to 521 g of butanol as a buffer, followed by an alcoholic reaction at T = 105 ° C. for 5 hours, followed by adding 261.6 g (1.211 mole) of HCA, followed by dehydration while removing butanol recovered by heating and stirring. Was carried out at T = 180 ° C. for about 10 hours. After completion of the reaction, the residual water and butanol were removed under reduced pressure to obtain 460 g (yield 91.26%) of a flame retardant compound having a phosphorus content of 7.38% and Mw 648 g / mol (FIG. 2). (FT-IR results: Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic))

<Example 3>

228 g (1 mole) of 4,4-Dihydroxy-2,2-diphenyl propane, aqueous solution of methyl aldehyde (41.5%), 288.4 g (4 mole), 30 g of water, and 14 g of 50% aqueous sodium hydroxide solution were added to the reactor and stirred while heating. The reaction was carried out at 75 ° C. for 5 hours. Thereafter, 116 g of water was added to the reaction tank, followed by neutralization with 0.1 N 6.7 g of phosphoric acid. After removing the water in the upper portion, 116 g of water and 127.12 g (0.93 mole) of meta-xylenediamine were added to the reaction tank. Remove aldehyde. Thereafter, the purification process was further performed three times using 116 g of water. Then, Buffer ethanol was added to 646 g of butanol, followed by an alcoholic reaction at T = 105 ° C. for 5 hours, followed by adding 675.6 g (3.128 mole) of HCA, followed by dehydration while removing butanol recovered under heating and stirring. Was carried out at T = 180 ° C. for about 10 hours. After completion of the reaction, the residual water and butanol were removed under reduced pressure to obtain 883 g (yield 97.42%) of a flame retardant compound having a phosphorus content of 10.34% and Mw 931 / mol (FIG. 3). (FT-IR results: Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic))

<Example 4>

228 g (1 mole) of 4,4-Dihydroxy-2,2-diphenyl propane, 216 g (3 mole) of methyl aldehyde aqueous solution (41.5%), 30 g of water and 10 g of 50% aqueous sodium hydroxide solution were added to the reactor and stirred while heating. The reaction was carried out at 75 ° C. for 5 hours. Thereafter, 100 g of water was added to the reaction tank, followed by neutralization with 0.1 N 5 g of phosphoric acid. After removing the water in the upper part, 100 g of water and 75.67 g (0.7 mole) of meta-phenylene diamine were added to the reaction tank, and thus unreacted. Remove methyl aldehyde. Thereafter, the purification process was further performed three times using 100 g of water. Thereafter, the mixture was added to 610 g of butanol as a buffer, followed by an alcoholic reaction at T = 105 ° C. for 5 hours, followed by the addition of 522.15 g (2.417 mole) of HCA, followed by dehydration while removing butanol recovered under heating and stirring. Was carried out at T = 180 ° C. for about 10 hours. After the reaction was completed, the remaining water and butanol were removed under reduced pressure to obtain 749 g (yield 91.9%) of a flame retardant compound having a phosphorus content of 9.3% and Mw 770 g / mol (FIG. 4). (FT-IR results: Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic))

Comparative Example 1

A flame retardant compound was obtained in the same manner as in Example 1 except that meta-xylene diamine was not used.

Comparative Example 2

Phenolic novolac epoxy resin YDPN-638 (Kukdo Chemical Co., Ltd., EEW: 180g / eq) 800g of DOPO 200g using catalyst ETPPI (Ethyl Triphenyl Phosphonium Iodide) for 6 hours bulk polymerization at 160 ℃ Resin was prepared. (EEW: 290g / eq, phosphorus content: 2.7%)

Comparative Example 3

The same procedure as in Example 1 was conducted except that no buffer butanol was used, but gelated during the reaction.

<Comparative Example 4>

A flame retardant compound was obtained in the same manner as in Example 1 except that ethyl methyl ketone was used instead of butanol.

Comparative Example 5

Toluene 216g, HCA 216g (1 mole), methyl aldehyde aqueous solution (41.5%) 72g was added to the reactor and reacted at 80 ° C for 10 hours, and the precipitated reactant was filtered and dried to obtain a flame retardant compound.

Comparative Example 6

A flame-retardant compound was obtained in the same manner as in Example 1 except that butanol and HCA were added at the same time.

Experimental Example

In order to evaluate the properties of the flame retardant compounds prepared in the above Examples and Comparative Examples, the formulations were carried out as shown in Tables 1 and 2, and the results are shown in the table.

Specifically, the resins prepared in Examples and Comparative Examples were blended at the compounding ratios shown in Tables 1 and 2 to produce varnishes, and impregnated with glass fibers was performed to prepreg. Prepreg (prepreg) was pressed to proceed at 175 for 5 minutes by applying a semi-cured state 15 minutes after pressing the back 120 minutes 40kgf / cm ² pressure to 25kgf / cm ² pressure for specimens of 8-fold at 190 after a. After cooling for 30 minutes with a refrigerant.

The flame retardancy test was carried out by the UL-94 method.

Glass transition temperature measurement experiments using a differential thermal analyzer (DSC). (20 / min)

Peel strength was measured by GIS C-6471 method.

Example 1 Example 2 Example 3 Example 4 Bisphenol-A resin (1) (g) 20 20 20 20 Bisphenol-A Resin (2) (g) 30 30 30 30 Bisphenol-A Novolac Epoxy (g) 50 50 50 50 Example Resin (g) 70 87.9 57 70 Bisphenol A-Novolac Hardener (g) 30 9.8 38 30 2E4MZ (g) 0.5 0.5 0.5 0.5 Propylene Glycol Monomethyl ether (g) 200 197.7 195 200 Phosphorus content 3.25 3.28 3.05 3.25 Flammability V-0 V-0 V-0 V-0 Glass transition temperature [] 175 163 173 178 Peel Strength 1.65 1.60 1.55 1.60

Comparative Example 1 Comparative Example 2 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 1 Bisphenol-A resin (1) (g) 20 20 20 20 20 Phosphorus modified epoxy resin (g) 100 Bisphenol-A Resin (2) (g) 30 30 30 30 30 Dicy (g) 4.34 Bisphenol-A Novolac Epoxy (g) 50 50 50 50 50 2MI (g) 0.15 Comparative resin (g) 70 70 70 45 70 MCs (g) 100 Bisphenol A-Novolac Hardener (g) 30 30 30 42 30 2E4MZ (g) 0.5 0.5 0.5 0.5 0.5 Propylene Glycol Monomethyl ether (g) 200 200 200 187 200 Phosphorus content 3.25 3.28 3.02 3.03 3.25 Phosphorus content 2.7 Flammability V-0 V-0 V-0 V-0 V-0 Flame Retardant (V-O) V-1 Glass transition temperature [] 155 145 120 135 157 Glass transition temperature [] 150 Peel Strength 1.0 0.9 0.5 0.8 1.0 Peel Strength 0.85

In Table 1, Dicy is Dicyandiamide as a conventional latent curing agent, and 2E4MZ is 2-Ethyl-4-methyl imidazole, Bisphenol-A Resin (1) as an accelerator, and epoxy equivalent of 186 g / eq and Bisphenol-A Resin ( 2) is epoxy equivalent 475 g / eq and Bisphenol-A Novolac Resin is epoxy equivalent 210 g / eq. Bisphenol A Novolac Hardener is also a hardener with an OH equivalent of 120 g / eq.

As can be seen through Tables 1 and 2, it can be confirmed that Examples 1 to 4 are superior in glass transition temperature and peel strength compared to Comparative Examples 1 to 6.

Flame retardant compounds produced through the production method of the present invention can be applied to various composite materials, such as PCB substrates and insulating plates, adhesives, coatings, paints.

Claims (3)

A flame retardant compound represented by the following formula (3).
(3)

n is each independently an integer of 0 or 1, and m is 1. The method of claim 1,
Flame retardant compound, characterized in that at least one of n in the formula (3) is 1.  A resin composition for a printed circuit board comprising 1 to 50% by weight of the flame retardant compound of claim 1 or 2 with respect to 100% by weight of the total resin composition.

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