KR20150112983A - Flame retardant agent for resins, flame-retardant resin composition containing same, and method for producing organophosphorus compound - Google Patents

Abstract

상기 식에서, R₁, R₂, R₃ 및 R₄는 각각 독립해서 탄소수1∼8의 알킬기 또는 할로알킬기이고, Z₁ 및 Z₂는 각각 독립해서 수소원자, 메틸기 또는 에틸기이고, n은 0∼10이다.A flame retardant agent for a resin containing an organic phosphorus compound of the formula (I), wherein the organophosphorus compound has a content of a compound of n = 0 in the formula (I) below, measured by gel permeation chromatography (GPC) To 3.0% by area, and an average degree of condensation (N) calculated from the content of each compound of n = 0 to 10 in the following formula (I) is 1.5 to 3.5.

Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group, and n is an integer of 0 to _3, and R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group or haloalkyl group having 1 to 8 carbon atoms, 10.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a flame retardant for a resin, a flame retardant resin composition containing the flame retardant, and a method for producing the organophosphorus compound. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a flame retardant for a resin, a flame retardant resin composition containing the same, and a method for producing an organic phosphorus compound. More specifically, the present invention relates to an additive type flame retardant which is excellent in flame retardancy as a flame retardant for resins, particularly as an additive type flame retardant when flame retarding a polyurethane foam, and also exhibits low fogging resistance (low volatility ), A flame retardant for a resin mainly comprising a polyphosphonate phosphate type organic phosphorus compound having a small amount of a volatile organic compound (VOC) and a low molecular weight monomeric compound, a flame retardant resin composition containing the same, And a process for producing the compound.

In order to impart flame retardancy to the resin, a method of adding a flame retardant agent at the time of preparing the resin molded article is employed. Examples of the flame retardant include an inorganic compound, an organic phosphorus compound, an organic halogen compound, a halogen-containing organic phosphorus compound, etc., and an organic halogen compound and a halogen-containing organic phosphorus compound exhibit excellent flame retarding effect. Organic phosphorus compounds, in particular organic phosphoric acid esters and halogen-containing organic phosphoric acid esters, have been commonly used as flame retardants to obtain a good flame retardant effect.

Examples of such halogen-containing organic phosphoric acid esters are disclosed in U.S. Patent No. 3,192,242 (Patent Document 1), Japanese Patent Publication No. S49-43272 (Patent Document 2), JP-A S56-36512 (Patent Document 3) And Japanese Laid-Open Patent H11-100391 (Patent Publication 4).

Among various resins, the polyurethane foam (polyurethane foam) has a limited use because it is flammable, and various studies have been conducted recently due to the flame retardancy of the polyurethane foam, but it is still not sufficient.

In general, the following conditions are required as the flame retardant for polyurethane foam.

(1) Scorching (no selection of form) should not occur

(2) The flame retardancy of the foam should be persistent.

(3) The viscosity should be appropriate.

(4) Good miscibility with foam components

(5) It is difficult to be hydrolyzed.

(6) Reduce smoke or poison gas

(7) Do not deteriorate the physical properties of the foam.

(8) Excellent fogging resistance

(9) VOC, low molecular weight mono-compound

Among the above-mentioned various conditions, it is particularly demanded that the polyurethane foam does not cause scorching, has good flame retardancy, has less deterioration of physical properties, is excellent in endurance, is low in VOC and monomolecular compound of low molecular weight do. Particularly, in recent years, there is a growing demand for endocytosis, VOC and monomolecular compounds of low molecular weight.

Conventionally, tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate and the like have been used as flame retardants for polyurethane foam.

Organic phosphorus compounds such as tris (2-chloroethyl) phosphate and tris (dichloropropyl) phosphate, when blended in a polyurethane foam, exhibit flame retarding effect at an initial stage, but the flame- There is a problem that gingability is poor, and monocomponent compounds of VOC and low molecular weight are also present. This is presumably because the molecular weight of these organic phosphorus compounds is small and the flame retardant is volatilized.

Tris (2,3-dibromopropyl) phosphate is excellent in flame retardancy and durability, but is poor in heat resistance. When added to a polyurethane foam, scorching occurs in the production of foam, Can not do it.

Tris (2,3-dibromopropyl) phosphate has also been used as a flame retardant for polyester fibers, but is not currently used because of suspicion of carcinogenicity.

(2-chloroethyl) phosphate (see Patent Document 1) and tetrakis (2-chloroethyl) phosphate, which are compounds having two phosphorus atoms in one molecule, 2,2-bis (chloromethyl) Ethylene diphosphate (see Patent Document 2) has attracted attention as a flame retardant for polyurethane foam. However, these compounds are not sufficient in terms of flame retardancy and persistence thereof, and it is necessary to use chlorine gas at the time of production, which is problematic from the viewpoint of production.

Therefore, in order to improve these, it is preferable to use a mixture of tris [bis (2-chloroethoxy) phosphinyl (dimethyl) methyl] phosphate and 2-chloroethyl bis [bis (2-chloroethoxy) phosphinyl (See Patent Documents 3 and 4).

However, these compounds contain a phosphorus compound monomer such as tris (2-chloroethyl) phosphate which is a by-product in the production process and do not sufficiently respond to the demand for reduction of endoggring property, VOC and monomolecular compound of low molecular weight, Development of such a halogen-containing organophosphorus compound and its production method has been desired.

U.S. Patent No. 3,192,242 Japanese Patent Publication No. S49-43272 Japanese Laid-Open Patent S56-36512 Japanese Patent Application Laid-Open No. H11-100391

An object of the present invention is to provide a flame retardant for a resin, particularly an additive type flame retardant for flame retarding a polyurethane foam, exhibiting excellent flame retardancy, exhibiting excellent long-lasting change with time, excellent endurance, A flame retardant resin for a resin mainly comprising a polyphosphonate phosphate type organic phosphorus compound, a flame retardant resin composition containing the phosphorus flame retardant, and a method for producing an organic phosphorus compound.

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that a monomolecular compound having a low molecular weight, that is, a polyphosphonate phosphate type organic phosphorus compound having a reduced content of a phosphoric acid ester monomer, The present inventors have found an excellent flame retardant which satisfies most of various conditions of the flame retardant and a method of producing the organic phosphorus compound, and have completed the present invention.

Thus, according to the present invention, in a flame retardant agent for a resin containing an organic phosphorus compound of the formula (I)

Wherein the content of the compound of n = 0 in the following formula (I) is 0.1 to 3.0% by area, and n = 0 in the formula (I) below, when measured by gel permeation chromatography (GPC) (N) of 1.5 to 3.5 calculated from the contents of the respective compounds of the following formulas (1) to (10):

Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group, and n is an integer of 0 to _3, and R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group or haloalkyl group having 1 to 8 carbon atoms, 10.

According to the present invention, there is also provided a flame retardant resin composition containing the resin-containing flame retardant and the resin.

Further, according to the present invention,

(A), compound (b) and compound (c) of the formula (a), compound (c) and compound (B) is reacted at a temperature of -20 to 60 占 폚 in a proportion of 1.3 to 2.0 mol per 1 mol of the compound (c) in a proportion of 1.5 to 3.5 mol, To obtain a compound (d)

Next, as the step (2), the compound (d) obtained in the above step (1) is oxidized with an oxidizing agent and is represented by the above formula (I) To obtain an organic phosphorus compound having an average degree of condensation (N) of 1.5 to 3.5 calculated from the content of each compound of n = 0 to 10 in the formula (I) , ≪ / RTI > wherein: < RTI ID = 0.0 >

Wherein R ₁ , R ₂ , R ₃ , R ₄ , Z ₁ , Z ₂ and n have the same meanings as defined in formula (I), R ₅ is an alkyl or haloalkyl group having 1 to 8 carbon atoms, Lt; / RTI >

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a flame retardant for a resin, particularly an addition type flame retardant for a flame retardant for resin, particularly a polyurethane foam, exhibiting excellent flame retardancy and exhibiting excellent long- There can be provided a flame retardant agent for a resin comprising a polyphosphonate phosphate type organic phosphorus compound as a main component and a flame retardant resin composition containing the same and a method for producing an organic phosphorus compound.

The flame retardant for resin of the present invention exhibits an excellent flame retardant effect by adding very little volatile organic phosphorus compound of formula (I) as a main component and adding it to a resin, particularly to a polyurethane foam component before foaming by a prescribed prescription . The obtained polyurethane foam exhibits excellent flame retardancy and endurance (low volatility) by the combustibility test method such as MVSS-302 as described later, and the volatile component is very small.

The above-mentioned effect is further exerted when the flame retardant for resin of the present invention satisfies any one of the following conditions:

The content of the compound of the formula (I) in which n = 1 is 10 to 50% by area, when the organophosphorus compound is measured by GPC,

The average degree of condensation (N) in the formula (I) is 1.8 to 3.0

When the flame retardant resin composition of the present invention satisfies any one of the following conditions, the above-mentioned effect is further exerted:

The resin is a resin selected from a polyurethane resin, an acrylic resin, a phenol resin, an epoxy resin, a vinyl chloride resin, a polyamide resin, a polyester resin, an unsaturated polyester resin, a styrene resin and a synthetic rubber, Urethane foam,

1 to 40 parts by weight of the resin-containing flame retardant is contained in 100 parts by weight of the resin.

Further, the above-mentioned effect is further exerted when the method for producing an organic phosphorus compound of the present invention satisfies any one of the following conditions:

The content of the compound of the formula (I) in which n = 1 is 10 to 50% by area, when the organophosphorus compound is measured by GPC,

The average degree of condensation (N) in the formula (I) is from 1.8 to 3.0.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram showing flame retardancy persistence of a flame retardant for resin according to the present invention. FIG.
2 is a graph showing the phosphorus content retention rate of the flame retardant for resin of the present invention.

The flame retardant for resin according to the present invention is a flame retardant for resin containing an organic phosphorus compound of formula (I)

Wherein the content of the compound of n = 0 in the following formula (I) is 0.1 to 3.0% by area and the content of n = 0 in the hermaphroditic formula (I) when measured by gel permeation chromatography (GPC) (N) calculated from the contents of the respective compounds of the following formulas (1) to (10) is 1.5 to 3.5:

Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group, and n is an integer of 0 to _3, and R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group or haloalkyl group having 1 to 8 carbon atoms, 10.

In the present invention, " A to B " representing the numerical range means A to B, inclusive.

Hereinafter, [1] an organic phosphorus compound of formula (I) (hereinafter also referred to as "organic phosphorus compound (I)") included in the flame retardant agent for resin of the present invention, [2] And [3] the flame retardant resin composition of the present invention.

[1] Organophosphorus compound (I)

The organic phosphorus compound (I) contained in the flame retardant for resin of the present invention is represented by the formula (I).

The substituents R ₁ , R ₂ , R ₃ and R ₄ in the formula (I) are each independently an alkyl or haloalkyl group having 1 to 8 carbon atoms, more preferably an alkyl or haloalkyl group having 1 to 4 carbon atoms, 4 > is more preferable.

Examples of the halogen atom of the haloalkyl group include fluorine, chlorine, bromine and iodine, with chlorine and bromine being preferred, and chlorine being particularly preferred.

Specific examples of the substituent include an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, cyclohexyl, n-octyl, isooctyl, 2-ethylhexyl and the like: chloromethyl, chloroethyl, chloropropyl, , Dichloropropyl, dichloroisopropyl, chlorobutyl, dichlorobutyl, dichloroisobutyl, bromomethyl, bromoethyl, bromopropyl, bromoisopropyl, dibromopropyl, dibromoisopropyl, bromobutyl, And haloalkyl groups such as dibromobutyl, dibromoisobutyl, bromochloropropyl, bromochloroisopropyl, bromochlorobutyl and bromochloroisobutyl.

Among these, preferred are chloromethyl, chloroethyl, chloropropyl, chloroisopropyl, dichloropropyl, dichloroisopropyl, chlorobutyl, dichlorobutyl, dichloroisobutyl, bromomethyl, bromoethyl, bromopropyl, The number of carbon atoms such as dibromopropyl, dibromoisopropyl, bromobutyl, dibromobutyl, dibromoisobutyl, bromochloropropyl, bromochloroisopropyl, bromochlorobutyl and bromochloroisobutyl More preferably 1 to 4 haloalkyl groups, particularly preferably chloroethyl, chloropropyl, chloroisopropyl, dichloropropyl and dichloroisopropyl.

The substituents Z ₁ and Z ₂ in the formula (I) are each independently a hydrogen atom, a methyl group or an ethyl group.

The number n of the repeating units in the formula (I) is 0 to 10, and the compound as the component constituting the organic phosphorus compound (I) is a mixture of the compounds in which n is 0 to 10, , And basically, the characteristics as a flame retardant for a resin are almost the same.

In the formula (I), n may be 0 to 10, but in view of workability as a flame retardant for a resin and a flame retardant resin composition and effects to be obtained, it is necessary that the viscosity is appropriate.

Further, in order to obtain flame retardant for resin having excellent endurance of gaining property and little phosphoric acid ester monomer, n of the compound which is the main component of organic phosphorus compound (I) is preferably any one of 1 to 5, Is particularly preferable.

The specific number n of repeating units is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10, preferably 1, 2, 3, 4 and 5, Do.

Here, the main component means a component having the highest content among the components constituting the organic phosphorus compound (I).

Therefore, the organophosphorus compound (I) contained in the flame retardant agent for a resin of the present invention has a content of the compound of n = 0 in the formula (I) when measured by Gel Permeation Chromatography (GPC) Is 0.1 to 3.0% by area, and the average degree of condensation (N) calculated from the content of each compound of n = 0 to 10 in the formula (I) is 1.5 to 3.5.

The specific content (area%) of the compound of n = 0 is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, , 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 and 3.0.

It is most preferable that the organic phosphorus compound (I) does not contain a compound of n = 0 in the formula (I), that is, an monomeric phosphate ester. 0 may be contained in an amount of 0.1 to 3.0% by area in the GPC measurement.

For the above reason, the content of the compound of the formula (I) in which n = 1 is preferably 10 to 50% by area in the GPC measurement. The upper limit is more preferably 45% by area, and even more preferably 40% by area. The lower limit is more preferably 15% by area, and more preferably 20% by area.

The specific content (area%) of the compound of n = 1 is, for example, 10, 15, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, , 35, 36, 37, 38, 39, 40, 45 and 50, and the like.

In view of the above, the average degree of condensation (N) of the organophosphorus compound (I) is 1.5 to 3.5. The upper limit is preferably 3.0. The lower limit thereof is more preferably 1.8, and still more preferably 2.0.

The specific average degree of condensation N is, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.4 and 3.5.

The average degree of condensation (N) can be calculated by the following equation using GPC area fraction (A _n ) of each component of n = 0 to 10 in GPC measurement.

N =? (N? A _n ) /? (A _n )

The content of each compound (component) of n = 0 to 10 in the organic phosphorus compound (I) by GPC measurement can be analyzed (measured), for example, as follows.

Concretely, 10 ml of tetrahydrofuran (THF) was added to 0.09 g of a sample by a hole pipette, and the sample solution was analyzed under the following instrument and analysis conditions. The area% of the RI detector was calculated as the content (composition) .

(device)

GPC analyzer (TOSOH CORPORATION., Format: HLC-8220 or equivalent)

Data analyzer (TOSOH CORPORATION., Format: SC-8010 or equivalent)

(column)

Guard column

(TOSOH CORPORATION., Format: TSKguardcolumnSuperHZ-L

4.6 mm I.D. × 2.0 cm) 1

Sample Column

(TOSOH CORPORATION., Format: TSKGEL SuperHZ1000

6.0 mm ID x 15 cm) 3

(TOSOH CORPORATION., Format: TSKGEL SuperHZ2000

6.0 mm ID × 15 cm) 1

(Analysis condition)

INLET temperature 40 ℃

Column temperature 40 ° C

RI temperature 35 ° C

Solvent flow rate 0.25 ml / min

Detector RI (Refractive Index)

Sample solution injection amount 10 ((roof tube)

(Data processing condition)

START TIME (minutes) 25.00

STOP TIME (minutes) 50.00

The organic phosphorus compound (I) of the polyphosphonate phosphate type of the present invention may be a compound having a combination of the above substituents and repeating unit numbers, or may be a mixture of two or more different substituents.

Among them, as the compound of n = 1,

1- [bis (2-chloroethoxy) phosphinyl] -1-methylethyl bis (2-chloroethyl) phosphate, and

1- [bis (2-chloroethoxy) phosphinyl] ethylbis (2-chloroethyl) phosphate, and

And a condensate thereof in which n = 2 or more is particularly preferable.

The flame retardant for resin containing the polyphosphonate phosphate type organic phosphorus compound of formula (I) of the present invention can be used as a flame retardant for various resins.

Preferable resins to be added include, for example, polyurethane resins, acrylic resins, phenol resins, epoxy resins, vinyl chloride resins, polyamide resins, polyester resins, unsaturated polyester resins, have. Among these, a polyurethane resin and an acrylic resin are preferable, a polyurethane resin is more preferable, and a foam of a polyurethane resin, that is, a polyurethane foam is particularly preferable.

The polyurethane foam may be soft, semi-rigid or rigid, and the flame retardant of the present invention may be suitably used as these addition type flame retardants.

Since the polyurethane foam has breathable continuous cells, the flame retardant for conventional resins is scattered by volatilization, and the flame retardancy is lowered, the function thereof is lost, and the endurance is lowered. There was also a problem that there were many phosphate ester monomers. In the flame retardant for resin of the present invention, the volatile component is small, the flame retardancy is continuously exhibited, the endurance is improved, and the phosphate ester monomer can be reduced.

[2] Method for producing organic phosphorus compound (I)

The organic phosphorus compound (I) of the present invention can be produced, for example, by a known two-step reaction under the conditions described below.

That is, the compound (d) is obtained by reacting the compounds (a), (b) and (c) by the step (1), and then the compound (d) obtained in the step And oxidizing it with an oxidizing agent.

Processes (1) and (2) can be theoretically represented by the following reaction formulas (1) and (2), respectively.

Hereinafter, each step will be described.

Step (1)

In the step (1), the compound (a), the compound (b) and the compound (c) are mixed at a ratio of 1.5 to 3.5 moles relative to 1 mole of the compound (c) (B) is reacted at a temperature of -20 to 60 占 폚 in a proportion of 1.3 to 2.0 moles to obtain Compound (d). That is, q = 1.5 to 3.5 and p / q = 1.3 to 2.0. By the reaction of the compounds (a), (b) and (c), RX (R is the same as R ₁ , R ₂ , R ₃ , R ₄ and R ₅ and X is a halogen atom) .

In the above formula, " + OA " means adding an oxidizing agent.

Here, the reason why q = 1.5 to 3.5 with respect to the value of the coefficient q will be explained.

Since the average degree of condensation (N) of the organic phosphorus compound (I) of the present invention is theoretically the degree of condensation corresponding to the coefficient q in the reaction formula (1), the average degree of condensation (N) , The proportions of the compounds (a), (b) and (c) may be used in the corresponding molar ratios.

In step (1), the coefficient q of the compound (c) must exceed 1.

This is because unreacted compound (a) necessarily exists when the coefficient q is less than 1, which is a cause of formation of the monomeric phosphate ester represented by n = 0 in the compound (d) and the formula (I).

When the coefficient q is 1, the theoretical reaction formula does not produce an monomeric phosphate ester represented by n = 0 in the formula (I), but the reaction rate can not be actually 100% Since the coefficient q must exceed 1 in order to reduce the content of the monomeric phosphate ester represented by n = 0 in the general formula (I).

The reason why the ratio of q to the value of the coefficient p is p / q = 1.3 to 2.0 will be described.

In the reaction of the step (1), the compound (b) binds between the compound (a) and the compound (c) and exhibits the same behavior as the condensing agent. Therefore, in the theoretical reaction formula, the compound (b) will form the compound (d) equimolar with the compound (c), but the reaction rate can not be 100% in practice. Therefore, it is necessary to add the compound (b) in excess.

(A), (b) and (c), and the unreacted compound (a) and the compound (c) are left unremoved and the average degree of condensation N is 1.5 to 3.5 , It is necessary to use the compound (c) in a proportion of 1.5 to 3.5 mol per 1 mol of the compound (a). That is, q = 1.5 to 3.5. The upper limit thereof is preferably 3.0, and the lower limit thereof is preferably 1.7. In addition, at the same time, it is also necessary to use the compound (b) in a proportion of 1.3 to 2.0 mol per 1 mol of the compound (c). That is, p / q = 1.3 to 2.0. The upper limit thereof is preferably 1.7, and the lower limit thereof is 1.4.

Specific values of the coefficient q are, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 and 3.0.

The ratio p / q of the specific coefficient p to q is, for example, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 and 2.0.

The reaction temperature in the step (1) is -20 to 60 캜.

If the reaction temperature is lower than -20 占 폚, the reaction may be delayed and the reaction may not proceed sufficiently. On the other hand, if the reaction temperature is higher than 60 ° C, the reaction proceeds rapidly, and the control becomes difficult. The lower limit of the reaction temperature is preferably -10 ° C, more preferably 0 ° C. The upper limit is preferably 50 캜, more preferably 40 캜.

Specific reaction temperatures (占 폚) are, for example, -20, -15, -10, -5, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, .

Here, it is preferable that the substituents R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are all the same.

When these substituents are all the same haloalkyl group, by reacting the corresponding alkylene oxide and phosphorus trihalide in a controlled molar ratio, the phosphite of the compound (a) in the step (1) and the phosphorus Halide can be prepared at the same time.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetramethylene oxide and the like. Of these, ethylene oxide and propylene oxide are preferable, and ethylene oxide is particularly preferable.

The amount of the required compound (b) can be calculated by measuring the active halogen atoms (X) in the reaction solution at this time and calculating the concentration of the X atom in the compound (c).

For example, when R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are chloroethyl groups and the active halogen atom is chlorine, the concentration of active halogen atoms is preferably 9 to 11% by weight, more preferably 9 to 10% Is more preferable.

Concentrations (wt%) of specific active halogen atoms are, for example, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7 , 10.8, 10.9 and 11.0, and the like.

Next, the raw material compound of the step (1) will be described.

The compound (a) is represented by the following formula.

Wherein R ₁ and R ₂ have the same meanings as defined in formula (I), and R ₅ is an alkyl or haloalkyl group having 1 to 8 carbon atoms.

Examples of the alkyl group having 1 to 8 carbon atoms and the haloalkyl group represented by R ₅ include those exemplified as the formula (I) as R 1 and R 2.

The compound (a) is a trialkyl phosphite or a tris (haloalkyl) phosphite, and can be prepared by a known method such as described in, for example, U.S. Patent No. 3803272, specifically, phosphorus trihalide and an alkyl alcohol or alkylene oxide ≪ / RTI >

Specific examples of the compound (a) include trimethylphosphite, triethylphosphite, methyldiethylphosphite, dimethylethylphosphite, tripropylphosphite, methylethylpropylphosphite, triisopropylphosphite, tributylphosphite, tri (N-octyl) phosphite, tri (isooctyl) phosphite, tri (2-ethylhexyl) phosphite, tris (chloromethyl) phosphite (Chloroethyl) phosphite, tris (dichloroethyl) phosphite, chloromethyldi (chloroethyl) phosphite, di (chloromethyl) chloroethylphosphite, tris Propyl) phosphite, di (chloroethyl) chloropropylphosphite, chloromethylchloroethylchloropropylphosphite, tris (chloroisoprop ) Phosphite, tris (dichloroisopropyl) phosphite, tris (bromomethyl) propionate, tris (dicyclohexyl) phosphite, tris ) Phosphite, tris (bromoisopropyl) phosphite, tris (dibromoisopropyl) phosphite, tris (dibromoethyl) phosphite, tris Among these, tris (chloroethyl) phosphite, tris (chloropropyl) phosphite, tris (bromo chloropropyl) phosphite and the like can be given. Dichloropropyl) phosphite, tris (chloroisopropyl) phosphite, and tris (dichloroisopropyl) phosphite are particularly preferable.

The compound (b) is represented by the following formula.

Wherein Z ₁ and Z ₂ have the same meanings as defined in formula (I).

Specific examples of the compound (b) include formaldehyde, acetaldehyde, propionaldehyde, acetone, methyl ethyl ketone and diethyl ketone. Of these, acetaldehyde, acetone and methyl ethyl ketone are preferable, And acetone is particularly preferable.

The compound (c) is represented by the following formula.

Wherein R ₃ and R ₄ have the same meanings as defined in formula (I), and X is a halogen atom.

X may be fluorine, chlorine, bromine or iodine as the halogen atom, preferably chlorine and bromine, and chlorine is particularly preferable.

The compound (c) is a dialkylphosphorohalidite or di (haloalkyl) phosphorohalidite, for example, by a known method such as described in U.S. Patent No. 3803272, the reaction is stopped with a diester Specifically, it can be produced by stopping the reaction of a trihalide such as phosphorus trichloride with an alkyl alcohol or an alkylene oxide with a diester.

Specific examples of the compound (c) include dimethylphosphorochloride, diethylphosphorochloridite, methylethylphosphorochloridite, dipropylphosphorochloridite, methylpropylphosphorochloridite, ethylpropylphosphorohydrate, For example, chlorides, chlorides, chlorides, chlorides, diisopropylphosphorochloride, ethylisopropylphosphorochloride, dibutylphosphorochloride, diisobutylphosphorochloride, dihexylphosphorochloridite, dicyclohexyl (2-ethylhexyl) phosphorochloridite, di (n-octyl) phosphorochloride, di (isooctyl) phosphorochloride, di (Chloroethyl) phosphorochloridite, chloromethyl chloroethylphosphorochloride, di (chloropropyl) phosphorochloridite, chloroethyl chloropropylphosphorochloride (Dichloroisopropyl) phosphochloridite, di (dichloroisopropyl) phosphochloridite, di (dichloroisopropyl) phosphochloridite, di (dichloroisopropyl) phosphorochloride, Di (bromomethyl) phosphochloridite, di (bromoethyl) phosphorochloridite, di (bromopropyl) phosphorochloride, di (dibromopropyl) (Bromoisopropyl) phosphochloridite, di (dibromoisopropyl) phosphochloridite, di (bromochloropropyl) phosphorochloridite, di (bromochloroisopropyl) Among these, di (chloroethyl) phosphorochloride, di (chloropropyl) phosphorochloridite, di (dichloropropyl) phosphorochloridite, di (chloroisopropyl) Force Po Laurie die agent, di (isopropyl-dichloro) phosphorothioate chloride is particularly preferable redirect agent.

Step (2)

In the step (2), the compound (d) obtained in the step (1) is oxidized with an oxidizing agent to obtain the organophosphorus compound (I) of the present invention. That is, in step (2), the phosphite moiety of compound (d) is oxidized.

Specific examples of the oxidizing agent include peracetic acid and hydrogen peroxide, and hydrogen peroxide is particularly preferable. Hydrogen peroxide may be an aqueous solution, and particularly preferably 35% (w / v)% hydrogen peroxide frequently used for industrial purposes.

In the step (2), if necessary, an aqueous solution of sodium hydroxide is appropriately added to the reaction solution, and hydrogen peroxide may be dropped while the reaction solution is maintained at a pH of 9.5 to 10.5. As the sodium hydroxide aqueous solution, 30 (weight / volume) aqueous solution frequently used for industrial purposes is preferable.

Specific pHs are, for example, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4 and 10.5.

The reaction temperature in the step (2) is preferably 5 to 50 占 폚, the upper limit thereof is preferably 40 占 폚, and the lower limit is preferably 10 占 폚.

Specific reaction temperatures (占 폚) are, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45,

As described above, the method of producing the organophosphorus compound (I) of the present invention has been described. However, it is possible to produce a large number of compounds depending on the choice of phosphite, phosphorohalidite, aldehyde and ketone And it goes without saying that they are within the scope of the present invention.

In addition, the method for producing the organophosphorus compound (I) of the present invention has an advantage that various phosphorus compounds (I) can be prepared according to purposes, because the phosphorus content, halogen content, molecular weight and the like can be adjusted.

In actual production, a desired compound may be selectively obtained from these compounds, and may be a mixture of two or more compounds or a mixture of compounds having different degrees of condensation. In order to achieve excellent endogogging, It is necessary to reduce the content of the monomeric phosphate ester represented by n =

[3] Flame Retardant Resin Composition

The flame retardant resin composition of the present invention is characterized by containing a flame retardant for resin and a resin of the present invention.

As the resin, resins exemplified as objects to which a flame retardant for resin can be added can be mentioned.

The flame retardant resin composition of the present invention preferably contains 1 to 40 parts by weight of a resin-made flame retardant per 100 parts by weight of the resin. The amount of the flame retardant for resin to be added may be suitably set in accordance with the type of resin and the degree of desired flame retardation.

The amount (parts by weight) of the resin-containing flame retardant added to 100 parts by weight of the specific resin is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, , 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35,

The flame retardant resin composition using the organophosphorus compound of the present invention may contain known resin additives, that is, other additives other than the flame retardant and other flame retardants, within a range not adversely affecting the physical properties of the resin.

Examples of other flame retardants include non-halogen phosphate ester flame retardants such as triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, resorcinol-tetraphenyl bisphosphate and bisphenol A-tetraphenyl bisphosphate; (Poly) alkylene glycol-based halogen-containing polyphosphate, tris (2-chloroethyl) ethylenediamine phosphate, 2,2-bis (chloromethyl) -1,3- Halogen-containing phosphate ester flame retardants such as neopentyl phosphate; Brominated flame retardants such as decabromodiphenyl ether, tetrabromobisphenol A and 1,2-bis (pentabromophenyl) ethane; Inorganic flame retardants such as antimony trioxide and magnesium hydroxide; And nitrogen-based flame retardants such as ammonium polyphosphate and melamine phosphate.

Examples of the additives other than the flame retardant include antioxidants, fillers, lubricants, modifiers, fragrances, antimicrobial agents, pigments, dyes, heat resisting agents, endurance agents, antistatic agents, ultraviolet absorbers, stabilizers, .

The flame retardant resin for a resin, which is an organic phosphorus compound of the present invention, can be used especially for polyurethane foam, and the flame retardant resin composition containing the flame retardant for resin and polyurethane foam of the present invention, that is, the flame retardant polyurethane foam, Which is superior in flame retardancy and durability as compared with the softened polyurethane foam by the flame retardant of the system, and further has excellent performance in endurance.

The production method of the polyurethane foam is already known, and the flame-retardant polyurethane foam to which the flame retardant is added can be produced by a known method.

For example, 1 to 30 parts by weight, preferably 3 to 20 parts by weight of a flame retardant for resin of the formula (I) of the present invention is mixed with 100 parts by weight of a polyol including a polyester polyol, a polyether polyol and the like. When a foam stabilizer, a catalyst, a foaming agent, or the like is added to the resulting mixture, stirred, and then reacted by adding an organic polyisocyanate, a flame-retardant polyurethane foam is obtained.

The amount (parts by weight) of the resin-containing flame retardant added to 100 parts by weight of the specific polyol is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, , 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29,

Examples of the organic polyisocyanate include tolylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, biphenyldisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, cyclopentane diisocyanate, cyclohexane diisocyanate, Butylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, isophorone diisocyanate, isocyanate, norbornadiisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, , 1,3-butylene diisocyanate, and the like.

Example

The present invention will be described more specifically with reference to the following examples and comparative examples, but the scope of the present invention is not limited thereto.

[ Example  One]

(Reaction step: step (1))

275 g (2.0 mol) of phosphorus trichloride, 0.55 g of triethylamine and 0.65 g of ethylenechlorohydrin were charged into a 1000 ml flask equipped with a stirrer, a thermometer, a blowing tube and a condenser. Subsequently, the obtained mixture was heated to 40 to 50 캜 under stirring, and 208 g (4.72 mol) of gaseous ethylene oxide was blown into the tube from the bomb through a flow meter and a blowing tube over 4 hours. (2-chloroethyl) phosphite as the compound (a) and di (2-chloroethyl) phosphorochloridite as the compound (c) were heated to 50 to 60 캜 and maintained for 1 hour (0.70 mol and 1.30 mol, respectively). The active chlorine concentration of the reaction mixture was 9.6%.

The resulting reaction mixture was maintained at 0 to 10 캜 and 113 g (1.95 mol) of acetone as 1.5 moles of compound (b) were added to 1 mol of di (2-chloroethyl) phosphorochloridite as the compound (c) , Over a period of 2 hours through a dropping funnel. After reacting at the same temperature for 12 hours, the reaction temperature was gradually raised, and the reaction was carried out at 30 to 40 ° C for 24 hours. The acid value of the reaction mixture was 2.2.

(Reaction process: process (2))

Then, the reaction mixture containing the compound (d) obtained was kept at 5 to 10 캜, and 6 g of a 30% aqueous solution of sodium hydroxide was added thereto through a dropping funnel. The pH of the reaction mixture was 10.5.

Then, the obtained reaction mixture was maintained at 10 to 20 캜, and 71 g (0.73 mol) of 35% hydrogen peroxide aqueous solution as an oxidizing agent was added over 4 hours. While the aqueous hydrogen peroxide solution was added, the pH was adjusted while adding a 30% aqueous solution of sodium hydroxide suitably so that the pH of the reaction mixture became 9.5 to 10.5. The total amount of 30% aqueous sodium hydroxide solution was 25 g. After the addition of the hydrogen peroxide aqueous solution was completed, the reaction was continued at 30 to 40 캜 for 2 hours.

(Post-treatment process)

10 g of a 30% aqueous sodium hydroxide solution was added to the obtained reaction mixture, and the mixture was heated to 40 to 50 캜 and stirred for 1 hour. Then, the obtained reaction mixture was stand with a separating funnel and separated into an aqueous phase and an organic phase. The obtained organic phase was washed twice with 200 ml of hot water at 60 to 70 캜, and then the low boiling point portion was removed at 90 to 100 캜 under reduced pressure of 1 to 3 kPa. The obtained product is referred to as flame retardant A.

The analysis of the flame retardant A bar, the main component is ethoxy in formula (I) of R _1, R _2, R ₃ and R ₄ is 2-chloroethyl, Z ₁ and Z ₂ is methyl, and 1- [bis (2-chloro ) Phosphinyl] -1-methylethyl bis (2-chloroethyl) phosphate.

As a result of the GPC measurement, 0.9% by area of the compound having n = 0, 37.2% by area of the compound having n = 1 and an average degree of condensation (N) of 2.12.

The content of phosphorus (P) was 13.8 wt%, the chlorine content (Cl) was 26.1 wt%, the viscosity was 4320 mPa ((25 캜) and the acid value was 0.03 KOH mg / g.

[ Example  2]

(2-chloroethyl) phosphite as the compound (a) and di (2-chloroethyl) phosphite as the compound (c) were obtained in the same manner as in Example 1 except that 208 g (4.72 mol) of ethylene oxide was changed to 206 g -Chloroethyl) phosphorochloridite (0.65 mol and 1.35 mol, respectively). The active chlorine concentration of the reaction mixture was 10.0%.

The obtained reaction mixture was maintained at 40 占 폚 instead of 0 占 폚 to 10 占 폚 and 1.5 mole of the compound (b), 116 g of acetone as the compound (b), was added per mole of di (2-chloroethyl) phosphorochloridite as the compound (2.00 moles) was added via a dropping funnel over 6 hours instead of 2 hours, and the mixture was reacted at the same temperature for 12 hours. 65 g (0.67 moles) of 71 g (0.73 mole) of 35% hydrogen peroxide aqueous solution as an oxidizing agent , Flame retarding agent B was obtained in the same manner as in Example 1. [

Analysis of the flame retardant B showed that the main component was 1- [bis (2-chloroethoxy) carbonyl, where R ₁ , R ₂ , R ₃ and R ₄ in formula (I) were 2-chloroethyl and Z ₁ and Z ₂ were methyl ) Phosphinyl] -1-methylethyl bis (2-chloroethyl) phosphate.

As a result of GPC measurement, the compound of n = 0 was 0.5% by area, the compound of n = 1 was 29.2% by area, and the average degree of condensation (N) was 2.41.

In addition, the phosphorus (P) was 13.9 wt%, the chlorine (Cl) was 24.8 wt%, the viscosity was 6200 mPa ((25 캜), and the acid value was 0.05 KOHmg / g.

[ Example  3]

A mixture of tris (2-chloroethyl) phosphite and di (2-chloroethyl) phosphorochloridite was obtained in the same manner as in Example 1.

The obtained reaction mixture was maintained at 40 占 폚 instead of 0 to 10 占 폚 and 1.7 mole of the compound (b), 128 g of acetone as the compound (b), relative to 1 mole of di (2-chloroethyl) phosphorochloridite as the compound (2.20 moles) were added via a dropping funnel over 6 hours instead of 2 hours, and reacted at the same temperature for 12 hours. 65 g (0.67 mole) of a 35% aqueous solution of hydrogen peroxide (0.73 mole) A flame retardant agent C was obtained in the same manner as in Example 1. [

Analysis of the flame retardant C showed that the main component was 1- [bis (2-chloroethoxy) methylene chloride in which R ₁ , R ₂ , R ₃ and R ₄ of formula (I) were 2-chloroethyl and Z ₁ and Z ₂ were methyl ) Phosphinyl] -1-methylethyl bis (2-chloroethyl) phosphate.

As a result of GPC measurement, the compound having n = 0 was 1.3% by area, the compound with n = 1 was 34.7% by area, and the average degree of condensation (N) was 2.16.

The content of phosphorus (P) was 13.7 wt%, the chlorine content (Cl) was 25.1 wt%, the viscosity was 2200 mPa ((25 캜) and the acid value was 0.02 KOHmg / g.

[ Example  4]

(2-chloroethyl) phosphite as the compound (a) and di (2-chloroethyl) phosphite as the compound (c) were obtained in the same manner as in Example 1 except that 208 g (4.72 mol) of ethylene oxide was changed to 198 g -Chloroethyl) phosphorochloridite (0.59 mol and 1.40 mol, respectively). The active chlorine concentration of the reaction mixture was 10.5%.

The obtained reaction mixture was maintained at 40 占 폚 instead of 0 占 폚 to 10 占 폚 and 1.5 mole of acetone as compound (b) to 1 mole of di (2-chloroethyl) phosphorochloridite as compound (c) (2.12 moles) were added via a dropping funnel over 6 hours instead of 2 hours, reacted at the same temperature for 12 hours, and 71 g (0.73 mole) of 35% hydrogen peroxide aqueous solution as an oxidizing agent was changed to 60 g , Flame retardant D was obtained in the same manner as in Example 1. [

Analysis of the flame retardant D showed that the main component was 1- [bis (2-chloroethoxy) methylene chloride in which R ₁ , R ₂ , R ₃ and R ₄ of formula (I) were 2-chloroethyl and Z ₁ and Z ₂ were methyl ) Phosphinyl] -1-methylethyl bis (2-chloroethyl) phosphate.

As a result of GPC measurement, the compound of n = 0 was 0.5% by area, the compound of n = 1 was 22.9% by area, and the average degree of condensation (N) was 2.70.

The content of phosphorus (P) was 14.2 wt%, the chlorine content (Cl) was 24.5 wt%, the viscosity was 7700 mPas (25 DEG C) and the acid value was 0.05 KOHmg / g.

[ Example  5]

(2-chloroethyl) phosphite as the compound (a) and di (2-chloroethyl) phosphite as the compound (c) were obtained in the same manner as in Example 1 except that 208 g (4.72 mol) of ethylene oxide was changed to 206 g -Chloroethyl) phosphorochloridite (0.73 mol and 1.27 mol, respectively). The active chlorine concentration of the reaction mixture was 9.4%.

The obtained reaction mixture was maintained at 40 占 폚 instead of 0 占 폚 to 10 占 폚 and 1.3 mole of 97 mole of the compound (b), based on 1 mole of di (2-chloroethyl) phosphorochloridite as the compound (c) (1.67 moles) was added through a dropping funnel over 6 hours instead of 2 hours, and the reaction was carried out at the same temperature for 12 hours, to obtain a flame retardant E.

The analysis of the flame retardant E-bar, the main component is, in the general formula (I) of R _1, R _2, R ₃ and R ₄ is 2-chloroethyl, Z ₁ and Z ₂ is methyl, and 1- [bis (2-chloro Methoxy) phosphinyl] -1-methylethylbis (2-chloroethyl) phosphate.

As a result of GPC measurement, the compound having n = 0 was 2.4% by area, the compound with n = 1 was 30.4% by area, and the average degree of condensation (N) was 2.22.

The content of phosphorus (P) was 13.8 wt%, the chlorine content (Cl) was 25.1 wt%, the viscosity was 3850 mPa ((25 캜), and the acid value was 0.06 KOHmg / g.

[ Comparative Example  One]

(2-chloroethyl) phosphite as the compound (a) and di (2-chloroethyl) phosphite as the compound (c) were obtained in the same manner as in Example 1, except that 222 g (5.05 mol) of the ethylene oxide -Chloroethyl) phosphorochloridite (1.03 mol and 0.95 mol, respectively). The active chlorine concentration of the reaction mixture was 6.9%.

The obtained reaction mixture was maintained at 40 占 폚 instead of 0 占 폚 to 10 占 폚 and 1.1 mol of 64 mol of acetone as the compound (b) relative to 1 mol of di (2-chloroethyl) phosphorochloridite as the compound (c) (1.10 moles) was added via a dropping funnel over 6 hours instead of 2 hours, and the mixture was allowed to react at the same temperature for 12 hours. A solution of 71 g (0.73 mole) of 35% hydrogen peroxide aqueous solution as an oxidizing agent was changed to 98 g , A flame retardant F was obtained in the same manner as in Example 1.

Analysis of the flame retardant F showed that the main component was 1- [bis (2-chloroethoxy) methylene chloride in which R ₁ , R ₂ , R ₃ and R ₄ of formula (I) were 2-chloroethyl and Z ₁ and Z ₂ were methyl ) Phosphinyl] -1-methylethyl bis (2-chloroethyl) phosphate.

As a result of the GPC measurement, the compound having n = 0 was 14.8 area%, the compound having n = 1 was 59.3 area%, and the average degree of condensation (N) was 1.19.

The phosphorus (P) was 13.0 wt%, the chlorine (Cl) was 28.9 wt%, the viscosity was 520 mPa ((25 캜), and the acid value was 0.03 KOHmg / g.

[ Comparative Example  2]

(2-chloroethyl) phosphite as the compound (a) and di (2-chloroethyl) phosphite as the compound (c) were obtained in the same manner as in Example 1 except that 208 g (4.72 mol) of ethylene oxide was changed to 215 g -Chloroethyl) phosphorochloridite (0.90 mol and 1.10 mol, respectively). The active chlorine concentration of the reaction mixture was 8.0%.

The obtained reaction mixture was maintained at 40 DEG C instead of 0 to 10 DEG C and 1.2 mol of 77 mol of the acetone as the compound (b) relative to 1 mol of di (2-chloroethyl) phosphorochloridite as the compound (c) (1.33 moles) was added via a dropping funnel over 6 hours instead of 2 hours, the reaction was carried out at the same temperature for 12 hours, and 87 g (0.89 mole) of 35% hydrogen peroxide aqueous solution as an oxidizing agent was changed to 65 g , A flame retardant G was obtained in the same manner as in Example 1.

Analysis of the flame retardant G showed that the main component was 1- [bis (2-chloroethoxy) methylene chloride in which R ₁ , R ₂ , R ₃ and R ₄ of formula (I) were 2-chloroethyl and Z ₁ and Z ₂ were methyl ) Phosphinyl] -1-methylethyl bis (2-chloroethyl) phosphate.

As a result of the GPC measurement, 9.0 area% of the compound having n = 0, 54.8 area% of the compound having n = 1, and an average degree of condensation (N) of 1.43.

The phosphorus (P) was 13.4 wt%, the chlorine (Cl) was 28.0 wt%, the viscosity was 850 mPa ((25 캜), and the acid value was 0.04 KOHmg / g.

The results obtained are shown in Table 1.

As a comparative reference example, commercially available tris (2-chloroethyl) phosphate (Supresta, product name: FyrolCEF) is shown in Table 1 as a known flame retardant (flame retardant H).

(I) wherein n is 0, R ₁ , R ₂ and R ₃ are 2-chloroethyl, P (P) is 10.8% by weight, chlorine (Cl) is 36.6% by weight and the viscosity is 45 mPa · s s (20 < 0 > C).

From the results shown in Table 1, it can be seen that, in the reaction of the step (1), the amount of di (2-chloroethyl) phosphorochloridite as the compound (c) relative to 1 mol of the tris (2-chloroethyl) (B) is used in an amount of 1.3 to 1.7 moles per mole of di (2-chloroethyl) phosphorochloridite as the compound (c) at a ratio of 1.74 to 2.37 mole In Examples 1 to 5, the organophosphorus compound (I) having a content of the compound of n = 0 in the formula (I) (monomeric phosphate ester) in an amount of 0.5 to 2.4% by area and an average degree of condensation (N) of 2.12 to 2.70 ≪ / RTI >

On the other hand, di (2-chloroethyl) phosphorochloridite as the compound (c) was added at a ratio of 0.92 and 1.22 mol per mol of tris (2-chloroethyl) phosphite as the compound (a) In Comparative Examples 1 and 2 using 1.1 mol and 1.2 mol of acetone as the compound (b) relative to 1 mol of di (2-chloroethyl) phosphorochloridite as the compound (c) , 14.8% by area and 9.0% by area of the compound of n = 0 (mono-phosphoric acid ester) in the total amount of the organophosphorus compound. For this reason, the average degree of condensation (N) of the organophosphorus compounds of Comparative Examples 1 and 2 was lower than those of Examples 1 to 5, and was 1.19 and 1.43, respectively.

In Comparative Example 1, the ratio of tris (2-chloroethyl) phosphite as the compound (a) to di (2-chloroethyl) phosphorochloridite as the compound (c) it is considered that the content of monomeric phosphate ester with n = 0 is increased.

[ Example  6]

Polyurethane foams (foams) were prepared by the following prescription and production method using the flame retardant A obtained in Example 1, and the flame retardancy, endurance, flame retardancy persistence, and phosphorus content retention were evaluated.

(Prescription)

100 parts of polyol (Mitsui Chemicals Inc., trade name: actcol T-3000)

Silicone oil (Dow Corning Toray Co., Ltd., trade name: SZ-584) 1.0 part

Amine catalyst

(Air Products and Chemicals, Inc., trade name: DABCO 33LV) 0.2 part

(Air Products and Chemicals, Inc., trade name: DABCO BL-11) 0.05 part

Tin catalyst

(Air Products and Chemicals, Inc., trade name: DABCO T-9) 0.35 parts

Foaming agent (water) 4.3 parts

  (Methylene chloride) 8.0 parts

Flame retardant (flame retardant A)

Isocyanate (tolylene diisocyanate: TDI)

(Mitsui Chemicals Inc., trade name: Cosmonate T-80 (80/20)) 58.2 parts

The above " parts " means parts by weight.

The addition number of the flame retardant was changed to 8, 10, 12 and 14 parts.

(Manufacturing method)

The polyol, the silicone oil, the catalyst, the foaming agent and the flame retardant were mixed with the above-mentioned prescription, and the mixture was stirred at a rotation speed of 3000 rpm for 1 minute using a stirrer to homogeneously mix the components. To the mixture was further added tolylene diisocyanate, For 5 to 7 seconds, and the contents were immediately poured into a carton of cubes (height of about 200 mm) having a square bottom (about one side of about 200 mm).

Foaming occurred immediately, and the maximum volume reached after several minutes. The obtained foam was cured by standing in a furnace at 120 캜 for 30 minutes. The obtained foam was a white soft-bubble type cell structure.

[ Example  7]

A foam was produced in the same manner as in Example 6 except that the flame retarding agent B obtained in Example 2 was used instead of the flame retarding agent A, and the flame retardancy, endurance, flame retardancy persistence, and phosphorus content retention were evaluated.

[ Comparative Example  3]

A foam was produced in the same manner as in Example 6 except that the flame retardant F obtained in Comparative Example 1 was used in place of the flame retardant A, and the flame retardancy, endurance, flame retardancy persistence, and phosphorus content retention were evaluated.

[ Comparative Example  4]

A foam was produced in the same manner as in Example 6 except that the flame retardant H of the Comparative Reference Example was used in place of the flame retardant A, and the flame retardancy and the endurance of the foam were evaluated. With respect to the flame retardancy persistence and the phosphorus content retention ratio, the evaluation of the endurance gingability was bad, so that the test could not be carried out because the test conditions could not be met.

(Evaluation of flame retardancy)

A sample was cut from the obtained foam, and a combustion test was conducted under the following conditions.

Test method: FMVSS-302 method (test method of safety standard of automotive interior goods)

Horizontal combustion test of polyurethane foam

Test conditions: The ventilation rate was adjusted to 200 ml / cm 2 / sec.

(The ventilation degree was measured in accordance with JIS K6400-7 B method.)

Sample: 2 types of thickness 5mm and 13mm

And the density was adjusted to be about 20 to 25 kg / m 3.

Acceptance criterion: The burning distance is less than 38mm.

The obtained results are shown in Table 2.

(Evaluation of endurance gingability)

A sample was cut from the obtained foam, and a fogging test was conducted under the following conditions.

Test conditions: A sample of polyurethane foam (diameter 80 mm, thickness 10 mm) was placed under the container using a wind screen fogging tester (Suga Test Instruments Co., Ltd.), and the sample was heated at 100 캜 for 16 hours , And the amount of the non-product from the sample adhered to the glass plate on the upper part of the container was measured in terms of the glass adhesion amount (mg).

Sample: 1 kind of flame retardant additive 8 parts

The obtained results are shown in Table 3.

From the results shown in Table 2, the polyurethane foam of Example 6 containing flame retardant A and the polyurethane foam of Example 7 containing flame retardant B had much better flame retardancy than the comparative example 4 containing conventional flame retardant H, , But it had slightly better flame retardancy as compared with Comparative Example 3 containing the flame retardant F of the conventional condensation type flame retardant, but there was no significant difference.

However, as clearly shown in the results of Table 3, the polyurethane foams of Examples 6 and 7 had significantly reduced glass adhering components, i.e., volatile components, of 1/4 or less as compared with those of Comparative Example 3, Ginging is excellent.

(Flame Retardancy Evaluation)

A sample was cut from the obtained foam, and a flame retardancy persistence test was conducted under the following conditions.

The sample was placed in a gear oven at a set temperature of 150 DEG C and after 2, 4, 6 and 8 hours of exposure, the flame retardancy was evaluated in the same manner as in the evaluation of the flame retardancy.

In addition, the same test was performed on a sample having a standard exposure time of 0 hours.

The results obtained are shown in Table 4 and Fig.

From the results shown in Table 4 and Fig. 1, the polyurethane foam of Example 6 containing the flame retardant A and the polyurethane foam of the Example 7 containing the flame retardant B had a slightly longer burning distance even when exposed at high temperature for 8 hours, It was found that the polyurethane foam of Comparative Example 3 containing the flame retardant F of the conventional condensation type flame retardant agent had a combustion distance twice as long as the exposure time (0 hour of exposure time) when it was exposed at a high temperature for 8 hours. That is, the flame retardants A and B of the present invention can maintain excellent flame retardancy as compared with the flame retardant F, and are excellent in flame retardancy.

(Evaluation of phosphorus content retention rate)

Samples were cut from the obtained foam, and the percentage retention of the phosphorus content was evaluated under the following conditions.

The sample was placed in a gear oven at a set temperature of 80 캜 for 14 days and the content of phosphorus in the sample after 3 days, 7 days, and 14 days after the high temperature exposure was measured according to ASTM D 1091.

Similarly, the sample was placed in a gear oven at a set temperature of 100 占 폚 for 7 days, and the content of phosphorus in the sample after 1 day, 3 days, and 7 days after the high temperature exposure was measured according to ASTM D 1091.

The ratio of the content of phosphorus in the sample after the high temperature exposure was calculated as the phosphorus content retention rate with the same content of the phosphorus content as the reference and the content of the phosphorus content obtained as 100%.

The obtained results are shown in Table 5 and Fig.

From the results shown in Table 5 and FIG. 2, the polyurethane foam of Example 6 containing the flame retardant A and the polyurethane foam of the Example 7 containing the flame retardant B are slightly degraded in the content of the phosphorus content even when the polyurethane foam is exposed at a high temperature of 80 캜 for a long time The polyurethane foam of Comparative Example 3 containing the flame retardant F of the conventional condensation type flame retardant can be maintained at 95% or more in the 14-day exposure, while the phosphorus content retention rate of 86% Could know. That is, the flame retardants A and B of the present invention have a high retention ratio because the scattering of phosphorus is very low as compared with the flame retardant F.

Also, the flame retardants A and B had a phosphorus content retention ratio of 82% or more and a phosphorus content retention ratio higher than 71% of the flame retardant F, similarly at an exposure of 7 days at 100 占 폚.

In the flame retardant F, the monomeric phosphoric acid ester component contained in the resin composition during the long-term exposure to the high temperature is lost by volatilization or scattering. As a result, the phosphorus content in the foam is reduced and the flame retardancy is lowered.

On the other hand, the flame retardants A and B of the present invention have a very small content of monomeric phosphoric acid ester component, which is a volatile component, compared to the flame retardant F, so that the number of phosphorus lost from the foam is also very small, and a high phosphorus content retention ratio and excellent flame retardancy persistence I think.

From the above results, the flame retardant of the present invention and the flame retardant resin composition containing the flame retardant exhibit particularly excellent flame retardancy among the required conditions. Further, the flame retardant resin composition of the present invention exhibits less change with time, excellent endurance and low volatility.

Claims (10)

A flame retardant agent for a resin containing an organic phosphorus compound of the formula (I)
Wherein the content of the compound of n = 0 in the following formula (I) is 0.1 to 3.0% by area, and n = 0 in the formula (I) below, when measured by gel permeation chromatography (GPC) (N) of 1.5 to 3.5 calculated from the content of each compound of the following formula

Z ₁ and Z ₂ are each independently a hydrogen atom, a methyl group or an ethyl group, and n is an integer of 0 to _3, and R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group or haloalkyl group having 1 to 8 carbon atoms, 10. The flame retardant agent for a resin according to claim 1, wherein the content of the compound of n = 1 in the formula (I) is 10 to 50% by area, when the organic phosphorus compound is measured by GPC. The flame retardant agent for resin according to claim 1, wherein the average degree of condensation (N) in the formula (I) is 1.8 to 3.0. A flame retardant resin composition comprising the flame retardant for resin according to claim 1 and a resin. The resin composition according to claim 4, wherein the resin is a resin selected from a polyurethane resin, an acrylic resin, a phenol resin, an epoxy resin, a vinyl chloride resin, a polyamide resin, a polyester resin, an unsaturated polyester resin, a styrene resin, Resin composition. 6. The flame retardant resin composition according to claim 5, wherein the polyurethane resin is a polyurethane foam. The flame-retardant resin composition according to claim 4, wherein the flame retardant for resin is contained in an amount of 1 to 40 parts by weight based on 100 parts by weight of the resin. (A), compound (b) and compound (c) of the formula (a), compound (c) and compound (B) is reacted at a temperature of -20 to 60 占 폚 in a proportion of 1.3 to 2.0 mol per 1 mol of the compound (c) in a proportion of 1.5 to 3.5 mol, To obtain a compound (d)
Next, as the step (2), the compound (d) obtained in the above step (1) is oxidized with an oxidizing agent and is represented by the above formula (I) To obtain an organic phosphorus compound having an average degree of condensation (N) of 1.5 to 3.5 calculated from the content of each compound of n = 0 to 10 in the formula (I) , ≪ / RTI > the method comprising:

Wherein R ₁ , R ₂ , R ₃ , R ₄ , Z ₁ , Z ₂ and n have the same meanings as defined in formula (I), R ₅ is an alkyl or haloalkyl group having 1 to 8 carbon atoms, Lt; / RTI > 9. The method for producing an organic phosphorus compound according to claim 8, wherein the content of the compound of n = 1 in the formula (I) is 10 to 50% by area when the organic phosphorus compound is measured by GPC. The process according to claim 8, wherein the average degree of condensation (N) in the formula (I) is 1.8 to 3.0.

Images