KR20140098641A - Flame retardant and phosphorous-modified hardener - Google Patents

Abstract

A phosphorous-modified flame retardant hardener of the present invention is a flame retardant hardener having high thermal resistance, thermal stability, low absorbing properties, improved electrical properties, high adhesion, and significantly improved toughness when compared to an existing non-halogen based phosphorous-modified flame retardant compound. To solve the described subject, the present invention provides a phosphorous-modified flame retardant hardener represented by the following chemical formula 1. In chemical formula 1, a is an integer of 0-4, b is 1, and the order of the combination for each structural unit in accordance to a and b can be randomly varied.

Description

Flame retardant and phosphorous-modified hardener < RTI ID = 0.0 >

The present invention relates to a phosphorus-modified flame-retardant curing agent, and more particularly, to a phosphorus-modified flame-retardant curing agent which is excellent in hygroscopic property and flame retardancy, and has remarkably improved heat resistance and electrical properties.

Currently, the use of plastic is widely used in various industrial fields such as electric devices, transportation equipment, building materials, etc. However, due to characteristics that are easily burned by organic materials such as carbon, oxygen and hydrogen, Is continuously increasing. In general, fuel, oxygen, and energy are essential for a fire to occur, and fire can not occur if at least one of these conditions is not met. That is, one of the methods of smelting the plastic can be realized by removing one or more factors of the fire occurrence factor. Flame-retardant hardeners are materials that can retard combustion by chemically or physically adding a compound that has a high flame-retarding effect such as halogen-based, phosphorus-based, nitrogen-based, or metal-based products to a polymer material that is easy to burn, It says.

Flame-retardant hardeners are divided into various types according to kinds and uses, and they can be broadly divided into reaction type and addition type. The reaction-type flame-retardant curing agent is a type that reacts chemically with a functional group in the molecule. It is a flame-retardant curing agent that keeps the flame-retardant effect without being greatly affected by external conditions. The addition type flame-retardant curing agent is physically mixed, And is mainly used for thermoplastic plastics.

There are various kinds of additive or reactive flame retardant curing agents known to date. Examples of the additive flame retardant curing agent include tricresyl phosphate, cresyldiphenyl phosphate, triphenyl phosphate, tributyl phosphate, tris (bromochloropropyl) phosphate, tris (Dichloropropyl) phosphate. Examples of reactive flame retardant curing agents include bromophenol, bromophenyl allyl ether, vinyl chloroacetate, antimony glycol, tetrabromobisphenol A, and the like.

Since the reactive flame retardant is chemically reacted with the substrate, it is mixed into the polymer structure forever. However, since the additive flame retardant hardener system does not cause a chemical reaction with the material exhibiting flame retardancy and the polymer substrate, And often are lost from the substrate.

On the other hand, as a technique for imparting flame retardancy to an epoxy resin, a halogen-containing compound (e.g., tetrabromobisphenol A) is reacted together at the time of epoxy resin synthesis, or a halogen-containing compound is added in an epoxy resin composition state. When such a halogen-based flame retardant is used to impart flame retardancy to the epoxy resin composition, toxic carcinogens such as polyhalogenated aromatic dioxin or dibenzofuran are generated when the flame retardant is burned. In particular, in the case of the polybrominated flame-retardant curing agent, toxic carcinogens such as decabromo phenyldioxide and octabromophenyl ether are generated. In addition, halogen compounds are harmful to the human body due to gases such as HBr and HCl generated during combustion, and metal is corroded. The phosphorus containing flame retardant system is preferred over halogen, especially bromine containing flame retardant systems in terms of environment.

However, in the conventional non-halogen flame retardant, a large amount of phosphorus raw material is injected in order to impart sufficient flame retardancy to the epoxy molecular structure, so that a gelation phenomenon due to an increase in molecular weight occurs, or even if a gelation phenomenon does not occur, And the heat resistance, adhesion and thermal stability characteristics, which are intrinsic physical properties of the cured product, are remarkably deteriorated. In other words, by reacting a large amount of phosphorus raw material, it can have sufficient flame retardancy, but by having a relatively large molecular structure of the compound, thermal properties and adhesion properties are lowered due to steric hindrance and low curing density in the curing reaction. However, recently, the use of certain substances (lead, cadmium, hexavalent chromium, etc.) is restricted partially or wholly due to environmental regulations such as RoHS and PoHS in printed circuit boards and various electrical and electronic parts heat- Accordingly, expectations of high heat resistance, thermal stability, adhesive strength, low water absorption, etc., which are required properties of flame-retardant polymer materials, are increasing. Especially, the technology for the synthesis of non-burnable phosphorous compounds with high heat resistance, heat stability, low hygroscopicity, improvement of electric characteristics and high adhesive force due to the rise of soldering temperature in the production of printed circuit board and technology for producing it smoothly .

The object of the present invention is to provide a modified flame-retardant curing agent which is excellent in hygroscopic property and flame retardancy and remarkably improved in heat resistance and electrical properties.

In order to solve the above-mentioned problems, the present invention provides a phosphorus-modified flame retardant curing agent represented by the following general formula (1).

[Chemical Formula 1]

(2)

In the above formulas (1) and (2), a is an integer of 0 to 4, b is 1, and the order of bonding of each constituent unit according to a and b may be randomly modified;

A is formula 2;

,

,

,

,

,

또는

이고,Y is, independently of each other,

,

,

,

,

,

or

ego,

,

또는

이고, Ar은 각각 독립적으로

또는

이고;Z each independently

,

or

, Ar is independently < RTI ID = 0.0 >

or

ego;

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently -H, -OH or a C _1-10 alkyl group;

R ₁₀ is C _{6 ~ 20} aryl group, C _{1 ~ 20} alkyl group or cyclo alkyl group is C _{5 ~ 12;}

n is independently an integer of 0 to 2, p is independently an integer of 0 to 2, q is independently an integer of 0 to 2, p + q is 1 or more, r is an integer of 0 to 2, s Is an integer of 0 to 2, r + s is 1 or more, and t is an integer of 0 to 2.

According to another preferred embodiment of the present invention, a in formula (1) may be O.

According to another preferred embodiment of the present invention, a in Formula 1 may be an integer of 1 to 4.

According to another preferred embodiment of the present invention, the R ₁₀ may be a cyclo alkyl group of C _{6 ~ 10} aryl group, C _{1 ~ 10} alkyl group or a C _{5 ~ 8} of the

According to another preferred embodiment of the present invention, a composition comprising a phosphor modified flame retardant can be provided.

Hereinafter, terms used in this specification will be briefly described.

Unless otherwise stated, the term " resorization reaction " means a compound obtained by addition reaction of phenols and formaldehyde under basic conditions.

The term "alkyl" means an aliphatic hydrocarbon group. The alkyl moiety may be a "saturated alkyl" group meaning that it does not contain any alkene or alkyne moieties. The alkyl moiety may be an "unsaturated alkyl" moiety which means that it contains at least one alkene or alkyne moiety. "Alkenene" moiety refers to a group in which at least two carbon atoms are composed of at least one carbon-carbon double bond, and "alkyne" moiety refers to a group in which at least two carbon atoms are replaced by at least one carbon- ≪ / RTI > The alkyl moiety, whether saturated or unsaturated, may be branched, straight chain or cyclic.

The phosphorus-modified flame retardant of the present invention has significantly improved flame retardancy, low hygroscopicity, high heat resistance, thermal stability, improved electrical properties, high adhesion and toughness compared to conventional non-halogenated flame retardant compounds .

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

As described above, the conventional non-halogen-based phosphorus-based flame retardant has a problem in that it has a low heat resistance due to high moisture absorption characteristics, and is insufficient in comparison with physical properties requiring electrical characteristics, adhesive strength and toughness.

Accordingly, the present invention provides a phosphorus-modified flame retardant curing agent represented by the following Formula 1 to solve the above-mentioned problems. The present invention provides a modified flame retardant curing agent which is significantly improved in flame retardance, low hygroscopicity, high heat resistance, thermal stability, electrical characteristics, high adhesive strength and toughness compared to conventional non-halogenated flame retardant compounds can do.

[Chemical Formula 1]

(2)

In the above formulas (1) and (2), a is an integer of 0 to 4, b is 1, and the order of bonding of each constituent unit according to a and b may be randomly modified. In other words, when a is 0 and b is 1, only B is present alone or when the constituent unit according to a and b (a parenthesized compound of a and the parenthesized compound of b) is A and B, AAB-, -ABA-, -AB-, -BAAA-, -ABAA-, etc. In this case, since b is 1 and a is an integer of 1 to 4, the number of A's is 1 to 4 Can be.

On the other hand, A in the formula (1) is the formula (2).

,

,

,

,

,

또는

이다.Y is, independently of each other,

,

,

,

,

,

or

to be.

,

또는

이다.Z represents a phosphorus compound, and each independently represents

,

or

to be.

또는

이다.At this time, each Ar independently represents Ar independently of

or

to be.

Each of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may independently be -H, -OH or a C _1-10 alkyl group, H, -OH, or a C _1-6 alkyl group.

R ₁₀ is an aryl group of _{C 6 ~ 20, C 1 ~} 20 alkyl group or a C _{5 ~} and cyclo alkyl groups of _12, and more preferably the R ₁₀ is C _{6 ~ 10} aryl group, C _{1 ~ 10} alkyl group or C of _And may be a _{5- to 8} -membered cycloalkyl group.

n is independently an integer of 0 to 2, p is independently an integer of 0 to 2, q is independently an integer of 0 to 2, p + q is 1 or more, r is an integer of 0 to 2, s Is an integer of 0 to 2, r + s is 1 or more, and t is an integer of 0 to 2.

The phosphorus-modified flame-retardant curing agent of the present invention represented by the above-described formula (1) is superior in flame retardancy, low hygroscopicity, high heat resistance, thermal stability, electrical property improvement, high adhesion and toughness Toughness) is significantly improved (see Table 3).

The compound represented by the formula (1) is preferably (1) a step of reacting a compound represented by the following formula (3) and a phosphorus compound represented by the following formula (4) to prepare a phosphorus-modified compound; (2) reacting the phosphorus-modified compound with an aldehyde-based compound under a catalyst to prepare a resolvated compound; And (3) reacting the resorptive compound with at least one phosphorus compound represented by the following formulas (5) to (7).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

,

,

,

,

,

또는

이며, Ar은 각각 독립적으로

또는

이다.In any one of formulas (3) to (7), Y is, independently of each other,

,

,

,

,

,

or

, Ar is independently

or

to be.

In any one of formulas (3) to (7), X is independently a halogen group, -OR ₉ , -OH or -H, and R ₉ is C _1-10 alkyl group. Each of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may independently be -H, -OH or a C _1-10 alkyl group, May be -H, -OH or an alkyl group of _{1 to 6} carbon atoms. And, the formula (4) R ₁₀ is C _{6 ~ 20} aryl group, C _{1 ~ 20} alkyl group or cyclo alkyl group is C _{5 ~ 12;} More preferably, R ₁₀ may be an aryl group having _{6 to 10} carbon atoms, an alkyl group having _{1 to 10} carbon atoms, or a cycloalkyl group having _{5 to 8} carbon atoms.

Specifically, in step (1), the phosphorus-modified compound is prepared by reacting the compound represented by formula (3) and the phosphorus compound represented by formula (4). The bisphenol-based compound is preferably selected from the group consisting of bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol A, M, bisphenol S, bisphenol P, bisphenol TMC, and bisphenol Z.

In the formula (4), the X moiety of the formula (4) is eliminated as the phosphorus compound, and the moiety P bonds with the OH moiety of the formula (4). Therefore, it is possible that X is a leaving group capable of carrying out the reaction, preferably X is each independently halogen, -OR ₉ , hydroxy or H, and R ₉ is C _1-10 alkyl group.

In the above step (1), the molar ratio of the compound represented by the formula (3) to the phosphorus compound represented by the formula (4) may be 2: 1 or more. If the molar ratio is less than 2 mol, the molecular weight of the modified phosphorus compound may rise and gelation may occur.

The step (1) may be carried out in a solvent, and the solvent may include benzene, toluene, xylene, ketones, and the like.

The catalyst may be a tertiary amine or an alkali catalyst. More preferably, the catalyst may be selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, potassium carbonate, calcium carbonate In addition to amines, most commercially available alkali catalysts and amines are mostly usable.

In the next step (2), the phosphorus-modified compound is reacted with an aldehyde-based compound under a catalyst to prepare a phosphorus-modified resolazolization compound. The catalyst which can be used in the present invention is a catalyst which can be used in the resorptation reaction of the compound, preferably an alkali catalyst, more preferably sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate , Calcium carbonate, amines, and most commercially available alkali catalysts are mostly usable.

In the meantime, the step (2) is a step of reacting the phosphorus-modified compound prepared in the step (1) with an aldehyde-based compound, wherein the reaction conditions are preferably 1: 1 to 1: 4 Molar ratio.

If the reaction molar ratio is less than 1: 1, the sites to be reacted with the phosphorus compounds represented by the general formulas (5) to (7) are decreased in the final step (3), and the phosphorus content of the final compound is lowered, When the molar ratio is more than 1: 4, the number of reactive sites of the phosphorus-modified compound prepared in the step (1) is at most 4, which causes unreacted aldehyde compound not participating in the resorization reaction,

The aldehyde-based compound that can be used in the present invention is not limited as long as it is capable of reacting with the phosphorus-modified compound to carry out the resorization reaction. The aldehyde-based compound is preferably selected from the group consisting of formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, , hydroxy-benzaldehyde, and the like naphthoic aldehyde, glutaraldehyde, hutal aldehyde, may more preferably be an alkyl aldehyde of C _{1 ~ 10.}

On the other hand, the phosphorus-modified resolvated compound can be obtained by reacting a slight excess of an aldehyde and a phosphorus-modified compound under an alkaline catalyst, whereby unreacted aldehydes and an alkali catalyst may be present in the phosphorus-modified resolvated compound . The remaining unreacted aldehydes tend to undergo reaction with the phosphorus compound in the absence of a catalyst, which may be a main cause of the flame retarding effect and the deterioration of the physical properties. Further, the remaining alkali catalyst is likely to provide a cause for causing self-polymerization of the resolved compound in the subsequent step 3), and also because of the chlorination with the phosphorus compound having the acidity characteristic, the phosphorus- Can not participate in the reaction with the resultant catalyst, resulting in a decrease in the molecular weight or phosphorus content of the final product.

In the present invention, the step of removing the remaining alkali catalyst and the remaining aldehydes through neutralization and a number of water washing processes using an acid catalyst such as sulfuric acid, nitric acid, and an aqueous phosphoric acid solution may be performed, but the present invention is not limited thereto. .

Meanwhile, according to a preferred embodiment of the present invention, the compound represented by the general formula (3) added in the step (1) may be further added in the step (2). Specifically, in addition to preparing the final compound through the steps (2) and (3) using the phosphorus-modified compound prepared in the step (1), the phosphorus-modified compound prepared in the step (1) The modifying compound and the compound represented by the general formula (3) are further added to improve the manufacturing process and cost, as well as to improve the heat resistance, the thermal stability, the low hygroscopicity, the electrical property and the high adhesive force remarkably. This can be achieved due to the low molecular weight of relatively low-cost bisphenol compounds, and synergistic effects can be obtained by simultaneously introducing bisphenol compounds having excellent heat resistance, low hygroscopicity, and electrical characteristics. The bisphenol compound is preferably selected from the group consisting of bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, Bisphenol M, bisphenol S, bisphenol P, bisphenol TMC, and bisphenol Z. Preferably 1 to 20 moles of the compound represented by the formula (3) per mole of the phosphorus-modified compound. If the compound of the formula (3) is added in an amount exceeding 20 mol, there may arise a problem that the high heat resistance, toughness, adhesion and the like may be deteriorated.

Next, in step (3), the phosphorus modified flame retardant is prepared by reacting the phosphorus-modified resolved compound with any one of the phosphorus compounds represented by the above formulas (5) to (7). More specifically, a phosphorus-modified flame retardant is produced by a dehydration condensation reaction of a phosphorus-modified phenol-modified compound with a phosphorus compound on a solvent. In the present invention, Reactive phosphorous compounds (phosphorus compounds containing -H or -OH) widely used in the art can be used. Phosphorus compounds represented by the above-mentioned formulas 5 to 7 can be preferably used, (3,4,5,6-Dibenzo-1,2-oxaphosphane-2-oxide), which is a phosphorous compound widely used as a phosphorus- (Hereinafter, referred to as 'DOPO') and diphenylphosphine oxide (hereinafter referred to as 'DPPO') is preferably used for improving the flame retarding effect and physical properties.

On the other hand, in order to prepare the final compound, the aldehyde compound may be reacted at a molar ratio of 1 to 1.5 with respect to 1 mole of the phosphorus compound represented by the general formulas 5 to 7.

When the aldehyde compound is reacted at less than 1 molar ratio, the unreacted phosphorus compound may cause deterioration of physical properties. When the molar ratio exceeds 1.5 molar ratio, a number of washing steps for removing the unreacted aldehyde compound may be performed, Is a cause of deterioration of the physical properties of the final compound due to the side reaction.

According to another preferred embodiment of the present invention, the reaction of step (3) may be carried out in the presence of a solvent, and examples of usable solvents include methanol, ethanol, butanol, propanol, propene, glycol, , Toluene, xylene, dioxane, DMF, and DMSO. However, it is preferable not to use ketones because side reactions with the phosphorus compounds occur.

Meanwhile, according to another preferred embodiment of the present invention, the step (3) is preferably carried out at 140 to 250 ° C, preferably 160 to 220 ° C for 5 to 15 hours, preferably 8 to 12 hours. If the reaction temperature is lower than 140 캜, the reaction between the resole compound prepared in the above step (2) and the phosphorus compound represented by the general formulas (5) to (7) There is a possibility that pyrolysis of the final compound occurs. If the reaction time is less than 5 hours, the reaction does not sufficiently take place. If the reaction time exceeds 15 hours, the productivity due to the long reaction time may be significantly decreased.

The phosphorus content of the phosphorus-modified flame retardant prepared by the above-described method is 1 to 15%, preferably 4 to 11%. If the phosphorus content is less than 1%, the flame retarding effect is insignificant. If the phosphorus content exceeds 15%, there is a problem that chemical structural modification is impossible.

The flame retardant curing agent of the present invention produced through the above-described method is preferably used in an amount of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the resin component, in consideration of balance between improvement in mechanical properties and improvement in flame- Can be added. In this case, it is an additive for engineering plastics such as polycarbonate, ABS and HIPS, and has excellent flame retardancy, heat resistance, physical and chemical properties, and can be used as a raw material for epoxy resin, cyanate resin and acrylate resin and as a hardener for epoxy resin .

As a result, it can be widely applied to insulating materials for highly reliable electric and electronic parts such as EMC, halogen-free compounds, various composite materials such as PCB boards and insulating plates which require excellent flame retardancy and thermal stability, adhesives, coating agents and paints.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

≪ Example 1 >

1044.9 g of methyl ethyl ketone, 501.6 g (2.2 mole) of bisphenol A and 207.44 g (2.05 mole) of triethylamine were charged into the reaction vessel and stirred at room temperature. Then, 390 g of dichlorophenylphosphine oxide (50% MEK Soultion, 1.0 mole) was uniformly added to the reaction vessel for 2 hours, and aging was performed for 1 hour. Then, 472 g of water was added thereto to dissolve the salt formed as a byproduct of the reaction. Then, the phosphorus-modified bisphenol A compound was obtained through a filtering process, and then 479.7 g of the final modified bisphenol A compound Yield: 90%).

(FT-IR measurement results; Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic) )

≪ Example 2 >

195 g of methyl ethyl ketone and 501.6 g (2.2 mole) of bisphenol A were added to the reaction vessel and completely dissolved in bisphenol at a temperature of 50 ° C. Then 164 g of NaOH solution (50%, 2.05 mole) was added dropwise evenly over 1 hour And aging reaction was carried out for 1 hour. After the reaction solution was cooled to room temperature, 390 g of diclophenylphosphine oxide (50% MEK Solution, 1.0 mole) was added to the reaction vessel for 2 hours and aged for 1 hour.

Then, 472 g of water was added to dissolve the salt formed as a by-product of the reaction, followed by filtering to obtain a phosphorus-modified bisphenol A compound. Through a number of washing and drying steps, the final modified bisphenol A compound was reacted with 463.71 g Yield: 87%).

(FT-IR measurement results; Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic) )

≪ Example 3 >

533 g of the phosphorus-modified bisphenol compound prepared in Example 1, 213.2 g of methyl isobutyl ketone, 150 g (2.0 mole) of formaldehyde aqueous solution (40% aqueous solution) and 10 g of aqueous sodium hydroxide solution (10 g) The reaction was carried out at 50 DEG C for 5 hours with stirring. Then, 100 g of water was added to the reaction tank, and the neutralization reaction was carried out with 0.1 N of sulfuric acid. Then, 100 g of water was used to separate the phosphorus-modified bisphenol-based resolved compound through three washing steps. Thereafter, 1359.4 g of butanol was added to dilute the silicone-modified bisphenol-based resorptive compound, and 345.6 g (1.6 mole) of DOPO was added thereto. Thereafter, water was removed by dehydrolysis reaction while heating and stirring. Lt; 0 > C for 10 hours. After the reaction was completed, 764.54 g (85% yield) of a modified flame retardant compound having a phosphorus content of 8.96% was obtained after removing the residue and butanol under reduced pressure.

(FT-IR measurement results: Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic) , Si-O-Aromatic: 904 cm ^-1 , Si-Aromatic 1430 cm ^-1 , 1892 cm ^-1 , 1961 cm ^-1 )

<Example 4>

266.5 g of the phosphorus-modified bisphenol compound prepared in Example 1, 108 g of methyl isobutyl ketone, 114.25 g (0.5 mole) of bisphenol A, 150 g (2.0 mole) of formaldehyde aqueous solution (40% aqueous solution) 10 g of the aqueous solution was added to the reaction vessel, and the reaction was carried out at 50 DEG C for 5 hours while heating and stirring. Then, 100 g of water was added to the reaction tank, and the neutralization reaction was carried out with 0.1 N of sulfuric acid. Then, 100 g of water was used to separate the phosphorus-modified bisphenol-based resolved compound through three washing steps. Thereafter, 1004.1 g of butanol was added to dilute the phosphorus-modified bisphenol-based resorptive compound, and 345.6 g (1.6 mole) of DOPO was added thereto. Thereafter, water was removed by dehydrolysis reaction while heating and stirring. Lt; 0 &gt; C for 10 hours. After the reaction was completed, the residue and butanol were removed under reduced pressure to obtain 704.6 g (yield: 91.0%) of a modified flame retardant compound having a phosphorus content of 8.4%.

(FT-IR measurement results; Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic) )

&Lt; Example 5 >

53.3 g of phosphorus modified bisphenol compound prepared in Example 1, 67.2 g of methyl isobutyl ketone, 205 g (0.9 mole) of bisphenol A, 150 g (2.0 mole) of formaldehyde aqueous solution (40% aqueous solution) and 50% aqueous solution of sodium hydroxide 10 g was added to the reaction vessel and the reaction was carried out at 50 ° C for 5 hours while heating and stirring. Then, 100 g of water was added to the reaction tank, and the neutralization reaction was carried out with 0.1 N of sulfuric acid. Then, 100 g of water was used to separate the phosphorus-modified bisphenol-based resolved compound through three washing steps. Subsequently, 718.9 g of butanol was added to dilute the phosphorus-modified bisphenol-based resorptive compound, and 345.6 g (1.6 mole) of DOPO was added thereto. The mixture was heated and stirred while removing water by dehydrolysis, Lt; 0 &gt; C for 10 hours. After the reaction was completed, the residue and butanol were removed under reduced pressure to obtain 556.4 g (yield 95.0%) of phosphorus-modified silicone flame retardant having a phosphorus content of 8.4%.

(FT-IR measurement results; Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic) )

&Lt; Example 6 >

53.3 g of the phosphorus modified bisphenol compound prepared in Example 1, 67.2 g of methyl isobutyl ketone, 195 g (2.5 mole) of an aqueous solution of bisphenol A (205 mole, 0.9 mole) formaldehyde (40% aqueous solution) and 50% And the reaction was carried out at 50 DEG C for 5 hours while stirring with heating. Then, 125 g of water was added to the reaction tank, neutralization reaction was carried out with 6.25 g of 0.1 N sulfuric acid, and 125 g of water was used to separate the phosphorus-modified bisphenol-based resolved compound through three washing steps. Then, 753.6 g of butanol was added thereto to dilute the phosphorus-modified bisphenol-based resorptive compound. Then, 449.28 g (2.08 mole) of DOPO was added, and then water was removed by dehydrolysis reaction while heating with stirring. The reaction was carried out at 160 DEG C for about 10 hours. After the reaction was completed, the residue and butanol were removed under reduced pressure to obtain 646.6 g (yield 88%) of a modified flame retardant compound having a phosphorus content of 9.19%.

(FT-IR measurement results; Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic) )

&Lt; Example 7 >

26.65 g of the phosphorus-modified bisphenol compound prepared in Example 1, 62.1 g of methyl isobutyl ketone, 216.6 g (0.95 mole) of bisphenol A, 218.4 g (2.8 mole) of formaldehyde aqueous solution (40% aqueous solution) 14 g of the aqueous solution was added to the reaction vessel and the reaction was carried out at 50 DEG C for 5 hours while heating and stirring. Then, 140 g of water was added to the reaction vessel, and the neutralization reaction was carried out with 7 N sulfuric acid (7 N). Then, the phosphorus-modified bisphenol-based resorptive compound was isolated by using 140 g of water through three washing steps. Then, 729.6 g of butanol was added to dilute the phosphorus-modified bisphenol-based resorptive compound, 452.48 g (2.24 mole) of DPPO was added, and water was removed by dehydrolysis reaction while heating with stirring. The reaction was carried out at 160 DEG C for about 10 hours. After the reaction was completed, the residue and butanol were removed under reduced pressure to obtain 661.6 g (yield: 91.0%) of a modified flame retardant compound having a phosphorus content of 9.7%.

(FT-IR measurement results; Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic) )

&Lt; Example 8 >

26.65 g of the phosphorus-modified bisphenol compound prepared in Example 1, 55.4 g of methyl isobutyl ketone and 190 g (0.95 mole) of bisphenol F (Songwon Industry, High Purity Bisphenol F, P, P content> 99%), formaldehyde 218.4 g (2.8 mole) of an aqueous solution (40% aqueous solution) and 14 g of a 50% aqueous solution of sodium hydroxide were placed in a reaction vessel and reacted at 50 ° C for 5 hours while heating and stirring. Then, 140 g of water was added to the reaction vessel, and the neutralization reaction was carried out with 7 N sulfuric acid (7 N). Then, the phosphorus-modified bisphenol-based resorptive compound was isolated by using 140 g of water through three washing steps. Thereafter, 667.5 g of butanol was added to dilute the phosphorus-modified bisphenol-based resorptive compound, 483.84 g (2.24 mole) of DOPO was added thereto, and water was removed by dehydrolysis reaction while heating and stirring, = 160 &lt; [deg.] &Gt; C for about 10 hours. After the reaction was completed, the residue and butanol were removed under reduced pressure to obtain 671.2 g (yield: 92.0%) of a modified flame retardant compound having a phosphorus content of 9.73%.

(FT-IR measurement results; Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic) )

&Lt; Example 9 >

26.65 g of the phosphorus modified bisphenol compound prepared in Example 1, 55.4 g of methyl isobutyl ketone, 190 g (0.95 mole) of bisphenol epoxide, 218.4 g (2.8 mole) of formaldehyde aqueous solution (40% aqueous solution) 14 g of the aqueous solution was added to the reaction vessel and the reaction was carried out at 50 DEG C for 5 hours while heating and stirring. Then, 140 g of water was added to the reaction tank, and neutralization reaction was carried out with 7 N sulfuric acid (7 N). Then, 140 g of water was used to separate the phosphorus-modified bisphenol-based resorptive compound through three washing steps. Thereafter, 867.84 g of butanol was added to dilute the phosphorus-modified bisphenol-based resorptive compound, 483.84 g (2.24 mole) of DOPO was added thereto, and the mixture was stirred under heating. While water was removed by dehydrolysis, T = 160 &lt; [deg.] &Gt; C for about 10 hours. After the reaction was completed, the residue and butanol were removed under reduced pressure to obtain 668.67 g (yield 82%) of a modified flame retardant compound having a phosphorus content of 8.7%.

(FT-IR measurement results; Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic) )

&Lt; Example 10 >

533 g of phosphorus-modified bisphenol compound prepared in Example 2, 213.2 g of methyl isobutyl ketone, 150 g (2.0 mole) of formaldehyde aqueous solution (40% aqueous solution) and 10 g of aqueous sodium hydroxide solution (10 g) The reaction was carried out at 50 DEG C for 5 hours with stirring. Then, 100 g of water was added to the reaction tank, and the neutralization reaction was carried out with 0.1 N of sulfuric acid. Then, 100 g of water was used to separate the phosphorus-modified bisphenol-based resolved compound through three washing steps. Thereafter, 1359.4 g of butanol was added to dilute the silicone-modified bisphenol-based resorptive compound, and 345.6 g (1.6 mole) of DOPO was added thereto. Thereafter, water was removed by dehydrolysis reaction while heating and stirring. Lt; 0 &gt; C for 10 hours. After the reaction was completed, the residue and butanol were removed under reduced pressure to obtain 760.12 g (yield: 84%) of a modified flame retardant compound having a phosphorus content of 8.96%.

(FT-IR measurement results: Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic) , Si-O-Aromatic: 904 cm ^-1 , Si-Aromatic 1430 cm ^-1 , 1892 cm ^-1 , 1961 cm ^-1 )

&Lt; Comparative Example 1 &

200 g of DOPO and a catalyst ETPPI (Ethyl Triphenyl Phosphonium Iodide) were added to 800 g of YDPN-638 (manufactured by Kukdo Chemical Co., Ltd., EEW: 180 g / eq), which is a phenol novolac epoxy resin, Epoxy resin was prepared. (EEW: 290 g / eq, phosphorus content: 2.7%)

&Lt; Comparative Example 2 &

228.5 g (1.0 mole) of bisphenol A, 218.4 g (2.8 mole) of formaldehyde aqueous solution (40% aqueous solution) and 14 g of aqueous sodium hydroxide solution (14 g) were charged into the reaction vessel and reacted at 50 ° C for 5 hours while heating and stirring. Then, 140 g of water was added to the reaction tank, neutralization reaction was carried out with 7 N of sulfuric acid, and 140 g of water was used to separate the bisphenol Arazole compound by three washing steps. Then, 464.9 g of butanol was added thereto to dilute the bisphenol Arazole compound. Then, 483.84 g (2.24 mole) of DOPO was added, followed by heating and stirring. While removing water by dehydrolysis reaction, The reaction was continued for about an hour. After the reaction was completed, the residue and butanol were removed under reduced pressure to obtain 703 g (yield 95.0%) of phosphorus / silicon-modified flame retardant compound having a phosphorus content of 9.3%.

(FT-IR measurement results; Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic) )

<Experimental Example>

The flame retardant curing agent compounds prepared in Examples 3 to 10 and Comparative Examples 1 and 2 were compounded in the usual proportions as shown in Tables 1 and 2 to prepare adhesive for printed circuit boards.

In order to evaluate the physical properties of the phosphorus-modified flame retardant compound prepared in the above Examples and Comparative Examples, blending was carried out as shown in Tables 1 and 2, and the results are shown in Tables 3 to 4.

Concretely, the resins prepared in Examples and Comparative Examples were compounded at blending ratios shown in Tables 1 and 2 below to prepare varnishes, impregnated with glass fibers, and prepreg work was carried out. Prepreg (prepreg) is then the radius goes from 175 ℃ 5 bungan-cured state, a specimen of 8-fold at 190 ℃ After pressing for 15 minutes 25 kgf / cm ² pressure, again 120 minutes 40 kgf / cm ² pressure Was added and pressed. Thereafter, it was cooled with a refrigerant for 30 minutes.

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

(2) The glass transition temperature was measured by a differential thermal analyzer (DSC) (20 ° C / min)

(3) Peel strength (1/2 oz copper peel strength) was measured by the GIS C-6417 method.

(4) Water Absorption [wt%] was measured by weight growth rate (wt%) after leaving a specimen of 5 cm × 5 cm (width × length) and 4 mm thickness at 85 ° C. and 85% (relative humidity) .

(5) Dielectric Constant and Dissipation Factor were measured by Agilent E4991A RF Impedance / Material analyzer according to JIS-C-6481 method.

(7) The modulus was measured by ICP-TM-650-2.4.18.3 method.

(8) Lead heat resistance was measured by the JIS-C-6481 method.

division Example One 2 3 4 5 6 7 8 SE-187 20g 20g 20g 20g 20g 20g 20g 20g SE-110M68 44.11 g 44.11 g 44.11 g 44.11 g 44.11 g 44.11 g 44.11 g 44.11 g KDT-4400A70 7.14 g 7.14 g 7.14 g 7.14 g 7.14 g 7.14 g 7.14 g 7.14 g SEB-400M80 56.25 g 56.25 g 56.25 g 56.25 g 56.25 g 56.25 g 56.25 g 56.25 g Example Resin Example 3:
98.33 g Example 4:
105.5g Example 5:
102.5g Example 6:
93.67 g Example 7:
86.8g Example 8:
86.7 g Example 9:
101.3 g Example 10:
101.3 g KPN-2110MC55 43.81 g 37.75g 31.54 g 39.74 g 41.5g 41.3g 40.46 g 43.81 g 2E4MZ 0.01 g 0.01 g 0.01 g 0.01 g 0.01 g 0.01 g 0.010 g 0.01 g Dicy 1.18 g 1.26 g 1.23 g 1.12g 1.04 g 1.04 g 1.21 g 1.18 g ATH 46.0 g 46.0 g 45.0 g 44.8g 44.0 g 44.0 g 46.0 g 46.0 g MCs 56.7g 57.7g 56.1 g 54.9g 53.3g 53.1 g 57.0 g 56.7g

division Comparative Example
2 division Comparative Experimental Example
One SE-187 20 g Comparative Example 1 Resin 100 g SE-110M68 44.11 g Dicy 4.34 g KDT-4400A70 7.14 g 2E4MZ 0.15 g SEB-400M80 56.25 g ATH 26.1225 g Comparative Example 2 Resin 56.19 g MCs 130.61 g KPN-2110MC55 45.09 g - - 2E4MZ 0.01 g - - Dicy 0.11 g - - ATH 45.38 g - - MCs 82.84 g - -

In the Tables 1 and 2, SE-187 is Bisphenol A epoxy (Shinat Tanni) having an equivalent weight of 186 g / eq, SE-110M68 is equivalent to 475 g / eq and MEK NV 68% Bisphenol A epoxy Tetra-phenylethane epoxy (Kukdo Chemical), equivalent to 220 g / eq equivalent to KDT-4400A70, and 70% of Acetone NV, KPN-2110MC65, which is equivalent to 210 g / eq of MEK NV and 80% DEW is a phenolic novolak type curing agent with an EEW of 103 g / OH and 55% of 2-methoxyethanol (Kangnam Hwaseong), Dicy is a common latent curing agent, Dicyandiamide, 2E4MZ is a 2-ethyl- 4-methylimidazole, MCs is 2-methoxyethanol as solvent, and ATH is aluminum hydroxide.

division Example One 2 3 4 5 6 7 8 Phosphorus content
[wt%] 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 ATH content
[wt%] 20 20 20 20 20 20 20 20 Tg
[° C] 154 157 156 157 160 161 162 154 T-288
[minute] > 20 > 20 > 20 > 20 > 20 > 20 > 20 > 20 Td
[° C] 390 385 382 384 389 385 382 389 Flammability
[s] 18 21 24 25 25 25 26 19 Flammability
[UL-94] V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 1/2 oz copper Peel Strength
[Kgf / cm] 1.38 1.36 1.38 1.38 1.34 1.35 1.39 1.38 Water Absorption
[wt%] 0.24 0.25 0.26 0.31 0.31 0.30 0.29 0.25 Dielectric Constant [1 GHz] 4.25 4.27 4.27 4.28 4.30 4.29 4.30 4.26 Dissipation Factor
[1 GHz] 0.010 0.010 0.010 0.010 0.010 0.011 0.011 0.010 Modulus
[GPa] 2.4 2.5 2.5 2.6 2.7 2.7 2.7 2.4

division Comparative Example One 2 Phosphorus content
[wt%] 2.3 2.3 ATH content
[wt%] 20 20 Tg
[° C] 145 160 T-280
[minute] 5 > 20 Td
[° C] 335 360 Flammability
[s] 37 35 Flammability
[UL-94] V-0 V-0 1/2 oz copper Peel Strength
[Kgf / cm] 0.85 1.14 Water Absorption
[wt%] 0.57 0.45 Dielectric Constant [1 GHz] 4.49 4.51 Dissipation Factor
[1 GHz] 0.013 0.015 Modulus
[GPa] 4.2 3.4

The results of Tables 3 to 4 show that the phosphorus flame retardants of Examples 3 to 10 of the present invention had higher peel strength, higher heat resistance, lower hygroscopicity, improved electrical properties, and higher adhesion And toughness are remarkably improved.

The phosphor-modified flame-retardant curing agent prepared by the method of the present invention can be applied to various composite materials such as a PCB substrate and an insulating plate, an adhesive, a coating agent, and a paint.

Claims (5)

1. A phosphor-modified flame-retardant curing agent represented by Formula 1 below;
[Chemical Formula 1]

(2)

In the above formulas (1) and (2), a is an integer of 0 to 4, b is 1, and the order of bonding of each constituent unit according to a and b may be randomly modified;
A is represented by the formula (2);
Each Y is independently,

,

,

,

,

,

or

ego,
Each Z independently represents

,

or

, Each Ar is independently

or

ego;
Each of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is independently -H, -OH or a C _1-10 alkyl group;
Wherein R ₁₀ is C _{6 ~ 20} aryl group, C _{1 ~ 20} alkyl group or cyclo alkyl group is C _{5 ~ 12;}
n is independently an integer of 0 to 2, p is independently an integer of 0 to 2, q is independently an integer of 0 to 2, p + q is 1 or more, r is an integer of 0 to 2, s Is an integer of 0 to 2, r + s is 1 or more, and t is an integer of 0 to 2.
The phosphor-modified flame-retardant curing agent according to claim 1, wherein a in the formula (1) is 0. The phosphor-modified flame-retardant curing agent according to claim 1, wherein a in the formula (1) is an integer of 1 to 4. The method according to claim 1,
Wherein R &lt; ₁₀ &gt; is an aryl group having _{6 to 10} carbon atoms, an alkyl group having _{1 to 10} carbon atoms or a cycloalkyl group having _{5 to 8} carbon atoms. A flame retardant curing agent composition comprising a modified flame retardant curing agent according to any one of claims 1 to 4.