JP2001131392A - Flame retardant composition and method for producing resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant composition which can give a flame- retardant resin composition that can maintain mechanical physical properties and has an improved color tone, when the flame retardant composition is compounded with a resin composition and even when the mixture is molded under the environment of a high temperature and a high humidity or at a high temperature, and to provide a method for producing the flame retardant resin composition which uses the flame retardant composition and has stable performances. SOLUTION: (B) This flame retardant composition comprising (&alpha;) an organic phosphorus compound and (&beta;) an epoxy compound and having an acid value of <=1, and the method for producing the flame retardant resin composition, comprising compounding 100 pts.wt. of (A) a thermoplastic resin with 1 to 30 pts.wt. of (B) the flame retardant composition for the resin and then melting and kneading the mixture to obtain the flame retardant resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame retardant composition having excellent heat resistance and hydrolysis resistance, and a method for producing a flame retardant resin composition using the same. More specifically, in a high-temperature and high-humidity environment, or at the time of high-temperature molding, mechanical properties are maintained, and a flame-retardant composition capable of obtaining a resin composition excellent in color tone, and a high-quality flame retardant composition using the same. The present invention relates to a production method for obtaining a flame-retardant resin composition with stable performance and high productivity.

[0002]

2. Description of the Related Art An organic phosphorus compound containing no halogen element is widely used as a non-bromine / non-chlorine flame retardant for making a resin composition flame-retardant. In particular, a flame-retardant PC / ABS alloy in which an organic phosphorus compound is blended into a composition of polycarbonate and ABS as a flame retardant is widely used as a material having excellent mechanical properties and light resistance in OA equipment, housing of electric equipment, and the like. It is used.

However, a flame-retardant resin material using an organophosphorus compound is resistant to heat when exposed to a high-temperature and high-humidity environment for a long time, or when molded at a high temperature for the purpose of enhancing the fluidity of a molten resin. Impact properties and elongation at break may be reduced. Such a phenomenon is a serious problem that limits the formability of the material and impairs long-term reliability in use.

[0004] Organic phosphoric acids present in organophosphorus compounds have been considered as a cause of reducing the physical properties of such resins. When an organic phosphorus compound containing a large amount of these organic phosphoric acids is blended with the resin, the resin deteriorates during melt-kneading or molding processing and the expected physical properties cannot be obtained, or the product discolors and appearance May be impaired. In particular, when the base resin such as a polycarbonate resin or a polycarbonate alloy has low stability to an acid or a base, the deterioration of the resin due to the organic phosphoric acids easily occurs.In recent years, the acidic substances contained in the organic phosphorus compound have been removed. Alternatively, attempts have been made to improve the quality of the resin composition by performing a neutralization treatment.

The acid value (KOH mg / g) is usually used as an index for the acidic substance content in the organic phosphorus compound, and attempts have been made to reduce the acid value of the organic phosphorus compound. As a method for reducing the acid value, for example, a method has been proposed in which a neutralization treatment is performed with a basic substance such as sodium hydroxide or calcium carbonate, followed by washing or distillation. However, this method can reduce the acid value of the organic phosphorus compound, but has a problem that a trace amount of metal remains in the final product, and the heat resistance and the heat resistance of the resin composition due to the metal residue are reduced. The hydrolysis resistance may be reduced. Therefore, in order to reduce the amount of metal residues as much as possible, a method of performing water washing many times or performing treatment with an acid again is required.
The work process is complicated, which is not preferable.

[0006] Japanese Patent Application Laid-Open No. 8-67685 proposes a method for reducing the acid value without using a basic compound such as an alkali metal compound. This publication describes a method in which a crude phosphorus compound is treated with an epoxy compound, heat-treated in the presence of moisture, then washed with water, and the remaining water is removed. However, this method is industrially complicated because a processing step of washing and removing after adding the epoxy compound is required. Further, the epoxy compound specifically described in the publication itself has insufficient chemical stability at high temperatures, and therefore, when added to a resin composition, heat resistance, impact resistance, color tone Etc. may be adversely affected. Furthermore, the retention of mechanical properties of the resin composition in a high-temperature and high-humidity environment or the retention of properties of a resin in repeated use is not sufficient.

On the other hand, as a method for compounding additives such as a flame retardant and a stabilizer into a resin to obtain a flame-retardant resin composition, a method is known in which these are charged into an extruder simultaneously with resin pellets and melt-kneaded. Is commonly done. However, when an organic phosphorus compound is used as a flame retardant, the compounding amount thereof is generally large and it is often in a liquid state, which may cause poor mixing of the resin and the flame retardant. Also,
Another method is to plasticize the resin in the kneading zone of the extruder and then blend the flame retardant in order to improve the mixing state of the resin and the flame retardant. Is not suitable for obtaining high productivity. As described above, the stability and productivity of the composition of the flame retardant resin composition using the phosphorus compound are greatly affected by the production method, and a flame retardant resin composition having stable performance is obtained with high productivity. Therefore, there remains an industrial problem.

[0008]

SUMMARY OF THE INVENTION Therefore, according to the present invention, when compounded in a resin composition, mechanical properties can be maintained even in a high-temperature and high-humidity environment or when molding is performed at a high temperature. To provide a flame retardant composition capable of obtaining a flame retardant resin composition having an improved color tone, and further to obtain a flame retardant resin composition having stable performance using the flame retardant composition with high productivity. It is intended to provide a manufacturing method.

[0009]

Means for Solving the Problems The present inventors have intensively studied a method for maintaining mechanical properties of a resin composition containing an organic phosphorus compound as a flame retardant under a high-temperature and high-humidity environment. As a flame retardant, by using a flame retardant composition containing an epoxy compound in an amount necessary to reduce the acid value of the organic phosphorus compound, in a high-temperature and high-humidity environment, or when molding is performed at a high temperature Have also found that a flame-retardant resin composition can be obtained in which the mechanical properties are maintained at a high level and the color tone is greatly improved.

[0010] Further, a method for producing a resin composition using the above flame retardant composition was studied, and a single-screw or multi-screw extruder having two or more screws was used to melt the kneading zone and / or to reduce the amount of the raw material compared to the melt-kneading zone. By mixing and melting and kneading the flame retardant composition at one or two or more locations located on the supply port side, the flame retardant is used as a plasticizer for the resin and its viscosity is reduced, so that high productivity melting is achieved. It has been found that kneading becomes possible, and even when a large amount of flame retardant is blended, a good mixed state of the flame retardant and the resin can be obtained, and the flame retardant resin composition can be stably produced. As a result,
Problems such as backflow of the flame retardant often generated in the production of the flame retardant resin composition and vent up caused by insufficient melting of the resin can be solved.

The present invention has been made based on the above findings, that is, [1] (α) an organic phosphorus compound,
(B) a flame retardant composition for a resin containing (β) an epoxy compound and having an acid value of 1 or less; [2] (α) an organic phosphorus compound represented by the following formula (1): The flame retardant composition for a resin according to the above-mentioned [1], which is an oligomeric organic phosphorus compound composed of a mixture of at least one kind.

[0012]

Embedded image [3] The flame retardant composition for a resin according to the above [1], wherein the (α) organophosphorus compound is an oligomeric organophosphorus compound comprising one or a mixture of two or more kinds represented by the following formula (2):

[0013]

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[4] The (β) epoxy compound is selected from alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, and heterocyclic epoxy compounds having one or more epoxy groups in the molecular skeleton. The above [1] to epoxy compounds comprising a mixture of two or more species
The flame retardant composition for a resin according to any one of [3] and [5].
(Β) The flame retardant composition for a resin according to any one of the above [1] to [4], wherein the epoxy compound is an alicyclic epoxy compound; [6] The (β) epoxy compound is represented by the following formula (3): The above [1] to which are aliphatic cyclic epoxy compounds represented by
The flame retardant composition for a resin according to any one of [5],

[0015]

Embedded image [7] The flame retardant composition for a resin according to any one of the above [1] to [6], wherein the acid value is 0.1 or less, [8] (A) With respect to 100 parts by weight of the thermoplastic resin, (α) 1) 30 parts by weight of (B) a flame retardant composition for a resin containing an organic phosphorus compound and (β) an epoxy compound and having an acid value of 1 or less, and melt-kneading. A method for producing a flammable resin composition,

[9] The method for producing a flame-retardant resin composition according to the above [8], wherein the acid value of the flame-retardant composition for a resin (B) is 0.1 or less; Using a multi-screw extruder having two or more shafts, a melt-kneading zone, and / or one or two or more flame-retardant compositions for resin located on the raw material supply port side of the melt-kneading zone (B) And the method for producing a flame-retardant resin composition according to the above [8] or [9], wherein the compound is melt-kneaded, [11].
(A) The above-mentioned [8] to [1], wherein the thermoplastic resin is a polycarbonate resin or a polyphenylene ether resin.
0] The method for producing a flame-retardant resin composition according to any one of the above,
It is.

Hereinafter, the present invention will be described in detail. The (α) organic phosphorus compound used in the present invention is a phosphate compound. In the present invention, among the phosphate ester compounds, an oligomeric organic phosphorus compound composed of one or a mixture of two or more compounds represented by the following formula (1) can be particularly preferably used.

[0018]

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In the above formula (1), the substituents R ^a , R ^b ,
R ^c and R ^d are aryl groups and one or more hydrogens thereof may or may not be substituted. Substituents R ^a , R ^b ,
A compound in which R ^c and R ^d are an alkyl group or a cycloalkyl group has insufficient retention stability of a molten resin in a molding machine at the time of injection molding, and tends to cause deterioration in physical properties of the resin. When one or more hydrogens of the substituents R ^a , R ^b , R ^c , and R ^d are substituted, the substituent may be an alkyl group, an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group. A group obtained by combining these substituents (eg, an arylalkoxyalkyl group) or a group obtained by combining these substituents with an oxygen atom, a sulfur atom, a nitrogen atom, or the like. (Eg, an arylsulfonylaryl group) may be used as a substituent. Preferred aryl groups are a phenyl group, a cresyl group, a xylyl group, a propylphenyl group, and a butylphenyl group, and the phenyl group is particularly excellent in both fluidity and flame retardancy.
Further, the substituents R ^a , R ^b , R ^c , and R ^d may be the same or different.

X in the above formula (1) is an aromatic group derived from a dihydric phenol, and is catechol, resorcinol, hydroquinol, 4-t-butylcatechol, 2-t-butylhydroquinone, Aromatic groups derived from bisphenol A, bisphenol S sulfide, bisphenol F, bis (4-hydroxyphenyl) sulfone, bis (3,5dimethyl-4-hydroxyphenyl) sulfone and the like can be mentioned. In particular, the following equation (2)

[0021]

Embedded image The hydrolysis resistance is improved by using an oligomeric organic phosphorus compound in which X is a diphenylol dimethylmethane group (an aromatic group derived from bisphenol A) represented by Stability can be improved, and generation of mold deposit (MD) adhering to the surface of a mold during molding can be reduced.

The oligomeric organophosphorus compounds represented by the above formulas (1) and (2) are usually those of compounds having different values of n (n is a natural number) in the above formulas (1) and (2). Often used as a mixture. The average degree of condensation N is the average value of n. N is determined by gel permeation chromatography or liquid chromatography to determine the weight fraction of each component having a different n,
Is calculated by the weight average. As the detector, a UV detector or an RI detector is used. However, in the present invention, n
Are excluded from the calculation of N, ie, compounds having only one phosphorus atom in the molecule.

The average value N (average degree of condensation) of n of the oligomeric organic phosphorus compound is usually from 1 to 5, preferably from 1 to 2, more preferably from 1 to 1.5,
One or more and less than 1.2 are particularly preferred. The smaller the N, the better the compatibility with the resin, the better the fluidity, and the higher the flame retardancy.
In particular, the compound of N = 1 is particularly excellent in the balance between flame retardancy and fluidity in the resin composition. When N is 5 or more, the viscosity becomes large, and it becomes difficult to obtain a composition having high fluidity, particularly a composition having excellent fluidity in a high shear rate region,
Also, the flame retardancy is reduced.

As a method for obtaining an oligomeric organic phosphorus compound in which N is 1 or more and less than 1.2, for example, an aromatic monohydroxy compound such as phenol or 2,6-xylenol is added to [a] phosphorus oxyhalide by Lewis. The reaction is carried out under an acid catalyst to obtain a diaryl phosphorohalide in advance, and subsequently an aromatic dihydroxy compound (a dihydric phenol compound) such as bisphenol A, hydroquinone or resorcinol is reacted under a Lewis acid catalyst. How to get. [A] An aromatic dihydroxy compound is reacted with a large excess thereof (about three-fold molar equivalent or more) of phosphorus oxyhalide in the presence of a Lewis acid catalyst, and then the excess phosphorus oxyhalide is completely removed by heating under reduced pressure. And then reacting the reaction product with an aromatic monohydroxy compound in the presence of a Lewis acid catalyst. And the like.

The acid value of the (α) organophosphorus compound used in the present invention is not particularly limited, but is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less.
mgKOH / g or less, more preferably 2 mgKOH / g
Or less, particularly preferably 1 mgKOH / g or less. When the acid value exceeds 10 mgKOH / g, a large amount of the epoxy compound (β) is added to obtain the flame retardant composition (A) of the present invention, that is, the flame retardant composition having an acid value of 1 mgKOH / g or less. When the component (β) increases, the flame retardancy of the resin composition decreases, which is not preferable.

The (β) epoxy compound used in the present invention is a compound having one or more epoxy groups in the molecular skeleton, and may be an alicyclic epoxy compound, an aliphatic epoxy compound,
One or a mixture of two or more selected from an aromatic epoxy compound and a heterocyclic epoxy compound can be used. An alicyclic epoxy compound is obtained by adding oxygen to a double bond using a peroxide such as peracetic acid to an aliphatic cyclic hydrocarbon compound having one or more double bonds in a molecular structure. It is synthesized by a method of introducing an epoxy group, and includes an alicyclic epoxy compound represented by the following formula (4) and is represented by the following general formulas (5), (6) and (7). Structures are included.

[0027]

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[0028]

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[0029]

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[0030]

Embedded image In the present invention, as the aliphatic epoxy compound, an epoxidized oil or fat compound and an epoxidized fatty acid ester can be preferably used. Here, the epoxidized oil / fat compound is obtained by adding oxygen to a double bond of a natural oil / fat and has the following general formula (8)

[0031]

Embedded image It has a structure shown by. Specific examples of such compounds include epoxidized soybean oil and epoxidized linseed oil. The epoxidized fatty acid ester refers to a compound obtained by epoxidizing an unsaturated fatty acid alkyl ester, and has a structure represented by the following general formula (9).

[0032]

Embedded image Specific examples of such a compound include epoxidized butyl stearate. In the present invention, as the aliphatic epoxy compound, in addition to the epoxidized oil-based compound and the epoxidized fatty acid ester, ethylene oxide, propylene oxide, butylene oxide, polyethylene glycol 400 diglycidyl ether, 3,4-epoxybutanol and the like are also used. be able to.

Examples of the aromatic epoxy compound or heterocyclic epoxy compound include phenyl glycidyl ether, bisphenol A diglycidyl ether, terephthalic acid diglycidyl ether, hydroquinone diglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate and the like. Can be mentioned. Among these epoxy compounds, in the present invention, those which are excellent in handleability, have thermal stability enough to withstand melt kneading, and have low viscosity and low volatility are preferable, and particularly preferable are alicyclic compounds. An epoxy compound of the formula

The alicyclic epoxy compound that can be particularly preferably used in the present invention is a compound in which an alicyclic epoxy structural unit is bonded by a bonding unit such as a dioxane structural unit or a carboxyl group structural unit. 4-epoxycycloalkyl) -5-5'-spiro- (3,4-
Epoxy) cycloalkyl-m-dioxane, 2-
(3,4-epoxycyclohexyl) -5-5′-spiro- (3,4-epoxy) cyclohexane-m-dioxane (trade name: ERL-4234, manufactured by Union Carbide) or represented by the following formula (3) 3,4-epoxycyclohexylmethyl-3-4-epoxycyclohexanecarboxylate (trade name ERL-4221)
Manufactured by Union Carbide)

[0035]

Embedded image In addition, the trade name ERL-42 was obtained from Union Carbide.
Examples thereof include aliphatic cyclic epoxy compounds that can be industrially obtained as 99 or ERL-4206. Among these specific examples, ERL
-4221 is particularly preferably used because it has excellent thermal stability, low viscosity and low volatility, and contains a large amount of highly reactive epoxy groups.

In the flame retardant composition of the present invention, the (β) epoxy compound is added to the (α) organic phosphorus compound so that the acid value of the flame retardant composition becomes 1 or less, preferably 0.1 or less. The required amount is blended. The lower the final acid value of the flame retardant composition, the more excellent the high-temperature and high-humidity resistance and the stability to high-temperature molding, and the improved color tone can be obtained when blended into a resin. Things. Further, the long-term stability of the flame retardant composition itself can be enhanced. The amount of the component (β) relative to the component (α) varies depending on the acid value of the component (α) and the epoxy group content of the component (β), and is not particularly limited. Component (β) is in the range of 0.001 to 20 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.05 to 2 parts by weight, and particularly preferably 100 parts by weight of component α). Is 0.1 to 1 part by weight. 0.0
When the amount is less than 01 parts by weight, the effect of reducing the acid value is often insufficient. On the other hand, when the amount exceeds 20 parts by weight, the flame retardant effect and the impact resistance of the resin composition are deteriorated, which is not preferable.

It is preferable that the flame retardant composition of the present invention is obtained by blending as little of the component (β) as possible because excellent flame retardancy can be obtained, and therefore, the acid value is lower (α).
It is preferred to use components. In the present invention,
The combination of the component (α) and the component (β) is not particularly limited.
It can be carried out in various cases, such as in the production process of the (α) component, during storage, at the time of shipping, or before blending into the resin composition. The flame retardant composition of the present invention can be obtained, for example, only by mixing a component (β) with a liquid component (α) and heating and stirring / mixing to reduce the viscosity in some cases. It can be obtained easily. Further, the flame retardant composition of the present invention is washed after mixing the epoxy compound,
There is no particular need to perform processing such as removal.

Further, the flame retardant composition of the present invention is extremely excellent in long-term preservability, and the flame retardant has hydrolysis resistance and heat resistance.
Furthermore, the stability against discoloration is significantly improved.
Therefore, the handleability of the flame retardant composition of the present invention as a flame retardant is dramatically improved. For the purpose of enhancing the long-term stability of the flame retardant composition, it is preferable to obtain the flame retardant composition of the present invention by blending a predetermined amount of the component (β) immediately after the production of the component (α). .

As a method of blending the flame retardant composition (B) with the thermoplastic resin (A), a method of melt-kneading the components (A) and (B) using a single-screw or multi-screw extruder is generally used. It is a target. In general, when an extruder is used to produce a resin composition composed of various components, the screw configuration of the extruder is such that a resin component composed of a flight screw is transferred and melted (a transfer / melting zone). ,
Using a shallow groove screw, kneading screw, reverse screw, or fin-like or dalmage-like screw to apply shear stress to subdivide and mix the components, and divide it into parts that perform uniform kneading (melt kneading zone) And the actual extruder screw configuration is used in combination with them. Generally, in an extruder, a load is applied most in the first melt-kneading zone, and particularly when the melt viscosity of the resin is high, a sufficient production rate of the resin composition may not be obtained due to an increase in the load. As a countermeasure in such a case, there is a method of increasing the cylinder set temperature, but there are cases where adverse effects such as discoloration of the resin and burns are caused.

The method for producing the flame-retardant resin composition of the present invention comprises:
(A) 100 parts by weight of a thermoplastic resin containing (α) an organic phosphorus compound and (β) an epoxy compound, and having an acid value of 1
A method for producing a flame-retardant resin composition obtained by blending 1 to 30 parts by weight of (B) a flame retardant composition for a resin, preferably 0.1 or less, and melt-kneading the mixture. Alternatively, using a multi-screw extruder having two or more screws, blending the flame retardant composition for resin (B) at one or more positions located on the raw material supply port side of the melt kneading zone and / or the melt kneading zone. And a method for producing a flame-retardant resin composition obtained by melt-kneading.

As the extruder used in the present invention, a twin-screw extruder is most preferably used. In the method for producing a flame-retardant resin composition of the present invention, (B) one part of a melt-kneading zone of an extruder and / or a transfer / melting zone on the raw material supply port side thereof, Alternatively, by blending in two or more places, the flame retardant composition for resin (B) acts as a plasticizer for the thermoplastic resin (A), thereby lowering the viscosity of the molten resin and dramatically improving the discharge amount. It becomes possible. In some cases, if a large amount of the flame retardant composition is blended in one place, the plasticization and melting of the resin may be insufficient. Therefore, it is preferable to provide a plurality of blended places of the flame retardant composition. Conversely, in the method of blending the flame retardant composition for resin (B) closer to the die than the melt-kneading zone, the load on the extruder increases, and the production rate of the resin composition decreases significantly.

In the present invention, (A) the thermoplastic resin
Flame retardant composition comprising (B) a resin flame retardant composition containing (α) organophosphorus compound and (β) epoxy compound prepared in advance and having an acid value of 1 or less, preferably 0.1 or less. There is a feature in obtaining. That is, according to the production method of the present invention, it is possible to obtain a flame-retardant resin composition having excellent composition uniformity and, as a result, excellent performance stability with high productivity. As a method for producing a flame-retardant resin composition different from the method of the present invention, a method in which a component (α) and a component (β) are independently charged into an extruder and melt-kneaded in a thermoplastic resin (A). However, in this method, since the amount of the component (β) is extremely small, the dispersion of the component (β) in the composition tends to be non-uniform, and it is difficult to obtain a resin composition having stable performance. .

In the present invention, the flame retardant composition for resin (B) is 1 to 3 with respect to 100 parts by weight of the thermoplastic resin (A).
It is blended in an amount of 0 parts by weight, preferably 3 to 25 parts by weight, more preferably 5 to 20 parts by weight, and most preferably 8 to 17 parts by weight. (B) If the flame retardant composition for resin is less than 1 part by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 30 parts by weight, the impact resistance and color tone of the resin composition are inferior.

As the thermoplastic resin (A) used in the present invention, a polycarbonate resin, a polymer alloy comprising a polycarbonate resin and an ABS resin or a HIPS resin, a polyphenylene ether resin, and a styrene resin blended therewith. Resins, styrene resins, polyamide resins, polyester resins, polyolefin resins, polyacetal resins, polymethyl methacrylate resins, polyvinyl chloride resins and the like,
Of these, particularly preferred are polycarbonate resins, ABS resins and polycarbonate resins, and H resins.
It is a polycarbonate-based polymer alloy in which an IPS resin, a polyester-based resin, or the like is blended, a polyphenylene ether-based resin, or a resin in which a styrene-based resin is blended.

In producing the flame-retardant resin composition, examples of the anti-dripping agent include perfluoroalkane polymers such as polytetrafluoroethylene, silicone rubber, polycarbonate-diorganosiloxane copolymer, and siloxane polyetherimide. , Liquid crystal polymer, silicon
An acrylic composite rubber or the like is compounded, but it can also be used in the present invention.

[0046]

The present invention will be described in detail with reference to the following examples. The materials used are shown below. 1. Organic phosphorus compound (α) component (Organic phosphorus compound (α1)) Organic phosphorus compound obtained by the method of Reference Example 1 below (Reference Example 1) In an autoclave (30 liter container) equipped with a stirrer, a condenser, and a heating jacket. Bisphenol A (1 molar equivalent) is added to phosphorus oxychloride (4
Molar equivalent) and magnesium chloride (0.025 molar equivalent)
, And the mixture was gradually heated and stirred, heated to 120 ° C., and further reacted for 7 hours. Hydrochloric acid by-produced in the reaction is led to a hydrochloric acid absorption tower. Phosphorus oxychloride was removed from the obtained reaction mixture under reduced pressure at 160 ° C. and 10 mmHg for 2 hours.
Thereafter, phenol (4.5 mol equivalent) was gradually added with stirring, and the mixture was reacted at 150 ° C. for 8 hours.
The resulting hydrochloric acid was removed by maintaining the solution at 200 ° C for 3 hours at 300 ° C to remove the generated hydrochloric acid. The obtained product was washed once with a 0.1N hydrochloric acid aqueous solution at 90 ° C, and further three times at 90 ° C using pure water. Thereafter, the resultant was dried and the remaining phenol was completely removed by a thin film distillation method to obtain an oligomeric organic phosphorus compound represented by the following formula (10). When the average degree of condensation N was determined,
It was 1.09. The acid value is 1.12 mgKOH /
g.

[0047]

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(Organic Phosphorus Compound (α2)) Product Name: CR733S manufactured by Daihachi Chemical Industry Co., Ltd. An oligomeric organophosphorus compound represented by the following formula (11) having an average degree of condensation N of 1.41. Acid value is 0.72mg KOH
/ G.

[0049]

Embedded image (Organic phosphorus compound (α3)) Product name PX-200 manufactured by Daihachi Chemical Industry Co., Ltd. An oligomeric organic phosphorus compound represented by the following formula (12) having an average degree of condensation N of 1.00. Acid value is 0.75mg KOH
/ G.

[0050]

Embedded image 2.2. Epoxy compound (β) component (Epoxy compound (β1)) Alicyclic epoxy compound represented by the following formula (3) (Union Carbide Japan Co., Ltd.)
ERL-4221)

[0051]

Embedded image (Epoxy compound (β2)) Aliphatic epoxy compound (EP-17 manufactured by Asahi Denka Kogyo Co., Ltd.) (Epoxy compound (β3)) Epoxidized oil-based compound (Kapox S6 manufactured by Kao Corporation)

The components (α) and (β) are shown in Table 1.
The mixture was blended in the ratios shown in Tables 1 to 4, heated to reduce the viscosity, and mixed and stirred to obtain a flame retardant composition. The acid value was measured by dissolving about 5 g of the sample in 50 cc of ethanol and using an aqueous solution of bromothymol blue as an indicator.
It was determined by titration with a 0.05 N NaOH solution. 3. Other Components (Polycarbonate: PC) Bisphenol A-based polycarbonate (acrylonitrile-styrene copolymer) having a Mw of 20,500 and a hydroxy group terminal amount of 29% produced from bisphenol A and diphenyl carbonate by a melt transesterification method: SAN) 25.0 wt% of acrylonitrile units, 75.
Acrylonitrile / styrene copolymer consisting of 0 wt% and having a Mw of 140,000

(Acrylonitrile-butadiene-styrene copolymer rubber: ABS) 10 mesh residue is 90%
Powdered ABS resin (Mitsubishi Rayon Co., Ltd.)
(Trade name: RC) (polyphenylene ether: PPE) US Patent No. 4,7
In the presence of dibutylamine according to the method described in 88,277 Pat (Japanese Patent Application No. Sho 62-77570), one produced 2,6 xylenol oxidative coupling polymerization to, eta _{SP / C} = 0.42 and the melt viscosity was measured at 280 ° C. at a shear rate of 140 sec ⁻¹
It is 9,000 poise.

(Polystyrene: GPPS) Stylon 685 (High Impact Polystyrene: HIPS) manufactured by Asahi Kasei Kogyo Co., Ltd. Styron H9405 (Fluorine-based resin: PTFE) manufactured by Asahi Kasei Kogyo Co., Ltd. Product name: Teflon 30J Polytetra Aqueous Fluoroethylene Dispersion Each test in Examples and Comparative Examples was performed by the following methods.

(1) Flame Retardancy Test The obtained pellets were dried and molded with an injection molding machine (Autoshot 50D, manufactured by FANUC) to prepare a test piece shaped body for a combustion test. The flame retardancy was evaluated based on the UL94 standard vertical combustion test (UL94). (2) Measured at 220 ° C. under a load of 10 kg according to MFR ASTM D1238. (Unit: g / 10 min) (3) Izod impact test Measured with a ＴＭ inch thick notch according to ASTM D256. (Unit: kgf · cm / cm)

(4) Evaluation of Color Tone The color of the obtained pellets or test pieces was visually observed. ：: Little yellowing Δ: Slightly yellowing X: Yellowing is remarkable (5) Hot water resistance A 1 / 8-inch thick strip test piece was placed in an autoclave to obtain 12
The degree of yellowing after leaving for 96 hours in a 0 ° C., 2 atm saturated steam environment was evaluated.

○: little yellowing ×: remarkable yellowing (6) High temperature and high humidity resistance 1/8 inch thick strips were stored in an atmosphere of 60 ° C. and 85% RH for 300 hours, and the Izod impact strength was measured. Was evaluated. (7) Evaluation of time-dependent change of Izod impact value Five minutes, ten minutes, thirty minutes after starting pelletization of pellets of the flame-retardant resin composition obtained using an extruder,
After 60 minutes, each sample was collected, molded, and subjected to an Izod impact test.

(Examples 1 to 5 and Comparative Examples 1 and 2) Pellets of a resin composition having the composition (unit: parts by weight) listed in Table 1 were melt-kneaded by a twin-screw extruder (ZSK-25, manufactured by W & P). It was prepared by pelletizing. The cylinder temperature was set to 250 ° C. for both Examples 1 to 5 and Comparative Examples 1 and 2. In Examples 1 to 4, a flame retardant composition was prepared by adding and mixing an epoxy compound at 70 ° C. in advance to an organic phosphorus compound, and the mixture was compounded by press-fitting the extruder at 80 ° C. with a gear pump. In Example 5, a flame retardant composition was prepared by previously adding and mixing an epoxy compound with an organic phosphorus compound at 120 ° C., and the mixture was compounded by press-fitting the extruder at 120 ° C. with a gear pump. Table 1 shows the flame retardants in each example.
The test was performed at the position shown in FIG. Each symbol in Table 1 represents a position in the extruder shown below. FIG. 1 shows the positions of these symbols. Upper: Raw material supply side from melt kneading zone Middle: Melt kneading zone Lower: Die head side from melt kneading zone The results are shown in Table 1.

[0059]

[Table 1]

Examples 1 to 5 are the results when the flame retardant composition of the present invention was used, and the color tone of the pellet was superior to the comparative example. In the discharge amount (kg / h) in the table, when the screw rotation speed of the extruder is set to 150 rpm, the discharge value of the resin composition is such that the current value indicating the screw torque of the extruder is 90% of the maximum allowable value. Express the amount. Examples 1, 2, 4, and 5 show that the ejection amount is large and the productivity is excellent.

Example 6 and Comparative Example 3 A resin composition having the composition shown in Table 2 was obtained by melt-kneading with a twin-screw extruder. The cylinder temperature is 280 ° C and the screw speed is 250
rpm. The flame-retardant composition was compounded at the position shown in “middle” in FIG. 1 and was press-fitted into the extruder at 80 ° C. using a gear pump. Table 2 shows the results.

[0062]

[Table 2] Example 6 was superior to Comparative Example 3 in hot water resistance.

(Examples 7, 8 and Comparative Examples 4, 5,
6) A resin composition having the composition shown in Table 3 was obtained by melt-kneading with a twin-screw extruder. The cylinder temperature was 250 ° C., and the screw rotation speed was 250 rpm. The flame-retardant composition was compounded at the position shown in “middle” in FIG. 1 and was press-fitted into the extruder at 80 ° C. using a gear pump. The obtained pellets were dried, and the cylinder set temperature was set to 240 ° C., 260 ° C., 2
The temperature was set to 80 ° C., the mold temperature was set to 60 ° C., and a 1/8 inch thick strip was molded by an injection molding machine, and the Izod impact strength was evaluated. In addition, the MFR was calculated using each pellet.
Was evaluated. Further, the test piece molded at 280 ° C. was evaluated for color tone. Table 3 shows the results.

[0064]

[Table 3]

Examples 7 and 8 show that the Izod impact strength is maintained even when molding is performed at a high molding temperature. Also, it can be seen that the color tone of the test piece molded at 280 ° C. is superior to that of the comparative example. Further, the MFR of Comparative Example 4 is higher than that of Example 7. Example 8
On the other hand, Comparative Example 5 has an increased MFR. Comparative Example 6 is a result of using a flame retardant composition in which (α) organophosphorus compound is blended with (β) epoxy compound, and the acid value of the used flame retardant composition is 1.07. This is an example outside the scope of the invention.

(Example 9 and Comparative Example 7) A resin composition having the composition shown in Table 4 was obtained by melt-kneading with a twin-screw extruder.
Cylinder temperature is 250 ° C and screw rotation speed is 2
It was set to 50 rpm. The flame-retardant composition was compounded at the position shown in “middle” in FIG. 1 and was press-fitted into the extruder at 80 ° C. using a gear pump. The obtained pellets were dried, the cylinder set temperature was set to 240 ° C., the mold temperature was set to 60 ° C., and 1/8 inch thick strips were formed by an injection molding machine, and the Izod impact strength was evaluated. Further, polycarbonate was separated and extracted from the evaluated Izod test piece, and the weight average molecular weight (Mw) of the polycarbonate was evaluated by GPC. Further, the color tone of the molded piece was visually observed. A 1/16 inch thick strip was molded by an injection molding machine, and a UL94 vertical combustion test was performed. Further, a test strip molded under the same molding conditions was left in an atmosphere of 60 ° C. and 85% RH for 300 hours, and the same test as above was performed using the test piece taken out. Table 4 shows the results.

[0067]

[Table 4]

In Example 9, a test strip was prepared at 60 ° C. and 85 RH.
%, The same performance as that immediately after molding was obtained even after being left in an atmosphere of 300%. On the other hand, Comparative Example 7 was at 60 ° C and 85R.
After leaving for 300 hours in an atmosphere of H%, various physical properties were remarkably reduced.

Example 10 and Comparative Example 8 The resin compositions having the compositions shown in Table 5 were obtained by melt-kneading with a twin-screw extruder. The cylinder temperature was 250 ° C., and the screw rotation speed was 250 rpm. In Example 10, the compounding location of the flame-retardant composition was the location shown in "middle" in FIG. On the other hand, Comparative Example 8
A mixture of resin pellets, ABS powder, PTFE dispersion, and epoxy compound blended together in a drum blender was charged from a hopper of an extruder. The organic phosphorus compound was blended at the same charging position as in Example 10 to obtain pellets of the resin composition. 5 minutes, 10 minutes, 30 minutes, and 60 minutes after starting the continuous melt kneading.
After one minute, the resin composition pellets are collected, each pellet is dried, and a 1/8 inch thick strip is formed by an injection molding machine at a cylinder set temperature of 240 ° C. and a mold temperature of 60 ° C., and subjected to Izod impact. The strength was evaluated. Also, M
FR measurements were performed. Table 5 shows the results.

[0070]

[Table 5] In Example 10, the values of Izod impact strength and MFR collected at each time were stable, and a resin composition having stable performance with little variation in performance could be obtained. On the other hand, in Comparative Example 8, the performance variation was large.

[0071]

As described above, according to the present invention, when blended in a resin composition, mechanical properties can be maintained even in a high-temperature and high-humidity environment or when molding is performed at a high temperature. To provide a flame retardant composition capable of obtaining a flame retardant resin composition having an improved color tone, and further to obtain a flame retardant resin composition having stable performance using the flame retardant composition with high productivity. Can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic view of an extruder for pelletizing a resin composition.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 101/00 C08L 101/00 // (C08L 69/00 (C08L 69/00 63:00) 63:00) (C08L 71/12 (C08L 71/12 63:00) 63:00) (C08L 101/00 (C08L 101/00 63:00) 63:00) F-term (reference) 4J002 AA011 BB001 BC001 BD041 BG061 BN141 BN151 CB001 CD01X CD02X CD04X CD05X CD10X CD14X CF001 CG001 CH071 CL001 EL026 EW047 FD137

Claims (11)

[Claims] 1. A flame retardant composition for a resin (B) comprising (α) an organic phosphorus compound and (β) an epoxy compound and having an acid value of 1 or less. 2. The method according to claim 1, wherein (α) the organic phosphorus compound is represented by the following formula (1):
The flame retardant composition for a resin according to claim 1, which is an oligomeric organic phosphorus compound comprising one or a mixture of two or more kinds represented by the following formulae. Embedded image 3. The method according to claim 1, wherein (α) the organic phosphorus compound is represented by the following formula (2):
The flame retardant composition for a resin according to claim 1, which is an oligomeric organic phosphorus compound comprising one or a mixture of two or more kinds represented by the following formulae. Embedded image 4. (β) an alicyclic epoxy compound in which the epoxy compound has one or more epoxy groups in a molecular skeleton,
The flame retardant composition for a resin according to any one of claims 1 to 3, which is an epoxy compound comprising one or a mixture of two or more selected from an aliphatic epoxy compound, an aromatic epoxy compound, and a heterocyclic epoxy compound. 5. The flame retardant composition for a resin according to claim 1, wherein the (β) epoxy compound is an alicyclic epoxy compound. 6. The (β) epoxy compound represented by the following formula (3):
The flame retardant composition for a resin according to any one of claims 1 to 5, which is an alicyclic epoxy compound represented by the following formula: Embedded image 7. The flame retardant composition for a resin according to claim 1, which has an acid value of 0.1 or less. 8. (A) A flame retardant composition for a resin which contains (α) an organic phosphorus compound and (β) an epoxy compound and has an acid value of 1 or less based on 100 parts by weight of a thermoplastic resin. Is blended in an amount of 1 to 30 parts by weight, and the mixture is melt-kneaded, thereby producing a flame-retardant resin composition. 9. An acid value of (B) the flame retardant composition for resin is 0.1.
The method for producing a flame-retardant resin composition according to claim 8, wherein the ratio is 1 or less. 10. A single-screw or multi-screw extruder having two or more screws, wherein one or more (B) melt kneading zones are located on the raw material supply port side of the melt kneading zone. The method for producing a flame-retardant resin composition according to claim 8, wherein a flame retardant composition for a resin is blended and melt-kneaded. 11. The method for producing a flame-retardant resin composition according to claim 8, wherein (A) the thermoplastic resin is a polycarbonate resin or a polyphenylene ether resin.