JPH11236497A - Flame retardant resin composition - Google Patents

Abstract

(57) Abstract: The present invention relates to a polycarbonate-based flame-retardant resin composition having excellent heat resistance and impact resistance and having high flame retardancy. SOLUTION: (A) polycarbonate resin (component A), (B) styrene resin (component B), (C) specific cyclic phosphate compound (component C), (D) carbonic acid of alkaline earth metal At least one inorganic salt (D component) selected from the group consisting of salts and phosphates, and (E) a fluororesin (E
Component), and when the total of the A component, the B component, the C component, the D component, and the E component is 100 parts by weight, the A component is 97 to 40 parts by weight, and the B component is 0 to 55 parts by weight.
Parts by weight, the C component is 2 to 20 parts by weight, the D component is 10 parts by weight or less, and the E component is 0.01 to 3 parts by weight.
A flame-retardant resin composition wherein the ratio of the number of moles of the component D to the number of moles of phosphorus atoms derived from the components is 0.02 or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate flame-retardant resin composition having excellent heat resistance and impact resistance and having high flame retardancy.

[0002]

2. Description of the Related Art Polycarbonate resins have good heat resistance, impact resistance and the like, and are used in a wide range of applications such as electric, electronic equipment and automobile fields. In addition, with respect to properties that are not sufficient with such a resin alone, a resin composition blended with a styrene-based resin typified by an ABS resin, an AS resin, or the like is used to reinforce the resin composition, thereby expanding the field in a wider field. And is used in many products.

In recent years, in order to enhance the safety of these products, flame retardancy has been required particularly in office automation equipment and home electric appliances, etc. In particular, in recent years, in particular, the absolute amount of materials has been reduced to make them lighter and thinner. In view of this, there is a need for flame retardancy in thinner molded products. In this case, since the molten portion (drip) of the resin is likely to occur in the thin portion of the molded product, there is an inherent danger of spreading to other combustible materials.
Therefore, the resin composition is first required to have a high degree of flame retardancy that does not drip.

There are various methods for developing flame retardancy. In the case of a polycarbonate resin or a resin composition of a polycarbonate resin and a styrene resin, a flame retardant of a halogen compound and an antimony compound are usually used. And the like. However, such a flame retardant generally generates corrosive gas at the time of processing or burning, and has a problem such as an increase in man-hours due to maintenance of a mold at the time of molding, and in some cases, at the time of product disposal in the future. At present, there is a need for a flame-retardant resin composition that does not contain a halogen-based flame retardant and an antimony compound because of concerns about the effects on the environment.

Various non-halogen flame retardants have been used for polycarbonate resins.
In particular, in the case of a resin composition of a polycarbonate-based resin and a styrene-based resin, an organic phosphorus-based compound is currently widely used and many studies have been made. Such compounds typically include triphenyl phosphate (TPP). However, the addition of TPP has a problem of lowering the heat resistance temperature of the composition, and has a problem that it is insufficient to replace a polycarbonate-based flame-retardant resin composition containing a halogen-based flame retardant which has been conventionally used. .

Therefore, in order to obtain a desirable flame-retardant resin composition, it is expected that a phosphorus-based flame retardant having a sufficient phosphorus content and having a high heat-resistant temperature is suitably used. JP-A-54-157156 discloses that a pentaerythritol diphosphate compound or a pentaerythritol diphosphite compound can be used as a flame retardant for a polycarbonate resin, and these flame retardants have extremely good thermal stability. There is a statement to the effect. These flame retardants also have a high phosphorus content.

[0007] However, when these flame retardants are actually used, the thermal stability is certainly good, and the heat resistance temperature of the resin composition is extremely low. When applied to a molded product thinner than the inch thickness, sufficient flame retardancy cannot be obtained. It is considered that the reason for this is that the pentaerythritol diphosphate compound and the like have a flame-retardant effect derived from the phosphate ester structure, but the effect is offset by the high combustibility of the pentaerythritol portion. Can be

On the other hand, JP-A-9-227772 discloses that
In order to remedy the drawback of using a pentaerythritol diphosphite compound alone, there is a description of using a condensed phosphate ester type flame retardant widely known as a flame retardant. However, even in this publication, in order to ensure sufficient flame retardancy, it is necessary to add more condensed phosphoric acid ester having a large decrease in heat resistance temperature, and flame retardation by a non-halogen compound still having a sufficient heat resistance temperature. No conductive resin composition was obtained.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a non-halogen flame retardant, particularly a phosphate ester flame retardant, which is excellent in heat resistance and impact resistance and has high flame retardancy. An object of the present invention is to provide a polycarbonate resin composition.

The present inventors have conducted intensive studies to obtain sufficient flame retardancy by using a cyclic phosphate compound having good heat resistance, such as a pentaerythritol diphosphite compound. It was found that by adding a specific inorganic salt thereto, a molded article excellent in heat resistance and impact resistance can be obtained, while exhibiting a high degree of flame retardancy not exhibited by the cyclic phosphate ester alone. Completed the invention.

[0011]

That is, the present invention provides:
(A) polycarbonate resin (component A), (B) styrene resin (component B), (C) the following general formula (1)

[0012]

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(Wherein R is a group having 3 to 20 carbon atoms;
A cyclic phosphate compound having a skeleton represented by a substituted or unsubstituted phenyl group, a naphthyl group, an anthryl group, a pyridyl group and a triazyl group) (C component), (D A) a resin composition comprising at least one inorganic salt (D component) selected from the group consisting of alkaline earth metal carbonates and phosphates and (E) a fluororesin (E component); and , B component, C component, D component and E component when the total is 100 parts by weight,
A component is 97 to 40 parts by weight, B component is 0 to 55 parts by weight,
2 to 20 parts by weight of the C component, 10 parts by weight or less of the D component, 0.01 to 3 parts by weight of the E component, and the ratio of the number of moles of the D component to the number of moles of phosphorus atoms derived from the C component Is 0.02 or more.

The polycarbonate resin used as the component A in the present invention is an aromatic polycarbonate resin or an aliphatic polycarbonate resin obtained by reacting a dihydric phenol alone or a dihydric phenol and an aliphatic diacid with a carbonate precursor. A polyester carbonate resin containing a diacid component in the main chain. Examples of the dihydric phenol used here include bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, and 2,2′-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A). ), 2,2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxyphenyl) octane, 2,2'-bis (4-hydroxy-3
-Methylphenyl) propane, 2,2′-bis (4-hydroxy-3-tert-butylphenyl) propane,
2,2'-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxy-
3-cyclohexylphenyl) propane, 2,2′-bis (4-hydroxy-3-methoxyphenyl) propane, 1,1′-bis (4-hydroxyphenyl) cyclopentane, 1,1′-bis (4-hydroxy Phenyl)
Cyclohexane, 1,1'-bis (4-hydroxyphenyl) cyclododecane, 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide , 4,4'-dihydroxy-3,3'-
Dimethyl diphenyl sulfide, 4,4'-dihydroxy diphenyl sulfoxide, 4,4'-dihydroxy diphenyl sulfone are exemplified. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes, with bisphenol A being particularly preferred.

Examples of the aliphatic diacid include those having 8 to 2 carbon atoms.
0, preferably 10-12 aliphatic diacids. Such an aliphatic diacid may be linear, branched or cyclic, and α, ω-dicarboxylic acid is preferred. Examples of preferred aliphatic diacids include straight-chain saturated aliphatic dicarboxylic acids such as decandioic acid, dodecandioic acid, tetradecandiodic acid, octadecandioic acid, eicosandioic acid, and sebacic acid and dodecandioic acid are particularly preferred. preferable.

Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate and the like. Specifically, phosgene, diphenyl carbonate,
And dihaloformate of dihydric phenol.

In producing the polycarbonate resin, the above-mentioned dihydric phenols may be used alone or in combination of two or more. Alternatively, the dihydric phenol and the aliphatic diacid may be used alone or Two or more kinds may be used in combination. Although the content ratio of the dihydric phenol and the aliphatic diacid can be arbitrarily adjusted, it is desirable that at least 40 mol% or more of the polycarbonate resin is derived from bisphenol A. Further, the content of the aliphatic diacid component in the polycarbonate resin is preferably 20 mol% or less from the viewpoint of suppressing a decrease in heat resistance and a decrease in flame retardancy. The polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a mixture of two or more polycarbonate resins. In the present invention, it is more preferable to use an aromatic polycarbonate resin from the viewpoint of flame retardancy.

The molecular weight of the polycarbonate resin does not need to be particularly limited, but if it is too low, the strength is not sufficient, and if it is too high, the melt viscosity becomes high and molding becomes difficult. Therefore, it is usually expressed in terms of viscosity average molecular weight of 10,000. ~ 5
0000, preferably 15,000 to 40,000
It is. The viscosity-average molecular weight (M) here is 0.7 g of a polycarbonate resin in 100 ml of methylene chloride.
The specific viscosity (η _SP ) obtained from the solution dissolved at ° C. was obtained by inserting it into the following equation. η _SP /C=[η]+0.45×[η] ² C [η] = 1.23 × 10 ^-4 M ^0.83 (where [η] is the intrinsic viscosity and C is the polymer concentration of 0.7)

Next, the basic means for producing a polycarbonate resin will be briefly described. In the solution method using phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. When an aliphatic diacid is contained, a method in which such an aliphatic diacid is previously in the form of a salt such as a sodium salt and added to a reaction vessel containing a dihydric phenol can be preferably used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction, and a terminal stopper such as an alkyl-substituted phenol such as phenol or p-tert-butylphenol can be used as a molecular weight regulator. It is desirable to use. Reaction temperature is usually 0 to 40 ° C,
The reaction time is preferably several minutes to 5 hours, and the pH during the reaction is preferably maintained at 10 or more. It is not necessary that all of the resulting molecular chain ends have a structure derived from the terminator.

In a transesterification reaction (melting method) using a carbonic acid diester as a carbonate precursor, a predetermined ratio of a dihydric phenol is stirred with a carbonic acid diester while being heated in the presence of an inert gas to produce alcohol or phenols. It is performed by the method of distilling. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be formed, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off alcohol or phenols produced by reducing the pressure from the beginning. At the initial stage of the reaction, a terminal capping agent is added simultaneously with the dihydric phenol or the like or at an intermediate stage of the reaction. Further, in order to accelerate the reaction, a catalyst which is currently used in a transesterification reaction can be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like.
Of these, diphenyl carbonate is particularly preferred.
When an aliphatic diacid is contained, it is preferable that such an aliphatic diacid is previously in the form of an ester such as diphenyl ester.

The styrene resin as the component B of the present invention includes a homopolymer or a copolymer of styrene derivatives such as styrene, α-methylstyrene and p-methylstyrene;
Copolymers of these monomers with vinyl monomers such as acrylonitrile and methyl methacrylate, diene rubbers such as polybutadiene, ethylene propylene rubbers, styrene rubbers and the like,
Alternatively, styrene and / or a styrene derivative are graft-polymerized with another vinyl monomer. Examples of the styrene resin include polystyrene, styrene / butadiene / styrene copolymer (SBS), hydrogenated styrene / butadiene / styrene copolymer (hydrogenated SBS), and hydrogenated styrene / isoprene / styrene copolymer (SEP).
S), impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), methyl methacrylate Resins such as acrylonitrile / butadiene / styrene copolymer (MABS resin), acrylonitrile / acryl rubber / styrene copolymer (AAS resin), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin), or the like; Mixtures are mentioned. Incidentally, such a vinyl-based thermoplastic resin may be one having a high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst at the time of its production. Further, in some cases, a polymer and a copolymer having a narrow molecular weight distribution obtained by a method such as anionic living polymerization or radical living polymerization, a block copolymer, and a highly stereoregular polymer or copolymer are used. It is also possible. For the purpose of improving the compatibility with the polycarbonate resin, it is also possible to copolymerize the styrene resin with a compound having a functional group such as maleic anhydride or N-substituted maleimide. Among them, high impact polystyrene (HIP
S), acrylonitrile / styrene copolymer (AS resin), and acrylonitrile / butadiene / styrene copolymer (ABS resin) are preferred.
S resin is most preferred. In addition, two or more styrene resins can be used as a mixture.

The ABS resin is a mixture of a thermoplastic graft copolymer obtained by graft-polymerizing a vinyl cyanide compound and an aromatic vinyl compound on a diene rubber component, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. is there. As the diene-based rubber component forming the ABS resin, for example, a rubber having a glass transition point of 10 ° C. or less such as polybutadiene, polyisoprene, and styrene-butadiene copolymer is used, and its ratio is 100% by weight of the ABS resin component. It is preferably from 5 to 80% by weight. Examples of the vinyl cyanide compound grafted to the diene rubber component include acrylonitrile and methacrylonitrile.Examples of the aromatic vinyl compound grafted to the diene rubber component include styrene and α-methylstyrene. Can be mentioned. The content ratio of the vinyl cyanide compound and the aromatic vinyl compound is such that the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl compound is 100% by weight based on the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Is 95-50
% By weight. Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used.
It is preferably 15% by weight or less in 100% by weight of the resin component. This thermoplastic graft copolymer B component may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization, and may be copolymerized in a single step.
Copolymerization may be carried out in multiple stages.

The cyclic phosphate compound used as the component C in the present invention is a compound having at least one skeleton represented by the general formula (1) in one molecule.

[0024]

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(Wherein R is a group having 3 to 20 carbon atoms;
Represents any one group selected from a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, pyridyl group and triazyl group)

The compound having such a functional group can be obtained by basically reacting phosphorus oxytrichloride with a skeleton having a diol which is in close proximity, and then appropriately reacting with a phenolic hydroxyl group. Such a reaction is carried out, for example, by the method disclosed in JP-A-9-183786, or
R. M. McConnell et al. Org. Che
m. 24, 630-635 (1959).

Compounds having such a functional group include:
1,3-propanediol, 2,2-dimethyl-1,3
By reacting phosphorus oxytrichloride with a compound having a divalent or higher hydroxyl group adjacent to carbon such as propanediol and glycerin, and then reacting with phenol, 2,5-dimethylphenol, cresol, etc. can get. Alternatively, it is also possible to modify a part of the chlorine of the phosphorus oxytrichloride in advance with these phenols and then react the same.

However, in order to exhibit a better effect in the present invention, it is generally preferable that the above functional group has a symmetrical cyclic skeleton. It is represented by the general formula (2).

[0029]

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(Wherein R ¹ and R ² may be the same or different from each other and are groups represented by the following general formula (3))

[0031]

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(Where Ar represents any one group selected from a phenyl group, a naphthyl group, an anthryl group, a pyridyl group and a triazyl group, R ³ represents a substituent bonded to Ar, and n = 0 R ³ may be the same or different, and may be bonded to any portion other than the portion bonded to a phosphorus atom via an oxygen atom on Ar, and methyl , Ethyl, propyl containing isomers, butyl containing isomers, the bond to Ar of which is directly or through oxygen, sulfur, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and has 5 to 5 carbon atoms. One or more organic groups selected from 14 aryl groups)

In the formula, preferred examples of R ¹ and R ² include phenyl, cresyl, xylyl, trimethylphenyl, 4-phenoxyphenyl, cumyl, naphthyl, 4-benzylphenyl, -Tert-butylphenyl group, 2,6-diphenylphenyl group, 4-
Examples include a phenylphenyl group, a 4-diphenylphenyl group, an anthryl group, and a 4-benzenesulfonylphenyl group. Such a compound can be easily produced basically using pentaerythritol as a raw material as described above.

The inorganic salt used as the component D in the present invention is one or a mixture of one or more inorganic salts selected from carbonates and phosphates of alkaline earth metals. .

Preferably, at least one inorganic salt selected from the group consisting of calcium carbonate, magnesium carbonate, barium carbonate, calcium phosphate and magnesium phosphate is used. Particularly, calcium carbonate, calcium phosphate and barium carbonate exhibit a higher flame retardant effect. . Calcium carbonate is the most preferable because it is nontoxic. In addition, such an inorganic salt can be used irrespective of the particle size, shape, and presence or absence of surface treatment.

Surprisingly, such an inorganic salt has an effect of remarkably improving the flame retardancy of the component C of the present invention, which does not sufficiently exhibit flame retardancy despite the phosphorus content. As inorganic substances having a flame retardant effect, for example, aluminum hydroxide, magnesium hydroxide, and the like used in polyolefins are known. However, in such a case, unless added in a large excess, the flame-retardant effect is not recognized, and the addition of a large excess significantly lowers the intrinsic mechanical properties of the resin, making it difficult to put into practical use. In other words, it has been clarified by the inventors of the present invention that it essentially does not contribute to improving the flame retardancy. On the other hand, the present inventors have found the surprising fact that the compound having a functional group constituting the component C of the present invention exhibits a combustion suppressing effect only as a flame retardant, and has reached the present invention. Therefore, it has been confirmed by the present inventors that some kind of interaction acts between the flame retardant as the component C and the inorganic salt as the component D of the present invention.

The function of the E component of the present invention is already generally known to those skilled in the art. Examples of such a fluororesin include homo- or copolymers of a fluorine-containing monomer such as tetrafluoroethylene, trifluoroethylene, vinyl fluoride, vinylidene fluoride, and hexafluoropropylene. The fluorine-containing monomer and a polymerizable monomer such as ethylene, propylene, and acrylate may be copolymerized within a range that does not impair the dropping prevention performance. Among these fluororesins, polytetrafluoroethylene is preferred. The preferred polytetrafluoroethylene is what is called type 3 according to the ASTM standard.

The fluororesin can be prepared by a conventional method, for example,
It can be obtained by the emulsion polymerization method described in U.S. Pat. No. 2,393,967. The fluororesin can be used in a solid state or an emulsion state, but in the composition of the present invention, it is preferable to use the solid state in view of the thermal stability of the resin.

Next, the content of each component will be described. The content of the component A used in the present invention is 97 to 40 parts by weight, preferably 90 to 50 parts by weight, per 100 parts by weight of the resin composition comprising the components A, B, C, D and E. If it exceeds 97 parts by weight, impact resistance and flame retardancy will be insufficient, and if it is less than 40 parts by weight, flame retardancy will be insufficient.

The component B used in the present invention is used in an amount of 0 to 55 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the resin composition comprising the components A to E. If it exceeds 55 parts by weight, good flame retardancy cannot be imparted.

The content of the cyclic phosphate compound as the component C used in the present invention is 2 to 20 parts by weight based on 100 parts by weight of the resin composition comprising the components A to E. Basically, the flame retardancy should be determined by the effective phosphorus content in the composition. Therefore, when the effective phosphorus content is 0.3% by weight or more in the resin composition comprising the components A to E. If the present invention functions effectively, it is preferably at least 0.6% by weight, more preferably at least 0.8% by weight. Also, since the presence of an excessive amount of the C component may lead to a reduction in the physical properties of the resin, it is desirable that the amount is 20 parts by weight or less, preferably 100 parts by weight of the resin composition composed of the A component to the E component. 18 parts by weight or less.

The 1 component selected from the group consisting of carbonates and phosphates of the alkaline earth metal as the D component used in the present invention.
The content of at least one kind of inorganic salt is 10 parts by weight or less in 100 parts by weight of the resin composition comprising the components A to E, and C
It is necessary that the ratio of the number of moles of the component D to the number of moles of phosphorus atoms derived from the component is 0.02 or more. Here, the ratio of the number of moles of the D component to the number of moles of the phosphorus atom means a value obtained by dividing the number of moles of the D component by the number of moles of the phosphorus atom. Preferably, it is not more than 8 parts by weight in 100 parts by weight of the resin composition comprising the components A to E, and the ratio of the number of moles of the component D to the number of moles of phosphorus atoms derived from the component C is 0.10. Is more than If the D component is more than 10 parts by weight, the decomposition of the resin component becomes large, and conversely the flame retardant effect becomes insufficient, which is not preferable. The ratio of the number of moles of the D component to the number of moles of the phosphorus atoms derived from the C component is 0.0%.
If it is less than 2, a sufficient flame retardant effect cannot be obtained. D
The main content of the present invention is that a relatively small amount of the component exhibits a sufficient effect, and that the amount of the D component does not basically impair the physical properties of the resin.

The content of the fluororesin, which is the E component used in the present invention, is 100 parts by weight of the resin composition 100 composed of the A component to the E component.
0.01 to 3 parts by weight, preferably 0.1 to 0.1 parts by weight.
To 2 parts by weight, more preferably 0.2 to 1 part by weight. When the content of the fluororesin is less than 0.01 part by weight, the effect of preventing drip is small, and it is difficult to impart high flame retardancy. When the content is more than 3 parts by weight, the appearance of a molded article is deteriorated. Absent.

The flame-retardant resin composition of the present invention may further comprise, in addition to the components A to E of the present invention, a polycarbonate-based resin having flame retardancy within a range not to impair the object of the present invention. It is also possible to use a phosphoric acid ester, red phosphorus, a metal sulfonic acid salt type, and a silicone type flame retardant other than the component C of the present invention, which are known from the group (A). In addition, the range which does not impair the object of the present invention means that the addition amount of the C component is 1
, The weight ratio is 0.8 or less, preferably 0.
It refers to use at 6 or less, more preferably at 0.5 or less. Further, for the purpose of improving the impact resistance, an elastic polymer such as an acrylic elastomer, an elastomer having an IPN structure in which an acrylic polymer and a polyorganosiloxane polymer have an IPN structure, a thermoplastic polyurethane elastomer, a thermoplastic polyester elastomer, and a thermoplastic polyamide elastomer are further added. It is also possible to add. Various additives already known, for example, antioxidants, ultraviolet absorbers, deterioration inhibitors such as light stabilizers, lubricants, antistatic agents, mold release agents, plasticizers, sliding agents, glass fibers, carbon fibers Further, reinforcing fibers such as aramid fibers and aromatic polyester fibers, fillers such as mica and glass flakes, and coloring agents such as pigments may be added. The amount of the additive to be used can be appropriately selected according to the type of the additive within a range not impairing the heat resistance, impact resistance, mechanical strength, and the like.

The flame-retardant resin composition of the present invention is usually prepared by adding a polycarbonate-based resin, a styrene-based resin, a cyclic phosphate compound, an inorganic salt, a fluororesin, and other components from separate feeders, or using such components. The mixture is prepared by supplying a mixture obtained by premixing a part or all of the mixture by a mixer and each component other than the mixture to a kneader from each supply machine and melt-mixing. As a mixing machine, for example, a tumbler,
Examples include a V-type blender, a super mixer, a super floater, and a Henschel mixer. As the kneader, various melt mixers can be used. For example, a kneader, a single-screw or twin-screw extruder can be used. Among them, a method in which the resin composition is melted and extruded using a twin-screw extruder or the like and pelletized by a pelletizer is preferably used. In this case, for example, 200 to 320 ° C., preferably 22
It is preferable to use an extruder having one or more degassing holes at a temperature of about 0 to 290 ° C. and to perform melt kneading under reduced pressure.

The flame-retardant resin composition of the present invention is useful as a material for forming various molded articles such as housings and enclosures of home electric appliances and OA equipment, housings and casings of portable information equipment and the like. Such a molded product is a conventional method, for example, a pellet-shaped flame-retardant resin composition,
It can be manufactured by injection molding at a cylinder temperature of, for example, about 220 to 290 ° C. using an injection molding machine.

[0047]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference Example 1 Synthesis of diphenylpentaerythritol diphosphate Phosphorus oxychloride 575 was placed in a 10-liter three-necked flask equipped with a stirrer, reflux condenser, dropping funnel and oil bath.
7.7 g and anhydrous magnesium chloride (15.35 g) were charged, and the oil bath was heated to about 110 ° C. under a reflux of nitrogen to bring phosphorus oxychloride to a reflux state, and then 1024.3 g of phenol was added to 1707 ml of chlorobenzene through a dropping funnel.
Was poured over about 30 minutes, and further reacted for 30 minutes. The generated hydrogen chloride was absorbed into a sodium hydroxide aqueous solution outside the reaction system through a reflux condenser.
Thereby, monophenyl dichlorophosphate was obtained.
After the reaction, the solvent and excess phosphorus oxychloride were distilled off. ³¹ P-
NMR (deuterated chloroform solvent) measurement, 3.4 pp
A single peak of m was identified.

Next, 3000 g of pyridine, 8% by weight of the whole, did not pass through a standard sieve having an aperture of 150 μm in a 5-liter three-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and an oil bath. 5% by weight of pentaerythritol powder 3 having a particle size distribution passing through a standard sieve having an opening of 22 μm
To this, 930 g of the above-obtained monophenyldichlorophosphate was gradually added dropwise while stirring. The rate of dropping was adjusted so that the temperature did not exceed 60 ° C. due to heat generation. After completion of the dropwise addition, the mixture was stirred for 30 minutes without heating. After that, the solvent was distilled off, and the residue was
After washing with 00 ml of water and repeating this three times, it was further washed with about 3000 ml of methanol and dried to obtain 760 g of a white solid. ^{From 31} P-NMR (deuterated chloroform solvent), it was confirmed that it was a single peak at 13.8 ppm, and that it was diphenylpentaerythritol diphosphate. The purity measured by high performance liquid chromatography was 99.5%. Hereinafter, this is referred to as DP.

Reference Example 2 Synthesis of di (2,6-dimethylphenyl) pentaerythritol diphosphate In the same manner as in Reference Example 1, except that 1024.3 g of phenol in Reference Example 1 was changed to 1330 g of 2,6-dimethylphenol. After synthesizing 2,6-dimethylphenyldichlorophosphate, 1053.7 g of this was reacted with pentaerythritol in the same manner as in Reference Example 1 to obtain di (2,2).
6-Dimethylphenyl) pentaerythritol diphosphate was obtained. The purity determined by high performance liquid chromatography was 99.3%. This is called DTBP
Called.

Reference Example 3 Synthesis of di (4-tert-butylphenyl) pentaerythritol diphosphate 1024.3 g of phenol of Reference Example 1 was added to 4-tert-
After synthesizing 4-tert-butylphenyldichlorophosphate in the same manner as in Reference Example 1 except that the amount was changed to 1634.8 g of butylphenol, 1176.5 g of this was synthesized.
Was reacted with pentaerythritol in the same manner as in Reference Example 1 to obtain di (4-tert-butylphenyl) pentaerythritol diphosphate. The purity measured by high performance liquid chromatography was 99.6%. Hereinafter, this is referred to as DDMP.

REFERENCE EXAMPLE 4 Confirmation of Interaction between Cyclic Phosphate Ester and Inorganic Salt (1) 1000 mg of DP prepared in Reference Example 1 was weighed with an electronic balance and made into a uniform fine powder with an agate mortar. 15 mg was weighed, and the temperature was increased from 23 ° C. to 300 ° C. at a rate of 20 ° C./min under a nitrogen gas stream by a TGA measuring instrument, and the temperature was maintained for 30 minutes. 15 minutes from the start of heating in this process
The weight loss ratio per unit time between the hour and the hour was calculated. Similarly, DP80 created in Reference Example 1
0 mg and 200 mg of calcium carbonate (special grade of reagent, manufactured by Wako Pure Chemical Industries, Ltd.) were weighed with an electronic balance, mixed, uniformly pulverized and mixed in an agate mortar.
mg was weighed and measured and the weight loss ratio was calculated under the same conditions as above. In this case, the weight was calculated based on the weight of only DP. As a result of the measurement, the weight reduction ratio of DP alone was 1.65% by weight / min, whereas that of calcium carbonate was 0.9% by weight / min. That is, it was confirmed that the weight loss of the cyclic phosphate component at a high temperature was reduced by calcium carbonate.

Reference Example 5 Confirmation of Interaction between Cyclic Phosphate Ester and Inorganic Salt (2) A sample for TGA measurement was prepared in the same manner as in Reference Example 4,
When the temperature was increased from 3 ° C. to 900 ° C. at a rate of 20 ° C./min, the temperature at which the weight loss rate was maximized was calculated. In this case, the temperature was 375 ° C. when DP alone was used, whereas it was 395 ° C. when calcium carbonate was mixed, and it was confirmed that the thermal decomposition temperature of DP increased.

Examples 1 to 28 and Comparative Examples 1 to 17 Using the cyclic phosphate compound obtained above, each sample was evaluated in Tables 1 and 2. The evaluation was performed for the following items (1) and (2). The parts in the table represent parts by weight.

(1) Flammability The flammability was evaluated using a test piece having a thickness of 1.6 mm according to a vertical flammability test defined in UL-94 of the US UL standard as a flammability evaluation scale. (2) Deflection temperature under load The deflection temperature under load was measured under a load of 18.5 kgf / cm ^{2 in} accordance with JIS K7207.

Each component in the amounts (parts by weight) described in Tables 1 and 2
And trimethyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd.) in an amount of 0.05 to 100 parts by weight of each of the components.
Add parts by weight and mix uniformly using a tumbler.
Twin screw extruder with 15mmφ vent (MP20 MP20
In 15), the mixture was pelletized at a resin temperature of 260 ° C., and the obtained pellets were dried at 95 ° C. for 4 hours using a hot air drier. The pellets are prepared by an injection molding machine (J75S manufactured by Japan Steel Works, Ltd.).
Each test piece was molded at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. in i). However, in the comparative example, the drying temperature was set to 70 ° C. and the mold temperature during molding was set to 6% for the sample containing not less than 20% by weight of the phosphate component and the sample containing not less than 30 parts by weight of the styrene resin.
Molding was performed at 5 ° C.

The symbols indicating the components shown in Tables 1 to 3 are as follows. (A component) PC; polycarbonate resin (manufactured by Teijin Chemicals Limited, Panlite L-1225WP, viscosity average molecular weight 22,50)
0) (Component B) ABS; ABS resin (Santac U manufactured by Mitsui Toatsu Co., Ltd.)
T-61) AS; AS resin (Styrac A manufactured by Asahi Kasei Corporation)
S769) HIPS; high impact polystyrene resin (Styrone manufactured by Asahi Kasei Corporation) (C component) DP, DDMP, DT described in Reference Examples 1 to 3
MP was used.

(Phosphate Esters Other than Component C) TPP; Triphenyl phosphate (S-4 manufactured by Daihachi Chemical Co., Ltd.) CR-733S; Condensed phosphate ester (Daichika Chemical Co., Ltd.)
CR-733S) PX200; Condensed phosphate ester (PX200 manufactured by Daihachi Chemical Industry Co., Ltd.) (D component) Inorganic salt CaCO3; Calcium carbonate (Wako Pure Chemical Industries, Ltd.)
Reagent special grade) MgCO3; Magnesium carbonate (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) Ca3 (PO4) 2; Calcium phosphate (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) BaCO3: Barium carbonate (Wako Pure Chemical Industries, Ltd.) (Special grade reagent) (inorganic salt other than D component) CaSO4; calcium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.)
MgO; Magnesium oxide (special grade of reagent, manufactured by Wako Pure Chemical Industries, Ltd.) Na2CO3; Sodium carbonate (special grade of reagent, manufactured by Wako Pure Chemical Industries, Ltd.) NaHCO3: Sodium hydrogen carbonate (specified of manufactured by Wako Pure Chemical Industries, Ltd.) K2CO3; potassium carbonate (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) (E component) fluororesin PTFE; polytetrafluoroethylene (polyflon FA500, manufactured by Daikin Industries, Ltd.)

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

As is clear from these tables, for example,
A comparison between Example 5 and Comparative Examples 2 and 3 shows that even when the same amount of the C component is blended, a sufficient flame retardant effect is obtained when the specific inorganic salt is not added or the required amount is not added. You can see that it cannot be done. In addition, when the component C of the present invention is compared with other phosphate ester compounds, from the comparison between Example 5 and Comparative Examples 11 and 12, in order to obtain an HDT value equivalent to that when the component C of the present invention is used, phosphorus It can be seen that the compounding amount of the acid ester is insufficient and flame retardancy cannot be obtained. On the other hand, it can be seen from Comparative Examples 13 and 14 that when the flame retardancy is sufficient, the HDT value is significantly reduced. Further, as can be seen from the comparison between these and Comparative Example 2, the C component of the present invention has a higher flame content than the phosphoric acid esters of Comparative Examples 13 and 14, but the C component alone has flame retardancy. Is not obtained.

When the component C is excessively added, not only a decrease in HDT value but also flame retardancy cannot be obtained, as seen in Comparative Example 4, even when an appropriate amount of a specific inorganic salt is blended. You can see that. In addition, when using an inorganic salt other than the specific inorganic salt from Comparative Examples 5 to 10, flame retardancy was not obtained,
It can be seen that the effect of the present invention is due to the specific inorganic salt. Example 28 shows the case of using together with another phosphate ester. However, from Comparative Example 15, when there is no specific inorganic salt, there is no flame-retardant effect and the other phosphate ester has no effect. It is understood that, when the content is high, V-0 is exhibited even without an inorganic salt, but the decrease in HDT value is large.

[0063]

The resin composition of the present invention has good flame retardancy without containing a halogen-based flame retardant in a polycarbonate resin and a resin composition of a polycarbonate resin and a styrene resin. Useful for OA equipment, home appliances, etc. that require flame retardancy, heat resistance, other chemical resistance, etc., as they have the property of less decrease in heat resistance compared to the case where conventional halogen-based flame retardants are used. It is.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 25:04 27:12)

Claims (5)

[Claims] 1. A polycarbonate resin (A component), (B) a styrene resin (B component), and (C) the following general formula (1): (Wherein R is a group having 3 to 20 carbon atoms and represents any one group selected from a substituted or unsubstituted phenyl group, a naphthyl group, an anthryl group, a pyridyl group, and a triazyl group). (C) one or more inorganic salts selected from the group consisting of alkaline earth metal carbonates and phosphates (D)
Component) and (E) a resin composition comprising a fluororesin (component E), and when the total of components A, B, C, D, and E is 100 parts by weight, component A is 97 to 100 parts by weight.
40 parts by weight, 0 to 55 parts by weight of component B, 2-2 of component C
0 parts by weight, the D component is 10 parts by weight or less, and the E component is 0.0
1 to 3 parts by weight, and the ratio of the number of moles of the D component to the number of moles of phosphorus atoms derived from the C component is 0.02 or more. 2. A component, B component, C component, D component and E component.
When the total of the components is 100 parts by weight, the A component is 90 to 5 parts by weight.
0 parts by weight, 5 to 40 parts by weight of component B, 4 to 18 parts of component C
Parts by weight, the D component is 8 parts by weight or less, and the E component is 0.01 to
The flame-retardant resin composition according to claim 1, wherein the ratio is 3 parts by weight and the ratio of the number of moles of the component D to the number of moles of phosphorus atoms derived from the component C exceeds 0.10. 3. The flame-retardant resin composition according to claim 1, wherein the component D is at least one inorganic salt selected from calcium carbonate, calcium phosphate, magnesium carbonate, and barium carbonate. 4. The flame-retardant resin composition according to claim 1, wherein the D component is at least one inorganic salt selected from calcium carbonate, calcium phosphate and barium carbonate. 5. The composition according to claim 1, wherein the component B is an ABS resin.
The flame-retardant resin composition according to any one of the above.